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I. STUDIES OF NEOHEXYL HALIDES II. STUDIES OF CHLOROPIVALIC ACID AND DERIVATIVES III. MISCELLANEOUS

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DOCTORAL DISSERTATION SERIES
mifL Sluiks of fid n jl M ies
LSklus ofChhmmlic hal WimA
1Miscell,MIMS
AUTHOR Thomis t Quwsy__ DATE O L
UNIVERSITY.
?i. Stile College
M
DEGREE JAJA_ _ _ _ _ _ _ _ _ _ _ _ PUBLICATION NO.
ill
11 1
21
8
u UNIVERSITY MICROFILMS
M ANN ARBOR
• MICHIGAN
THE
PENNSYLVANIA
STATE
THE GRADUATE
DEPARTMENT
I. S T U D I E S
II.
III.
SC P O O L
OF C H E M I S T R Y
OF N 2 0 H E X Y L
STUDIES
COLLEGE
HALIDES
OF C H L G A O P I V A L I C
ACID AND
DERIVATIVES
MISCELLANEOUS
A THESIS
t»y
THOMAS
p.
C a u NEY
IN P A R T I A L F U L F I L L M E N T
DOCTOR
J
OF
w
,
FOR
THE
DEGREE
OF
PHILOSOPHY
1 9 4 1
S 7
A r . P r c ■/ e < y .
,
)1 r e p t o r
o f
V.
h o s e ^ r c !
49 ■A
AC hd O'Ji
The
aopreclatlon
Frank
made
author desires
a nd
thanks
C# W h i t m o r e ,
thi s
T
to e x p r e s s
to h i s
whose
research
interest
h i 3 sincere
director,
and helpful
Dean
guidance
work possible#
The
author
Berns te in for his
is
help
also
Indebted
during
the
to D r#
early
Herbert
staples
of
this
work •
It is
of the
E.
I.
Reilly
du Pon t
also
Tar
de
h pleasure
a nd C h e m i c a l
Nemours
ox' till 3 lr ves t ipa tion •
and
to
acknowledge
Corporation
Company
during-
and
the
th e h e l p
of
the
course
TABLE
O F CO b T E A T S
P A H T JC
OF
S T U D IE S
n E O A E X Y L
H A L ID E S
1
■,it
q ro v-? v
A •
i.E v'
■h hiA A ■
.P S ......................................... * ..........
£
O » i'- u r. 'V\ L iiiiiA .'
4
C.
6
D .
T H E YYJA TZ A F A C T I F P ...................................
A S A C i 1 Ob
A L K Y A
v l 1'
A i.C J t . O L I C
i\ O h
Oh
i o i L I D S S ..............................................., ...............................................................................................
1 7
D I x j \J i J o ■j I o i
^V •
tx J. X_-Vx11I ii
-• .
r i :S
v„.v .'.x
O •li I'u i C i i v i
A
.A
v - H
. A A - i C n l ' I
X l '■-■i\
:A
F
A 'A C I ' i .......
' >F
i .
--J1"*. * _JX. L1-1A X~*- ,, •.X • » • •• « * • « •
A-
M
l
OF.
•• » • • • * •
.....................................................................................
n L i . . A ! ’ '...’j I O
i :>vi". I
•••
A
''
*- -1
AA
I - -•
i
A 7
T A . A 'A.
■.,t 'I-
.. A
.................................... -’A
.X.X. x.\I >:L*A,*.jn. i_*
1
A hOf.iAn.
D :;I ux\Xisi’
.S.
i A!lur,
lO A 0
OF
i1' Y
I O - A A n . .!l
1:1
*o Cb. 1 or Ii ia t i on
FI
b)
a ■. 3 , Vat. o r
Ci: I OI’.1p
t I ' r. in
F I .•;iA 1:., L i q u i d
PiAS!T ailA i I. ', oF
a)
b)
TI
- i:a 3 e
A.a
or,
Cb 1 o r-i r a t o r ...............
. r.1-'» • • • • • • <• • • • » •
i,l M -XX X T>iUi
1 i.a h r
t.(j \Ji.
0 hiI o r I t a t o r . ..... ...... . 4 5
,. 0 v :\IF
CnLvoIhn
P i n c o o 1 y 1 or I I'tisrnl ’U:!<..''Tit
O ■'it' V.1.
or
s ri,7:,urj
0 7
a
■Xn .T<»i;t
47
to
r ’i<;
PR'EPAH A TI 0 M O F 'LHP iViE'RCURIC S A L T O F
1 — CI1LORO— 2, 2— D I L E I L Y L B U T a N E
a ) Grigrnard R e a g e n t o f l - c h l o r o - 2 , 2 d i m e t h y l b u t a n e . ..............
b)
A d d i t i o n of G r i g n a r d R e a g e n t
to M e r c u r i c C h l o r i d e ..........................
PREPARATION
OF PIFAU G L Y L
48
49
IODIDE
a)
In H o t
S o l u t i o n .........................................
52
b;
In C o l d S o l u t i o n ........................................
52
c)
properties
54
IREPARATION
OF
Properties
P RE T A K A rlOt
OF
Properties
S O .. A K Y
of F I n a c o l y l
J L Odide. .....................
3 - Brt O m O - 2 , 2-DIi..K iiiYLb^ T A Y F .............
54
of
56
1 - Br o m o - 2 , 2 - d i m e t h y l b u t a n e .........
1 - I O D O - 2 , 2 - D I i.iETHYLBIJTAN E ...............
56
of
58
1 - I o d o - 2, 2 — d i m e t h y l b u t a n e ...........
OF T KOPEK TIES
OF NEOiiEXYL H A L I D E S ..............
59
R E A C T I O N O F P *<0P A i\>.L 1 0 K u R ON
PI . A CU L YL C H L O R I D E ......................................
a) S u m m a r y ...............................................
60
65
R E A C T I O N O F P R OF AI' L I C R O P O':
l - C H L O H O - 2 , 2-OJ.,.ErUi"LdP i'A- I..........................
a; S u m m a r y ......................................
65
68
K ’iAO ilui\ O r* r KOI-AN O L I C
r! 0.<
l - B A O F O - 2 , 2 — DIiviETfil'LidJ'fANE* ........................
a; S u m m a r y .
.......
69
72
R E A C T I O N OF I’R C P A N O L I C K O u ON
P I P A C C L Y L B R G L I D E .......................................
a) S u m m a r y ...........
73
74
R E u C T l O r u F PrUY AliuLlC K O O 0 8
lvriR0it0-3 , 5 - D l ...E I'H YL;i'STAKE...........................
a) Sum: n a r y ...............................................
75
77
^
^X j j <j P’ !"■'u u P n 8 o L I 0 K.0 ii C i.
1 - I C D G - £ , £ - r I E K I Y L S •.JTa K E .............................
a; S u m m a r y ..............................................
77
80
R E A C T I O N U P I - C H L O r O - 2 , : - D IiA :T .i' 1i YL. 8 9 T A E
V I T i i S O D I U i v i ...............................................................................................................
3 Yft I h E S I S
a)
b)
c)
d)
e)
OF
80
1,1 , 2 - I n'1 T-:■!:TV LO rdl.OF KOPA'i F .......
Pr e j i & r a i i o n
Airalfram. . . ...........
86
He d u c t i o n of ]>i a c e t o n e A l c o h o l
1. Ati
Fed A l u m i n u m l a o ^ r o r. y la t e
R e d u c t i o n ......................................
£• R e d u c t i o n W i t h S o a i u m A i n a b T i m * ..........
3» C a t a l y t i c H y d r o g e n a t i o n ....................
87
38
39
r r e p a r a t i o n of 0 - To FI > y 1 — V , 4 —
dibrononf fntanfc...................................
89
C y c l l z a t i o n of f-iv e t h y ] - 2 ,4dibrorr.open te ne ...............
91
Isolation
of S o d i u m
of
1 , L , 2- ’fr* I m e tb v 1 r y
c
1 or r o • ;.rie . .
KblKC 'iI0i\ O F 1 - B R O T O — 3 , o — DIi.i‘% ii :YL:i FI'A n F
'.Vl i H S G D I I! .............................................
:iiiAG rlu!.
OF
1 — C;:LOi<0 — 3 , vV— O I n rv: ■V j.j T l T A
94
97
v
v.i;i. SoL/
SUftiJiAii V of1' F Aiff I . . . . . . . . ............ . .............
} A .R 1
U n l m
n j H V / . i . l C
ICO
I i
A G IO
A'A'.j
lA F R l'/n
. 1
Jo
:
I ■.T x t o D U C T I U N ...........................................
104
.-18 i O K I ......................................................
105
u l - > G o 3 n 15 9 , ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
107
dXJ;ait I ivi vN i’Ali
- R F ’ T-i.n.n
iv
.
v.. F
C l :1 0 R
a;
A t 1 ernr. te d
Fr
b)
Chlorination
I V n l, i C
a m t i on
n C I F
In
Venor
’Vitr. C u l f n r v i
Tum
e . .. 1 0 9
C d o r i d e .. .. 109
PREPARATION
OF ChLORO'L'R I^.EIRYLACETIC A N H Y D R I D E . Ill
PREPARATION
OF T R I SJ!ETHYLa C E T Y L C H L O R I D E .........
11 2
F HEF a R A ' i ITT OF Gi,LuH>'I'KI...ET11YLACETYI. C R L ^ R I D E
a) A c t i o n of P C 1 R on
C h l o r o t r line t hy l ac e ti c A n h y d r i d e ..............
11 2
b)
Chlorination
PREPARATION
Chloride...
OF C- C H L O R u T R I .iE T H Y L AC ETA.*'.IDE......
113
114
ATiEr-iPTED H U F k a NN DE'THa DA'J 101. OF
C — CliLORC'iRI. .E jiiYXACETAniIDE* . . . . . . . . . . . . . . . . . . . .
11 5
C'dKTIl’3 D E l n A t i i r i O ^ O p
O h L O A O 'i'Rliv.0 iiiY L h C *1 YI. Oi.LGrvIi II . ............
116
a Cl I oh v.’r1 A Q U E O U S h a Oil O N
C HL O R O F I V AL I C A C I D ...................................
1 18
R E D U C T I O N OF C h L C R O TRIi. E T H Y d AC E T Y L C H L O R I D E
T U' h t - A F Y L I K I ' U T H n R K A T C N T
a) P r e p a r a t i o n of _t-Ainyl Crlrnard. Reaper: t .....
120
b)
a
of T r i m e t h y l a c e t y l
Addition
EY OF P A R T
of Chi cr o t r 1rr:e thy 1 a c e t y l
Chloride.
I I .........................................
120
1 22
P A R T III
.'.iSC dDD a isa o o o
DIOCHOTioT
A.
D E H Y D R a T Iu T
o.
S Y N T n E S lo
C.
0 X 1 h i-i i l ^ i s
OF
D l- t-
O F ,<U\ T n Y L
d U T Y L C a R o 1 h OL......................................1 2 3
i> - - A
'X Y I
K E T O r . E ...........................
126
128
EXt' o KI-.v v N T a L
F Uni FICA 1'loh
v F U L o c h i H Y L K H - u E ................
131
Frt.ypik.HA :lOP
OF' 3 CT..'An.IDE. ....................... 13 2
F I G U R E 3, Soclarulde A n p a r e t u a ................
13 3
Fit iFii.i MO IdU
Or*' T
'!Hiv,EV;;F L aC E'iVP i' I ••.' 1OLU EX
• 1 37
RE*- A:iA ,lv.;P OF 1 Tv 'A ■0 ;r Y.Lad ■!. OP"-i I.. D-.CAL.1.. . 140
FtiEPArta .lod
u F hKXAiv.E'l' -iYLaCE I’O U E
I 1'. -FOLUEPE..
TREFjdtA'.i.'IuN UP1 HEXa. Til YLaCEOoUP:
.<ED<:C TIO\
OF
14 2
Ii. D E C A L I N . . 144
iiE.vAiAKlri YL a CLF JRE
a)
Attempted
Alumim-un Iaoot’^ i v l R t e
b)
ReuucLicn
,/ith 3 odium-..- o i s t
DEPYDrtA iIvPv
Reduction
b e n z e n e ......
144
144
OF DI-t-OlJTYLCAi'.oIT.OL
a) ”’lth
1-Ch.l oro-4-nsinh t h c l e n e s ulf oni c A c i d
14 5
b)
Feta— Naphthaleneem]Ionic
a c i d .......
147
With
PrtFPaHa !I...V OF ...O' OYL
a)
b)
KO.VOE
preuarstir.t: of th ••
ii’*nar*d .Rea
r.t cl’
2 - OP. .1o o — P , 2 - -.1I >L: iv 1 p>\:t:<r. ..................
154
Ado; I Lion cl
r 1 r r• rtea^e;. t to
A c e t v 1 C t: 1o r I<i e ...............................
1 4
Art :j1iuu-. i
;^X .
:
NEOFEXYL
F
i 1.j
.\ : ?I P.. ■ _£..0:* ■
1
.j '■ I.fi
1i
A.•••••• •
13/
ii.'.ii 1 ■>.
r*ill I i .a.ij ;. i .0 o .. . v F
CL..’:..!jY L 1 3 0!' K OF' Y LOA o o 1 idYL C n L c K D i , ......
13d
DLI j1 , 0
.F a O' Yi. O.u.;!': . !0
'0-’ ■:i1 j‘ artD
rtFA' Ji n \ I OF D T n Y1.1.0C]0\P0 Y LO ji.p:".II-.YL 0t:L0.-;I;.) ■' 15b
h
A. .OP.iF “jD OX I
II'.
OF 1,3 — 3 1 1.'To!' 23 i’V L O ’:iA?- '• L60
A* . '....10’00
OIOj. j I o ;, v.F
2, 2,7 ,7-Y:pYrtA.-.: •’Y v 1,0CY A 0 0 ...................
OX IDA '’I '0 YF 3 'TL'- ■: *3 -O', iA A C I D ..............
Y left r*ome tr i e n 1 t :• t i or: o j;•v ~ e '•n -* t!,o
1 x I.•i*s*
-1 ’
c *-e ......
................ .
1 "3
3 63
1A
•;
SI
Y OR P
I L I ................................
Z 7J>
OlOLIoOrtAV-.Y F A R r
I ................................
17 3
B I E L I O MilT-.F f i u C
I I ...............................
177
OISLIGCtRaPHY F A R T
IJ I ...............................
173
PART
STUDIES
OF
X
NEOHEXYL
HALIDES
1
I NT H OP i JC T Iu N
Sine©
halides
an a
produced
reactions
the n e x t
study
conrr.ounds
interesting
, 2-di me th.ylbu tane •
the
13
were
syntheses
available
of
as
The
as
inr,
well
radicais,
by
and
important
as
ma y,
an
in
Neohexane,
decided
a good
h ow ,
product,
source
halides
organlc
and
groio
had
the
field
in
to s t u d y
should
easily
handled
Chloride
rinacolyl
Chloride
be
extremely
of
valu­
Previously,
the
neohexyl
however,
a nd
the
the
group­
this
p;roup-
- i n a c c tyJ-
r e a g e n t s , be
units:
ch3
CICHp-C-CHo-CrU,
(!H,
ch3
CIw
- c - C vR - C b*
'O
%L> 1
“*
CH-, Cl
1 - Chi or 0-5 , 5 - d i m e t h 'y l b u t a n e
neohexane
chlorination
Ch5
C H 3 -C - C H p -C H 3
ch3
Neohexyl
in
the h a l i d e s .
Now,
dr i c m a r d
encountered
however,
syntheses.
contain!nr
their
the n e o h e x y l
an d
cf
n e o n e n t y 1c a r b i n y l
through
of
difficulty
impossibility.
the
complete
the
compounds.
of a c o m p o u n d
almost
as
rives
neonsnt.yl
of n o o p e n t a n e , n a m e l y , n e o h e x a n e ,
comirercini
neohexy]
ing was
duced
a
reagents
n r e p a r a 1 1 on
as
those
of
trie n e o p e n t y l
The early studies
hammered
the h y d r o c a r b o n
a bl e ,
the r e a c t i o n s
containing;
higher homolo^
chlorides
of
1 9
rearrangements-'-'^ it w a s
of m o l e c u l a r
2
the
CH-*
O -C* -§ N o
*-C H o*—C
•l
ch3
intro­
2
T
A_^_ 'N"HQliKXAftE
rir.»t
2 , _ -
"1
t ! ... 1 i-
•li
: •• ,
' '•••;■ — ■a !
. v . »• '
' 1 •
/.!•.(: :■1 ^ 1 v. ♦
Ow i Lacii" ,
-
V
c.-' i;;.
!
■
;.. i i- ; t - ■>' '*1
d
.V .■ .-v. r ’.
a.Yf.l/!’ w
•' ,
'!
<
U
i ‘
^ i
. .--'.v' •••. 1 .. .V
■i"
■-■!.<:
-
,
•
’>■■..7 L
„,::J S i m o n -
.'■ „ .;;1
,
_' L •<1 :. *.:
v
]’
iT 1 ■
.
m a t u r e ted
3 1
<<
>
1’ L 1 : * '
;! I .
3
to L<Ia rs v.;i
hexano
ii,l Li v.-stii t ?■.'*
rod *r>3J ;>inacol
ir: 3 b, 1 ;3 o 1 d us In*-’ t.o'] '’bdMiiUM ^ u l T i
raiaor a r, i '.tid •ty'Oi1^ , 5 n 19 36,
tayie
!•:
- 3 9 ’b y iie l1 d(iss
•f-. o ! a .
;e
+w* o
1 •• 3 7
u / ‘e
3
J /i i 1
aOl
fiydro^ouu tod
r* 3 0 h e x a n e
>1
c
c ihillo
oo
ri
l db oe
>b t
t—
— urrivl
urriyl
! '> -: 1 .b.i t y 1
tha t
••r.d
c o a r -oxaii ‘ti •
-- -j
c h l o v if"
' 11 ’’ JT’
Tj
LL-'
oil •* .
■•■11 • ■•);
;-.<.bi<.
by
;;■
S > ••■•
ti:
to
oro
ctyl-
O trie ;* •
de
B.
NEOHEXYL HALIDES
A search
only
or
one
namely
the
the n e o h e x y l
the p i n a c o l y l ,
availability
was
of
thought
of
the
considerable
they h e a t e d
used
ethylene.
the
is
the o n l y
KCl
tertiary
Richard^®
and not
r e a c t i o n of
this
what he
with
thesis
of
tained by
tris
ozidized
Grifrnnrd
in 1 9 1 0
and
method,
this
the
complex,
3howed
Silva.
the p r e ­
and,
alcohol
He
synthesis
tube.
when
Couturie
was
potassium
and
tetraraethyl
found
that Jt-buty
reaction
of
bromide,
the
alcoholic
Indicat­
rearranged
definitely
took
Friedel
alcoholic
has
chloride
n r e r a r *d the
product,
it
called pinacolyl
pure p i n a c o l y l
the s e c o n d a r y
Friedel
this
t-butylethylene
product
with
from which
in a s e a l e d
bromide
both
the
discussion*
that wha t Couturier p r o b a b l y had
bromide.
it,
alcohol
to a t t e m p t
and
of
Investigated,
from pinacolyl
to p r e p a r e
author
potassium hydroxide
ing
first
that
be made*
chloride
obtained
been
p r o b a b l y beinp;
contrav^rsial
method
The
ha s
shows
the p o s s i b i l i t y of
Ur' reactin'1; his
h y d r o x i d e he
ethylene
of
the a l c o h o l
the s a m e
bromide.
could
question
a nd Silva^^- w e r e
halides
corresponding
p a r a t i o n , of pinacolyl.
aroused
literature
the r e a s o n
the h a l i d e
T he
early
t ha t
the
was
formed
In
the
chloride
the
ob­
'-ricnurd reajsrent f r o m
on d e c o m p o s i t i o n
of
the
o b t a i n e d d ime thy 1 is on r op y 1 ca rb i nol .
Wl'ii t m o r e
m/on
at
and
R o t h r o c k ^ obtained
room
thoroi.'*t
tonoruiure.
i n ve a t !,■'.* ! n
V.
•f]
t i m e v;l til r.'Cl a n • a! th
ed
t or, ’ y
t,v,p)-.ed 1 r:
oh] (>iddo
w
'
r;n
r•
a
fir;.-] ]y
L"
1
t r ■■: T
:.v i
n . ’f-r
.
t.
r■
•
,h
r,
: .•
n!;. -
valnri
c i l o r ! Jie,
''lnacdyl
y true ture
o f
; ‘
conclud­
chloride
- 3 tad'.1 1 a h e n ’ 1 >i 1 9 3 1
1c
r 1 •.a c
h ha t race
y1
,.-d i ;i i r e or r-1.--.-*
a ;• I :
■ e t 1c
-
-
was
n l r o inr l y l
err.n t e l n L - m o v e d
h
a
1■
,;
-if irohtxaf.'.-
o n 1 n :•I -d e »
r. I n n c o l y l
;d:*
In
•->-1 .i “ o l
\
f .
of
the
.' 7
, : ,. ^
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t
an
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The
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:nu !■.
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ilo o n i f r ^ 13,
chloride
r e -j 11 1 I ;i.- fro.-1 tr - c h i o r I r.a f I 'c»
t/ r 1 r
presence
if
t> 1.3 r*e a c 1 1 or. •
r" i f" ° r o ,
t
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v» ■.r
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i m
t
or* •• 1oyj
o ■:1I.
j.
T J n T Z
1
v ■ •j■
V
M
i
.
.
!
4
1.
nn - «
co:
■1
)
r - a. ■I
r
o
"h
T .. 4
r.
from
a mixture
i.e.,
of
the p o s s i b l e
paraffin
dimers
bromide
water
and
is
and G r e e n ^
give
an
a
bromide
temperature.
i-propyl
paraffin
that
iodide,
monomers,
ether
reaction.
reaction
30% yield
in
No
in d r y
little
immediate
obtained
f r o m ja-butyl
and
and
obtained.
reports
2
sodium
added,
iodide
olefins,
were
Silva^
room
i-amyl
moist
of
If
takes
a
trace
place.
of
Norris
3,4-dimethylhexane
ether
r e a c t i o n was
i-propyl
during
24 h o u r s
obtained
in
at
anhydrous
ether.
Young
and
Fortey^
and
2
,5 - d i m e t h y l h e x a n e
and
i^-butyl b r o m i d e s .
prepared
4
from
ethereal
Csrleton2^ further
in s o l v e n t s .
dimethyl
Using
aniline
in d i e t h y l
i-amy1 bromide,
the
ether,
studied
reaction
four
days;
was
in
2,3-dimethylbutane
solutions
of
the
reaction
he
Vurtz
found
completed
benzene,
that
in
i— p r o p y l
in
a few hours;
1 0
/& r e a c t e d
to p r e p a r e
n-hexane
in
15 days «
Schorlemrner2 ® w a s
out
the
sealed
sults
was
use
tube
when
heated
of
a solvent
with
sodium.
tried with
to
155°
able
by heating
n-propyl
iodide
However,
th e m e t h o d
gave
n-butyl
with
bromide.
sodium,
Then
i-amyl
2,7-dimethyloctane
with­
in
no
a
re­
bromide
was
ob­
t a i n e d .^
n-Decane,
( L a c h o w i c z 2 ^) , 3 , 6 - d i m e t h y l o c t a n e ,
( J u s t 2 ® ) , 7 , d - d i m e t u y l t e t r a d e c a n e , (A l e c h i n 3 0 ), d i n o n y l .
(K r a f f t 3 -*-) , and. d i m y r i c y l ,
pared from
found
the
No
coupled
with
possible
which
when
amyl
to
of a
take
be :ti o b s e r v e d
Michael3 3
found
the
reactions
In
both
The
was
also
initiated
was
also
used
from
all.yl
very
slow.
as
the
by
he
of
on
and
all
adding
able
adding
in
the
of butyl-
acetonitrile
does
and
not
the
iodide
acetonitrile
cyanide
of diallyl
reaction
47.6%
as
a
is
yields
catalyst.
lsobutylb9 nzene
the
sodium
Methyl
the
in
to
reactions
with
formation
alter
small.
conditions.^
cyanide.
cyanide
of
n-propyl
iodide
sodium.Normally
and methyl
were
reactions
vigorous
n-hexane
iodide
difficulty.
and
of
to g e t
methyl
the
normal
trace
of e t h y l
of
sodium.
when he
cases
great
iodide
a
with
been made
some
only with
reaction
by
in
sodium under
was
bromide
preparation
presence
place
Erdheim3 ^ obtained
using n-propyl
In
catalyst
a catalyst
iodide
yields
b u t no
and n-butyl
no m e n tion has
with
that
cases.
n-propyl,
that methyl
very u n r e a c t i v e
reacted
drawn by Welt^^
The
time
Is
pre­
Dobbin33
and h y d r o g e n ,
chloride
ethyl,
this
influence
above
monomer halide.
were
iodide.
ordinarily
It h a s
t-butyl
individually
active
a n d H a g e l a 3 ^) , w e r e
triisobutylene,
conclusions
Up
were
corresponding
isobutylene,
diisobutylene
(Hell
yield
the
of
the
hydrocarbon.3 ^
The
well
as
ketazine
that
in
catalytic
of
the
activity
of d i p h e n y l
tetraphenylethylene
reaction
and
between butyl
ketone
as
acetophenoneiodide
and
sodium
lias b e e n
organic
Investigated.3®
compounds
may
It
serve
is
as
sliown
tliat o n l y
catalysts
in
the
such
reaction
w h i ch
1
) annex
away w it hout
2
carbon
becoming
) join
ceeding
reaction
atoms
which
velocity
of
of d i - s o d i u m
Ethyl
bromide
or
sodium
carbon
sodium with
and
to
give
them
th e n e i g h b o r i n g
the
In m o i s t
A
catalysts
when
ether.
systematic
co-workers.
The
is
being
reaction
greatly
given
away*
corresponds
with
butyl
ex­
The
to
t he
Iodide,
and
reaction.
acetate was
octane
a velocity
sodium
the
a pseudobimolecular
25,^ o f
of
alkylized;
two
annex
that with
measurable
and
atoms
atoms;
3)
Is
two
used
sodium
O T.
as
is
of
catalyst
reacted
survey w a 3
results
a
with
undertaken
their
work
to
give
3-butyl
by
are
Huckel3^
summarized
below•
HALIDE
METAL
SOLVENT
PRODUCTS
C H 3 C1
Na-K
alloy
No
C 2 H 5B r
Na-K
alloy
c 2h 6
C 2H 4
C 4H lO
c 2 h 6 ci
Na—K
% YIELD
reaction
14-33
1- 3 . 5
27-29
Na
8-11.5
6 7.5
55-65
alloy
20-32
2 5
3-16
con tinued
PRODUCTS
SOLVENT
METAL
HALIDE
Na
n - C 3 H 7 CI
% YIELD
19-22
7-11
18-24
C 3H Q
<^14
Na-K
I - C 3 H 7 CI
alloy
c
3 5 - 40
14-18
2 .1 - 2 . 6
3H 8
C3 H 6
C 6H 14
i-C3 H 7Br
Na-K
alloy
decalin
c3h3
C 3H 6
27
25
l^-C3 H 7 B r
Na-K alloy
benzene
C3H8
C3 H 6
40
31.5
C H 3 Br
Na-K
alloy
xylene
C 2H 6
12.5
C2 H 5Br
Na-K alloy
xylene
c2 h 6
c 4h i o
28
40
CH 3Br plus
CgHoBr
Na-K
alloy
xylene
c2 h 6
c2 h4
C3 h 8
C 4H lO
7
9
15
28
CH 3 Br plus
H - c oH 7 Br
Na-K
alloy
C 2B 6
c 3H 6
C 4H 1 0
C 6 Hl4
3
9
7.5
44
C H 3 13r plus
i— C 3 H 7 B r
Na-K
alloy
c2 h 6
C ■iH
I - G 4 H 10
As
a nd Y o k e
4.D
a supplement
made
Wurtz reaction.
high yield
of
or a n e x c e s s
volume
the u s e
or
a low
of f i n e
this w o r k , L e w i s ,
as
bromide,
their goal,
50 m o l e p e r c e n t
two a n d
reaction
on e h a l f
and
times
of s o d i u m ,
Hendricks
the
taking
a
they r e c o m m e n d
or sodium,
temperature,
particles
affecting
condltions
Using n-butyl
octane
of eth--r
bromide,
a s tudy of
to
15-16
15
41-45
the
the
the
use
volume
or
of
a snort r e a c t i o n
and
agitation.
use
a
the
time,
In
11
this
Investigation
they fo u n d
Michael*a w o r k 3 6 , namely,
ether hinder
the
the r e a c t i o n
completely.
temperature
reaction,
by e x p e r i m e n t a l
poses
that
leaving
traces
and
In
the
stops
that a h i g h e r
formation.
mechanisms have
evidence.
The
are
free
which
can
been proposed
strongly
radical
is r e m o v e d f r o m
a free radical
of water
to
that a c e t o n i t r i l e
b o t h of w h i c h
the h a l i d e
ooposed
They also say
olefin
Two principal
the W u r t z
that
reaction,
favors
two f a c t s
the
either
for
supported
theory p r o ­
alkyl
group,
combine
or d i s ­
proportionate :
2 RC1 + 2 Na
2 R-
>
2 R-
--- > R-
---->
2 N a C l + 2 R-
R-R
R-
+(-B)
The
halide
sodium
reacts
with
sodium halide,
the
In 1 9 0 8 ,
a Wurtz
sodium
alkyl
bromide
other
to e x p l a i n
as
that
the
‘
.Then a m i x t u r e
is r e a c t e d
corresponding
i3
giving
the u s e
of
of
i— amyl
with sodium,
5
- 10/6
to the d e h y d r a t i o n p r o d u c t
obtained.
He
explained
f ol l o w s :
R X r 2 Na --- >
R N a V- R •COR ' '
on e
alkyl
a compound from
said necessitated
it.
the
alkyl.
S c h o r i g i n 4 ^- i s o l a t e d
diphenylisoamylcarbinol
reaction
of s o d i u m ,
giving sodium
and b e a z o p h e n o n e
of a n o l e f i n
theory states
two a t o m s
reaction which he
alkyl
(/H)
R N a y- N a X
^ R
R
»
r
» 'C O N a
the
of
12
When
i a o a m y lm a gn e si u in b r o m i d e
phenone,
t ha t
of
tertiary carbinol
the s o d i u m
this
hla
no
type
studies
i-amyl
the
la
obtained*
He
much more
th a n w a s
the
Grignard reagent.
using ethyl
an d
iodide
tertiary
In b o t h
carbinol.
used during
d i e t h y l m e r c u r y , and s t u d i e d
w as
the
o th
Its
intermediate.
through a whole
series
below:
CARBONYL
COMPOUND
Die t h y 1
Benzophenone
Di e tiiy 1
Benzaldehyde
In
a reaction
He
continued
of
SOLVENT
^ther
c a se s h e
of
car­
-butyl
bro­
sodium from
as
extended
compounds.
1
later
recovered.
reaction
He
these
and
a pressure
reaction
acid
t h a t of a W u r t z
of
when
the
Schorigin prepared
reactive
concluded
and benzophenone,
acetonhenone.
and sodluir., i s o v a l e r i c
tabulated
with benzo-
was
bon dioxide was
mide
reacted
alkyl
bromide
obtained
la
His
compared
this
to
study
results
are
PRODUCT
Diphenyle thylcarbinol
Phenyle thylcarbinol
Die thy1
co2
F r op1 on 1 c acid
D i m e thyl
co2
Acetic
Di i s o a m y l
co2
Isohexoic
Die thyl
co2
Toluene
Die thyl
co2
m-Xylene
Zn d i e t h y l
CO n
Toluene
acid
acid
Phenylacetic
m-Tolylacetic
acid
acid
P h e n y l e c e tlc
plus
£ - T o l u I c acids
13
F r o m ills r e s u l t s
HgRgy-2
lie p o s t u l a t e d ,
the
--------- H g / 2
RNa
Na
R N a ^ R *C O R ’ ’
>
2 NaR^R'CO^R’’
>
------ >
NaR/R'CHO
R R*
R
1
followings
'C O N a
N a O R » ' /- R gR * C O N a
R R ' — CHONa
NaR ^ C 0 2 — > RCOgNa
He
from
explained
th©
a sodium-hydrogen
C 6H 6 * C 2H 5 N a
---- >
C 6H 5 N a
C 6 H 5 Na
---- >
C6H
volumes
acids
as
resulting
interchange:
-a C 0 2
Wher. s o d i u m w a s
equal
aromatic
of e t h a n e
5
^ C2h 6
C 0 2 Na
reacted with
an d
ethylene
diethylmercury,
were
formed:
H g ( C g H 5 )r>-/ 2 N a -- > H g -f 2 C o H g N a
No
trace
2
C r.Hb N a
of
butane
~f~ 2 H g — ^ 2 N a H g
was
found.
Scliorlgln p o s t u l a t e d
( CrpH ^ )j-jONa,
tnercury,
as
an
sodium,
e t h y l ate ,
etiiylene,
As
ethyl
and
a result
intermediates
by
quite
and
like
addition
cf
ether.
ethane
were
studied
from
1 t3
a Grignard
I n this
reagent,
but
of d i e t h y l -
reaction
sodium
formed.
and
of
They
more
sodium
Ochs^^
triphonylmethyl
reactivity.
compound,
the r e a c t i o n
the p o s t u l a t i o n
.dehorlgin, I c h l e n k
triphenylmethylsodlum
sodium,
an
I n t e r m e d i a t e In
and
v- C ^ H ^ C g H g
prepared
chloride
found
alkyl
It
reactive.
and
to b e
14
When
bromobenzene
the p r e s e n c e
was
benzene
in
ketone,
t r i p h e n y l o a r b i n o l , and
covered*^
The
same
of* p h e n y l s o d i u m a n d
sodium
in
ether
of* c a r b o n
compounds
exist
with
on
gave
the
sodium
benzyl
as
Tree
from
were
re­
a reaction
bromide
and
trie thyl c a r b i n o l •
in
there
that
the
radicals,
In
diphenyl
Ethyl
and
sodium
alcohol
resulted
3-pentanone
assumption
transiently
monoxide,
carbon monoxide*
T h e hydrogen-sodiurr. e x c h a n g e
explained
reacted with
reactions
organic
and
has
groups
then e i t h e r
been
do
react
of* d i s p r o p o r t i o n a t e :
R X y- No ---- >*R- y- N a X
R- y-Na --- > R N a
2R
R-R
e-
^
r-
y-
(-H)
(t H )
R N a y X R -- > N a X Y“ R - R
R-
R-
-t
(— K )
To
groups
support
Schlenk4 4
a n d s o d i u m can u n i t e
Free
actions.
By
Polanyi,
and
radicals
eight
trie b r o m i d e
radicals
the u s e
have
form sodium
been
deteood
Style4° observed
free
methyl
and
the
source
of
dioxide,
from
compounds.
In W u r t z
technique
centimeters
that aryl
alkyl
tube
and
of
to
Indicated
vacuum
re­
Horn,
ethyl
contact
of
sodium*
Bachmann
carbon
this,
(y-H)
and
and
Clarke,4 6
in
the
dl-£-tolylmercury
reaction
In b e n z e n e ,
of
sodium,
isolated
£-raethylbenzoic
They
used
acid,
benzoic
the f o l l o w i n g
acid,
reactions
and nhenylacetic
to e x p l a i n
the
acid.
formation
of £-dlpherjylbenzen« :
C 6 H 5 C 1 -a 2 N a
C6 H 5Na
C 6 M 5Na +
>C
C 6 H 5 *C 6 H 4 N a y - C 6 H 5 C l
to e x p l a i n
o ne
use
must
gave
than
9% h e p t a n e ,
Isoamyl
bromide
obtained
benzene
and
-^C6 H 5 -C6 H 4 Na
^ N a C l + ( C 6 H 5 )2 C 6 H 4
aliphatic
the d i m e r
of
triphenylene
compounds
coupling pro­
formed*
n-Heptyl
tetradecano,
€>r7%
and
analogous
to
by B l u n - B e r g m a n n
sodium
in b e n z e n e
those
4-7
in
the
under
an
are
in a b e n z e n e
on
amyl
T he
presence
any
alkyl
a nressure
studies
C 2 1 H 44*
co-workers
chloride
of
and
of
Clarke
brcmo-
of
t r i p h enylene, were
solution,
and
sodium
diphenyl
and
formed.
ivlorton^^ a n d
sodium
3%
atmosphere
'Vhen d i p h e n y l m o r c u r y , b r o m o b e n z e n e ,
triphenylene
and
reaction
isolated*
to s t a n d
o - P h C g H 4 Ph,
of B a c h m a n n
Diphenyl,
allowed
bromide
gave pentadecane*
nitrogen*
are
H ^ C g —■
V 'C 6 H 4
were
3& h e p t a n e ,
Results
were
a NaCl
^
C g H 4\ r a d i c a l *
the
higher
6
the p r e s e n c e
Even with
ducts
H 5Na
^ C 6 H 5 C 1 - ^ C 6 H 5 « C 6 H 5 /-N a C l
C6 H 5 *C 6 B 5 - ^ C 6 H
However,
6
the
sodium
of 9 0 0
carbon
formed.
pounds
i/iorton d r e w
under
the
a pressure
dioxide
Butyl
of
observed
following
of
acid
dioxide*
action
carbon
immediately
malonic
carbon
the
dioxide*
consumed
appeared
From his
conclusions:
of
at
1)
Free
simultaneously
radicals
with
th e
are
formed
formation
of
either
alkyl
before
sodium
or
com­
pounds •
2)
ation
The
rather
decane
The
free
than
is
amyl
radical
coupling
formed
by
to
the
C 5H l l Na
3)
is
formed
radicals
It
from
is
the
rather
Morton
of
toluene
change
than
on
further
the
of
-y-
the
sodium.
Na y c 6 H
6
from
th e
by
formation
the
sodium
ar aylsodium.
6
that
on
C 1 0 H 22
the
t he
alkyl
free
the
products
sodium
alkyl
account
for
of
reaction
the
inter­
proposed:
~ > C 5H 1- + C 6H 5 N & *
N a C 1
C 6H 5 C H 2 TJa y- C 6 H 6
H 5 C H 2 C 0 2Na
C H ( N a ) C O r , N a ^ C 6 H 5 GII3
> C6 H & CH(CO gNa )2
of p h e n y l e n e d l s o d i u m wa s
Isolation
exchange
least
N a C 1
mechanism was
> C gH
-f- G O g
at
halide.
To
following
C02 — > C
C 6 H . G H ( N a ) C 0 2 Na
suDDorted
alkyl
studied
C6 H 5 C H 2 C 0 2Na ^ C 6 H b C H 2 Na
The
--- ^
sodium
C 6H b * C H 3 --->
C 6 H b CHoNa
of
disprooortion-
reaction
C 5 H 1 1 C1
action
C 5 H 1 1 C1 +
C 6H 5 N a
extent
entirely possible
and p h e n y l
reaction,
the
undergoes
of
i s o-
reactions
and
further
terephthalic
between
benzene
acids
and
17
D.
REACTION
OF ALCOH O L I C KO H
Balard,^^
in 1 334,
ON A L K Y L H A L I D E S
reported
of a l c o h o l i c p o t a s s i u m h y d r o x i d e
alcohol
to s p l i t
out potassium
and ethyl
hydroxide,
isolated anisole
from
chloride
iodides
with
of w ine
In 1851
phenol
and
and o h e n e t o l e
Cahours^
potassium
respectively
the r e a c t i o n s .
The
r e a c t i o n was
first report
VI th a m y l
of e t h e r
by W i l l i a m s o n . ^
sium ethylate he
iodide he
compound which
recovered
hexone
and
the y
and d e c y l
Heboul
this
length
gether
of
isolated
this
recovered
with
Truchot'-^
series
of
on
alcoholic
found
and p o t a s ­
ethyl
amyl
ether.
the
action
chloride.
53
who
some
amyl,
found
ether
n-butyl
and
iodide
with some
h e p t y l , octyl,
and
they s h o w e d
the m i x e d
that
wa s
ethers.
Increased
f r o m jt-butyl
butylene
sodium butylate.
the
potassium hydroxide,
e t h y l Jt-butyl e t h e r
Mostly dibutyl
of
'This
chain favored ether formation.
c:i-.
B u t l e r o w , ° in 1867, r e n o r t e d I s o b u t y l e n e
with
other.
ether.
the o l e f i n s
reactions
this
a low b o i l i n g
from
on n - h e x y l
the m i x e d
and
ethyl
a hexene
type r e a c t i o n
chlorides
and
the m i x e d
considered
iodide
iodide
r e p e a t e d by S c h o r l e m m e r ,
also
In
From ethyl
an d C a h o u r a ^ ^
alcoholic potassium hydroxide
e x p e r i m e n t was
formation by
obtained potassium
Pelouze
From
the
first reaction
chloride.
reacted methyl
and
on
the
to­
Iodide©
obtained
from
From
Fawlow^®
2
the
iodide
of dime t h y l l s o b u t y l c a r b i n o l
obtained unrearranged
- m e t h y l - l - i o d o b u t a n e , gave
Lengreld^ 7
the
alcoholic
sodium hydroxide,
percent
relative
reacted
Active
a series
s t a b i l i t y of
alkyl
bromides
% R E ACTE]
N/5 NaOH
58.0
2 0 . 8
32.5
18.3
29.3
i-Propyl
4.8
8.5
i-Butyl
5. 7
9.3
_I-Amyl
9.1
14.5
87.9
87.9
ropyl
Butyl
_t- B u t y l
Couturier^
tetramethylethylene
bromide
by
the
the
with
alcoholic
author
of
rearranged
this
bromide
idzkowski
In
1899,
reported
are
formed
that jt-butylethylene
In
the
reaction
potassium hydroxide.
the3 i3
and
that C o u t u r i e r
not pinacolyl
a n d '•Vagner^® r e p o r t e d
Nef®^
as
solution:
38.0
1
to
with
results
In s o d i u m h y d r o x i d e
% REACTED
N/IO NaOH
Ethyl
Iodide,
of e x o e r i m e n t s
and r e p o r t e d his
In f o u r d a y s
BROMIDE
amyl
u n a y m .-methyle thylethylene .
performed
determine
olefins.
showed
that
and
of p i n a c o l y l
It
is
believed
started with
bromide.
a p e c u l i a r reactfcn:
isobutyl
chloride,
b r o m l d © , and
Iodide
in
named.
the
order
Madsen,
in
distinction
between
alkyloxides
of
mination
gave
the
increasing
1913,
Both
reactions
or
W i t t l e , 6 ^ in 1937,
alcoholic
75^ h y d r o g e n ,
ethyl
ether,
residue.
3-5,% n e o p e n t y l
with
This
75%
r e a c t i o n wa s
Popkin^^
hydroxide
with
h a d p r e v i o u s iy
reaction
These
of
seven
positive
the
process
of
sub­
due
to
and
acid
studied
the
seven
2-e t h y l - 1-hutanol
chlorides
were
and
being
*
formed
12-13%
the
of
by
neopentyl
from
the
equation:
CH3 C °8K
alcoholic
ootassl
Karnatz^^
chlorides
zinc
with
neopentane,
chloride.
isomeric
with
75%
H 2 y'K I ^
reaction
eli­
iodide
recovered
by
and
alkyloxide.
obtained
die thylearbincarbinyl
isolated
the
neopentyl
described
no
of h y d r o x i d e s
the
■*“ c 2 H 5 0ii ---> C 5 H 1 2
C 5H 1 1 I v 'KC)H
i3
to
alcohol,
acetic
there
respect
reacted
potassium hydroxide,
isobutylene
with
to
were
of
that
solutions
metals
of h y d r o g e n h a l i d e
stitution.
indicated
alcoholic
alkali
yields
chloride
from
and
a rearrangement
the
4C1.
of
th e
fragment,
G — G
VC — C *r
C —
F o p k l n ’a c h l o r i d e
moval
of
the
ed p r o d u c t s ,
carbinyl
would
chlorine.
2 2
ethyl
%
give
this
However,
C'
same
he
found
d i e thyl e t h y l e n e , a n d
ether.
fragment
65%
only
on
re­
unrearrang­
d i e tl i y l c a r b i n -
20
Popkin
ethylene
With
of
and
isoaxnyl
the
also
9 2 t ether
iodide
olefin.
obtained
when
a 12% yield
isoamyl
of
chloride
Flinn6° had previously
isopropylwas
used.
obtained
37%
21
D IS C U 33IO N
C h L u a 1 u A I'lO iN
The
both
the
dary
chloride
this
In
v
pas
found
in
-'<cv
m o n
larpe ^ > mount
t. sc fps
chloride,
phHS°3 •
rmmelv,
phn •e c;d or l n a t i o n ,
oinocolyi
the
chlorine
was
M iic *:-y 1 no t . :e
er-co h a s m e n
to s e fcUit ■• it
f itare.
from
It
the
01'
.secon­
two m e t h o d s
r h l o r in** t i o n
of
thn t *»t t,I•<» h iyiier t e m p e r ­
1 1 • 1&
r V
f
the
be
found#
secondary
or. t-pe n e o h e x a n e
tie? lew
c: •1 or J nr tin;
will
#H
t e m n e r a taro
of
cor-
used
pina r o l y l
h-moa.
Ir* r.oi-<» of
f
^ t,
stioo fchlv in
or* on or t i on a
for
f ^ l o r i l e , based
1 1auid r. hU "
roes
o f nrimrjiy n r r d u c t
s uir.ed , wr s r ^ c o v - r^d , rhi 1 e
for
The
the p r o d u c t s
t
z
neohexane
thos- n r e d i c ted b y
tyre* h.vdr
ature
f O h h X - a . t\ h
b
chlorlnatic.'i of
li q\:id and
u r reo w i t h
f
t h ••>■ ohlorir;s ti m s
;*--r o
: *e r• •
f’o ..j.d , nut
from
the
it
-•5d**;ic e
ti.e 1 - o h l C i ‘C
for
,.8.i n< .
•t h e e r. f o u n d
i sc m e r i c
ti.os, h o w e v e r ,
K
'u-n was
its
ones -
possible
1 - c h l o r o - f , f-di trie thyl -
beer. o v o; a r ^ d
fr-hii t:.e c o m e s —
•iOnulny a 1 c c :•e 1 , ru'd its r r o* •jr t i e a de te r m i n e d #
22
T H E WTJRTZ R E A C T I O N :
The
r e a c 11 or
nf
1 •o 2
di rr.ethyl^uts ne wi tti r»n s t o I o
ma tico
of
of
of
29.38,
2.34,
12.70
ac f i or
and
the
foIlCA'ine b a a 1 :
radical
with
In
the
s enso
f*h'.: 'leo-’-rty]
c
m
as
that
to a c ” <‘u i.jt.
it
V--
1 ec.l sr
;■eon -jn •. 3 n. •
n >■**. I - r
3
,1c 'i
;nd ,
on
odd
f or-minr
now,
1” ,
s
f ;4<
one
h?
for­
riilef. in
a fr- e
electron,
reacts
o<i I*.or. oh 1 o r i d e
free
nodical
ra d I o a 1
c 4~h-n‘ ♦ r<•i•^ h y
the
i/o
v?roee ",t s t u d y o n
.ne ch ani s w
h
*
f f -•? e . ‘t • y 1
*_ .e
be
]I
1.7 n e w
ticce.M-'orv
L::e
.v
.-.c) I d s
v
**0
:••• r
, ••
.■: .jv
h i t-
d 1 c •-1 •
1.1 or. c
of
-jet
1 1” m o d i f l e d
to
r r 1 1,1,2>.d n ^ t o
b Imoiec.-l er
this
oelei'eh
• y v .,.,.7 4
i
a
re ohc xyl
h ;;1 ef'yhe.i-
° 3 a- ■'I'-.’e n 4: the
bcv^ .
; - !. / r h-
must
h * i o. ■ o °
Tt
ti. ? f c rtt.-- tier
and
strikes
aft
m a y
cb t^l: .e d
exrd s i n o d
t 11 •*t. 3 +■m r-»i ] I •.*■d h v tf - for
ebc-ve por. t',;] a t i o n
ted
c. I c r l d e ,
for ::lap tie G v'e v fa•.<.» ....-'d >' di - r»»—
r r;
f’
bna
re*uh:t f r c n
f'.yl eye 1 orir*C'';i ic' •
3e
the
In p e r c e n t a g e
eye] i^.a tl-' n w o n
od 1 .!rr *•tow,
If
a resul t of
oh 1 or i de , the
: -•
a
th-u ■-tn*-*r
T :‘1 o d i— fr • •
Lr 1
-fn In
A
rt.d 5 .y-1 •
fiiod.i:’ ;■ r*a d l c e l ,
a cyoi io
in
reapectivelv.
O
e oh ta 1 r;ed b y t o p k i r f ' w n e n ,
tyL
’ie rmih e: d y 1 o’!1 o r l d -
O e 1 f‘ to
pesulta
4.29
of s •',,•}I ■j-- (
1 , l-’li r'e ti jlcyolot roi'ano,
on
s odium
and. 3,3, 6 , 6 — to trametl.yloctor.e
Si.riilnr "es .'lta •-*.*c r
I-. too
c f 1 — c:i1 o i •c — 2 , 2-
noot’e x a n e , t - b u t y l e t h y l e n e , 1 , 1 , 2 - t r 3 m o t h y l —
cycl oi. r o p s r e ,
yieJds
•'>o I *-:<
3?
.d
:.
-■
In.
23
the
w crh
or
R ice
Free
7^
and
rr;e t h y l
o th e rs
on
ra d io .'.Is
rv d i c a 1 a •
fre e
r nd
e thane
can
fiv e
+he
o I ] ow !I' ’ o !irtr.go 3 :
CH^
Cr
“/■
'
Cii3* ~t~ C n ^ C i i g G h j
u a *2G i ' oQ i
*
"
n e O T . e x i ] raoicai
C H 3G H r C H 5 y H •
^
r
A n a s o/-;ous
Ti:us
A®
-+■
CiigOr.T
Cii^G!i
Gi13 Cii
ch a r-.ges
for m e d
r»*y l o r 1a 1 y r,e A
—G f
rr.i i**: t
froir
ch anne
^
Ge
H
*
A®
m
Go
assumed
«voold
w i t h i r;
chloride
ncnientyl
C fi*z
to-
::.ol •.•<•!..■ie •
o ■ o-'t
r.>vr.,-c
A ohm
-
: • •-•• o f
thr"
G h 0#
—---------- ^
C h , —
V ‘*'6
C 2~ r G I i r ,
v'-‘3
1: «c y c i o r u ' o p a n e
a;..C'rjthee--
in
re m u r a
Of
c curs e
distinct
by
.vay
Ip
of
steps
©n
‘:7Le
toe
but
free
f cti.nl
at .id?
with
hydrogen
changes
n r a e t i ct
activated
t he - r e s e n t
of
■/- h
*
2
ca) . t t-*ce •■J a c e
,no t: y i g r o u p s •
n e op u n t a r e •
occur
c 1 os ui* e
symmetry
-\i ve
'7n 3
— C —
and s o d i u m #
G ii-z
•'!' Tor * h '.vsuld
C h .,
free
C K 3 -G'CII^
° V.hQ
At.
#
0
m ; - r e r er.ts
tne
/<;
Gh^ - C - G H ^ *■' VA>Xi
T 2
;:
■i'3
B.
11
v
s
any
one
atoms
n.rio h i b l y
1
o.f
give
do
not
rri’il t a u o ''nsly,
crrnolex •
of . e o n e x r '
co j o r i h -
the
Lne
24
chief
effective
change
aopoara
Gi;^
CII, - G H o — 6 — Ch,
C-..
* -C
The f r e e
g r o u p 3 w o uld
give
I n v o l v e m e n t of
nc n e t
’-03 el
r*.i•:g cloaur » with
by
change •
e Tyr.e h ch a r g e
cyclopropane.
to
fo^r
one
r ••
‘Hul.caI
1
f ■n
t
t ;•e
a
a;i .
- 'o r
takes
olfice
be h
through
Type
of
the
throe
e c u ]
methyl
1 ,1 ,2
ft*
It
la
change
neopentyl
now
° f wp.I ch
ni r a c o I yl
fr n e
rearrange—
r>; d 1 e>i ] h a s
-or t; *.<>/•
\ ■r
evident
that;
involving,
the
c a rbo.n
w o
g-’Ouns
gonent,
•>..
d
trine thyl -
-
and
Incar a u l e , the
1 o f 1 :]
C
t h e
Ch,.
CH - CH -C — CH.*
O 0
»
O
Cri.,
O
h 1 n^-l»*c if nr- d l a n a r
a
’a c r i d
t - h u tgrle t h y 1 ‘-ne ,v1 t h o u t
t he oarfll' f i n •
me t r . y l
give
w i tl.out
e -it, I r, i>f a • i
ho
c l e f I t. c o d
.1 v f s
tw o
oth^r
the ivnihexy 1 rndirni
a n ;> a r * T 1 1 v
e /id*-::* t.] v
I’r• a
•
• uv,
I
the
t> e o b s e r v e d
1c?< 1 c mi - r •••.'•t nl're c n - f l n a
fr—
On
of the
free r l u a c o l y 1 "ad l c a l
n py
oh m e a n
one
group- w o u l d
------ >■
ting
B:
neohexano.
involving
the r '*t h y l e n e
<?h,
Cn’^ - C H o - C - CH.,
O
AO
Cn0
#
The
fhve
A change
of T y p e
9HCIU" O F - C — CH, ^ H •
^ ^ 4 F d0 ^
------ >
hydi* ven atoms
A Typo
tc be
r 'J•
tc
give
this
adjacent
25
It
1 3 s ign ifi ce n t
chives r.o c l e f in o t h e r
t h a t the f r e e
than
pinacolylradical
t-butylethyl^no , whereas
del y d r a t Ion
of »* lr.aco.lyl
o l r c h o l r i ves v e r y
tnis
tut
reerrar.yed
olefin,
ethyl one
as s one
free
of
the
free
dime”
product,
nintcolyl
to oe
;.i e r •
V. J
s
r f
the
•» o f
a
t :i n r-sioti'n.
I:- f •.o
the t O 1 ‘f I •
J. r n
h r ; - ;
Of
a;
cbsr r ved«
T't•c a n 1 r. • p r o p o s e d
o c •.
’.udtiry o n
r>1 ’■sc 0 1 y 1
c <.1 ■
-i
*o
j
• f : v ;;
T> I
13
Tne
In
f ■'
*-‘.ererr
’ o . • *. d e
I
^ >r.*.“ o r *■>-■o 1
::V,
0
hv
*'
In
I.-*- • ; IV
t.nyf.
are
rirtior.
die
, t-dirm- t.tiy] r.-in1 v
y
<
view
•
<-;c.ue .
r tunr •
ac ccrd.'i..o
r~:e
d '' r y o ]I c
i tr
fh -
•*1 ->n of a eve.I o p r op m e
,<•p o f on
from
i r 1 n -irm ry
.’I
-..0
-■
I
iv ^ u — _
*
\
tb e
s ,1 /
f r- : • rr;»1 o a 1,
d<,
of
r.c: ' I h r r ip:;,
/ L
..
dpr"
e <-.>1i r t-r; j .
■ 1 ’
f••
-
d * '••L - y ' >u t •
ub '■/*•*.
*•
i... t - r e 1’* i
cf (11 i p X'rvp ....•11
3. -..II • .-Iff
t-!n y
.one
.. ,2c:\<- •• * n r -jf f Ino
- ■ i. h
: .■‘t, %vr..-> ' , ■ , 7
d e r l v a t i vo
HO'.v .v^r,
Is
I
.'no.
d
I— r:. 1c
' ’^ y 3 -•iO.S U;
coil'pour'vi was
arid if
in
? o •■ n | 1 . . tcr.P'j
r u '■ “ ' t
for m o d ,
!- ,f ,3,4 , 6,5-bexam'; t h y l h e x a n o
.'V'lptz rt'H C hi C 0 3 b ? C '•U2
.
is
two
fror:
it 1 I o r
1 '
: '‘tin* I>>
t
13 tr a me thy I-
of
?*I'u
b ut r.'e ,
of
coup li ny
f r o •' r.‘-d ' o >- d ■" .
r-Mac: f I o n
olefins,
radical
f c.rvied by
error;,..! v.T'C f ■- ?« fi.
fOi’Ii.'i" f ~ o~
of
tdo
r a d i c a l s , then
ocsolnle
t. 13
little
-.nd tie thy 1 1 s on r on yl e tr>y'I ene •
if
we
ma inly the
trie
./
Ir y
26
It
••i*--'ton to
13
tbe
highly
nclj ac";: t c a r b o n
iio’.v Vi'’-o " • J 1 0 ■•J -voul d
expulsion
ov-r*,
3
cf
irnnrcb.ible
it
tnis
uj t w o u l d
L:o
Lino e x p u l s i o n
_t-butyls t h y l e n e •
with more
atom with
i- r-rof.Ti or;ci hue
atom with
free
anift
the
did
fornri ti on
ta k e
3
h i f t of
The f r e e
of
the
hydrogen
to f o r m
a
hb*» f o r m a t i o n
el
an
p 1 * cm # the
or a p r o t o n
formation
radicals
tnis
tOrCy : 1 a e ‘ i r n;1 :•fe to ::c o
oven
ounbon
that
from
same
atoms
neohexane.
Lm
of a
the
olefin •
ultimo, te
the
Howi^e —
terminal
olefin,
would
combine
27
REACTION
tn
OF ALCOHOLIC
KQH WITH
According
the
tc
w! ien " n t r o n g l y
^
Whitmore
e l e c t r o os , lee v i n y
f r o yur-:i1. mfiy r e •*-*o t in
.1 )
or;;nnio
f< n u m b e r
It- m a y r e s e t with.
««ac t* o n
of
re/rrangeis
octet
»*•-■t.o ved
of
f.-ayu-ent .
I.’h l 3
r-ys :
>< rn-yytive
inil; >
. »•**» , in w n i c ’
s c<se
of
atom
1 1-3 conioi^te
r os i M
v
theory
e 1 e e f r noryyt, t l v e
me J «-ci >Ieit y r n s e r v e s
h
NEOHKXYL H A L IDES:
icn
rreceot
in
the
n o r e •s “ran <"exrien t ta.ee a
■-1 u e e •
2 )
It
,'!!••Y <„•xi e l
?■ o
; tf r> vcri
3 )
It
:,..oy r’o u
:a"-i
to
I'rai. ."ji’n t ,
t :v
o
All
jvnl cn
In
turn
*»s
of
form
V * a
a;
ole f i n •
1 i f f e iv;i t
c o: 12 <i u n . l a r ^ o
e J t b r*r
Organic
of
t: :o
f I r*a t
r* e ;.> o 1 1 c v u s .
o f tl e r e
:>1 j C e
ty;
:*ti <a c * i 1 7”
Tl
r-
r-.
c.
1 or
• lit-
c h
•., I"
' . l
>■*(- c C
con t s i n I c y
reurrn
n
orck'- ■ Iti
study
lino
ry.iro:;iJf
c:
.n’<Jlor..,
" .
or
to- 1 :os
r e
^rour. i nrs
»i
c.*t3e
c 1' 0
J
i
7
alkalhie
<■"'
'“ 'octior
c
; •
v ;
. 1
i . r: ! r -■ X
If
tr^
is
t.n'ia bsci
solution
vt-;i «v; .«’•»e s u s c - n ti b l e
py*o.;- i >
,/ is
tue
1’ ».c r iy
to L a k -j
icYx*#* «• I f f '
tin* *v» s.c tlona in
3 v . r i;
h.*-- n I'ouna
• '!'r-i ire • ' :■n 1 •u •
If 1: r * HCvV/t:
it. a :
nave
srtil ;:rr..
0
r
Imp or tin. t- tc
ha i i dec
1 1. r c I
r e a c 11 m s
of
tv
nir'-s.e-'ly 1 , ( C h ^ ) ^ C - C C
jyc.c * i --.IS s.1 1 o
tr.'-js - l a c e
>f s !c oho *ic p o te a » i uin
;1oriel - :::ir'-t t.<* •v.xyy*c ted
to yo
28
The
octet
chlorine
leaving
ini^ht b e
a positive
remover?, w i t h
organic
#^
• «/“I# #
♦
“
•*
i•
..
• #
cc\ld
t ' v & >T :r • -n
case
t
to
♦# # •
:c : c
. *,->
c rc ; ^c_ ;
•♦
- #
i* # ♦
> • # -» 9
••-**#
ir.
complete
f r s r m . ’rt
# #
.*
1 13
an
»•
:c:
react with
4P
*
£i n e p o t l v p
ion,
e the r
KOH +
> ROK
ROi:
;,K
: c;
»«
#
Ho0
-> liO
#
;c:cic : c;
-/
••-x ,, ..
>
r c
r o r
»
*
c #
*
•o
#•
The
p o a 1 l.ivr-
frjicrMiep t :r.1 ,’:i.
■•. s tu b! l i e e <1 d ;:
lose
•*-.** {\; >-:t:h t i on
c,
f
a
ao
proton,
and
o 1 e V L zi •
••
•
• *
••
* *
« •
^
.
: c ; c : c : o ;_____ - h O __ c c =- c — c — c
••
One
n.i y h t shift,,
of
>
#
r' «
#
#*
• *\-'r
hvi v R . t e
’T 1
p r* ':>j - .*»
d 3 T fe p e n t
-V !. t d
i r " n ” ir
i
p
1
■;!*; ' R o o r
m i :
f r a.rrno n t
• •
:c/
•
• •-V^
This
:
V
•
*v/\v ^ r*:i
• /'t 0
______ -—
« # #*"
V'
\
/l
/
• n * f' • i1 * f' m
*• •#
•O
r-i«
#
# «#
1 o h n ;:j »■*r
o Io t 3 re t e t r*a re * '.by i •"*t\.y 1 e ^ o
-
. «•
4<
•
•
•9
<-/*•
and
t^ n
t>o; l'or*e
1 , ?.— • t’ y 1 —
J I
T o n ;ilcch<
1
c o r m 3 •.r •.:!i :,v
! c th<-* a b o v «» e ,1 o r i d e ,
29
pinacolyl
to
sri
alcohol,
ve m a i n l y
has
d e h y d r a tod
t e t r a m o thyle thyl ene
e b ;y
'/ji , >vi tr. ••• e m a i l
same
products
alcohollr
been
rnirht be
exp ec t e d
Lalaorato^y®^
ar-d i n e t h y l i s o n r o p y l -
r’Ov; f o u n d
*.ve he ve
tiaa t
reaction
of o i n a c o l y 1 c h l o r i d e
t uy 1 er: o •
f r o m th*-
the
aid
ho
'Ftiese
reaction
or! n l n a c o l y l
However,
t — b v ty 1
thi3
a m o u r t o f _t— b o tye t h y I a 1:e •
potassium hydroxide
hydroxi de
In
only
of
cii T o r l d e •
product
of
this
r rop .onoi io. pota3 : d u r a
;> 1 m m o l y l
;-ro" vl
? ther w a s
f or. ■id •
The
same
d i f f u x‘0 n c»- in
fra. ,i tin.-de.hy.d rat! or.- of
>f halid---o
■f.e
in
b as ic
rlc^l.olr
aoluticnj
t-o;-riyl o a r b u i c ]
is
tin- p r o d uc ts
has
dehydrated
u l o - :;i hi,Th-.-
mluui
pi’e.-i-n.l '.v.uh.
f o r ned •
1
t
nas
is
(‘Cu';na ti o n
hoekin,^'-*
or.
t'
1-0
La t e d
c
from
•'* ."e-.-.!-
on 1y
ixi a c i d
LhaL
1
—n a
cril
-c t h ' : , ,
1
'.non
<ri v e s
only
7':-:;!-:
r^i-c * i^:.
o-d ,1— b
on.'
7
before •
medium,
u n tu rne d *
;'r ■ - tn-or
renc M e n s
1
m tt ■ry 1 b u turn* •
.-eu
’.hunt
or
no
of
products
ol e f i n
is
1- h a l o - 3 , 3 -
. t uren r m n g e d
p r o d u o ts , w i t h
th ■ cl.efin.
Kftfr.’.tz®^
th*-. r-mctio.i
AQ
the
noticed
n o t a p ? iuxn . h y d r o x i d e
also
of
up.
a i i. .*r
Alcoholic
m e thyl b u t a ne
tit;
-■:-n"-oh
^-c t us o.1 urn u r d r o x Id*-
re.; u j *- f •• m
d
•• Is •' b *
he a
one
h— h ,Le -y] - ; p.: 3 - m o th yl — 1 - m . to n e s
.in,'is
.d free:
m
ohtaiaod
xirc
isolated
s ever,
df.orlh.'
ft. * •,e(,c + ir;. of
o .d l-iy
cel c : I h e ,
ar.d
is n m
HO
1 on
■!.' e c h o 1 lc
r i c o.hloridos
frotr.
f.— e thyl — I — V ’tanol •
r o ta3 •?turn riyorox ide
•j i o t ny I c - m r ) I n c : - I ' u b y j.
u.nr ea r r a iyyc1. 1 , 1 - d l e t:.yl “ f'-.y1 er;e a n d
c:
1 o r-
i e
diethyl —
30
carblncarblnyl
ether.
It Tins t n o t ,
ment
Is
necea.iarj ly
frapinent w i t h
Is
formed
butanol.
sextet
the
In
the p r e s e n t
from
ot
th e o r e i 1 cal
by
Is f o r m e d ,
action
the
3 , 3 —dimethylbutat e
be
a a turned
Ir.e vi table , o v e n
an o p e n
e x e m p l e , an a l m o s t
however,
\vhen a posi t i v e o r g a n i c
electrons
yield
of
work
o1nacolvl
ecu Id
form
sIruificent
od tai n o d
a 1 v rye
Then
or
from
oi^fins
without
excess
of
possible
that ro
results
are
lb — 1 3 t n'-'Op':.. tyl
was
observed.
As
remain:
or
e thyl
a result
hither
else
of
th Is work,,
a r-p l i e s
in has Lc s o lutio/
one.
tc
re a rra r "vb
takes
p lace
by
trerr.ercious m a s s
In
those
he
is o —
c.lcohol ,
•r o d u o t
alternatives
rearrangements
1-, a c i d m e d i u m
r e a r ra n.pervert s , trie s e c o n d
true
thie
only
of
e 7 1de
tue
rearrange­
chi or i do w i t h
then, two
In v i e w
uoly
of
theory
bo
it
a
recovered
a rial a g u u s
me Ci':an ism.
on
Is
n e o p o n tyl
ehne r •
the p r e s e n t
it
from such
75 ^ h y d r o g e n , 3 — br4 re o p e n tyl
9
if
rearrangement,
without
c l e f in
bromide
1-halo—
a l c o h o l ic rctaariar, h y d r o x i d e .
and
reaction
not
r»y ’Vi t t.le who n be he.-- teo
1 a t e a 7 r>-*> n e o p e n t u r m
wrong,
Is
For
on n o r m a l
halides
f r o m l»hal o-1, T-diire t h y i b n t s n e
hue re r e a c t i o n s .
the n o r m a l
fragment,
fragment
is
formation
formeci.
a positive
olefin
It
Is
of h y d r obr omi c a c i d
however,
ment.
that r e a r r a n g e ­
and
is
the
a d i f f e -»er, t
of p o s i t i v e
el t~» r n a ti ve
io
r»r o b —
1
Hauser 70 has
theory,
present
Eliminations,
effected
are
by
acids,
by
group,
of e l e c t r o n s .
describe.:: by
the
fatluh:
of
an
The
the
ef
arc
L-» *n
acl t t see
1 i fur
follow!;,;
X
is
c o u r s e s of
nt a - s :
re 1 e a s e d
molecule
is
and
toird
in
react
1
s i m n .1 t a n e o u s ly,
stabilised
moves.
three
of
is
system,
on
r.
may
r e a r rar.gemen ts
is
tn-
Two
reaction
are
th e
an
e q u i l i b r i nm
of
of
or: th o a i d e
th
j
e y .1 1 1 h r-i u.r: of
the
s id e
of t .c o r l g i n a l
acid.
ar«-
of
w n i cn
*h'-
type
I,
may
molecule
tut
<*:,.♦» at i m
3
the
toe
p>r o c e 3 c e 3 ,
s te; s
the
the
a n rotor: ;
electrons;
of
ru.uT h e
o'" the
■Ie s c '•i u e d b y
s y s t e m f‘ o .<i v.h i c h
mol-c.ule
by
e x t r e m e types
the
a1 1 three
frc-m
i t n o r e w1. th
simul t a n e o u s l y .
s i m u l t* n e o n s
in
'Ph.
far
Octet
be
salts
trie e l e c t r o ­
1 rii t i n t e d
reactions
II*
r ■ ru. !/*-*u
the
follows:
octet
x’c g •?r 1 -3 r-e-o„- : as
muiu.er
or on
aa
the
complete
by
occur
T,
reactions
In
tvr.e
The
d-n e n d s
.-hen h X
atom
a
s tens
may
ir- typo
co:.r I n t o
stabilized.
second
the
a
the
outlined
ty. « II,
the
Th;-, » y
wi th
of
hydrogen •
reaction
on
wi tv: its
h a a i c mcdi aare
nuiii t i n ;" s e l + , w« •i
renertl
store
c<snn i d e r e d t
rr a c t i o n
"eagent
courser
the
th • tri m a r y a c i d - b a s ^
The
the
removed
the
tn.i I ua tj on
reactions
of
g e n e r a ' ir.a tie as
c t e ci by
are
of
r e a g e n t s , arid h e a v y m e t a l
general
that
of w h i c h
a .id in traino] eenl ar
a; t a c k
ir
a modification
features
acidic
which
mod i f 1 c a t i o n
Elimination
chief
me tnhl.es is,
ini tia* ec
negative
the
oostulated
occur
is
is
or
tab H i r e d
whii e
rea
by
re-
32
arrangement
whereas
from a
the
or d i m e r i z a t i o n ,
w)nn
HX
four
removed
a tori' ays ten
forn;a ticn
rnent •
13
When
of
the
removed
trie m o l e c u l e
:
vc t a t h a t i c a l
In
tneue
of
the
te tra);t»d r o o
of
tiie
anion
cases
the
and
B a r t3
m e o':a o 1 s a- f o r
ry
ts-'
tent
X
sible
1
rr-ou;
t.h e
the
or.o
the
:. l.gre t i .
tyr e
t*
r <•!d leal
c-c i r r n
i n a p :’:
tir
h-e
t h*-
o e c >ira ,
oi
.
'j v i*v c t ” f'rc- r‘
studied
or
basic
of a l k y l
Ia
the
To.
tn e
face
X ,
the
add. i t i o n
s Imul tnneoualy.
a
located
lac.;.
*h-u
at
.? t a t e s
'.o,
remains
The
n *•»a .** t'>e
he
•"*>
Oi
of
in ** on ] In
what
ezirb o n
c a r Lon.
three
oyclizatior,
involving
cccurrinr
.1
:< *■j*o ;i
l'c"
There
'r or « s m
s ’ tu a t o d
"■ •t
to
t:c
n i c r a te •
•s i m u l t a r e o n s
Is
by
t h •: c a r b o n
i o', iIn
*.o r
by
rsarrang?-
containing
hydrolysis
r **.. e t i -c .
of
or
a ta b i 13 z e d
without
r- t s I t i o n
of
:•r«j f n* •*o c e
be
atoms
tide, w i t i e l i m i n a t i o n s •
t t t [.ek ,3
ti:e
products,
cai’b o n
sr&bilized
by
s u ' g o d t?
spc t
:«f
!de
t*^
i.i -;
'Of
r.
rele.us e
O r o o r 1 Le
to
he
ulka'i ire
op; oo J te
tr in
r.ly ■a: t i c n
to
may
products
may
auior
«i t:. t h i■■ id ' u
before
molecule
hi ie
t *■>r< b y
.ul gj ’i
toe
adjacent
froni s y s t e m s
e x a m p l e , the
ha J Ides , runt'o-il v occ -ur
near
unsaiurated
( 3 vbs 11 1 u t i r - n ) r e a c t i o n s
an i o n s , f or
r';‘o.n
from
u n a a t *r a ted
riX is
Piore a t o m s ,
giving
1
tho t
in
tc.
'his
k
be* 3 a r 1 1 •?11
that
is
occur led
inconsis­
removed
redicid
most
would
purely
1
the
r'rel’e r r e d
■r!rf 1 e '
hie
space
eti;t. 1 Iy
th e
acces­
r c a a ibll i ty
ten 3 t.; . e ic-^lci o n
b a c ,c o f
Mr u s h - p u i l "
of
m l y r a tiori
curbo*- a t o m
th a t
X
r t»
o 4'
*rp'
he..
r■■• o • t .v-•■1 ' t ►•«.> - 1
•••d
be
1
«• e - '•
y .•.n■* u- • Ia • - v . t
33
reactions
attends
•.vi th
in w h i c h
every
act
it h a s
inversion
that W a l d e n
Bartlett,
me c-hrr. i s m
inversion
wo^/ing
'•'! i-"J c l - l , f', p c s t.u 1 \ tos
'
fo *» tl e r i r a c o l
t:i c f c-T .1 ow-
rearrangement
>■ <SZ3>
£>
O H
shown
replacement. 7 2
of
J ,L- d i m e thylcy:i
in;j W a l d e n
been
6/j.
J
In poir.p f r o m or-cduct
•° 1 rul t ; . , ^ u.s
opposite
rih.'ctio;!
:i !de.!
Pear
pc.eolble
In
or
vol /irs^ o ! t b e r
Initial
of
Whi tmere
basic
r:c:h
of
r/o
rod
xTI
there
e x r u l e J on
Is
of
a
POP
r roe
»
s e t>;-'or t s
ti .e
t; r3
Pol
difterert
m s < P a :1 1 »
1
cwiug
reactions
r e y r ticn?.
or o l e f i n s
in
nrrbaol y
acid
fo
by
us
a
obtained
in-
. edt a
way
of
an
a proton:
f
1 s a e r: th at w h e n
CI;^
1
for
>
R,.C = C H cj
It
cf
a i c 'b o i a
addition
to p r o d u c t
<••>. rl. or;
erp Inna tion
':c'dii'
II
7-
r
H
7
L R : p . :}l[
II1’’-------- >
£
^
r
9C-CU
tl1e s « '■1:1 t .1c j. e ore or: n f 3
z
h ? q -t £
r
J*'
V■>r *•»a k , on
*J*
54
unstable
The
In
fragment
acid, r e a c t i o n s
a a. ,iI o .ne lie
possible,
approach
if
i:Id
olefin
he
In
ana
trie
whet*
hr c r
cl •f 1 ns
were
the
eo
creased
from
her
h r o»r-. t '
x-
t.h~
r c.nI d<
-
cr-e-si-
in ole d-ol
crease
oh a c t i v i t y
fur th~r
s c-lntior
--'/1 d e n c o
la
the
he
h or;; a t i or
that
work,
.vhenc
than
of
Tex1 th-
to the b r o m i d e .
^ o r m c d , rue sic ob o 1
Tne
the-* b r
The
to
:rield of
1 ? » 8 J4 f o r
vie 1 d oh e t h e r
iide , a n d chett d e ­
d e c r o s.e <-• of.' e the r h or-no tl o n
1 .-.r,,e
ct] c r i i e
hris
this
ca s e s
rront«r
cr.lo.r1do,
Isolde*
in
The yields
r.roduc ts •
4'. *1 od I 1-j I i
from
a-re net
clos e l y
these
1 o r 1 ido
not
r rincinal
. 1 the .
in
-.vore
or
wei*-*
cnl oc Ids to
the i c.
more
r'-errengement,
f " r* the
tho
replacements.
studied
•rcduct
i n c r e a s e d f r o m 0,6 for*
••he or .•>.:!•{*-, to
I n ■:r-O'
: rinclr.ul
u : .-d i w r e a s . d
“ then
alcohol
of* eon.rounds
tne a e c c n d a r v h a l i d e e
can -
the
the
forced*
reactions,
^ : tied wi friout
ft-o-
P x* 1 11 t 7 ,
series
Is
ocmromida
tflrie r e a c t i o n s
true r e n l a c e r e n t
the
direct
tl •o n e a d t i 11 on
c ens e q u e n tly
ol'-'-fI n was
c.>:
cl' r e a r r a n g e m e n t
are p r o b a b l y n o t
howevir,
and
In
the
capable
type
.1r.cldsr.t
r
w 1 th
M a.c.e o r d e r .
to
oh
bromide
reaction
a x*en lacemer, t tyr>e r e a c t i o n .
tho
The
to
in —
in­
iodide
is
In a l k a l i n e
55
SPECIFICATIONS
All
used
in
this
off,
with
columns
OF D I S T I L L A T I O N
were
laboratory:^®
of
total
electrically heated
or s t a i n l e s s
th o
EQUIPMENT
conventional
condensation,
jackets.
steel
design
partial
The p a c k i n g
take­
Is
either
glass
single-turn helices.
Column
I --------
1 . 5 X 64 cm ., 1 2 t h e o r e t i c a l p l a t e s ,
p a c k e d wi th one e i g h t h Inch glass h e l i c e s .
Column
I I --------
0 . 9 X 40 c m . , 9
p a c ke d w i t h one
theoretical plates,
e i g h t h inch glass h e l i c e s .
C olunrn H I -------
Same
Column
0 , 6 X 40 c m . , 2 0
packed with 3/82
theoretical plates,
Inch stainless steel
helices
0 . 8 X 74 cm., 80
packed with 3/64
theoretical plates,
inch stainless steel
helices
i
1
1
1
-----1
C ol U31/1
2
=3
i
rp
i
c-t
►J
*
Column W -
1
Column
y ---------*
I
M
Column
I V -------
as
Column
II
0 . 7 5 X 108 I n c h e s , 8 7
packed with 3/32 inch
theoretical plates,
st ai n l e s s 3 toel h e l i c e s
1.0 X 120 inches, 85 theor e t i c a l plates,
packed wJth 3/32 inch stainless steel helices
1. 1 X 1 4 8 c m ., 51 t h e o r e t i c a l p l a t e s ,
p ack e d with 3/52 Inch stainless steel h e l i c e s
C o l u m n E M J ---- -
1.0 X lOO cm., 35 t h e o r e t i c a l plates,
pa cked with 3/32 inch stainless steel h e l i c e s
Column
0 . 7 X 40 c m . , 2 0
p a c k e d "'ith 3 / 3 2
c w --------
theoretical plates,
inch glass helices.
56
E X P E R I M E N T
CHLORINATION
gases
w as
80°,
Chlorination
in
T he
aoparatus
shown
were
was
started.
T.Vhen the
neohexane
increase
the
in
relative
liquid
rate
been
was
sodium hydroxide
and
A summary
No.
the
of
NEOHEXANE
U S ED , g.
of
the
of
the
gases
held
cc
were
at a b o u t
through
with
dried
A
.125°.
tho
chamber
Th e
sudden
caused
flashing.
that
the
a ll
the
When
apparatus,
The
over
of
1 O
layers
sodium
oT
g.
the
of
were
sep­
carbonate.
follows:
NEOHEXANE
CONSUMED
415
460
480
507
432
537
525
545
558
4509
189
156
151
154
124
114
126
124
l'JO
1238
through
the
regulated
a solution
of w a t e r .
layer
110°.
so
in
started.
chlorine
shaken
noohexyl
were
flow
distilled
runs
the p a s s a g e
temperature
chlorine
Nine
as f o l l o w s :
to
was
500
is
on b e f o r e
NEOHEXANE
RECOVERED
604
616
631
661
606
651
6 51
8
669
9
658
T o t a l 5 7 47
The
in
run
I.
Immediately
the
organic
1
2
3
4
5
6
7
tionated
of
temperature
product
arated,
almost
flows
had
and
phases
in F i g u r e
typical
turned
ro3 e
neohexane
A
light w a 3
the
reaction
run.
is
th o gas
The
temperature
The
NEOHEXANE.
A.
experiments
the
OF
A L
chlorides
C o l u m n \V— 1,
and
NEOHEXYL CHLORIDES O B T A I N E D
179
170
165
162
169
152
137
127
151
1412
50
50
60
55
obtained
above
the
on
data
REACTION
TIMS,MIN,
were
frac­
f o l l o w i n g page:
I/ < 2 f > o r ~
/ ~ ^ / ? a s e ^ _ C /?/ o r / ' K o l /
o
/
38
LEGE N D FCK
A.
Cn.l o r i n e
Cylinder.
B.
Sulfuric
held
C.
Reaction Chamber.
D.
Thermometer.
FldUrtK I
Trans.
%
E • lOO
F.
Watt Electric
Flask
F r o m ’.Ynich
Light
Bulb
Necliexane
Is
'/arorized
Into
C,
ri• 1-ieotiii/;- Co.11s,
Hm
Spiral
Condenser,
J.
F lask,
Cooled
K.
3od! -in: H y d r o x i d e
In
Ice-.Sslt b a t h
Traps.
For
Collecting
Products,
39
TABLE 2
TI I.LE
CUT
WT.
n 20D
B .P .
50
71 .4
1.3691
1.3769
3 3 «6
50
25.0
105
3
1.3833
108
3:30
3.6
1.4148
4
106.5
6:00
5
8.6
1.4132
9.7
107
6
7:00
1.4134
7
1.4188
16.6
106.5
8:0 0
108
8
1.4191
19.1
8:30
D e c o m p o s i t i o n was q u i t e e v i d e n t .
w as c o n t i n u e d a t 2 5 2 mm.
4.8
10:25
76
9
1.4152
1.4181
76
11:25
10
12.4
40.7
2:25
11-13
76
1.4186
1.4187
76
5:00
13.6
14
13.6
1.4188
6 :1 0
76
15
7 :10
1.4187
16
18.2
76
17-18
32.3
1.4186
76
9:15
1.4187
10:15
19
76
16.0
76
12:15
20-21
33.3
1.4183
1.4189
22
76
19.0
1:10
3
4
.
7
76
3:15
23-24
1.4192
4:15
25
16.9
1.4198
76
5:13
76
26
17.3
1.4200
27
17.2
'3:1 o
76
1.4210
7:13
23
17.3
78
1.4219
77
29
17.1
8:40
1.4253
78
17.9
10:15
30
1.4248
11:50
31
18.4
1.4253
80
81
1:20
32
18.4
1.4245
2:45
35
81
18.0
1 .42 20
4 :G O
16.3
34
1.4219
81 .5
3:30
35
17.0
82
1.4212
7:00
36
19.3
1.4208
82
37
8:30
20 .7
82
1.4206
15.7
9:55
38
82
1.4205
3:00
39-42
68.5
82
1.4201
4:00
43
17 «8
82
1.4200
7:00
56.5
1.4199
44-46
82
47
8:10
19.8
82
1.4195
9:10
48
18.2
82.5
1.4195
12:15
49-51
56.5
1.4192
82.5
1 :2 0
52
83
18.5
1.4193
7:00
53-62 176.4
1.4192
83
8:40
63
16.3
1.4190
83
10:30
64
17.0
1.4183
83
12:30
19.1
65
1.4132
33
c,:0 o
66
15.3
1.4179
83
67
4 :0 0
16.4
1.4128
83
5:00
68
Re 3 idu e, 1 37 p.
1
ci
The
fractionation
40
Cuts
1-3
Inclusive,
neohexane.
The
fore,
to 1 3 0 8
drops
Cuts
coyl
chloride,
based
total
amount
g.,
11-21
Cuts
167.7
on
39-46
47-67
2.2-dlmethylbutane
weight
373.5
were
mostly
consumed,
there­
moles.
were
g.,
1.4
shown
to be p l n a -
moles,
11.13, y i e l d
used.
Inclusive
tile n e o h e x a n e
Cuts
g.,
neohexane
12.9
2.2-dlme t h y l b u t a n e , weight
based
or
Inclusive
weight
neohexane
or
130
142.8
shown
g.,
to be
1.19
1-chloro-
moles,
9.2^,
used.
inclusive
and
g. , 3.1
were
were
a mixture
of 1 - c h l o r o -
1-chloro-3,3-dimethyloutane,
mole3,
24^
based
on
the n e o h e x a n e
cons u m e d .
(a)
Idantification
To
O.rt g.,
of
flask
a nd
c o n d e n s e r was
14 a b o v e .
The
fitted
reaction
oxygen was
two h o u r s ,
throughout.
and
passed
the w h o l e
The
the m i x t u r e
rated
and dried.
at 7 4 — 7 6 ° .
The
with
wa s
of o thylmagn.es i u m b r o m i d e .
dry
11-21
as
pinacoyl
O.C>33 m o l e s o f m a g n e s i u m
tliree-ne cked
a reflux
Cuts
over
a d d e d 4 g.,
started
When
the
mixture
resulting
a mercury
being
solid
A phenylure than
point
th e
of
0.033
adding
of
cooled
was
The
of
sealed
a 50
moles,
this
Cut
drops
completed
the m i x t u r e
decomposed
o il
of
several
in an
cc
stirrer
r e a c t i o n was
surface
steam distilled.
melting
by
in
chloride:
for
ic e
bath
with
i c e,
lay e r was
carbinol
the p h e n y l u r e t h a n
sepa­
melted
of
41
plnacolyl
alcohol
la
79°.
A mixed
known derivative
of p l n a c o l y l
It h a s
been
therefore
shown
melting point
alcohol melted
that
Cuts
with
a
at 75-78°.
11-21
are p l n a c o l y l
chloride o
The
chloride
(b)
melted
a t -1
Identification
of
to -2°.
Cuts
39-46
as
1-chloro— 2,2—
dimethylbutane:
To 0 * 8
three-necked
a reflux
The
g.,
flask fitted
condenser
reac t i o n was
bromide.
After
passed
over
cooled
in an
with
the
Ice,
la y e r s
0.033 mole3,
the
was
with
added
started
surface
Ic e
of
bath.
resulting
the
mixture
In
the
distillate
This
was
sulting
carbinol
washed
dried
stirring,
the m i x t u r e ,
The
sealed
a few drops
of
and
bincl.
a mercury
4 g. , 0 . 0 3 3 m o l e s ,
with
three hours
of m a g n e s i u m
of
dry
the
with
over
resulted
5 cc
In 4.7
of w a t e r ,
anhydrous
carbinol.
ether,
of
After
two
recrystalllzatlons
the m e l t i n g p o i n t
the p h e n y l u r e t h a n
Mixed melting point,
of
was
quite
readily
at
The
of
flask
Cut
room
43.
decomposed
cc
and
of
of
car-
the
re­
carbonate.
made
of
this
petroleum
melting point
is
oC-naph thy lure t han
temperature,
and
being
6 6 — 67 ° .
64-66°.
An
cc
was
Senaration
2,2-dimethyl-1-butanol
<= <-Naphylure t h a n :
made
64-65.5°.
from
stirrer
oxygen
potassium
Pheny lure t h a n - A p h e n y l u r e t h a n was
50
ethylmagnesium
s o l i d was
steam distilled.
in a
melting
was
point
after
of
o ne
the
recrystallization,
«<-naphthylure than
83-84°.
82-83°.
of
2 , 2-dI:ne t h y l - 1 - b u t a n o l
Mixed melting point,
In
order
to s h o w
and
that
the
of
2,2-dimethyl-1-butanol
83°,
was
was
not
t he
M.P.
taken.
83,
Melting
therefore
been proven
that
Cuts
3 9 — 46
l-chloro-2,2-dimethylbutane•
(B)
Chlorination
The
To
t he
light
flask
In s u c h
flask
was
tube was
bulb
the
was
a position
bubbles
second
surface
placed
that
heated.
chlorine
the
against
the
upper
the
reaction
at
th e
weight
taken up
about half
ducts
were
then
neohexyl
chlorides.
shaken with
an
equal
about
The
of
the
portion
of
the
started,
and
of
about
three
acid
trap.
The
cooled
that
The
be
the n e c k
continued
indicated
to
liquid.
rate
flask was
2.
placed
was
sulfuric
C h l o r i n a t i o n was
chlorine
the
Agitation
begun
through
of
ice-salt mixture.
of
I n Figure.
inlet
above
of
shown
chlorine
of
portion
Is
th e n e o h e x a n e
t he p a s s a g e
lower
used
added
sligntly
per
the L i q u i d P h a s e .
f l a s k was
The
centimeters
electric
In
apparatus
chlorinated.
was
carbinol
70-82°.
It has
t wo
above
melting point
3 , 3 - d i m e t h y l - l - b u t a n o l , M. P .
point,
are
of
is
82-84°.
3,3-dimethyl-1-butanol, a mixed
oC-naphthylurethans
The m e l t i n g p o i n t
with
until
the
the p r o d u c t
chlorinated
volume
an
of
pro­
20/° s o d i u m
F 'ou re
2.
L i a u i d
T
P h
a s e
F
C h l o r i n a i o r
44
L.EGEND FOrt K I G U H h
A . Chlorine
Cylinder,
B • Sulfuric
Acid
Traps•
C,
Reaction Flask,
D»
l O O Watt
E,
S o d i u m B y dr o x i d e
F. A i r
C,
Electric
Light
Bulb,
J’r up a .
Stirrer,
Mercury Seal
fo r
Stirrer.
P
45
hydroxide
then
solution,
d r i e d over p o t a s s i u m
the u n r e a c t e d n e o h e x a n e
presentative
chlorinations
stripped
are
carbonate,
off*.
Data
and
for r e ­
shown below:
TABLE 3
No.
£6*Ll4 u s e d
Recovered
7 8 0 g.
805
643
4 89
1780 g
154 4
1585
835
1
2
3
4
The p r i m a r y
in
3 3 7 3 g.,
fractionated
2 3 1 . 5 g.,
The
was
6:15
10:40
12:15
2:15
3:50
5 :0 0
6 :lo
1 1 :45
4:45
t':0 0
1 2 : 1 0
3:00
4:10
7:05
8 : 1 0
9:25
10:35
1 1 :35
12:30
1 :45
2:00
5 :3 0
8:15
a distilling
Chlorides
1259
978
1159
496
g.
739
942
346
flask.
through
stripped
The
from
CUT
2
3
4
5
6
7
8
9-13
14-18
19
20
2 1 - 2 2
23
24-26
27
28
29
30
31
32
33
34-37
38-40
was
C o l u m n W - 2.
c a r r i e d out at
table 4
B .P .
’VT." '
17.4
15.7
16.5
15.6
16.8
15.6
16.9
84.2
91.8
8 .8
18.2
32.2
19.8
46.3
18.2
16.5
18.5
16.1
24.5
13.5
1 2 . 2
55.0
55.3
59
70.5
72
72
75
73.5
72.5
72
73.5
71
72
72.5
72
72
72.5
73
73
72.5
74
73
73
73
73
g.
the
monochlorides,
neohexane.
fractionation
TliwE
1 0 0 0
chlorides were
polychlorides
were
Consumed
244-247
mm.
n 2° D
1.4060
1.4114
1.4165
1.4172
1.4178
1.4178
1.4178
1.4178
1.4178
1.4179
1.4168
1.4172
1.4176
1.4178
1.4178
1.4178
1.4178
1.4178
1.4178
1.4178
1.4178
1.4178
1.4179
cont inued
Cut
1,
Hours
132
95
86
56
46
TABLE
TIulE
l O :15
1 :05
£: 1 0
4:20
6:25
7:35
1 1 : 2 0
5:40
6 :45
7:55
8:45
9:30
CUT
WT.
B.P.
n 20D
41-42
43-44
45
46
47
48
49-52
53-59
60
61
62
63
64
65
36.6
25.6
14.3
14.0
16.4
15.0
73.5
140.0
19.3
73.5
73
73
73
73.5
73.5
73
72.5
72.5
72.5
72.5
73
73
74
75
77
78
79
80
8 0 .5
80.5
1.4178
1.4172
1.4178
1.4168
1.4172
1.4174
1.4178
1.4179
1.4188
1.4192
1.4201
1•4216
1.4229
1.4248
1.4260
1.4260
1.4249
1.4230
1.4220
1.4211
1.4204
1.4202
1.4200
1.4199
1.4201
1.4199
1.4199
1.4198
1.4198
1.4196
1.4192
1.4193
1.4192
1.4191
1.4190
1.4189
1.4183
1.4182
1.4179
2 : 0 0
66
3:15
4:45
6:15
7:2©
10:40
12:05
67
6 8
2 0 . 1
1 2 : 2 0
2:40
5:00
7:00
7:15
5: 25
1 0 : 25
10 :00
10:55
12:25
2 : 0 0
3:50
7:00
8:05
69
70
71
72
73
74
75
76
77
78-00
91-96
97-109
H O
1 1 1 - 1 1 2
113-114
115-116
117-119
1 2 0
1 0 : 0 0
1 2 1 - 1 2 2
l O :55
11:50
3:55
123
1 24
125-129
C ut s
chloride
1
16.8
18.2
15.8
19.9
19.7
17.3
18.7
23.7
2 1 . 2
251.9
llu.3
247 . 8
19.7
36.5
38.9
39.6
58.7
19.6
39.3
19.4
2 0 . 8
99.1
6-59 , 385 . 1
contaminated with
Cuts
of
2 0 . 6
17.8
19.7
19.9
17.3
19.2
18.5
1 1 : 0 0
4
74-109
8 0 .5
80.5
82
82
80.5
80.5
81
81
31
81
81
81
81
81
81
81
81
g. ,
2 2
.8 % w e r e
a small
weighed
- c h 1 c r o - 2 ,2 - d i m e t h y l b u t a n e
673.6
amount
of
olefin#
g. , a n d w e r e
composed
47
Cuts
110-lh9,
331.9
chl o r o - 2 , 2 - d i m e t h y l b u t a n o
'Die 3 e come c u r d s
metnocis
vapor
as w e r e
phase
used
on
PKEFARATIoN
(a)
T iracolyl
and
a mixture
identified
compounds
described
OF
w ere
by
the
formed
In
ether
In
n s o l u t i on of
.fmO
lOO
ether*.
cc
of
several
ary
cc
of
' lace
ever
ve r y
ilt'dr
for
a
above.
iieayent:
heat.
Two
To
chloride
added
the
(dried
two
heat.
At
ti. ici(
that,
three
h o u r s , witj;
the
an
re a c tion
in
an
was
added
ny
addlnp:
addition
the
In
took
evolution
of
<„vas s t i r r e d
a tmos *.h er e
cf n i t r e i-en.
.n e d .
1
identical
of
310
P.-0,kJ ) in
a dropninr
reH^-nt
The
mixture
r* -ri ■•n°rd l e a r e u t
over
of
oidoride
3 tar* ted
Trlp-rifard.
f 1 1 r.e red
ob t
^Ir.acolyl
r e a c t i o n was
Tr.e t o t a l
c
of
cc
a n p a r a tus
ethvJ
a susnension
through
in
of
serara-ta
Iriynard
, lace
The
then
Ad_ltl< n
d-rlynard
. , 3 moles,
ner 1o d
cI' i>0 /:, a as
(v.)
3 - 1 1 ter
r^actiny
s e v -•n h o u r s ,
a y 1 e Id
p
same
°IiriC OLYL.,KK0 U ti I C C H L u r t l D F .
irt^nard
a usual
1-
the
To 72: p'. , 3 m o l e s , cl* marries lurr. In
cry
of
1 — chl or o - 3 , 3 - d i m e t h y l b u t a n e •
were
the
chlorlnstior
ft • f
h r u r 3 , went
aduitlcnal
were
cc
made.
m o l e 3 , of m e r c u r i c
of d r v
ether
was
*'
abou t half,
above.
smoothly*- w i t h
cor:: 1 e * i o r: of
:’er c or i c Cr. 1 or ido :
r;• , 1 . 1 5
130'
fun- el
prepared
runs
to
The
4 n ' cc
of
dry
cc,
addition,
the
tr:-’ n '*■-'* t i n .
300
e /olutl on
tie* m i x t u r e
ether
was
of
takinp
of
whs
a d le a .
so
'"his
48
mixture
when
was
allowed
an a d d i t i o n a l
t o t a l m i x t u r e was
The
The
layers
to s t i r T o r
2 00
allowed
to s t i r
salt.
The w a s h e d p r o d u c t was
an d
added.
300
th e e t h e r w a s
The s o l i d w a s
dissolved
The
over night.
decomposed with
separated,
the s o l i d m e r c u r i c
and a half h o u r s ,
cc of d r y e t h e r w a s
c o m p l e x was
were
three
cc of w a t e r .
blown
off
washed with water#
in acetone,
the
insoluble
material
wa s
f i l t e r e d off,
and
t he p i n a c o l y l m e r c u r i c
chloride
reprecipitated by
the
addition
two r u n s
a t o t a l y i e l d of 1 # 3 6 m o l e s ,
45%
based
the p l n a c o l y l
of
on
salt melting
chloride
a t 9 0 - 9 1 ° was
preparation
;
of
used,
of
In
the
theoretical
the m e r c u r i c
obtained.
m e r c i 'r i c
th
of water.
salt
of
l - C H L Q R u - 2 , R-DI^iF'i JrlYLbUTAR K
(a)
in 4 0 0
cc
apparatus
tion
60 g . , 2 . 5 m o l e s ,
of m a g n e s i u m
of a r y e t h e r
In
the u s u a l
Grignard
was
ethyl
allowed
to
filtered under
was
of 1 - c h l o r o - 2 ,2 - D i m e t h y l b u t a n e :
of
added over
obtained.
a period
2#5 m o l e s ,
cc of d r y e t h e r .
reacting
Reagent
To a m i x t u r e
of 3 0 0 g.,
in 7 0 0
was
Grignard
of
three hours
a solu­
of 1 - c h i o r o - 2 , 2 - d i m e t h y l b u t a n e
The r e a c t i o n w a s
Grignard reagent.
3
3 - 1 1 ter
tlr o v e r n i g h t #
an a t m o s p h e r e
The
The
started with
reaction mixture
Grignard
of n i t r o g e n .
r e a g e n t was
A yield
of 8 5 %
49
(b)
Addition of Grignard Reagent
Two Identical
T o 300 g.,
(dried
o v er P g O ^ )
a d d e d 650
mixture
500
became
the
very
were
m erc u r i c salt.
alcohol,
and
in 1 3 0 0
t hick.
After
Chloride:
chloride
cc o f d r y
adding an
the m i x t u r e w a s
allowed
accomplished with
separated,
T he
of m e r c u r i c
e t h e r was
Grignard reagent prepared
D e c o m p o s i t i o n was
layers
Mercuric
were made.
1.12 moles,
suspended
cc of d r y e t h e r
night.
The
cc of
runs
to
and
the
solid w a 3 put
ether
above*
The
additional
to s t i r
300
over
cc of w a t e r .
distilled
into s o l u t i o n
off
the
in h o t
filtered hot.
A yield
i ng c h l o r i d e
of
of S 0 %
of
theoretical
the m e r c u r i c
based
salt m e l t i n g
on
the
start­
8 9 . 5 — 90.5° was
ob t a l n e d •
PRSFARATION
(a)
mercuric
with
In
concentrated solution:
To
a suspension
chloride
stirring
when
stirred
for
in 50
room
s u d d e n l y all
evolution
a tir
at
of
cc
In 1 5 0
18 g.
the m e r c u r i c
two h o u r s .
noticed.
O nl y
0.1
cc
for
of p i n a c o l y i -
mole,
of w a t e r
of b r o m i n e
of w a t e r .
temperature
of h e a t w a s
recovered.
of 32 g.,
suspended
a solution
potassium bromide
was
OF P I N A C O L Y L B R O M I D E .
The
about
was
a n d 25 g.
minutes,
three
mixture
a f ew g r a m s
of
of
r e a c t i o n .mixture
salt disappeared.
The
added
was
crude
A small
allowed
bromide
to
was
(b)
In
dilute
To
a
suspension
mercuric
chloride
of
of
36
200
g*
cc
No
bromine
in
ice,
mixture
an h o u r
There
was
no
and
and
25
Two
layers
formed
to
stand
The
washed
with
weight
of
the
(c)
A
third
of
bromine
water.
crude
A
bromide
(d)
100
yield
of
was
and
dried
material
totalling
or.
of
solution
bromide
room
An
of
the
IB
of
g.
The
stirring
night.
separated,
was
and
was
made
using
the
with
600
potassium
1 2B
cc
oil
bromide
loot
of
so
but
bromine
were
added
was
layer
water.
g*,
of
of
mixture
g * , 9B,T o f
2 1
In
and
then
once*
flask,
water
immediately*
over
at
colorless*
additional
:_5 g*
was
temoerature.
bottom
In
all
in
20 m i n u t e s ,
absolutely
bromide
of
end
to
th e
u>3 g . , o v e r
was
The
theoretical.
0.4
moles,
water,
72
g.
In
cc
of
300
theoretical,
of
obtained.
crude
comolned
come
chloride
g.
the
was
mass
Fractionation
The
to
bromide
pinacolylmercuric
and
at
bisulfite,
of
a
added
were
run
added
solution
without
crude
was
or p i n a c o l y l -
bromine
almost
sodium
water
moles
suspension
layers*
layers
0.2
g . of p o t a s s i u m
solution
defined
g*,
chloride
g . of p o t a s s i u m
allowed
50
64
of
place
a semlsolid
clearly
cc
allowed
the
of
mercuric
the
taken
was
After
350
The
and
reaction had
the
in
of w a t e r .
cooled
solutions
of
plnacolyl
broorrlde
from
over* p o t a s s i u m ,
4B
g.
was
(b)
Bromide:
and
(c)
carbonate.
fractionated
above
The
through
was
dry
Column
II
51
TABLE
CUT
■IME
2 : 0 0
1
:2 0
3:00
3:35
4:10
4:40
5:20
5:55
2
8
6 : 0 0
9
2
3
4
5
n 20D
1 .7
1.7
2.7
1.4321
1.4375
1.4450
1.4485
1.4492
1.4494
1.4494
1.4493
1.4494
2 . 6
3.3
4.3
3.9
1 .O
6
7
A solid, f o r m e d
bottom
of
through
the
b.P .
WT .
2 . 8
column.
Cuts
3-9
Column
II:
In
63
67
70
71
71
71.Q
72.5
73.2
74
the
Inclusive,
WT.
n 20D
1
:2 ©
1:50
1
1 .8
2
2 : 2 0
3
4
5
3.6
2.5
4.1
3.4
1.4454
1.4482
1.4494
1.4495
1.4495
1.4494
1.4492
Res Idue -
(e)
6
2 .2
7
1.4
Properties
The
for p l n a c o l y l
lOO mm
71.5
72
72
73
73.5
75
77
80
84
pot,
lOO mm
lOO m m
lOO m m
and sublimed
to b e m e r c u r i c
TABLE
5,
B ,P .
were
onto
the
bromide.
refractionated
JACKET
71
75
72.o
72.8
73.8
73.8
73.8
O .o g •
of p l n a c o l y l
following physical
P R S3OURS
71
74
73
74
76
85
08
lOO mm
lOO m m
bromide:
procertles
were
obtained
bromide;
Valentine
I nd e x ,
Bolling point,
Density
PRESSURE
6
CUT
3:00
3: 25
3:45
4 :OG
JACKET
Tills p r o v e d
TABLE
TIME
5
at
20°,
C u ts
3,4,5,
(Column),
TABLE
6
1*4491
72.8/100
1.1782
mm
52
P R E P A R A T I O N O F PINACO.LYL
(a)
IODIDE.
In H o t S o l u t i o n :
To
suspension
e
o in a colylraercuric
a solution
of 2 10
chloride
g
., 0 * 6 3 m o l e s ,
In 8 0 0
cc
of w a t e r was
of 1 7 5 g., 0 . 6 8 m o l e s ,
of
iodine
p o tassium iodide
in 450
was
the a i r bath, h e a t e d
stirred,
hours.
about
and
in
lighter
t ha n w a t e r was
the n o t was
fractionated,
t ai n ed ,
total
then p l a c e d
cc of l o w - b o i l i n g m a t e r i a l
residue
was
cc of w a t e r .
The m i x t u r e was
20
while
obtained*
by Its
for
distilled
off.
and
The
and a m a t e r i a l
this
light material
at 6 3 - 7 0 ° was
d e c o m p o s e d a t 1 0 0 mm.
A'ith n l t r o s y l
of
three
o n a s t e a m bath,
’T h e n
refractionated
t e t r a m a t h y l e t h y l e n e b y its
reaction
an d 225 g.
to 90°
some p r o d u c t b o i l i n g
the r e m a i n d e r
added
The r e a c t i o n m i x t u r e
steam distilled,
low b o i l i n g m a t e r i a l was
f i e d as
of
physical
and
ob­
The
identi­
properties,
chi or* i d e , an d b y
the f o r ­
ma ti on of a u i b r o n i d e .
(b)
In c o l d s o l u t i o n :
To a suspension
mercuric. c h l o r i d e
of 26 g.
water.
i odine
The
reaction mixture
wltnout
separated,
cc of w a t e r wa s
and 38 g. p o t a s s i u m
for s e v e r a l h o u r s .
minuses
in 15 0
of 32 g . , 0 . 1 m o l e ,
and
A
3
mall
evolution
of p i n a c o l y l -
added
Iodide
a solution
in 10 0
was
stirred
lower
layer
formed
a f t e r fiv e
The
layers
were
of h e a t .
the s o l i d m e r c u r i c
iodide
at r o o m
cc of
was
temperature
filtered
from
tiie b o t t o m layer.
The
Iodine was
w i t h a s o l u t i o n of s o d i u m
63.75;fc of t h e o r e t i c a l ,
washed from
thiosulfate.
based
on
this
A yield
layer
of 1 3 . 5 g.,
the m e r c u r i c s a l t ,
was
obtained.
T wo m o r e
r u ns
were made,
pinacolylmercuric
chloride,
In these
% and 64% respe ct iv el y were
cases,
(c)
8 8
Fractionation
After drying
I od i de p r e p a r e d
This was
in
temperature
reached
d i s t i l l a t e had
43 m m b ut
be-n
decomposition
above
The d i s t i l l a t e was
The r e m a i n i n g
The w h o l e
d a r k cloth so as
maintained
through
only
dried
constant
at
45
about
1
the h e a d
cc
of
reduced
thiosulfate
li g ht .
to
car­
f l a 3 k at 4 5 mm.
fractionated
mm.
cr u d e
65 g*
ov er p o t a s s i u m
c o l u m n s y s t e m wa s
any
the
The real d u e was
a Claisen
38 g., w a s
to e x c l u d e
totalled
took o l a c e w h e n
again w a s h e d with
io d i d e ,
obtained.
'Hie p r e s s u r e was
thiosulfate,
.1 B m o l e s *
t h r o u g h C o l u m n II*
an d w h e n
collected.
a nd d i s t i l l e d
C o l u m n II.
°,
0
of
Io dide:
the d e c o m p o s i t i o n p e r s i s t e d .
washed with sodium
was
three ru n s
1 0 1
other using
potassium carbonate,
se t up f or f r a c t i o n a t i o n
A t 100 m m p r e s s u r e
bonate,
the
of P l n a c o l y l
over
the
and
one u s i n g 0 . 1 m o l e s
and dried.
through
covered with
The pre s s u r e
a
54
TABLE 7
WT.
C UT
TIME
7 1. 8
1.4970
71.8
2
3.6
1.4979
71.8
1.4983
3
4. 3
71.8
1.4986
4
3.3
72
4.5
1.4985
5
72
1.7
1.4983
6
7
4 .7
72.2
1.4983
8
5 .2
1.4972
75
D a c o m p o s i t i o n s t a r t e d at
R e s i d u e , 5. 2 g.
3:20
3:45
4 :1 0
4:35
5 :0 0
5 :1 0
5:35
5:45
The
pinacolyl
of p i n a c o l y l
index,
PREPARATION
3a.lt of
20°,
Cuts
45 m m
i odide.
were
Cuts
obtained
for
3 ,4 ,5 ,6 , above,
1.4982
72°/45 mm
3,4,5,6 ,
of* 32 g.,
0.1
1 - ch lor o - 2 , 2 - d l m e thyl
added a solu t i o n
in 7 5
cc
temperature
of 18 g.
1.4468
at r o o m
with
Aft-r
s t i r r i n g f o r one h o u r ,
butane
The
The w e i g h t
of
cc of
a n d 2 5 g.
reaction
the b o t t o m l a y e r
1 6 . 5 g . , 1 00 %
the
in l o O
a slight evolution
and w a s h e d w i t h s o d i u m b i s u l f i t e .
p r o d u c t was
n o l e .3 , of
of b r o m i n e
of w a t e r .
place
undried
45 m m
OF 1 - B R 0 M 0 - 2 , 2 - D I M E T h Y L B U T A N E .
To a s u s p e n s i o n
potassium bromide
!
45 m m
Column,
D e n s i t y at 20°,
w a t e r was
45 m m
iodide:
Boiling point,
mercuric
th i 3
following properties
Valentine
(a)
PRESSURE
78
78
78
78
78
78
78
78
point.
2.6
1
(d) P r o p e r t i e s
^
JACKET
B.P.
n 20D
wa s
of
of
took
of h e a t .
filtered,
the
crude
theoretical•
I
(b) A
larger r u n was
O.er a period
of
made.
15 m i n u t e s
a solution
of
135
g«
55
of b r o m i n e
w a t e r was
of
and 1 9 0 g.
added
to a s u s p e n s i o n
the m e r c u r i c
1299
of p o t a s s i u m b r o m i d e
s a l t of
cc of w a t e r *
1
of
240
g.,
A lower
l a y e r w as
m i x t u r e was
allowed
b r o m i d e was
steam distilled.
(c)
oil
Then
layer was w a s h ­
then w i t h w a t e r .
1 1 5 g.,
the
The w e i g h t
92.7%
of
of
theoretical,
F r a c t i o n a t i o n of 1 - B r o m o — 2 , 2 - d i m e t h y l b u t a n e .
Th e
bromide from
and after drying
1 0 5 g. was
fractionated
CUT
12:25
1: lO
2 :4 0
4:15
5: OO
9: 25
10:15
3
4
5
1 1 : 1 0
8
12:30
9
1
2
6
7
2 : 0 0
10
2 :5 5
3:30
4:05
12
11
13
(a)
and
(b)
a b o v e was
ov er p o t a s s i u m c a r b o n a t e ,
through C o l u m n
TABLE
TIME
in
The r e action
The b r o m i d e
l ay e r was
butane
a p p a r e n t a f t e r one
to s ti r fo r s i x h o u r s .
ed w i t h s o d i u m b i s u l f i t e ,
crude u n d r i e d
0 . 7 5 mo l es ,
- c h l o r o - 2 ,2 - d i m e t h y l
h a l f h o u r s t i r r i n g at r o o m t e m p e r a t u r e .
the
i n 60 0 cc of
WT.
resulting
II.
8
n 2° D
1.4489
1.4489
1.4489
1 0. 0
1.4489
11.2
4.7
1.4489
1.4489
11.6
1.4489
9 .6
4 .3
1.4489
9 .5
1.4489
1.4489
1 0 . 8
7. 6
1.4489
4.9
1.4489
1.7
1.4489
Residue , 1 . 2 g .
4.1
5.0
the
combined,
LS.P .
74
74
74
74.2
74.2
74.2
74.2
74.2
74.2
74.2
74.2
74.2
74.2
JACKET
P R 33SURE
73.5
74
74
74
74
74
74
75
75
74
75
82
l OO inm
110
100
mm
1 00
mm
l.no m m
Decomposing
56
(d) P r o p e r t i e s
of 1 - B r o m o - £ , 2 - d i m e t h y l b u t a n e •
T he f o l l o w i n g p h y s i c a l p r o p e r t i e s
2
,2 - d i me thyl b u t a n e w e r e
Valentine
i n d e x at 20°,
1.4438
1.1787
Cottrell boiling points, pressure
1.
2.
3.
4.
3 & 4
135.0
135.4
135.8
135.8
(a)
736.5 mm
Cut 7
1.
2.
3.
4.
PREPARATION
Cut 9
135.8
135.8
135.8
135.8
1.
2.
3.
4.
135.8
135.8
135.8
135.8
OF 1 - I 0 D 0 - 2 .2-P I M E T H Y L B U T A N E .
To a s u s p e n s i o n
of 32 g.,
0.1 mole,
m e r c u r i c s a l t of 1 - c h l o r o - 2 , 2 - d i m e t h y l b u t a n e
of w a t e r was
g.
a d d e d a s o l u t i o n of 26 g.
of p c t a s a i u m i o d i d e
formed after
evolution
of
the
an d w a s h e d w i t h
larger
a
r u n wa s
- chi o r o -
a solution
1
The
sodium
in 150
layer
was
allowed
was
no noticeable
of the
85%
to s t i r
reaction.
oil l a y e r was
g.,
cc
a n d 38
A bottom
thiosulfate.
18 . 5
of
separated,
The w e i g h t
theoretical.
ma d e.
of 275 g.
,2 -dl me t h y l b u t a n e
of 225 g.
There
o> u r s e
s t o o d ov e r n i g h t .
To a s u s p e n s i o n
1
the
crude w e t p r o d u c t was
(b)
of
The m i x t u r e
of the
of i o d i n e
cc of w a t e r .
three h o u r s .
of h e a t d u r i n g
The m i x t u r e
filtered,
in 100
25 m i n u t e s .
for an a d d i t i o n a l
1-bromo-
obtained:
D e n s i t y at 20°,
Cut s
for
of i o d i n e
in
and
of
1 2 2 0
the m e r c u r i c
salt
cc of w a t e r was
340 g.
of p o t a s s i u m
added
57
iodide
In 900
15 m i n u t e s *
h ou r s,
A lower
T h e m i x t u r e was
and t h e n was
iodide was
The
cc of w a t e r *
allowed
s t i r r e d for
washed
Fractionation
A small
ab ove w a s
se t up
a pressure
of
hour.
cut w a s
One
he If hour.
composing
charged,
lOO m m
When
the
and
total
the
thiosulfite*
3 6 8 * 5 g* , 9 2 * 5 %
of
the d r i e d i o d i d e
fractionation
the
taken
I t w as
The
Th e
of
theoretical,
of 1 - I o d o - 2 , 2 - d i m e t h y l b u t a n e *
portion
for
a half
the r e a c t i o n m i x t u r e *
with sodium
y i e l d of cr u de w e t p r o d u c t w a s
(c)
tw o a n d
to s t a n d o v e r n i g h t .
steam distilled from
oil l a y e r was
layer f o r m e d after
Iodide
through
refluxed
a nd r e f l u x i n g
seen
weight
t h at
Column
at 9 5 °
the I o d i d e w a s
start'd
over
.F.
JACKST
II*
for
continued
of I o d i d e p r e p a r e d ,
fractionation
prepared
At
one
fo r a n o t h e r
not de­
141
g,,
was
again.
TABLii 9
TlSfcE
;1 o
C :40
7:50
8 ;45
9:50
10:50
11 *50
1 1 :55
12: 40
1: 55
3:05
4: 25
5: 20
6 :2 0
7:25
8 ; 25
9:20
9: 55
10:15
6
C 51
i
2
3
4
5
6
7
o
9
10
11
12
13
14
It
16
17
18
19
WT .
p
^Od
1 .4 9 0 2
1.4952
1.4948
6 .6
1.4951
8 . 2
1.4952
9.0
1.4955
1 0 . 6
1.4955
5.5
1.4955
1 *9
1.4952
9 .0
1.4955
8*7
1.4955
1 2 . 1
1.4955
7.7
1.4955
1 0 . 1
1.4955
9*d
1.4955
1 0 . 2
1.4955
8.5
1.4955
4.3
1.4955
3.2
1.4952
R e s i d u e , 1*0 g.
•0
3 .7
8
90
9 6. 8
96
96.2
96.2
96.2
96*2
96.2
96.8
96.8
96 .8
96.8
96.8
96.8
9 6. 8
96 .8
9 6. 8
96.8
95
96
96
96
95
95
95
95.5
95.5
94
94
96
97
93
98
95
93
96
98
1 09
PKSShUHE
loo m m
mm
l OO m m
l OO m m
1 00
100
lOO
100
100
58
(d)
Properties
The
for
of 1 - i o d o - 2 , 2 - d i m e t h y l b u t a n e •
following physical properties
were
obtained
l - i o d o - 2 ,2 - d i m e t h y l b u t a n e :
Valentine
i n d e x at
20°,
1.4951
D e n s i t y a t 20°,
Cottrell
boiling points,
Cu t 12
1.
2.
3.
4.
1,4473
162*7
163.0
163.0
163.0
Pressure
Cut
1,
2.
3.
4.
736,5 mm
16
163.0
163.0
163.0
163.0
Cut
1.
2.
3.
4.
7
163,0
163.0
163.0
163.0
59
SUGARY
OF P R O P E R T I E S
OF N E O H E X Y L H A L I D E S
n 2°D
B.P.
HALIDE
739 mm
1*4188
72.8°
at 100 m m
1.44S1
72.0°
at
45 m m
1.4468
116.1°
at 735 m m
1.4200
at 7 3 6 . 5
109*8°
pinacolyl
chloride
pinacolyl
bromide
1.1782
Pinacolyl
iodide
1.4468
1 - c h i o r o - 2 ,2 diine t h y l b u t a n e
l - b r o m o - 2 ,2 dimethylbutane
1.1787
1.1787
135.8
l - i o d o - 2 ,2 dimethylbutane
1.4473
163
at
at
736.6 mm
mm
1.4487
1.4951
60
REACTION
OF PROPANOLIC
PINACOLYL
To
In 24 0 g
n 2 ®D,
a mixture
4 moles,
1.3858,
chloride.
was
The
Column
II,
A d ry
Ice-acctone
column.
During
belling
39
of
oil
layer
retical.
the
Some
column
The
ated
through
I n a on e
trap
was
time
connected
a total
distilled
the
fraction
Column
oil
7:45
CUT
1
2
3
4
5
6
12:30
7
1 :00
8
2:05
9
10 :00
lO
11:30
11
of s t i c k K O K
17.2
o ff .
The
was
alcohol,
of p l n a c o l y l
f l a s k was
to
for
the
113.7
g.
set up
13.5 hours.
outlet
g.
water
retained
of
was
on
and
80%
of
theo­
cutter.
was
fraction­
10
n 20D
B.P .
1.3769
39.5
1.3772
14.6
39.5
13.4
39.5
1.3770
12.4
39.5
1.3770
13.9
39.5
1.3770
14.5
1.3770
39.5
1 . 8
1.3790
42
1.3810
52
1.4
3.7
1.4029
74
Discontinued overnight
4.4
1.4058
108
4.4
1.4178
109
F l a s k was dry
6.1
96.5
trie w a l l s
II.
WT.
the
of m a t e r i a l
of w a t e r
l a 7ger fror: a b o v e
TABLE
TIME
of
of
however,
96. h g.
liter
to r e f l u x i n g
consisting
water,
ana
146 g . , 1.2 m o l es ,
and heated
th is
was
3.3 moles
of r e f r a c t i o n a t e d n - p r o p y l
added
to 72^
ON
CHLORIDE
of* 1 8 7 g.,
mixture
under
KOH
JACKET
37
37
37
37
37
50
65
69
80
98
109
of
g.
61
I d e n t i f i e s ti on
Precedinp
Aa.'iur.in.q
0 .1
1
or
Cut
m o le ,
e th e r,
of
C uts
17
and
to
4
ozone
lit e r s
o f
6
per
each
tn e
s
water
i
8. 5
o f
p.
fro m
3 ay or
s o lu tio n .
p r e c i y 1 ta
t <.? ,
h .p .
w itn
a
fo rm a ld - h y d e
p o in t
wav*-*
nc
cc
hydrazine
tely •
w t- '■ s «1d e d
in
The
alcohol.
meltiro
f O b - ; 1(1°.
no
a
o f
a
a t
p e t
The o z o n id e
and
s ilv e r
o f
w a te r,
n it r a te .
d e c o m p o s 1 11 o n
ste a m
d im e to l
fo rm e d
d im e to l
g. ,
th e r a t e
10cc
s a tu ra te d
know n
o z o n iz e d
h o u rs.
Id 9 -lb 0 °
of' t.h**. <'11
H u j i f i or
A
. oinl
of
im n e d ia t e l y .
d e riv a tiv e
of
.vithout
derivative
formed
almos t
inune d l a ­
r e c r p r a t a 1.1 i z*> t i o n
point
of
lav-:*r f
. , 4 - d i n * t r c* 'senyl —
•' recir- i ta f e
:Ixe 3 n h : i : e
r ii e n y l h y d r a z i n e
th e
8 .4
de sire s s i o n .
o s e v- -r r 1 d r u m
co.tr ''.11 1'■ n
o f
d u s t,
I
50
r r .e l t:.in r ,
5 .o
h y d ro c u in c n e
added
m ixe d
cc
th e s o lu t io n
o f zlr.n
was
A
.1 5 0
hour fo r
d i s t i l l a* lo r .
A
the
t- b u ty le th y ls n o ,
w ith
oxypen
tw o
o f
m ixe d
be
th ro u g h
and
cc
to
passed
u
I'o 5
aoove
was
decomposed,
V
From
Pane:
was
c ry s ta ls
c>r t - B u t v l e t h y l e n e
wit;,
tri
a
rit o w n
was
1 ,i-dini trc-
e thylace taldehyde
nave
depression.
From
the
above
derivatives,
ozonized
lias b e e n p r o v e n
to
C ut s
Inclusive
pure
1- 6
tiieoradlci.il w as
c
ccr.s
1
s t 1 ;s o f
was
uc
n ■
to be
the
original
be _t— b u ty 1.e thyl e no .
product,
a yield
material
As 'tuning
of 7 4 i
of
obtained.
Li.-; r-si.iue
in
ti •
U'l-l.nal
r-pro'i'u
v e s :-i,
u n r o a c ter. o h
K _i:, a.lc oh o 1 , anc
po ri.aps
cc
1 ji’r r ’” f cr-o': , r ^ h u L l v
cd' \va te r* .
itvo
1
or idr ,
because
of
layer was
vered
the
this
sufficient
acted
out
extracted with
from
layer,
salting
ether.
extract.
water
to
consisting
chloride,
To
cause
of
was
two
n20D
1
0 . 8
j
1 . 0
1.4172
1.4183
1.4187
1.4187
1.4187
1.4187
1.4187
1.4192
Res i d u e ,
rC
3
4
5
1 1 :00
1 1 :45
1 :00
8
2.4
3.8
3.9
4.6
3.7
0.4
Cut s
2-7
1:40
6
2 : 1 0
7
2
:2 0
To Cuts
sufficient water
layer,
after
The w e i g h t
to
of
th e
was
charge
two
1:30
:50
2:30
3:05
4:00
4: 50
5: O o
1
CUT
1
i
<2“v,
3
4
5
water
Only propanol
was
reco­
oil
layer was
added
to fox-m•
The
upper
of b e i n g
unre­
through
Column
JACKET
.
61-76
76.5
76.5
76.5
76.5
76.5
76.5
77
1.1
g.
were
was
150
mm
150
mm
86
3.50 m m
chloride.
TABLE
was
It y e n s
11.3
10,
to f o r m .
through
JACKET
0.7
0.5
1.4160
1.4180
1.4186
1.4138
1.4187
1.4188
1.4190
ResIdue,
65-71
75.5
76.5
76.5
77
77
70
1. 0
g.
79
74
77
77
77
78
81
6
2 . 0
(
0.3
Cuts
3-7
The
just
upper
Column
CW.
12
B .P .
rw
added
g.
n 2° D
1 . 0
PRESSURE
77
70
78
79
78
78
81
•T.
1.9
3.6
just
III.
pinacolyl
fractionated
TABLE
TlttE
The
Inclusive,
cause
drying,
KOH•
suspected
B.T
inclusive
7-11
t he
11
WT.
30:20
or
layers
fractionated
CUT
1 0 : 0 0
the
g. , a n d
2 2
TABLE
TIME
effect
inciui) I ve w e r e
pI n a c o l y l
PRESSURE
150
mm
150
mm
loO
mm
chloride.
65
SUMMARY
'/Mien o i n a c r l y l
mixture
of* p r o p a n o l i c
chloride
KOH,
the
In
refluxed with
following products
a
are
obtained:
1. _t-Dutyle t h y l e n e , 7 4 . 9
2.
Unreacted plnacolyl
0.24 moles,
g.,
0.89 moles,
chloride,
total
7 4.2^.
28.1
G.,
20
A material
balance
REACTION
Cr
of 9 4 % wa s
PilOPAhO-LlG K O H
obtained.
OK
1-CH.LQRQ — 2 ,2-DI.V)HTHYL 8 U TnK E .
To
190 g.,
4.8 m o l e s , o f K O H
of r e f rac t i o r a ted n r o p a n o l ,
1
20
D,
.1.3858,
to
trap,
in a one
tre
ana
liter
cutlet
d .;3. f l a s k was
of vvulcn was
refluxed
of d i s t i l l a t e ,
was
3.P«
for
21 h o u r s .
48-78,
Durinr
consisting
The K O H h a d eat e n a h ole
a nd s o m e
the
the
of
f l a s k was
separated.
p r o d u c t was
mixed with
he w a t e r
the
e t he r
layer
was
fractionated
througn
of
In
two
of w a t e r ,
the
Column
oil
III.
ice-acetone
time,
14.4
layers,
residue
extracted
g.
was
flask,
remaining
and
the
w i t h ether,
l a ye r .
g.,
Column
the r e a c t i o n
500
cc
15 0
reaction
under
this
The
with
The
up
lost.
l a y e r was
combined
set
4 moles,
added
attacl'.ed a d r y
colJected.
in
240 g.,
rr:cl es , of 1-cihl oro-2i , 2 - d i m e t h y l b u t a n e •
mixture
II,
n
In
layers
and
rhi.e s o l u t i o n
64
T A B L E 1.3
3 . P.
n 2° D
7/T .
T h e e t h e r was atrloped off
4.6
79
2 :1 5 #: 50 2
31
3
5
.
7
3:30
33.5
4
4 .1
4:10
84
5
4:50
3.5
3 toed overnight
89
5.2
1 1 : 1 0
6
1
.
3
9
9
8
7
9
.
7
91
1 2 : 1 0
8
1.3998
92
9.6
1 : 1 0
9
92.5
9.2
1.4000
2:15
93
lO
10.3
1.4000
3: o b
93
7
.1
1
.
3
9
9
9
4:20
11
1.3999
93
1 2
3 .9
5:00
3 tood overnight
8 . 6
1.3998
13
4:00
92.5
14
9.8
1.3999
92.5
5:50
15
1.3998
6:50
5.6
92.5
1.3998
3:45
16
11 . 3
92.5
17
9 .1
1.3993
10; 25
92.5
1.3909
18
92.5
11: 30
3 .0
S tood overn i g h t
1:55
19
7.8
1.3908
92.5
7 .9
3:35
20
1.3999
92.5
4 : 50
21
5.8
93
1.3930
6:24
22
7 .8
1.3945
94
TIME
CUT
The
f 1 I t e red , a nd
r e s Idu e,
the
f or f r a c t i o n a t i o n
75!
92
93
94
94
ex tr* a ct e d
the e t h e r
through
extract
Column
III.
Two
li
n
n
M
M
94
94
95
97
97
97
94
94
94
97
96
96
98.5
99
lOO
lOO
cental n i n g p o t a s a l u m
ca r b o n a t e
l i q u i d re s idue , p 1 US
JACKET
carbonate,
1th
ether
war
awain
T he
© the r w as
T he
set
uj
3
tr 1 p -
p e d off.
TABLE
TIME
9:15
li :no
2:25
CUT
1
£
Stood
3
>VT .
14
n?0 D
< •O
^
1.3861
1 .4
1.3870
o v e r n i g ht
4.3
1.3869
<■'
B.P.
94
95
96
JACKET
103
10 3
11 4
c ontinuod
7 3 5 inm
TABLE
CUT
TIMS
4
5
4:45
7:30
9:00
9: lO
9:30
10:05
10:35
11:15
8
9
0.9
neohexyl
inclusive,
material
added
of an
oil
50
cc
layer
ated
Column
1
2
3
4
5
6
Cuts
3-6
believed
n.^^,
fo r
charge
1,4000,
to be a m i x t u r e
T o a 40 g*
layers
were
This
drying,
separated,
layer was
wa s
fraction­
15
6 dr op s 1 . 4 1 4 2
ft
1.4180
4.9 g
1.4200
4. 0
1.4200
4.2
1.4200
3 .0
1.4201
inclusive
4,
The
after
n 20D
Identification
C ut
up
III.
TABLE
WT.
and,
set
9 3 — 94°,
being recovered.
with water,
3:00
3:30
4: O O
4:25
4:55
5: 20
wa s
were
From a starting
ooiling
of w a t e r .
again washed
CUT
13,
l-chloro-2,2-dimethylbutane•
was
TIME
m o l e s , were
ether*
TABLE
of m a t e r i a l
This
and
through
240
through C o l u m n EMJ*
1 2 3 g.,
of p r o p a n o l
7.2
Ether
2 1 0
'A
C
.
7-21
143
145
145
140
144
o
to be n - p r o p y l
114
118
1 64
164
164
165
•t
inclusive,
JACKET
1 2 2
to
7 -1 1
recovered.
50 g.
96
96
11
g.,
sample
1.3869
1.3371
1.3916
1.4016
1.4033
1.4033
1.4033
1.4050
2.2
refractionation
was
6.5
1 . 6
Cu ts
of 1 2 8
B. F.
10
Cuts
assumed
n 2° D
1.9
0.8
1.7
6
continued
7/T.
1 0 . 0
7
14
were
JACKET
B.P.
98-112
115
116
1 16
116
116.5
1
- chioro-
120
120
120
121
123
128
8
,2 - d i m s t h y l b u t a n e .
of A b o v e :
4.0 g ., was
mixed
with
10
cc
of
anhydrous
ether,
and
crystal
but when
started
the
of
Iodine
drops
6
added
to
cooled
believed
to be
in Ice.
bromide
The
passed
and
the
M.p.
After
over
the
turned
separated.
the r e a c t i o n
stirring for
surface
of
solid.
Ice w a s
was
T he u p p e r
dried
carbinol was
65-67°,
’.vith k n o w n p h e n y l u r e t h a n
added,
A
the r e a c t i o n
the r e s u l t i n g m a t e r i a l
s o l u t i o n wan h e a t e d
a solid,
of m a g n e s i u m .
to s t a r t
heating.
t-amylcarbinol,
of
g.
were
The m i x t u r e
layers were
a small p o r t i o n
cooling,
of e t h y l
the m i x t u r e ,
T he
to 0 , 8
not sufficient
o x y g e n gas w as
tilled.
cyanate.
was
after a few minutes
five hours,
mixture
solution added
the
steam dis­
la y e r ,
2. 5 g,
over K CO3 .
To
added phenyliso-
for several
crystallized.
of t - a m y l c a r b i n o l
minutes.
On
A m i x e d M.P.
gave
no
depression.
To f u r tlier p r o v e
Index material,
1
a s er i e s
the
composition
of m i x t u r e s
- c h l o r o - 2 ,2 - d i m e t h y l b u t a n e
was
made,
of
the 1 . 4 0 0 0
of p r o p a n o l
an d
the
and
of
i n di c e s
de t e r m i n e d •
T A B L E 16
WT PROPANOL
WT
IO g.
O
IO
CHLORIDE
O g.
5
5
6
7
8
IO
10
10
Therefore,
the
mixture
1.3860
1.4200
1.3960
1.3980
1.3990
1.4001
contains
about
44.4%
of
l - c h l o r o - 2 ,2 - d i m e t h y l b u t a n e .
to
the r e s u l t s
was
o b t a i n e d in T A B L E
recovered*
Assuming,
material under
54 g.
or 0 * 4 5
of Cuts
7 — 21
moles was
TABLE
layers
that
contains
in
40%
the
4 4 % of
the
closely
of
chloride
1*4000
the
index
chloride,
fractionation
13*
from
chloride-propanol mixtures
The u p p e r
15, w h e r e
recovered
inclusive,
corresponds
therefore,
investigation
The w a t e r
the
This
the
were
above
treatment
of
s a t u r a t e d wi t h KOH.
layer which separated or o v e d
to b e
only oro-
panol.
The
refluxing
of
1 4 * 4 g*
the
with fractions
was
original
2 -6
layer separated
of m a t e r i a l
inclusive,
through
TABLE
TIKE
C UT
WT.
1
0 . 2
2
0 . 1
6:30
7:30
9:15
3
4
Stood
2: 25
5
3:15
6
7
4:05
1 1 : 0 0
Cuts
water*
ate d
The
through
oil
T A B L E 13,
The
Column
dried
combined
the
rroduct,
oil
19 g*,
II.
n 20D
1 4 * 5 g.,
JACKET
B .F .
48
76.5
92
94
83
35
85
92
102.5
119
83
118
129
130
3—7 inclusive were
Co Lunin CW.
and
the
17
1.3942
2.5
2 .6
1.3995
overnight
6.0
1.4012
4 .9
1.4140
1.6
1.4198
la y e r ,
o ff d u r i n g
r e a c t i o n mixture was
and d r i e d *
fractionated
taken
washed
after
with
drying,
10
was
cc of
fraction­
TABLE
CUT
TIME
9:00
9:25
9:45
10:30
11:05
11:30
12:30
WT .
1
0 . 2
2
0.4
3
0 . 8
4
1.4
5
2 . 2
6
2.5
3.0
7
1 : 0 0
8
2 . 0
1:40
9
1.4
Cuts
3-9
18
B.P.
n 20D
1.4090
1.4099
1.4194
1.4199
1.4200
1.4200
1.4200
1.4200
1.4200
JACKET
97
98
118
119
1 1 2
1 2 0
114
114
114
114
114
118
118
118
118
118
118
no
I n d u s ive , 13.3
g .,
mol
0 . 1 1
l - c h l o r o - 2 ,2 - d i m e t h y l b u t a n e .
SUivlMAKY
7/heri 1 - c h l o r o - 2 , 2 - d i m e tiiylbutane
with
alcoholic
were
obtained:
1
4/o of
(propanol)
* n-Propy]
K O H # the
neohe xyl
ether,
Is
following
7,2
g .,
refluxed
materials
0.05
mole3 .
theoretical.
2.
Unreacted
c h l o r i d e , g.
6 7,, 30 . 5 6
moles,
45%
theore tlcal,
A material
balance
of
only
49% was
obtained.
of
69
R E A C T I O N OF P R O P A N O L I C K O H
ON
1-BRQiViQ— 2 ,2 - D I M E T H Y L B U T A N E •
T o a s o l u t i o n of* 8 2 . 5 g. #
2
,2 - d i m e t h y l b u t a n e
n-propyl
alcohol
1.5 moles,
column
at
taken
of
the
tr ap
fractionated
through
T he
Column
TABLE
TIiviE
C UT
attached
of r e f l u x i n g ,
off i n t e r m i t t e n t l y .
77T .
w as
12 h o u r s .
from
a d d e d 84 g«,
s e t up u n d e r
T he
boiling point
38-84°.
to the
3 5 g.
of 1 - b r o m o -
of r e f r a c t i o n a t e d
f l a s k wa s
The m i x t u r e
column ranged
in a d r y ice
the p e r i o d
2 moles,
cc R . B .
and r e f l u x e d f o r
the h e a d
During
in a 5 0 0
of s t i c k K O H .
III,
collected
In 1 2 0 g.,
0.5 moles,
N o t h i n g w as
column
outlet.
of d i s t i l l a t e
d i s t i l l a t e was
were
dried and
III.
19
n
B.P .
D
1 2 : 2 0
1
1.0
38
1 : 1 0
2
0 . 8
66
JACKET
96
96
96
3
1.2
95
4
3.4
1.3920
95
A l l o w e d to 3 ta;.d o v e r n i g h t .
3:45
1.3939
5
7.5
95
4:30
6
6.0
1.3939
95
7
8 : 0 0
4.0
1.4041
133
1:50
4:00
The r e s i d u e w i l l
be
added
10 5
106
161
to a s u b s e q u e n t
fractIone tio n •
To
the r e s i d u e
a c t i o n m i x t u r e was
separated.
portions
layer.
The w a t e r
of e ther,
The
added
and
in
the p o t
cc
of w a t e r .
layer
was
extracted
the
ether
extract
s o l u t i o n was
200
from
fractionated
the
original
The
la y e r s
-vith t h re e
added
through
to
the
Column
re­
were
100
oil.
II:
cc
70
TABLE
12:55
1:50
2: 50
3: 40
3:55
4:40
5 s50
7:40
1 0 : 2 0
1 1 :30
12: 5 o
2 : 2 0
3:30
4:10
2:45
3:30
5:55
6 :1 0
7:00
7:55
8 : 1 0
1 :3 0
i :2 o
3:40
4 :45
5 :0 0
W T.
CUT
TIwlE
The
1.3898
1.3910
8 6
1.3913
8 6
6
7
8 6
1.3910
8
1 0 . 2
1.3914
8 6
A l l o w e d to s t a n d o v e r n i g h t
96
9
1.3925
90
8 . 0
1
.
3
9
2
6
9.2
96
94
10
8.3
1.3928
96
94
11
14.2
12
1.3930
96
94
1.3935
96
13
1 1 . 1
96
6.9
1.3942
96
110
14
T r a n s f e r r e d to 50 cc p ot .
:o 9
96
15
1.3951
1 . 8
16 7
16
2 . 2
1.4200
130
17
132
1.4
1.4230
170
137
18
1.4235
1 . 6
175
19
2.3
1.4232
148
138
139
2 . 2
20
1.4230
160
177
21
1.4220
1.1
140
T h e r e s i d u e l'roin T A B L E 19 w a s a d d e d , and
a t ion c o n t i n u e d a t a o r e s s ure of 1 5 0 m m
22
1 . 8
1.4310
95
85
2.4
1.4291
96
96
c
C « C
L4
1.4232
96
8 8
r'
A8.0
1.4145
109
90
26
1.4090
2.1
8
6
H O
3.2
5.9
5.8
5.4
An
were
oil
fractionated
1
4-15
a mixture
fractions
water.
80.5
82
82
94
96
96
96
96
79.5
81
83
83
2
3
4
5
B.P .
JACKET
n 20D
1
Cuts
of b e i n g
20
Inclusive,
of p r o p a n o l
washed
la y er ,
through
32
TABLE
and
Column
- b r o m o - 2 ,2 — d i m e t h y l b u t a n e
II,
w as
were
suspected,
the u n r e a c t e d b r o m i d e *
first with
g . , was
20,
15 0
cc,
recovered.
28.8
g.,
recovered*
0.17
then
50
When
tdis
moles,
cc
of
of
was
2X
TABLE
TIME
9 : 20
9:40
CUT
WT.
n 2° D
B.P.
JACKET
P R E S S Ui
1
0 . 6
1.4052
1.4400
1.4480
1.4487
1.4488
1.4488
1.4483
1.4488
1.4483
1.4488
1 , 0 g.
68-72
73
73.5
74
74
74
74
74
74
74
75
75
75
75
75
75
75
75
75
77
lOO m m
10 O IT17IJ
r-
0 . 8
1 1 :00
3
4
5
1 2 : 0 0
6
o.s
1.5
1.7
4.0
1 :00
7
4.6
2 : 0 0
8
5.1
1 0 : 0 0
10:30
9
IO
3: I O
4: IO
6 . 0
5.1
Residue,
Cuts
3 — 10
above
were
unreected
Cuts
3-6
Inclusive,
manner,
6*7
g.,
lOO
mm
lOO m m
lOO
mm
l-bromo-2,2—
d i n e thylbutarie •
When
in
the
was
same
0*04
TABLE
moles,
19,
of
were
the
treated
bromide
recovered.
Cxits
TABLE
were
19 ,
tctal
17-21
inclusive,
weight
reiTactionated
22.0
through
TABLE
TIME
;2 0
8:45
9 :30
1 0 :3 0
11:15
1 1 :55
1 :05
1:25
8
2 : 0 0
2:30
3:15
3 :5 0
4 :3 5
5:15
6 : 0 0
g.,
i
TABLE
( 1 .1
Column
WT .
n 2° D
B.P.
1
0.3
0.9
1.4242
1.4221
1.4213
1.4^07
1.4208
.1 . 4 2 0 6
1.4200
1.4119
1.4091
1.4041
1.4040
1.4039
I .4038
1.4037
1.4036
85-131
132
134
134
134
134
134.5
136
140
143
14 4
144.5
144.5
144.5
143
3
4
5
1 . 1
1 . 2
6
o #o
SB
2 .1
7
1 . 0
8
9
IO
0.5
0.7
0 . 8
11
1. J
1 2
1 . 8
13
14
15
2.4
3.5
1.4
&>
nnd
lost
II.
2
CUT
2
20,
JACKET
136
139
141
141
142
144
146
147
149
149
149
149
149
149
152
Cut
on
7,
standing)
72
C ut s
odor.
2-8
inclusive
A p h e n y l u r e t h a n was
crystallizations
64-66°.
from
3-6
assumed
M.
inclusive,
to be
C ut s
assumed
made
of
ether,
cut
P.
6 6 — 67°,
g.,
6 . 6
a definite
5.
After
carblnol
tw o
re-
the m e l t i n g p o i n t w a s
A nixed melting point with
of t - a m y l c a r b i n o l ,
C ut s
pet
above h a d
a known phenylurethan
gave
0.064
no
moles,
depression.
were
therefore
t-amylcarbincl.
10-15
inclusive,
to be n — p r o p y l
neohexyl
11.0
g.,
0.071
moles,
were
was
refluxed
ether.
SUMMARY
Wien
with
1
-bromo-2,2 -dimethylbutane
propanol i c KOH
the
1. _t-Amylcs r b i n o l ,
following
6 . 6
materials
g ., 0.064
were
moles,
obtained:
12.8%
of
the ore t i c a l •
2. n - P r c n y l
14.2%
of
ether,
11.0
g. * 0 . 0 7 1
moles,
theoretical.
3. U n r e e c t e d
t h e o r e tic a] •
«
neohexyl
bromide,
35.5
g.,
0.21
moles,
42%
of
REACTION
OF F R O P A N O L I C
KOH
ON
PINACOLYL BROMIDE.
To
a mixture
colyl
bromide
panol
was
of
In 37 g.,
added
25.6
0.62
26 g. , 0 . 4 6
g .,
0.155
moles,
moles,
of s t i c k
wa s
set
up u n d e r
Column
II,
fluxing
for
three ho urs.
During
this
the
off
intermittently
boiling point
remained
above
the r e a c t i o n
T he
water
for
one
temperature
half hour
la y e r w e i g h e d
2.2
g.,
theoretical.
oil
layer,
after
fractionated
1 1 : 2 0
2.4
3.5
0.9
1.3722
1.3770
1.3770
1.3770
1.3770
11:30
6
0 . 8
residue
residue.
N o t h i n g was
tached
the
C ut s
outlet
1-5
was
through
Column
over p o t a s s i u m
II:
JACKET
3 9 o5
39.5
39.5
39.5
40.0
94
39
41.5
42
60
92
96
734
added
to
the
orlginal
recovered
In
the
dry
of
the
ere
Ice
trap
at­
column.
Inclusive,
theoretical
dried
•
0.9
2
3
4
5
The
of
being
•
CQ
1
2 . 6
80%
separated.
23
n 20D
of
head
were
WT .
7y.2t
reflux
dropped below
distillate
was
layers
CUT
to
distillate was
temperature
the
to r e -
discontinued.
TABLE
1 1 : 1 0
time
pro
The
the
carbonate,
IO: 20
10:40
10:55
end h e a t e d
When
total
KOH.
in
The
TIME
the
of p r o p a n o l .
S0 ° a f t e r
was
The
as
of p l n a -
of r e f r a c t i o n a t e d
mixture
taken
moles,
weight,
10.3
t— b u t y l e t h y l e n e .
g*,
0.122 moles
74
To
the p r o p e n o l - K O H
reaction mixture,
was
added
75
the w a t e r
ether*
cc
the w h o l e
boiling
at
residue
continued
The
there
at
1*3858,
were
about
£ g.
n 2° D
1 : 1 0
1
0 . 6
1:30
2
0 . 6
2 :00
3
4
5
0.7
0.7
0.9
6
1.0
1.4010
1.4400
1.4481
1*4490
1.44 90
1•4490
1.4492
0.5
Pot dry*
Cuts
4-7
theoretical,
two
50
the
set
cc
of
Column
above
and
cc p o r t i o n s
oil
up
came
£3
separated,
layer,
for
stripped
next
6
were
original
and
fractionation
off*
over.
of
Propanol,
Reflux:
residue
in
CW,
fractionation
and
the
pot*
are
came
over.
£4
WT.
7
was
of p r o p a n o l
CUT
2:30
3:10
3:45
4:30
to
from TABLE
to
was
t he
mm :
TABLE
TIME
with
added
ether
transferred
lOO
About
The
from
layers
solution
n^^D,
was
The
extracted
II.
96°,
stopped when
residue
layer was
dried*
Column
The
was
ether
through
t he
of w a t e r .
layer
The
plus
residue
B.P .
JACKET
71
78
73
75
75
76
78
6 8
70
73
73
73
73
60
i n c l u s i v e , 3.1
pInacolyl
PRESS.
lOO
mm
lOO
loo
lOO
g . , 0.019
moles,
12%
bromide •
SUiVUviAKY
1*
79,2%
of
12
10*3
g.,
0.122
moles,
theoretical*
2*
moles,
t-Butylethylene,
a of
Unreacted
pinacolyl
theoretical.
lViUter ial
balance,
91.0%
bromide,
3*1
g*,
0*019
REACTION
OF P R O P A N O L I C
KOH
ON
X-BRQM0-3.3-DIMKTHYLBUTANE
To
a 30lutior.
of
74 . 2 g. , 0 . 4 6
l-bromo-3,3-dimethylbutane
refractionated
stick
KOH.
heated
was
added
mixture
was
set
The
t hi s
time
head
temperature
temperature
mained
at
ing w a s
93°
During
after
from
most
42°.
one
half
the
The
water
oil
layers
in
layer was
layer
weight
The
through
is
the
10:15
10:28
10:42
11:05
ll:5o
12:55
1:10
1.8
g«,
moles,
lo35
under
of
moles,
Column
II,
a half hours.
the
boiling
the
’T h e n
hour
point
reaction
the
total
the
boiling
reflux
of
and
During
imtermlttently
weighed
layer
Column
CUT
1
2
3
4
5
6
7
WT.
1.4
1.4
4.2
4.5
3.3
4.1
1.1
over
9.2
probably
oi l
distillate
dried
of
to
the
were
potassium
g . , 113%
due
as
the
of
head
point
the
re­
heat­
of
separated,
carbonate.
theoretical.
The
propanol.
distillate
was
fraction­
II:
TABLE
TLSS
up
off
of
at
78
and
taken
dropped
g.,
of
discontinued.
and
ated
throe
was
remained
The
extra
for
distillate
96°.
108
propanol
to r e f l u x i n g
propanol,
In
moles,
25
n 2° D
1.3766
1.3768
1.3770
1.3770
1.3770
1.3770
1.3775
B.P.
38.5
39.5
40
40
40
40
94
JACKET
40
41
41
41
41
82
95
735
mm
76
The
layer.
residue
Nothing
was
attached
to
51.35
theoretical
of
the
The
mixture
The
liquid
dried
were
was
column
layer
was
oft.
were
to
the
and
dry
original
propanol
i c e - a c e tone
Cuts
1-6
inc.,
trao
19,4
g. ,
t,— b u t y le t hy l o n e •
th e
washed
from
the
solid
with
carbonate.
The
the
original
extracted
200
The
residue was
cc
reaction
with
of w a t e r ,
ether
and
eth^r.
then
propanol
fractionated
through
II:
TIME
CUT
1: 40
1 : 45
1
a-
1
2 : 0 0
3
4
5
1 . 2
1.7
6
2 . 1
7
3.2
3.0
1 .3
1 .8
rj
8
9
IO
Cuts
trough
in
mixture
TABLE
2:15
2: 45
3:05
3 :25
3: 4 5
3: 5 5
4 : 15
added
outlet.
residual
over po t as s iu m
Column
found
filtered.,
stripped
was
Column
TI ME
GUT
3:30
3: 40
5:15
5 :45
6 :2 0
7:10
8 :O O
8 : 25
8:45
1
2
a
4
5
6
7
8
9
WT .
0 . 6
•8
1 .2
3-10
26
B.P .
n^°D
1.3920
1.4001
1.4059
1.4070
1.4073
1.4071
1.4068
1.4051
1.4045
1•4050
.TACKET
87
62-64
89
91.5
95
93
93
93
93
95
98
above
w e re
TABLE
27
set
150
mm
8 8
8 8
150
92
93
93
94
96
103
up
fcr
150
fractionation
IV:
WT.
n 1:° D
1.4083
1.4100
0 . 8
1.4094
0.7
1.4085
1 . 2
1 . 4 0 55
1 . 6
1.4048
1 . 6
1 . 4 0 48
1 .O
1 . 4 0 48
1.9
1.4048
H e s u d w e 0 . 7 rr.
1 . 2
O .o
B. P.
121-138
139
1 * 0
144
147
148
148
148
128
»JA G K E
152
146
155
155
155
155
1 56
156
158
734,6
mm
Cuts
ic al,
was
4-S,
8*0
g.,
3,3-dimethylbutyl
0.056
moles,
n-nronyl
1 2 . 4>
of
theoret
ether.
SUMMARY
0.036
1*
t-Butylethylene, 19.4
2*
3,3-DImethylbutyl
m o l e s , 1 2 . 4 /o o f
R E A C T I JK
OF
of
KOH.
stick
and h eated
fractions
In
the.
ped
3
separated
of
120
the
from
boiling
Column
whs
12:55
0.5
moles,
was
set
of
g.,
uo
and
noint
an
03
"ef lux
and
the
carbonate,
g*,
WT.
1
l.C
n 2° P
oil
was
The
time
collecte
continued
drop
wat<-*r w a s
layer,
after
fractionated
JACKET
41
mole
II,
term-era tu re
28
B . P .
1.5
thi3
water
II:
Cr
JT
1-lodo-
Column
Durinr
of p r o o a n o l .
distillate,
ootasslum
the
84
under
intermittently
of
refractionated
added
20 h o u r s .
TAB HE
TIME
g.,
flask
for
off
well,
the
106
mixture
taken
over
3*0
KOH.
g •, 2 moles,
K.B.
to r e f l u x l n g
dried
through
In
cc
The
top - c o c k
below
being
a 500
were
ether,
thepretlcal.
1 - 1 0 D 0 - 2 . 2 - D 1.,'iEXii 1 h o J T A N E
2,2-dimethylbutane
In
of
theoretical.
a solution
propanol
51*3%
n-propyi
WITH FROPANOLIC
To
g.,
TABLE
TIME
WT.
n 20D
B.P .
2
3
4
5
1.3733
1.3729
1.371o
1.3701
1.3695
1.3840
1.3872
1.3880
1.4042
1.4042
1.4040
42
43
45
46
46
94
95
95
84-91
91
90
91
91
6
lei
0*9
1.4
1.3
1.3
7
1. 0
6
10
8
5.5
7
9
9
9
30
OO
OO
15
15
OO
9
8 . 0
10
1 . 0
11
1 .7
0.9
11
12
13
14
0 . 2
1.4055
1.4
R e s idue , 0 . 6 g.
Cuts
1 - 6
i n c •, T A B L E
11. F l e m i n g ' s
th r oi*gh G.
1 : 2 0
1:45
2 :IO
3:05
3: 25
3;5b
4;ift
4:30
5: O O
5:30
5:35
Co ’1
WT.
1
0.3
0.5
0.5
6
7
8
9
10
11
The
mixture
was
ether
whole
layer
dried
mss3
washed with
s e n a r a t e d , an
The
n 2° D
residual
the w a t e r
was
734.1
50
75
85
96
109
109
104
104
104
105
109
wee©
734.0 mm
150 mm
150
150
150
15 0
refractionsted
29
1.3740
1.3742
1.3740
0 . 6
1.3736
0.4
1.3729
0.4
1.3720
0 . 8
0 . 6
1.3705
1.3699
0.3
1.3697
0.5
0 . 2
1.3693
ho res i d u e .
2
3
4
5
28,
JACKET
micro—column:
TABLE
'PX i«LE
conti nued!
CUT
id: 15
3:20
3 50
4 IO
4 23
5 OO
10
28
JACKET
39.5
41
42
42
42
44
45
46
46.5
46.5
40
39
41
43
44
44
45
45
47
48
48
48
from
200
th e
combined
was
with
737.2
original
cc, of w a t e r .
layer
over n o t a a a l u m
id. P.
The
extracted
the
carbonate*
oil
The
mm
reaction
layers
with
were
ether*
Layer,
and
the
ether
was
atrip-
79
ped
off
through
through
Column
th© s a m e
II,
CUT
n 2° D
I .3992
1.3888
1.3888
1.3878
1.3380
1.4081
1.4059
1.4150
1.4155
1.4159
1.4175
1.4205
6 : 1 0
1
2
8 : 1 0
3
4
5
6.3
13.8
12.7
15.1
17.0
6
1 . 6
7
8
2.5
2.4
9
2 . 0
1 2 : 2 0
3:00
3:15
3:40
4:00
4: 25
5:30
5: 45
Table
30,
of w a t e r .
10
2 . 8
11
3.3
3.1
12
was
had
TABLE
80
Inc*,
c c , were
at
20 a n d
95
94
94
95
97
126
126
129
133
135
140
143
Cuts
completely
1-5
Inc*,
misclble
In
25
out with p o t a s s i u m hydroxide,
96°,
n 2 <^D,
1*3885,
was
cc
a
obtained*
propanol.
1-14
inc.,
a definite
Cuts
made
7-9
On s a l t i n g
probably propyl
22 ;£, h a d
95.5
96
96
96
96
109-133
135
136
138
142
145
148
C ut s
Cuts
7*2%,
JACK
of p r o d u c t s :
ru’o d u c t b o i l i n g
This
B.P.
Identification
total
cont i n u s d
30
W T.
7:20
11:40
til© f r a c t i o n a t i o n
column:
TABLE
TIME
and
a definite
of c u t #9.
from petroleum
higher
neohexyl
6-10
TABLE
Inc.,
ether
TABLE
known phenylure than
of
0*036
odor*
30,
odor.
melting point,
was
5*2
This
moles,
product
Is
ether*
carbinol
etr:-r,
28
11.3
0.11
moles,
A p h e n y lure than was
after
64-65°.
g.,
The
t-amylcsrtlnol
recrysta11 1 zation
melting point
taken
on
Lie
of
same
a
melting
point
point
is
urethan
bath,
66-67.
of
carbinol
Cut
gave
A
9
was
65-66.
mixed
and
melting
the
64-66.
The
imown
Cuts
reported
point
melting
with
the
phonyl u r e t h a n
6-10,
phenyl­
o f _t— a m y l -
therefore,
contain
_t- a m y l c a r b i n d •
Cuts
absorbed
1-5,
bromine
TArtLR 2 8 ,
without
boiling
point
contain
t-butylcthylene.
The
product
of
this
might
be
the
2.3
g.,
0.027
evolution
comnound
indicates
However,
a mixture
of
of
the
moles,
HBr.
that
index
The
it m i g h t
is
low.
t— b u t y l e t h y l e n e
and
nsohexane•
Cuts
2
. 2 ,1b w e r e
9-11,
TABLE
'-8 , 1 . 0
p.,
0.011
moles,
neohexane.
S U viil;J±tL 1
1.
Propyl
neohexyl
ether,
o*2
g . , 0.036
moles,
7 . 2 o oi' t h e o r e t i c a l .
2.
t-Amylcaroinol , 11.3
g.,
0.11
moles,
22;u o f
theore t i c a l .
3.
Iveohexane,
1.0
g. , 0 . 0 1 1
moles,
2.2^b
of
theore t i c a l .
REACTlot
OF
1 — CiihOHQ — 2 , 2 —
D I m T 111Y L 5 U T a h E
The
necked
tne
flask
liquid
a
paratus
fitted
level,
jvlth
and
a
.71 Til S O D I U M
consisted
a
of
a
t n e r m o m e ter
reflux
500
cc
three-
extending
condenser,
to
the
below
outlet
bl
of^ w h i c h w a s
acetone
which
attached a Gilman
trap.
the
T he
third n e c k
sodium was
the
about
to
3 mm
mixture
1 0
flask was
was
vigorous
° in an
cube3 .
reaction
Trie t e m p e r a t u r e
and
lowering
the r e a c t i o n was
five h o u r s
added
was
4 0 - 1 2 0 ° was
with
ice b a t h
kept
stripped
the l i q u i d
a t i o n of this
a d r y icethrough
chloride
was
material
cooling
took place.
By
the
Over
in
the
through
Column
dry
ic e
again.
fl a s k ,
a period
The
II,
w a s
was
boiling
and
tr a p .
Column V gave
of
temperature
mixture
The material
through
a
raising
of s o d i u m
reaction
the
cooling
reaction
quantities.
The
cu t i n t o
When
alternately
of
the
temperature
o ne m o l e ,
12 h o u r s .
collected
1«02 moles
of s o d i u m
control.
23 g.,
off
after
5 g,
around
under
of
for
the
necessitating
to 9 2 ° ,
at 5 5 - 7 0 ° .
to s t a n d
flask
1 2 2 g,,
to r o o m
or f o u r g r a m
maintained
allowed
bath,
occurred,
a tot al
in t h r e e
ice
and,
to c o m e
rose
the
into
added
No r e a c t i o n
allowed
the
through
stopper.
l - c h l o r o - 2 ,2 - d i m e t h y l b u t a n e
chloride
of
introduced
closed with a rubber
To
t ra p
at
combined
Fraction­
the f o l l o w i n g
results;
Long table continued
f o l l o w i n g page.
on
This
resaure
fractionation was
run
at
of 7 6 0 rrrm, a n d a r e f l u x r a t i o
a constant
of 4 0 - 5 0 / 1 .
T A B L E 31
TIME
CUT
11:45 AMI
o
12:05
3
12:25
12:45
4
5
1 : 0 0
1 :30
6
7
1 :5 0
8
2:15
9
2:35
2:55
IO
3: 25
11
3:55
12
4: 25
13
4:45
14
5:15
15
16
5:40
17
6 : 0 0
18
6:25
19
6 : 45
7:05
20
7:25
21
7:45
22
8 ;1 0
23
8:30
24
9:00
25
9:20
26
27
9:40
28
1 0 x0 0
1 0 : 2 0
29
10:40
30
1 1 : 0 0
32
1 1 : 2 0
32
11:40
33
1 2 : 0 0
34
1 2 : 2 0
35
12:40
36
1 :00
37
1 : 2 0
38
1: 40
39
2 :0 0
40
2 :2 0
41
2: 40
42
3:00
43
WT.
0.75
0.81
0.85
0.83
0.31
0.83
0.95
0 . 8 8
0.82
0.87
0.83
0.81
0.73
0.94
0.69
0.74
0 . 8 6
0.94
0.87
0 . 8 6
0.89
0.82
0.82
0.84
0.77
0.83
0.78
0.75
0.76
0.77
0.73
0.76
0.78
0 . 8 0
0.77
0.76
0.73
0.71
0.74
0.75
0.72
0.71
0.7 0
n £0D
1.3760
1.3758
1.3760
1.3759
1.3759
1.3759
1.3744
1.3722
1.3712
1.3703
1.3703
1.3699
1.3697
1.3692
1.3690
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3639
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3689
1.3690
1.3690
1.3690
1.3691
1.3695
1.3698
1.3699
1.3704
B.P.
39.41
40.61
40.80
40.94
40.99
41.28
4 2 . 66
45:10
46.33
47.09
47.58
47.91
43.43
48.81
49.08
49.12
49.27
49.17
49.27
49.27
49.33
49.43
49.46
49.55
49.46
49.39
49.39
49.39
49.39
49.39
49.41
49.43
49. 43
49.43
49.43
49.43
49.43
49.43
49.53
49.53
49.60
49.64
49.64
JACKET
38.57
38.46
38.70
39.08
39.38
39.81
40.08
40.45
40.66
40.70
40.80
40.70
40.87
41.01
41.71
43.50
43.78
43.86
43.86
43.74
43.52
43.43
43.35
43.31
43.37
43.62
43.64
43.60
43.61
44.19
44.21
44.31
44.21
44.27
44.24
44.67
44.81
44.93
44.93
48.03
45.03
4 5 • IO
45.17
continued
83
TABLE
TIME
3: 20
3:40
4:00
4: 20
4:50
5:10
5:30
5:50
6:15
6:35
7:00
7: 2 0
7: 40
8 : 0 0
3:20
3:45
9:15
9:45
10:05
10:35
10:55
11:15
11:35
CUT
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
1 2 : 0 0
67
12:30
12:50
1: 3C
1:45
2:05
2 :2 0
2: 45
3:05
3:25
3: 50
4:15
4:40
4:50
4:55
5:10
5:15
68
69
70
71
72
73
74
75
76
77
78
79
80
31
82
83
WT.
0.67
0.69
0.62
n
31
D
continued
B.P.
JACKET
1.3711
49.74
45.10
49.86
45.12
1.3720
1.3733
50.04
0 . 6 6
50.49
1.3755
0.63
1.3780
50.96
51.20
0.64
1.3799
0.65
1.3813
51.38
0.63
1.3825
51.95
47.80
0.63
1.3835
52.90
1.3849
0 . 6 6
53.75
0.63
1.3853
54.12
0.65
1.3851
54.69
0.55
1.3864
55.25
52.74
0 . 6 8
1.3869
55.27
54.53
0 . 6 6
1.3870
55.43
54.53
0.67
5
5
.
4
8
1.3872
54.81
0.72
1.3872
55.62
55.25
0 . 6 6
55.97
1.3878
54.20
0.67
1.3879
55.83
53.00
0.72
56.18
52.76
1.3879
0.73
1.3879
53.37
56.18
0.62
1.3880
56.16
54.10
0.59
56.18
54.24
1.3880
0.58
56.88
1.3880
57.76
0.74
1.3830
56.04
72.90
0.84
56.87
79.34
1.3884
0.77
82.46
1.3935
61.00
0.48
79.94
1.3980
0.26
90.39
1.4046
100.74
1.31
1.43 6 8
113.54
107.10
116.18
114.09
1.09
1.4179
116.79
13 4 . 6 0
0.95
1 .4192
0.39
1.4188
116.06
114.43
.116.69
118.19
0.89
1.4192
0.79
1.4193
T h e s e cut s w e r e t a k e n o f f
0.81
1.4192
b y s u p e r h e a t i n g t he p o t
0.73
1.4192
and jacket*
0.71
1.4192
1 . 1 0
1.4192
1 . 2 2
1.43 9 2
N o r e s i d u e r e m a i n e d i n the p o t *
84
5 6 — 60 I n c . ,
Cuts
frfict-i ons. fci on
tlii'cugh C o l u m n
TAELS
TIME
CUT
84
85
C ut s
rough
Column
7-13
3
CUT
9:00
9:40
10:30
89
90
91
92
93
94
95
96
97
98
1 1 :00
1 1 :35
12:30
1 :G 0
1 : 2t>
2:30
3:35
Cute
set
up
I n c . were
52-53.5
54
54
several
55
55
s e t up
JACis ET
61
61
61
hours
61
64
730 m m
for r e f r a c t i o n a t i o n
CW:
WT.
o .e i
0.64
0.65
0.41
0.53
C.59
0.39
0.28
0.58
0.82
33
n20D
B.P.
1.3764
1.3766
1.3768
1.3756
1.3742
1.3730
1.3712
1.3696
1.3689
1.3689
41
41
41
42
43.5
44.5
47
50
50
50
4C-35 were
aet
up for
JACKET
fra e t i o n a t i on
lurcn C W :
TABLE
TIMS
9: OO
9 : 25
9:45
CUT
99
lOO
10.1
1 0 : 1 5 1C 2
11 : 0 0 1 0 3
1 1 : 4 5 10 4
12: 25 1 0 5
1 : 0 0
1 .6
1:40
10 7
for
CW:
B .P .
1.3854
1.3870
1.3876
tand for
1.3877
1.3878
TABLE
TIME
c u t 69 w e r e
32
n soD
W T.
0.31
0.64
0.76
8 6
A l l o w e d to
87
0.79
1 : 2 0
38
0.71
3: 40
2:45
3:45
4:30
and
WT.
0.62
C .4 3
0.48
0.54
0.62
0.64
0. 69
0.73
0.70
34
n^Oj}
1.3679
1.3688
1.3689
1.3689
1 . 3 689
1.3694
1.3708
1.3738
1.3741
B.P.
JACKET
49
50
50
50
50
50.5
51
52
52
continued
thx'CUj
35
TABLE
TIME
CUT
ITT.
2 : 0 0
103
109
n o
i n
0.64
0.61
0.67
O. 60
0.63
0.67
0.61
0.43
2: 50
3:50
4:10
5:00
5:45
6:15
7:00
1 1 2
113
114
115
The
mi xture
T ho
was
weight
strlppod
of
off
fractionated
n 2° D
B.P.
1.3758
1.3777
1.3836
1.3869
1.3874
1.3877
1.3377
1.3878
52.5
53
54.5
55
55
55
55
55
residual
washed
the
the
solid
with
ten
solid
CUT
1 : 0 0
m 6
117
118
119
1 :10
Column
2 : 0 0
:2 0
3:00
5: 30
2
n 2° D
1 . 0
1 . ^ 230
1.4231
1.4230
1.4230
1.4232
1.-1238
1.7
1 . 8
1 2 0
1 . 6
1 21
0.7
Identification
The
82-91
physical
i n c . , total
In
of
material
tl ve,
cc p o r t i o n s
was
65
g.
Column
I,
reaction
of
dry
ether*
The
ether was
and
the
residue
II:
JACKET
B.P.
118-122
1 09
125
125
125
PRESSURE
127
135
139
144
147
140 m m
140 m m
121
6*63
1— 6
of
g.,
were
cuts
1-6
correspond
ozonized,
Inc*,
to
and
those
cf
decamp o s e d •
the
distillate
of
the
forrualaehyde was
Identified
by
a d i m e t o l d e r 1 va-
M. p *
layer
original
of P r o d u c t s :
weight
Cuts
the w a t e r
th^
properties
t - butyle t h y 1 ane.
JACKET
55
WTh
1 . 2
lOO
through
TABLE
TIiVE
from
residue
extract
chrcugn
continued
34
139— 190°.
A portion
of
the
oil
decomnossd
layrr
was
added
86
to a s o l u t i o n
tive
formed
of
2|4-dinitrophenylhydrazine.
almost
immediately,
li zp.tion f r o m
alcohol-water
melting point
with
hydrazone
at
of
based
on
The
the
erties
as
14-39
g.
were
after
recrystal-
at 2 1 0 — 211°•
A mixed
of a 2 , 4 - d i n i t r o p h e n y l -
olefin,
of 0 . 0 7 9 5
starting
Cuts
24.18
sample
original
A yield
weight
melted
trimethylacetaldehyde,
2 1 0 — 211°.
ethylene.
a known
which,
A deriva­
M . p.
210-211°,
therefore,
moles,
7.8% was
was
melted
t— butyl
obtained,
chloride.
inc.,
97-98,
100-103
i d e n t i f i e d by
neohexane.
A yield
inc.,
total
their p h y s i c a l
of 0 . 2 8
moles,
prop­
27.1% was
obtained.
Cuts
properties
yield
as
of 8 . 0 9
75—83 were
g.,
moles,
0.067
116-120
A yield
g.,
Inc..,
closely
literature
to j u s t i f y
the
C.5% was
probably
8 6 — 8 8
suspected
enough with
being
properties
those
be
112-115
of
on
this
of S o d i u m A m a l g a m :
To
aodlur. h e a t e d
toluene
was
of
added
slowly
485
tota
do not
in
the
basis*
snythosized.
Preparation
1 5 g*
inc.,
1,1,2-tri­
reported
identification
compound will
obtained*
obtained.
inc.,
the
A
3 , 3 , 6 ,6 - t e t r a m a t h y l -
4.29% was
However,
correspond
under
g.,
12.5% were
m e t h y I c y cl o p r on a n e .
Accordingly,
are
of 7 . 3
61 — 6 6
j
to
g.
its
melting
of m e r c u r y
to
point
give
r-»
10.3
their p h y s i c a l
1 - c) 3 o r o - 2 , 2 - d i m e t h y l b u t a n e •
Cuts
weight
from
unreacted
Cuts
oc ta n e •
identified
a 3%
of
sodium
amalgam.
it b e i n g
the
runs
very hard,
were
made
(a)
To
1
mole,
heated
232
g*,
The
of
of
go
Ther e a c t i o n m i x t u r e
isopropyl
was
poured
tracted
with
layer was
This
one
fi^e
The
ether
Column
and
I,
the
12:15
12:30
12: 40
12:45
1 :05
1 :30
1:40
CUT
1
r->
3
4
5
6
7
V/T .
6 . 2
3.5
5.8
5.3
5.2
5.2
4.9
to r e f l u x
warmed
0
were
an
combined
204
dry
g*
iso­
I end
immediately
overnight*
and
the
mixture
residue
was
ex­
The
water
a steam
bath.
additional
and
stripped
fractionated
250
dried
off
through
cc
of
over
through
Column
I:
36
D
1.4391
1.4402
1.4397
1.4462
1.4570
1.4360
1.4300
N o n e of th e d e s i r e d
fractionation•
with
on
alcohol
in s e v e n hours
ether.
gently
ether was
residue
n2
of
of
off
was c o l l e c t e d
Dcrtlons
Reduction:
added
g.
coming
The
The
of m a t e r i a l s *
Column
of w a t e r .
TABLE
f Xwlii
under
liter
extract®
carbonate.
up
360
off,
and
All
was
distilled
extreotad
potassium
and
allowed
cc
spongy.
diocetone
was
250
acidified
s o l u t i o n was
ether.
v/aa
alcohol
into
95%
started
acetone
some
amounts
practical)
set
Acetone
being
uniform,
Isopropylate
isopropylate
was
not
Alcohol:
2 m o l e 3 , of
mixture
176
The
above
Laboratory,
tc r e f l u x .
A total
the
rest
of D i a c e t o n e
aluminum
propanol.
the
Attempted Aluminum
Testing
of
amalgam was
and
using
Reduction
(Paragon
The
B.P .
JACKET
PRESS.
50-70
70
70
74-90
134
145
160
172
173
184
40 m m
1 0 2
118
121
1 2 1
glycol
was
obtained
40
in
the
mm
abcv
88
(b)
Reduction
of* D l a c e t o n e
Alcohol
Two
Identical
r*uns w e r e m a d e *
The
apoaratu3
c o n s i s t e d of
with
Sodium
Amalgam:
necked
flux
flask
fitted
condenser,
dioxide
was
ring
and
37*5
g.
about
was
the
250
with
of
one
COg were
hours.
end
of
until
solutions
and d r i e d
stripped
the
sodium
it
the
chloride,
and
each
Tfo© e t h e r
potassium
fractionated
through
C o l u m n II:
TABLE
:5 5
12:15
1:15
1 :50
2 :IO
2 !3 5
3:10
3:45
1 1
3
4
5
9.0
8.4
5.1
6.7
7.9
6
1 0 . 8
7
1 0 . 1
8
1 1 . 1
1
2
added
of
95J&
Stir­
two
overa
warmed
The
room
up
to
mixture
temperature*
runs
were
sat­
extracted
with
four
extracts
carbonate.
C o l u m n I*
mole,
A t o t a l of
reaction*
above
over
WT .
was
to
carbon
of w a t e r *
started*
the
through
Cl'T
liter
cooled
a re­
mixture*
g* , o n e
from
ether.
which
The s o l u t i o n
off
TI iviIf
116
three-
stirrer,
through
reaction
added
in
two-liter
sealed
sodium amalgam
three
to s t i r
cc p o r t i o n s
bined
in
toward
The
of
tube
the
dissolved
sodium
of a b o u t
40°
inlet
through
the p a s s a g e
allowed
urated
an
a mercury
flask was
alcohol
of
period
and
bubbled
To
diacetone
with
a
The
Thecombined
were
com­
ether
was
residues
were
37
n 2°D
B.P.
1.4210
1.4249
1.4262
1.4280
1.4262
1.4282
1.4282
1.4282
85-108
116
119
1 2 2
1 2 2
1 2 2
1 2 2
1 2 2
JACKET
107
PRES3
.
40
mm
40
mm
40
rnm
1 2 1
1 2 0
1 31
131
129
123
131
coot inued
89
TABLE
WT.
n 20D
18.4
7.9
7.6
7.1
7.4
5.9
1.4282
1.4282
1.4282
1.4282
1.4282
1.4282
CUT
TIME
4 :15
4:35
5: 20
5: 4 5
6 :2 0
7:00
9
IO
11
1 2
13
14
Cuts
was
2
37
4-14
I n c •,
continued
B. P.
JACKET
PRESS.
131
131
131
131
133
140
1 2 2
1 2 2
1 2 2
1 2 2
1 2 2
1 2 2
l O O • 9 g- >
of
40
mm
theoretical,
- m e t h y l - 2 ,4 - p e n t a n e d i o l •
A solid
compound might
residue,
be
12
g.>
was
obtained.
This
2 , 4 , 5 , 7 - t e t r a h y d r o x y - 2 , 4 , 5 , 7 - t e t r a m e t h y 1-
oc t a n e •
(c)
Catalytic
When
hydrogenated
a 98/b y i e l d
five
Hydrogenation
moles
of
(hydrogenation
of
the
glycol
diacetona
by
was
PKElAKA'i'lOL
at 0 °
with
1.
To
HBr was
2, 4 - p e n t a n e d i o l •
ately with
was
etimed
The
layers
/vitJi t w o
water.
The
the
weight
cc
added
senfiratior!
were
of
a solution
g.,
the
was
crude
0.85
seemed
an
th e
of w a t e r .
made
this
laboratory)
to
product
at
of
saturated
2—methyl-
take p l a c e
immedi­
la y e r .
The
mixture
60°
six
hours.
oil
196
for
layer
It w a s
Isolate
was
of w a t e r
moles,
to
upper
and h e a t e d
cc p o r t i o n s
of
OP .:P 'i'AN E .
separated,
attempt
of
lOO
Cook
were
obtained.
of
A reaction
vigorously,
1HQ
No
600
N.C.
alcohol
Alcohol.
Oh
2- ..xFfjnA Y L - 2 , 4 - D 1B h 0
Run
of D l a c a t o n e
the
g.
was
washed
heavfer
than
pure
dibromide.
90
Run
saturated
or
at O 0
To
300
with
cc
HBr
or
was
a solution
added
^-m6thyl-?',4-pentanediol.
vigorously,
layer
was
was
made
crude
and
It w a s
to
was
Run
with
HBr
not
with
over
332
over
and
soliuT,
g.
the
washed
3
To
was
900
cc
th e
sulfate
Tor
eight
was
vigorous
layer
Tee
for
was
drying.
1.57
The
The
over
No
The
ell
sodium
attempt
or
weight
of
water
moles,
at
dried,
t he
of
60°
The
mt horia.l,
2-methyl—
for
12
layers
without
crude
saturated
washing,
Layer
after
were
was
standing
fractionated
through
C o l u.rruII:
TA3L2
r I iwiw
Ce
CUT
A'T •
n20D
IO
1
10
2
4.0
6.4
9.5
1.4836
1,4907
1.4926
1.4926
1.4926
1.4917
1.4916
1.4916
1.4910
±.4910
1.4910
1.4912
1.4938
1.4920
1.4933
ub
4b
11
IO
11
35
12
15
12
55
1
40
2
15
55
2
3 40
4 3d
4 50
5 20
5 35
6
15
3
4
5
1 1 . 8
6
2 0 . 0
7
2 0 . 1
8
9
10
11
12
13
14
15
2 0 . 0
16.8
1 6.5
18.5
20 .3
3.4
b
.r .
72-77.5
78.5
78.5
78.5
78.5
78.5
78.5
78.5
78
7S
79
31
33
33
107
t he
117.1.
heated
lb n o u r s , w a s
moles,
stirred
and. d ^ l e l
w e i g h h of
c;•
0.48
stirring.
was
water
hours.
« solution
183. g . ,
T h e o r e ci c al , 3 3 2
sodium
mixture
dibromide.
mixture
oil
sulfate.
The
before
of
or
g.,
Theoretical,
added
The
57
//ater,
th e p u r e
continuous
separated,
60°
1 0 6 . 4 . g.
,4 - p e n t s n e d l o l .
hours
at
from
i.solate
layer
at 0 °
lie a t ed
separated
sulfate.
2
2.
JACKET
74
75
76
76
76
77
78
73
78.5
79
80
31
35
87
91
20
mm
2 0
mm
2 0
nun
2 0
mm
91
Cute
war©
3-12
Inc.,
g.,
161.9
2-ine tiiyl — 2 , 4 — dibroir.Opentane .
showed
signs
cf
d e c or,ip os 5 t i o n
0.663
All
after
moles,
the
41.6%,
above
e tending
cuts
Tor
several
hours.
CYCLIZATIOh
Run
three-necked
f u n n e l , and
1.
H O
g.
The
flask
set
Into
and
OP1 2 - M E T H Y L -
of
taneously
l ow
of
vl th
boiling
70
over
-vltb a
30
B 45
9 10
9 40
io 0 0
io 25
IO 4 5
11
IO
25
11
11
40
11
55
8
12
The
mixture
heated
to r e -
t he
di brornide p r e p a r e d
in R u n
addition
of
dropwise.
head
the
was
was
and
1
6
7
2 . 6
9
2.5
1.3
11
1.3
1.7
1.9
? 25
13
of
took p l a c e
to
30°.
d 1 bromide-
off
at
The
95;6 e t h a n o l
th e
to
immedi­
Simul­
the
head.
zinc,
A
distillate
through
1
total
was
Column
IV:
39
1.3837
1.3326
1.3826
1.3826
1.3825
1.3823
1 •3813
1.3815
1.3813
1.3326
1.3342
1.3856
1.3373
1 2
the
cc
wa3
fractionated
1.9
1.9
2.4
3.1
2.3
O
O
0 <
1 . 8
of
t nk^xi o f f .
1
10
400
reaction
taken
n ^ D
•
o laced
A
addition
product
II«
t< mr. or a t'n*e d r o p p e d
T/T .
10
dropping
dust.
CUT
3
4
5
and
zinc
carbonate,
2
th«rmorne t e r
liter
were
TABLE
TIME
a one
flask
distillate
ft• of
dried
ted
of
the
started
the
1
consisted
Column
aDove
and
apparatus
under
The
ately,
.4 - D I B R O M O F E N T A N E .
up
fluxing.
was
f1
2
JACKET
44-47*5
47.5
48
43
48.5
49.5
50
51.5
52.5
54
54.5
55
55.5
49
49
50
50
51
52
52
53
53.5
54
54
55
55
739.5
mm
continued
92
TABLE
39
continued
TIME
CUT
WT.
n 2° D
B.P.
JACKET
12: 4 5
i :on
1 :15
1 :35
1 :50
2:05
2:15
14
15
16
17
18
19
20
.1 .9
1.6
2,0
2.2
2.2
1.4
1.3886
1.3902
1.3912
1.3922
1.3933
1.3970
1.4114
56.5
57
57
58
58
60
64
56
56
56
56
56
61
67
All
ingly,
3 mm
Cuts
cubes
ceased
the
cuts
1- 16 w e r e
above
set
of* s o d i u m w e r e
t he p r o d u c t w a s
1:05
1: 20
1 :35
1 :50
2: 10
2 : 25
2: 4 5
3:00
3: 15
3:30
3: 5 0
4:00
4: 15
4:30
4:45
5:00
under
IV,
added.
Column
When
the
n 20D
B.P.
JACKET
1
2
3
4
5
6
7
3 .1
2.2
1.5
1 .7
2 .0
2.2
2.7
1 .6
1 .6
1 .3
1 .7
1.1
1.0
1.2
1.1
1.0
1.3825
1.3825
1 .3825
1.3825
1.3825
1.3325
1.3324
1.3820
1.382?
1.3816
1.3816
1.3828
1.3872
1.3903
1.3936
1.3954
47-48
48
43
43
48
43
48.5
49
50
51
52.8
56
60.5
62
63
65
49
50
50
51
51
51
51
52
53
53
59
59
60
61
62
64
9
IO
11
12
13
14
15
16
-r a d d e d
17
18
19
20
21
22
23
24
25
to
17-20 , TABLE
t he
0.4
0.6
0.3
0.5
0.5
0.4
0.4
0.3
0.4
had
40
WT.
ft
and
reaction
CUT
C u ts
3:40
4:00
5:30
7:00
8:15
8:50
9:00
9:20
9 :40
s odium.
fractionated:
TABLE
TIME
up
reacted with
above
39
residue
1.3903
1.3912
1.3916
1.3924
1.3922
1.3934
1.3942
1.3974
1.4091
and
7 4 0 • 5 mrr*
th e res
and
distil
55^56
56.5
56
56.5
57
57
58
59
62
57
57
57
57
57
57
59
68
76
732.4
mm
C u t 3 1 — 10
Inc*
have
the o h y a i c a l
oi’o p e r t i e s
of
4—methyl-l-pentene•
None
was
of
the
desired
1 , 1 ,2-trlmethylcyclopropane
removed*
Hun
M c B e 2 7w a s
2.
fitted
f u n n e l , and
were
apparatus
with
To
the
the
method, of H a a s
and
were
agitated
recrystallized
by
was
recovered
was
a period
material
collected
The
of
constantly*
2 above
was
mean3
in
in
the
low
added
of
came
the
one
of
zinc
off
dry
second
boiling
air
g.
dry
dropwlse
ore
throumi
The
flask
while
the
dibromide
to
the
fourth
th e
lea—acetone
dust,
carbonate,
bath,
crude,
and
of w h i c h
series*
acetamide.
an
The
outlet
In
sodium
of
a dropping
traps
g.
150-165°
end
the
12*5
at
boiling
to
iodide,
kept
over
stirrer,
38
of d r y ,
low
lce-acetone
three-necked
added
g.
flask
condenser
a
were
72*5
the
of
flask
of sodium
in R u n
consisted
air
two d r y
4 g.
Column
run
a mercury-sealed
a small
attached
pared
this
used.
The
flask
In
air
trap*
and
was
contents
pre­
mixture
hours*
in
The
conden3or,
Nothing
trap*
material
was
fractionated
through
IV:
table
Tliv E
2:15
3:10
4:15
5: 45
6: IO
7:45
41
CUT
WT.
n 2oD
B.P .
J A C K PIT
1
O
3
4
5
6
1.4
1 .O
0.9
1.2
1.3
1.3842
1.3872
1.3876
1.3886
1.390*
46-51
53
55
58
59
61
56
56
57
60
61
65
731.2
mrn
Ail
Since
the r e m a i n i n g m a t e r i a l
th9 desired
of 5 5 - 6 0 ° ,
the f l a s k w e r e
acetamide,
iodide,
The
a n d 52 g.
of s o d i u m
of
to 1 5 5 ° ,
in R u n 3 a b o v e w a s
in
tillate,
mixture,
z i nc
T he
the f l a s k
over
7:55
B: 25
8:40
8 :55
9:15
9:40
9:55
10 :15
IO :45
1
2,5
1.9
1.4
1.3
1.9
1,3851
1.3884
1.3893
1.3897
1.3906
1.3920
1,3932
1,3940
6
2.0
1 . 6
8
2 .4
the
in
the f l a s k
prepared
stirring
dry
to
reaction
the
The
ice-acetone
added
through
low
trap.
to the d i s ­
took place.
B.P.
9
The
of s o d i u m
Column
The dry
IV:
42
n^°D
7
in
fractionated
WT.
3
4
5
5 * 6 g.
of s i x h o u r a .
of s o d i u m w e r e
CUT
2
i n R u n 2*
recrystallized
The m i x t u r e
a period
65°.
vicinity
fractionated dibromide
TABLE
TIMS
the
that used
of d ry ,
dust.
Only a negligible
<3 ., w a s
was
above
continued.
carbonate,
collected
small pieces
44
not
added dropwise with
boiling product was
Several
apparatus
a d d e d 1 0 0 g.
1 7 . 2 g.
was h e a t e d
mixture
compound boils.in
the f r a c t i o n a t i o n w a s
R u n 3.
To
cyclic
boiled
JACKET
4 2 — 55.5
55
57
57,5
59
60.5
61
62
65
f r a c t i o n a t i o n w as
not
57-59
59
59
60
61
62
62
64
6 6
continued
beyond
this
Doint.
Isolation
Cuts
weru
1-5
refractJonated
of P u r e
inc.,
1, 1 , 2 - T r i m e t b y l c y c l o p r o p e n e •
TABLE
through
41
Column
an d
IV,
Cuts
2-5,
In thi s
TABLE
42
95
fractionation
the
technique
TABLE
CUT
T IM E
WT .
of* I n t e r m i t t e n t
10
1.2
1:45
11
2 :10
1 2
2:25
4:30
4:30
13
14
15
0.5
0.4
O •5
0.5
0.3
3-7
inc.
0 . 6
12:30
1:35
2: 30
3:30
4:1 0
4:30
2
0.5
0.9
3
4
5
1.6
1.9
1.7
7
1.9
A l l o w e d to
6
1 2 : 0 0
8
1 .6
12:35
9
1 .5
Cuts
clopropane•
Cu ts
T r i m e thy 1 cy c lo n r o p a n e
Pro'n the
Cuts
734.9 mm
57
57.5
58
58
58.5
59
59
60
731.5
as s u m e d
to be
be
to d e t e r m i n e p r o p e r t i e s
used
Properties
with
55
55
53
54
54
55.5
55.5
those
of
1,1
,2 - t r i m e t h y l -
of Bynthetic- 1 , 1 , 2 the
Product
O b t d ned
iVurtz R e a c t i o n :
Cot s
with
were
3-5 will
Comrariaori of
JACKET
B. P.
n 2uD
1 : 2 0
1
61-63
TABLE
^1
wore
used
for
co^rmnrison
5 - 5 T A B L E 43.
PRODUCT PROM
DIBROMIDE
WUKTZ PRODUCT
d 2°
Cottrel
B.P.
0.6967
0.6941
56.5-57.0
55.5-56.6
1.3830
T ne
products,
used:
43
40-52
1.3830
1.3870
54
1.3876
54
1.3876
54
1.3876
54
1.3877
54.3
1.3878
54.5
stand overnight.
1.3883
55.5
1.3888
57
1.3898
58
1.3900
59
1.3906
59.5
1.3908
60
1.3912
60.5
1.3920
61
1 2 : 0 0
t a k e o f f was
therefore,
1.3876
tie
the sa/ne.
96
T he c y c l i c
viously
to h a v e
is o e l i e v e d
was
c o m p o u n d has
that
a mixture
penteno.
of
This
a density
the
product
the
cyclic
latter
of
compound
c o m pound has
4 - m e t h y l - l - n e n t e n ? , the
arid the
broniido was
solution
u nt i l
further-
those
known
and 4— methyl-3 density
h
cf 0 . 6 6 4 7 .
t o v a r d permangar.ete
coranound
olefin
made
The m a t e r i a l
reacted
only
minutes
being required
from
v e ry s l o w l y
one
with
from
of
this
c c of
0 . 2
material
was
and
t o o k up d i l u t e
then a c t e d s i m i l a r l y
r e a c t ! on.
This
prepared from
•mall
amount
der.clty and
that
The m a t e r i a l
leads
to
permanganate
mixed with
of
olefin.
index.
the original
To
This
further
compound
one
from
the
r a n i d l y at f i r s t ,
conclusion
the d i b r o m l d e m i g h t be
ab o ut
not dlscolor-
crepared
to that, o b t a i n e d
the
10
the d i l u t e
st i ll
dibromlde
volume
the w u r t z r e a c t i o n
the nerrangar.ate whs
three d a y s .
the
r o rriar. vans t e , a b o u t
to d i s c o l o r
cc
in 5 0 0 0
impractical by
quarter
i ze d a f te r
the dl-
took un p e r m a n g a n a t e
to o x i d i z e
it,
of
the W u r t z
s u f f i c ? urit one sei’c ^ n t r >rrr>nnr err. te
of
it
authors
compound prepared from
addition
'’’h e n
by
of p o t a a s i m n p e r m a n g a n a t e
The
the s o l u t i o n .
solvllcn,
at 14*5.
To e a c h was added a quantity of a
of one p a r t
of w at e r.
of
cyclic
made.
parts
cyclic
reported p r e ­
0 * 6 8 8 8
reported
A c o m p a r i s o n of the r e a c t i v i t i e s
reaction,
been
f r o m the 77urtz
that
the p r o d u c t
con ts.rrinated w it h
would e x p l a i n
substantiate
in q u e s t i o n w & 3
the
lower
the p r o o f
l,l,f-tri—
a
97
m e t h y l c y c l o p r o p a n e , all
pounds
w er e
other
olefins
w h i c h m i g h t p o s s i b l y be
eliminated
t he i r p h y s i c a l
obtained.
A
properties
is
on the b a s i s
properties
table
of
formed
of
with
these
and cyclic
the
in this
com­
reaction
l n c o m p n t l b i l i t y of
those
of
compounds
the
compound
together with
their
l i s t e d be l o w :
COi.T OUhD
n 2° D
d P0
B.P.
53.5-55.5
at 735 mm
0.6941
1.3876
56.5-57
at 7 3 5 m m
0.6967
1.3880
3-jVe t h y l - 1 - p e n tone
5 3. 6
0.6700
1.3855
4- \-e thyl — 1 — p en tene
53 o 8
0.6647
1.3825
cis — 4-iV:e thy 1 - 2 - p e n tene
58
0.6704
1.3885
2 , 3 — D i me t h y 1 - 1- b u tone
55.8
0.6825
1.3915
3 ,3 — D i m e tiiy 1 — l - b u t r n g
41.2
O .6519
1.3766
2 , 3 — Pi me t h ^ l - 2 - fcutene
73.3
0.7054
1.4116
1,1, c-Tr imethyl c y c l o p r o p a n e
F r o m d Ib r o m i d e
Prom Wurt reaction
hACdO:,
up 5 C D 11'
Oh
1— B K O M U - 3 .5 - D 1 M E T H Y L B U T A N E .
T he
H.3.
apparatus
flask fitted with
t c the o u t l e t
To
of
which
consisted
a thermometer
was
the f l a s k wa3
l - b r o m o - 3 , 3 - d i m c thy 1 b u t a n e •
cut
into
e
b ou t
3
of a t h r e e - n e c k e d
rnm c.nhea •
attached
added
The
fT'he
£30
end r eflux
a dry
ice-acctone
reaction
to
he
flask
cc
condenser,
g fc, 1*3 9 m ol e s,
sodium
500
tr ap*
of
a d d e d was
ccntsini
n p
the b r o m i d e was
waa
ad de d.
ros e
minuter.,
of a b o u t
to
105°,
In a b o u t
even
allowed
did
and another
6 g.
repeated,
then
though
more
the
Ice
temnerature
b a t h w&3
without
The
a total
then se t up u n d e r
TABLE
cooling.
The
o f 31 g*,
The m i x t u r e was
low
of
lowered,
f l a s k was
the
boiling
liquid
Over
liquid
I n ice.
falling,
and
the
cooled,
above proc ed ur e
1.35 moles,
II.
of
to s t a n d
over­
H e a t i n g was
fractions
were
start­
t a k e n off:
44
TI iv,E
C UT
WT.
n 20D
9:4b
1 0: 1 5
10:35
1 1: 0 0
12:25
1 2:40
1 :10
1: 25
1:45
1 :50
?! IO
1
2
3
4
5
6
7
Q
9
10
11
0.9
1.2
1.0
0.7
1.3
0.6
1.1
0.9
0.5
0.2
0.9
1.3740
1.374 4
1.3734
1.3728
1.3720
1.3734
1.3720
1.3786
1.3771
1.3846
1.4022
B. P .
41
42
43
45
47
49
47
49.5
53
61
103
a
The
again
allowed
Column
the
bottom.
temperature
of s o d i u m a d d e d .
the f o l l o w i n g
the
began
ni g h t ,
and
to
of
the
added.
ed,
the s u r f a c e
of a o d i u m
cooled
to p r o c e e d
until
e n d 6 g.
the m i x t u r e wa s
s o d i u m was
and
on
sank
the
not rise*
temperature
was
and
ten m i n u t e s
Ice bath.,
floated
20 m i n u t e s
'vhen it r e a d i e d 50°
reaction
in a n
The s o d i u m
for s ev eral
period
cooled
JACKET
47
52
61
66
66
69
73
74
135
POT
LIQUID
135
145
145
145
1 48
155
175
175
176
177
18 0
99
Cuts
1- 5
inclusive were
s e t up
for f r a c t i o n a t i o n
t h r o u g h C o l u m n CW:
T A B L E 45
CUT
TIME
4:30
6:30
7: 00
7:35
8:00
TIME
11 :55
12:35
1:0 0
2:05
2: 55
3:40
WT.
1
2
3
4
5
0.63
0.63
0.50
0.46
0.41
Cuts
6-8
2:0 0
2: 40
3: 20
4: 10
4:15
Table
r>2 0 D
6
7
8
9
10
11
0.38
0.50
0.51
0.58
0.56
0.55
1.3751
1.3739
1.3722
1.3700
1.3690
1.3689
CUT
3T.
12
13
14
15
16
0.60
0.64
0.40
O .53
0.30
1 -5
to
C ut s
9- 1 1
t ur n ed
44 w
42.8
44
45.5
47
47
48
Table
44 w e r e
n"°D
B.P.
1.3722
1.3707
1.3698
1.3752
1 . 3 8 82
44.5-4
43.5
48
55
50
1n c . ,
properties
solid
ce c f h a i l i n g
2*13
the p h y s i c a l
residual
on
728 * 2 mm
2 . 6 3 g. , 0
inc. , ttnd 14,
to
730 aim
B.P.
the p h y s i c a l
correaDonded
The
In 900
40.5
40.5
41
41
42
WT .
corresnondftd
mixture
1.3760
1.3760
1.3759
1.3755
1.3754
CUT
Cuts
1.80&
B.P.
inc.,
Cu t3 9-1.1,
T I ?
n 20D
liquid
from
standing*
methanol*
c ry s t a l s
ser a r e t->d.
methanol
-nether l i q u o r w as
Weight
93.1
g.,
0*025 moles,
oroperties
of n e o h e x a n e *
hhe original
The
On
of t— b u t y l e t h y l e n e •
s o l i d was
ecol log p u r e
g.,
2.P.,
ovaromted,
and
reaction
dissolved
whi te
52-53°.
2 9 2 g.,
The
of
a
IPO
solid
melting
solid
is
moles,
50— 5?° was
2,2,7,7-tetramethyl
9 b . 3 g.,
ACTION
The
200
cc R,b.
Ice
BO,6%
of
OF S O D I U M
apparatus
extending
tr ap
To
was
the
ON
The
prepared
consisted
with
below
f l a s k was
reaction
flask was
liquid was
added
one
Inch
eighth
took place
R.
with
three
8.
to
B.p,
The
was
under Column
The
ro led
been
room
in s m a l l e r
added.
mm,
II,
and
the
lo w
distillate,
3.B
g ,, w as
boiling
of
n^D,
To
the
the f o r m
was
out,
the r e a c t i o n
q u a n t 1 ties
until
reaction
it w a s
material
r e f r a c t I o n a ted
of
reaction
blown
vhen
V/hen the
temperature,
condenser.
moles,
explosive
lost.
a
laboratory.
condenser
was
and
liquid.
the
0.363
118°/736
immediate
sodium
to
of
Into
ceased,
cooled
g.,
the
cut
had
mixture had
of
of s o d i u m
flasrdng.
g . had
condenser
outlet
43
necked
ba t n .
of m a t e r i a l
live
three
ice
amount
of
a
an
in
a large
total,
obtained,
tl'Is
An
the
or 0 * 5 6
of
a nd
a
of
the
added
cooled
cubes.
w as
surface
Enyert
g.
a yield
a reflux
the
attached
by
octane,
that
l - C H L Q R Q - 3 ,3 - DIlvl5 T H Y L 3 U T A N E .
1— c h l o r o — 3 , 3 - d i m e t h y l b u t a n e
1*4164,
Assuming
theoretical
flask fitted
thermometer
A dry
recovered.
set
up
stripped
through
off.
Column
CW,
1Q1
TABLE
46
20 _
D
B. P .
TIME
CUT
WT .
2: 45
3:30
4:00
4:30
5:05
5: 45
1
2
3
4
5
6
0.6
0.7
0.4
0.4
0.5
0.5
1.3768
1.3769
1.3712
1.3699
1.3692
1.3690
Cu ts
1 and
2,
1.39
g.,
015
6,
1 ,0 9
ft.,
0 .0 .1 1
about
one
cc,
did
to 1 1 0 ° .
Any
cyclic
n
41
42
44
46
49
49
731,2 mm
m o l e s , 4.13
jt-b u t y l e thyler.e •
5
Cuts
were
oil
residue,
b a t h was
heated
formed would boll
T he
was
m o le s,
3.04,
neohexane*
The
the
and
extracted
e the r was
a mo u nt
f o i-rr.e d
.
product
t ha t
below
residue
from
th*;* o r i g i n a l
ICO
of:
tb r o u g h
of m e t h a n o l
was
added
Is
g
when
compound
o ,
Column
to
•O 3 5
reaction
n o r 11 oris
cc
stripped
C .1
boll
70°*
'Ai tl. t ' r e e
.e 1 g i1 1 ,
not
J
II,
ether.
Wher
residue,
the
mc 1
of
|
iV e p •
mixture
a small
a solid
■hi •
p
2 , 2 , 7 , 7 - to t c a m e thy'] oc tane , c o r respo nding?
found
In
t he
anfda^ous
reaction
of
Th e
sodium
Tills
to
on
l - b r o m o - 3 , 3 - d ime t h y l d u t a n e ,
The
under
The
Column
residue
methanol
II,
was
and
filt rate
rr.os t
of
f r e e Li o n e t e d
tin-
from
above
methanol
t h r o e oh
was
set
stripped
Column
CW
•
un
off.
1 0 L■
TABLIi 47
TIiVIL
GOT
9: 10
9 :30
I O :Id
11: IO
13:00
1 :00
1:5b
3: 4b
1
L
3
4
5
6
7
8
Cuts
w e no u n r e ar ted
Leart h e
d i m e r ',
w y^
WT_._
n£°D
ire th dr. cl
0.4
I .4203
0.5
1.4180
1.4171
0.4
0.4
1.4165
0.6
1.4155
0.8
1.4165
1 .1
1.4165
5-8
b.r
.
10 3
112
11^
118
118
3 33
118
Inclus i v e , 2.9
7 3 2 .3
mrc
g
1- eh 1 o ^ o - S , 3-dl.no t) lyl b u t a n e .
than
0.5
r
r e c o h e r e d *
. of
t* r*c l i d
residue,
n rob ably
103
SUMMAKi
1)
liquid
and
Neohexane
the
vapor
phases.
l-chloro-£,L:-dl.Tie t h y l o u t a n e
or
could not
%)
the
The
chlorides
bromide
and
by
be
were
separated
the
iodide,
of
the
and
mercuric
1-bromo-
pure
were
the
and
but
this
state.
nrepared
salt:
and
both
A derivative
obtained,
in
in
chloride
isolated.
following halides
way
chlorinated
Pinacolyl
1 - cliloro- 3 ,5 - d i m e t h y l d u tane w a s
compound
d u
was
from
P i n a c o iy i
1 - i o d o - £, l:-dlme t hy l —
tane•
3)
the
ha.lides
Physical
of
4)
propanolic
ment
1)
All
properties
an d
of
determined
halides
hydroxide.
In
were
no
reacted
case
was
v it h
rearrange­
observed,
5)
Wurtz
reactions
were
d i me thy lb u t an e , 1 — ch 1 or o — 3 , o - d l
3,3-dimethylbutane.
With
run
on
1 - c h l o r o - L , 2-
thy 1 b u t a n e , a n d
tire f i r s t
compound,
_t— b u tyle thy l e n e , 1 , 1 , 1 - t r i m o t h y l c y c l o p r o p a n e ,
3,3,6,6— tetramethyloctene
tw o
on all
i-) .
trie a b o v e
potassium
were
halides,
only
tetramethyloctane
6)
formation
of
A
formed.
bith
_t— D u t y le t h y l e n e , n e o h e x a n e ,
were
neohexane,
and
the
and
latter
2,2,7,7 —
obtained.
mechanism
the
were
1-bromo-
has
products
b e an proposed
from
these
to e x p l a i n
i''urtz r e a c t i o n s .
the
PART
CHLOROPIVALIC
ACID
II
AMD
DERIVATIVES
104
I N T R O D U C T I O N
The
oxidation
has
of
resulted
compound
pivalic
development
the
in
dithe
containing
acid
or
and
the
been
view
of
of
will
deal
of
its
theory
principally
pivalic
reaction
process
of
ud
neopentyl
t r i m e t h y l a c e tic
compound have
substituted
the
triisobutylenes
onening
this
the
of
studied
a
acid,
orodicts.
an
in
source
grouping,
acid.
The
before
from
rearrangements•
with
for
The
the
this
of
laboratory^
another
namely,
reactions
the
of
point
present
analogous
study
of
chloropivalic
acid,
and
of
work
the
some
105
H I S T O R Y
Chloropivalic
tically
by
chloride
was
Kharasch^
In
1^40
by
pivalic
acid
in
the
on
peroxide.
The
Blaise
and
Marc 11ly,^
action
of
mide
acid
brcmoplvalic
and
phosphorous
oy
the
phosphorous
on
hydroxy
several
ways •
panediol
tne
with
is
obtained
a mi x t o r e
of
sulfuryl
benzoyl
synthesized
and
Schmidt^
and
of
Iodopivallc
acid
by
by
both
the
nydro^en
bro­
acid
syn­
from hydrogen
has
oxidized
to
been
was
iodide
and
prepared
in
h , £.— d 1 me t h y l — 1 , 5 — p r o ­
obtain
from
of
of
prac­
acid.
p ei*;r:e n r e n a te
nldo]
c a r b o n e tr, o n
dehyue
';es ;--,ly3
action
was
Kohn
workers
Hydroxyoivalic
nnen
by
prepared
presence
r-entabroir.ide
latter
the
the
acid
o n h y d r o x y o 1 vs 1 1 c a c i d .
thesized
first
th e
the
desired
reaction
product,
of p o t a s s i u m
is e o n ter a l d e h y d e
end
forrnal-
oxidized
h y d r o y y p 1valic
with, p e r m a n ^ s n p t e , d i m e thvi m a l o n i c a n d
0
acids are o b t a i n e d .
The p r e s e n t w o r k has
shown
that
the
reaction
valic
acid
is
a
of
rot d m e t h o d
sodium
for
hydroxide
the
on
chloropi­
preparation
of
hydroxy—
->i v a 1 i c a c i d .
C — Ch.loro— t — d u t y 1 airi ne , a
this
research,
literature.
In
is
mentioned
tr.at
i
n
reference,
only
7
compound
one
*^reoered
: lace
a compound
In
in
the
as o I m e d
tne
106
above
of
mentioned
structure
was
praoared
1 - c h l o r o - 2 - n l tro-2-rae t h y l n r o p a n e
chloric
acid.
crudely,
a
The
properties
ten d e g r e e
Another
boiling
determined
only
very
compound prepared
here,
3-chloro-2,2-
compound,
was
prepared®
by
t he
not
been
previously
reported*
3-iodo-2,2-dimethyl-l-propanol,
action
of h y d r o g e n
iodide
and
2 ,2 - d i m e tiiylpropanediol .
Chlorotrimethylacetamlde
chloride
and h y d r o ­
reported*
analogous
acetyl
zinc
reduction
being
The
on
with
the
range
d l m e ttiyl- 1 - p r o p a n o l , h a s
phosphorous
were
from
were
both
reported
and
chlorotrlraethyl-
by K h a r a s c h . ^
107
D I S C U S S
i/ftiitmore
products
acid
in
the
of
--- > t r i m e t h y l a c e t y l
changes
acid.
gave
rearrangement.
each
Langloia
series
trimethylacetic
these
and
reaction
no
They
Is
Intermediate
addition
to
group
,
RCOC1,
gives
On
an
initial
carbonyl
such
the
an
chloropivalyl
to
or
the
the
groun
, and
run,
RCOOH.
ion
of
No
which
R-^-ONO
or
these
compounds
the
of
of
cause
through
system.
capable
on©
might
neooentyl
neooentyl
cycle
the
NH2
ionization
groups,
of
in
r
and
hand
step
OH
ammonium, with
chloride
acid was
t he
other
Initial
neooentyl
When
RCONHg,
cause
as
R-JJ-OH
intermediate
oxonium
attached
Therefore,
the
^
that
might
NH2
through
pivellc
which
'
become
unstable
the
therefore,
Cl
OH
formation,
rearranged
t r im© t h y l a c e tic
Ion
that
products
1
react
no
concluded,
postulated
R-y-0PCl2
rangement.
found
oh l o r i d © - > t r i m e t h y l a c e t a j n i d ©
Cl
changes
g
reactions:
They
trime thylace t y l , giving
which
I O N
must
compound
hydroxyl
When
or
these
rearranging,
reactions:
rear­
amino
break,
a r e fxmecU
chloroplvallc
acid
--- ^ c h l o r o p i v a l a m i d e — > c h l o r o no
presence
rearranged
of
the
products
chloride
makes
were
no
isolated.
difference
>
lOB
in
t he
results
or
That
by
the
No
mation
of
pivalic
from
the
acid
the
of
a good
the
was
action
The
on
tendency
The
No
when
of
of
directing
chlorine
thionyl
does,
the
of
the
to
will
be
studied
degradation
giving
the
ran
anhydride
on
may
be
made
was
chloride
reduction
the
acid
is
for­
and
formed
considerably
adding
aqueous
exerted
was
Hie
ammonium
from
by
reacted
nroduct,
the
hot
the
water.
chlorine
vith
t-amyl
7>- c h l o r o - 2, 2-
recovered.
i3
evidently
of
amine
smoothly
by
recrystallized
influence
further
down
to h y d r o l y z e .
be
acid.
chlorotrimethylacetic
cut
concentrated
products
expected
the
however,
may
on
chloropivallc
chloride
compound
The
expected
from
since
C-chlorotrimethylacetamide•
none
sodium
the
C-chlorlne
the
aqueous
shown
of
d i m e t h y l - l - p r o p a n o l , was
in
with
is
influence
arnarent
The
acid
active
hydroxypivalic
amide
reagent.
quite
the
chlorotrimethylacetyl
drignard
is
of
possible,
chloride
hydroxide.
atom
chlorides
chlorine
acid
reaction.
yield
C-chiorotrimetnylacetamide
chloro
of
chloropivallc
acid
acid.
the
of
to g i v e
comparison
type
tlie c h l o r i n e
reaction
hydroxide
this
by
degradation
When
reaction
the
this
recovered.
other
degraded
imnortant
a Hofmann
was
on
an
Tills
investigators.
chloro
amine.
acid
was
factor
on
the
run,
reaction
A
Curtiua
chloride,
109
E X P E R I M E N T A L
PREPARATION
(a)
Attempted
An
In
the
and
the
phase
method
"boiling p o i n t
was
made
using-
employed
H o w e v e r , almost
CHLOROPIVALIC A G I O .
Preparation
attempt
vapor
OF
constant
of
the
to
the
in
In
Vapor
chlorinate
apparatus
the
and
Phase:
pivalic
shown
chlorination
flashing
acid,
The
in
Figure
of
took p l a c e
I
neohexane•
at
only u n r e a c t e d
acid
the
acid
was
re c o v e r e d o
lb;
Chlorinatlon
Tp
306
necked
1-1 iter
denser
was
The
fla3k
was
hot-plate,
c:., 3 m o l e s ,
R.B.
added
elude
all
1 g. »
furyl
chloride
the
light,
in
added,
334
waa
rive
hours.
The
off,
no
being
The
CUT
6:30
1
ai r b a t h
of
£.2
mixture
taken
6.7
a
to
lonv
402
heated
g.,
m o l e s , of
was
avoid
in
heated
3
was
light.
by
so
Chloride:
twocon-
oeroxide.
an
electric
as
to
ex-
nole3,
of
sul —
carbon
to
a
reflux
benzoyl
covered
tetrachloride
Column
»YT.
with
apparatus
g •,
carbon
through
P11»‘E
In an
solution
acid
of p i v a l i c
fitted
Sulfuryl
Acid with
o.(;04 m o l © 3 , o f
whole
A
ride
fractionated
flask
immersed
and
care
of P i v a l i c
tetrachlo-
refluxing
s trinDed
then
The
residue
I:
o.P .
Ja c k
60-90
90
et
for
PRESSURE
55
continued
mm
was
n o
11
1
1
1
1
2
2
2
2
2
2
3
3
3
4
4
4
4
5
5
o
5
6
6
7
7
Cuts
good p i v a l i c
melting point,
amounts
inclusive,
11-26
70.7
inclusive,
41-42°,
were
other runs
of s u l f u r y l
MOLES ACI D
S'i'a R t I N G
51 m m
51
51
51
51
51
51
51
51
53
53
53
53
53
53
g ., O .69 m o l e s , w e r e
ac id.
Cu t s
Two
2-7
PRESSURE
99
103
103
1 20
124
140
14 1
1 41
14 1
141
146
14 6
146
146
1 47
148
148
148
152
152
153
150
146
1 53
153
1 55
93
95
95
95
95
98
125
136
138
138
139
13 9
140
141
141
142
142
142
142
142
142
142
142
142
142
147
12.6
13.1
12.9
11.6
12.8
7.7
4.5
4.9
7.2
9.5
5.2
13.4
17.4
17.0
17.0
19.4
18.5
16.6
16.0
5.1
15.4
16.5
19.4
17.6
12.9
-
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
lo
00
05
20
45
10
20
25
35
45
50
00
25
40
00
15
30
45
15
20
30
5o
20
50
20
45
JACKET
B.P.
WT.
CUT
TIME
0.76
2.29
2 . 31
good
MOLES
CHLORIDE
moles ,
acid.
using different
A summary
1
2 .b
3
1.74
chloropivallc
were made,
chloride.
MOLEl ACID
USED
2o>6.9 g.,
is
given below:
,*>YI E L D E A S E D ON
STARTING ACID
27.5
38.7
58.0
ACID
USED
72.5
50.6
75.4
ohlcr
USED
o5
46.4
oB.O
:
Ill
PHEPAKATION
OF ChLOKOlRIkFTHYLACETIC
To 68 g.,
added
60 g.,
thionyl
period
of
0.5 moles,
thionyl
chloride was
fractionation
chloronlvalic
chloride,
driven
of f o u r h o u r s ,
of
and
ANHYDRIDE.
0.5 moles*
s c i d was
The
off o n a s t e a m b a t h
the r e s i d u e w a s
excess
over a
s e t up
for
t h r o u g h C o l u m n II:
TABLE 2
TIkE
4:05
4:20
5:40
6:15
1 1 :00
1 1 :40
11:55
12:25
12:45
1:15
1:40
2:10
2:15
2 :20
2: 30
2 :50
CUT
WT.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
0.5
3.3
5 .7
5.0
1.6
5.0
3 .4
3.7
3.9
6.6
2 .9
4 .5
6.2
5.8
4.9
5.1
1.4518
1.4555
1.4582
1.4591
1.4578
1.4591
1.4600
1.4605
1.4611
1.4620
A sma 11
D o r tion
A reaction
oil,
and
flask.
took place.
the
oil
A white
ing p o i n t w i t h
was
known
83
83
76
87
138-142
154
172
186
186
186
188
190
190
192
1 95
195
of G ut
place.
of c u t
ammonium hydroxide.
On c o o l i n g ,
a white
60 m m
60 m m
60 m m
hea
separated
a IO
acid,
from
the
cc d i s t i l l i n g
M . P • 41-42°.
chloropivallc
To a small p o r t i o n
centrated
wa s
from
collected;
FRES3.
100
98
125
166
190
247
266
266
278
25 6
283
274
274
274
273
2 30
12 w a s
T he w a t e r
distilled
solid
JACKET
B.r.
n 2° D
Mixed m e l t ­
41-42°.
12 w a s
added
some
A vi.o;oroua r e a c t i o n
solid separated,
which,
con­
took
after
112
recrystallization
from
water,
me l t e d at 110-111°.
A
m i x e d m e l t i n g p o i n t with, k n o w n O - c h l o r o t r i m e t h y l a c e t a m i d e
melted
at
110-111°.
PREPARATION
To
was
s o l u t i o n w as
g.,
gently
wa s
1.54 moles,
1.54 moles,
allowed
The m a t e r i a l
sidue
LR1METHYLAC 2TYL
15 7 g.,
added 102
heated
OF
of
to s t a n d
to d r i v e
off
b o i l i n g up
fractionated
of
CHLORIDE.
trimethylacetic
tnionyl
for
24 h o u r s .
the e x c e s s
to 6 0 °
through
chloride.
wa s
stripped
Column
'Ihe
It w a s
thionyl
acid
then
chloride.
off.
The
re­
I:
TALL?: 3
TIME
CUT
WT.
1
2
3
4
8.2
6 .5
9 .3
12.4
4.2
13.5
14.7
6.3
8.1
1:30
2:00
2:50
4:45
5:15
6:45
7:20
7:40
8:00
6
7
8
9
T hi 3
40.6/6 of
fied
by
n
represents
JACKET
3 .P •
60-104
1 04
1 04
104
1 04
1 04
104
104
1 07
1.4180
1.4180
1.4122
1.4121
1.412 2
1.4122
1.4122
1.4182
t r i m e t h y l a c e tyl
the
D
a yl e I d
105
105
105
105
1 14
114
114
116
1 21
of 75
cnloride.
g.,
0.625 moles
The p r o d u c t
was
veri­
a m id e .
F REP .hRA T I Of
O F C H L 0 K 0 TR I M E ftfY L A C E T I L
(a)
Action
CtiLORIDE .
of r h o s p h o r o u s
Pentachloride
C h l o r o t r i m e t h y l a ce tic A n h y d r i d e :
To 7 3 g.
two-necked
P^-n 8 f u n n e l
of P C 1 5 , 0 . 3 5
flask fitted with
was
added
43.6
moles,
a reflux
g. , 0 . 1 9
In a 1 0 0
condenser
moles
of
cc R.B.
and drop-
chloro-
on
trimethylac©tic
anhydride•
quit© hot.
mixture
The
one h o u r .
The
The d i s t i l l a t e was
through Column
was h e a t e d
p r o d u c t was
in g f l a s k at 3 0 nun.
filtered,
CUT
10:2c
1
2
10:40
3
11:00
11:15
4
5
11:50
6
12:15
7
12:35
8
1:00
9
1:25
1 : 5 5 IO
C ut
added
was
Sulfuryl
In a one
of P C l ^ a l s o
the
distilled.
filtrate
fractionated
JACKET
PRESS.
n
4.8
6.7
4.4
2.4
5.3
5.7
5.2
4.8
5.4
4.2
1.4623
1.4610
1.4610
1.4592
1.4555
1.4542
1.4540
1.4533
1.4540
1.4540
6 gave
4
B. P.
WT.
D
39
39
65
80.5
86
36
87
87
n87
87
82
90
100
104
104
104
104
104
104
108
6 0 min
60 m m
60
C -c h 1 o r o t r i m e t h y l a c e t a m i d e
Chlorination
mm
when
were
g.,
liter
of
covered
1.25
Trimethylacetyl
R.B.
moles,
1.23 moles,
s o l u t i o n was
of
Chloride
trimethylacetyl
flask fitted with
benzoyl peroxide.
3 0
as
t io n of 19 6 g . , 1 . 2 3 m o l e s
1 65 g.,
of
Chloride:
a d d e d 0 . 5 g.
denser
The
a distill­
II:
To 1 4 V
ride
from
for
to a m m o n i u m h y d r o x i d e .
(b)
with
amount
and
got
on a steam ba t h
then d i s t i l l e d
A large
TABLE
TIME
Th e r e a c t i o n m i x t u r e
of
to e x c l u d e
of
carbon
sulfuryl
refluxed
a long
The f l a s k
all
light.
condenser
and
for f i v e h o u r s •
was
then
The
con­
A solu­
tetrachloride
chloride
chlo­
and
added.
oroduct
b o i l i n g up
to 8 5 ° at 70 nun w a s
stripped
off
through
tbe r e s i d u e
was
continued
>
Column
l.
through
Fractionation
Column
CUT
TIME
5:30
5:50
6:25
6: 5 o
7:45
8:30
9:15
9:55
10:35
1 1 :10
1 1 :45
12:15
12:45
1:15
added
allowed
thionyl
bath.
crude
0.59
f or
of
cooling,
water.
70
70
70
70
70
of
theoretical,
chloropivallc
thionyl
made
and
chloride
as
the
were
was
ammonium hydroxide
The
The m i x t u r e
the
excess
109— 110.5°,
on a s t e a m
one
just d e ­
combined.
The
added slowly
cooled
resulting
and r e c r y s t a l l i z e d
Melting point,
acid was
off by heating
exactly
took p l a c e .
filtered,
chloride.
hours,
two r e a c t i o n p r o d u c t s
concentrated
was
of
several
chlorotrimethylacetyl
cc of
1 07
107
107
107
107
108
108
108
108
108
108
112
120
125
chloride*
then d r i v e n
A s e c o n d run was
A violent reaction
hot
moles,
to s t a n d
The
PRESS.
OF C-CHL0R0PRI..1 E T H Y L A C E T A M I D E .
c h l o r i d e was
scribed.
JACKET
I n c ., 0. 52 m o l e s , 4 2 %
68 g. , 0 . 5 m o l e s ,
70 g.,
.
85-94
94
94
94
95
95
95
95
95
95
95
96
98
n o
1.4526
1.4539
1.4541
1.4541
1.4541
1•4o40
1.4540
1.4541
1.4541
1.4542
1.4561
chlorotrimethylacetyl
To
500
B.F
n 20D
3-11
PREPARATION
was
.
4 .7
6 .2
5.3
6.5
8.2
10.5
10.4
11.2
8.4
10.0
9.4
10.0
7.8
4 .0
Cuts
were
II:
’.VT
1
2
3
4
5
6
7
8
9
IO
11
12
13
14
of
from
weight,
to
In Ice.
solid,
3no
cc
7 5 go
after
of
ll o
The m o t h e r
lOO
cc.
liquor
A white
from above was
solid precinitated,
recrystallizationa
5 g.
The
from water,
to t al p e r c e n t a g e
An analysis
in the u s u a l
concentrated
way*
for
melted
yield
on
chlorine
Calculated
m e t h y l a c e t a m i d e , 29.66%*
after
three
at 1 0 9 - 1 1 0 ° ,
weight
the r e a c t i o n w a s
was
made
chlorine
Found.,
ATTEMPTED HOFMANN
which,
to a b o u t
59*3%.
in a P a a r
bomb
in C - c h l o r o t r i -
29*53%.
DEGRADATION
OF
C - CH L O R 0 T R I M E TiiYXiA 0 A TA M I D E
To a s o l u t i o n
of H ^ O
kept
of 9 6 g . , 2.4
834
cc
at - 3 ° b y m e a n s
w as
a d d e d 30 g . , 0 * 5 m o l e s ,
one h o u r .
The
bromine
additional
one
and
added
6 7 , 5 g.,
Stirring
NaOBr
was
color,
turned
ten m i n u t e s .
which had
and
After
the
became
perfectly
elapsed
from
heating
was
for
The
quite warm.
s t a r t e d was
the
two
fo r
-3°.
amide
To
of
an
this
was
stirring
and
allowed
reaction
The
solution by
ice b a t h
was
brown
The
in a b o u t
a t - 3 °,
the
colorless.
The
dissolved
the m i x t u r e
On s t a n d i n g
that w h e n
a period
a slightly reddish
and
and
over
o ne h a l f h o u r .
one h a l f h o u r
clear
in
ice-salt mixture
stirred
at
NaOH
C-clilorotrlme t h y l a c e t a m i d e •
beon
removed,
temperature.
the f l a s k
time w a s
of
a faint yellow.
ice s a l t b a t h w a s
to r o o m
was
a quarter hour3
c o n t i n u e d at - 3 °
solution
of a n
of b r o m i n e
mixture
0.5 moles,
m o l e s , of
the
to c o m e
continued,
this
total
time
removed until
one h a l f h o u r s .
The
re­
116
action mixture
Nothing was
o u t l e t of
and
was
caught
the
refluxed
in
collected
almost
to d r y n e s s ,
insoluble
in w a t e r ,
gave
a nd e v o l v e d
N on e
of
HC1
in e t h e r ,
for
attached
added
desired
s o l i d wa s
the m i x t u r e ,
DEGRADATION
was
evaporated
was
T h is
soluble
silver nitrate,
sodium hydroxide.
ammonium
was
the
distillate
did not melt,
chloro-amine
CURTIUS
to
solid separated*
t e s t w i t h aqueous
this
to
The
gas w h e n h e a t e d w i t h
that
one h alf hour*
s o l u t i o n was
when a white
ammonia
the
W a t e r was
The
a halide
concluded
tr an
steam distilled.
in 18% HG1.
s o l i d was
It was
the d r y - i c e
condenser.
the p r o d u c t w a s
vigorously
chloride*
recovered.
OF
CHLQRQTRIi.iETifYLACETYL C H L O R I D E .
To
a solution
trimethy]acetyl
one-liter
R.B.
of 8 0 g.,
chloride
flask
in 3 1 5
fitted
0*52 moles,
with
of s o d i u m
azide h a d
activated
by b e i n g
was
solution
required.
The
about five m i n u t e s
of
the m a t e r i a l
This
was
1os3 , however,
cool ed,
minutes.
and
allowed
by
acetone*
mixture
lost
was
The
wa s
sodium
freshly precipitated
A large
the
amount
took place.
top
inappreciable.
of
and
the
for
After
Some
condenser.
'Hie m i x t u r e
spontaneously
again started,
of acetone
to r e f l u x i n g .
reaction
through
to r e a c t
H e a t i n g was
azide.
w as h e a t e d
a vigorous
in a
a reflux condenser
1.3 moles
from w a t e r
chloro-
cc of d r y t o l u e n e
a d a e d 4 3 . 8 g.,
been
of
about
the m i x t u r e
was
15
was
117
refluxed
Tor
45 h o u r s .
n i t r o g e n was
filtered
being
from
At
evolved.
of
funnel
was
The
wa s
boiling
acid
toluene
took place
tinued
then
at such
lo
then
made
cc
residue
was
ether
after
with
three
and
precipitated,
The
from
th e
in
half
NaCl was
the
toluene
of
steam
layer
On
This
cc
distillation
original
reaction
funnel
to
addition.
the
of
The
the
addi­
con­
cc
basic
dry
cooled,
of
of
treated
water.
It
s o l u t i o n wa3
e x-
ether.
then
The
The
gas.
with
layers
carbonate.
HC1
water
extracted
ether
The
was
were
dry
A white
solid
ivi.p. 1 9 7 - 2 0 2 ° .
distillate
as
was
ether*
standing
600
D i s t i l l a t i o n was
200
ether.
g.,
water
ether.
In
with
treated
portions
with
NaCl , and
was
The
layer.
28.5
until
dropping
flask was
The
with
added
and
hour.
over potassium
weight
t he
three hours.
saturated
separated.
toluene
more
a condenser
acid heated
4*-0 cc n o r t i o n s
dried
mixture
of
no
that 3 team d i s t i l l a t i o n
NaOH.
saturated
Layer w a s
reaction
t he
f lask was
the
simultaneously
‘it'd cc p o r t i o n s
combined,
cooling,
To
c o n c e n t r a ted. h t d
basic
with
time,
with
through
a rate
residue
of
tracted
two mortf
t he
an a d d i t i o n a l
The
with
t h is
fitted
filtrate
added
complete
for
flask
and
toluene
mixture
tion was
of
After
s e t up.
concentrated HC1,
started.
end
the m i x t u r e .
A distilling
dropping
the
from
fellows:
the
The
e x t r a te d w i t h
layer
overnight
was
added
a white
original
layers
two
200
to
the
were
cc
precipitate
118
separated
M.p.
from
206-207°.
melting
made
basic
tions
gave
water
with
Weight
the
4.0
g .,
197-202°
198-200°.
layer
The
layer.
melting point with
KOH , and
oi' eth'ir.
from
the
steam
extracted with
ether
was
blown
distillate
three
off.
300
No
was
cc p o r ­
residue
obtained.
It
would not
an
toluene-ether
A mixed
material
The
was
the
was
affect
attempt
was
ror
the
made
hydrochloride.
cipitated
assumed
Cl
Pound.,
The
yield
added
The
It h a d
a
siderable
were
was
chance
heat
connected
fluxed
98°.
g.,
a solution
mixture
was
Accordingly,
Chlorine
added,
weighed.
and
or
the
the
Calculated
assumed,
45.5%
NaOH
0*5
ON
pre­
chlorine
t h e r e r o r e , to be
g.
set
up
under
heat
up.
was
to
evolved.
the
was
ChLOHOPIVALIC
or
column
The
collected
In
Column
II
As
acid
the
Two
dry
cutlet.
head
In
ACID.
the
200
cc
traps
The
Ice
In
mixture
was
or w a t e r .
dissolved,
temperature
dry
acid
immediately,
ice
A
obtained.
w&3
chloropivailc
NaOH
t he
propane.
theoretical,
o r riake
50
to
or
moles,
or
i'cr tliree h o u r s .
Nothing
the
atom.
nitrate
2-amino-2-methyl-1 - chloropropane,
was
moles,
68
carbon
silver
2-amino-2-methyl-1-chlcro
OF AQUHQOS
To
aqueous
24.22%.
or
or O .228
ACTION
or
product
hydrochloride
the
nitrate
chloride
the h y d r o c h l o r i d e
24.47#.
on
cold
to d e t e r m i n e
Silver
silver
that
belore
con­
series
was
remained
traps.
re­
at
119
The
At
the
end
ofthat
had
separated
and
drying,
of
th e
mixture
f 1 a m e ,l e a v i n g
in
melt.
lO
cc
Sodium
8
cc
sodium
25
A
25
A portion
the
of
After
again
taking
ether
until
the
t hi s
material.
Pound,
up
solid
is
burned
tnese
crystals,
15
cc
been
of
days.
crystals
56
g»
Some
steam distilled.
solid
in
of
was
and
A neutral
about
off
extracted
with
then
to f o r m ,
dissolved
filtering
blcwn
off
the
four'
with
air.
104-110° •
blowing
th e
did
added.
after
h.p.
melting point
125°.
They
5 g , , was
was
remained,
oegan
The
After
ether
ether
a yellow
residue.
solution
liquor
The
with
concentrated KC1
added.
Calculated
off
melting
reported
equivalent
for hydroxypivalic
th e
point
for
was
hydro—
run
acid,
was
on
118,
116.9.
Assuming
original
pivellc
reaction
acid,
The
the
and
of w h i t e
ether,
122-125°.
acid
above
the m o t h e r
crystalline
xypivalic
Tour
After filtering
to w e i g h
acidified
forced, o u t
acid h a d
cc p o r t i o n s
to
mixture.
found
Tor
of* w h i t e
amount
of
and
was
chloride,
raised
was
a large
of w a t e r ,
white,
cc,
were
stand
amount
the r e a c t i o n
crystals from
chloride
of
large
to
recovered.
The
not
allowed
a
crystals
filtrate,
N o t h i n g was
time
from
the
was
o g,
that
the
mixture
a yield
weight
of
crystals
were
ant
the
was
recovered
sodium
salt
from
t he
of h y d r o x y -
cotained.
of
the
sodium
neutralization
was
1.7
g.
chloride
recovered
Theoretical
i3
in
2.07
g.
1 :o
REDUCTION
OF
WITH
(a)
To
Grignard
several
of
acetyl
was
Grignard
It was
The
lOO
The
layers
with
layer
added
was
ether
Column
TIME
7:35
to
was
of
dry
was
stripped
The
residue
cc
of
was
added.
that
for
one
with
cc
ether
usual
and
t-amyl
going
To
of
the
ether,
vigor­
this
already
molfls,
a period
a
total
added)
three
of
hours.
hour.
of
Chloride.
chlorotrimethyl-
was
added
to
the
of
on<n a n d
three
was
allowed
to s t i r
overnight*
Ice
and
separated,
the
in
Chlorotrimethylacetyl
over
2oO
20
a period
stir
Reagent.
anhydrous
reaction
over
mixture
were
four
of
g . , 0.5
cc
then d e c o m p o s e d
extracted
the
6b
Grignard
magnesium
About
the
to
of
reagent
hours.
cc
ether
added
of
of
(including
Addition
in
150
When
allowed
total
o f _t-Amyl
iodine*
was
chloride
quarter
of
moles,
chloride
A
added
CHLORIDE
REAGENT.
2.5 moles,
additional
(b)
HCl.
was
2.5
The m i x t u r e
above
g.,
added.
cc
g*»
t-amyl
60
was
GRIGNARD
Preparation
crystals
425
265
t-AMYL
setup
chloride
ously
C H L OR O T R I ME T H Y L A C R TYL
and
portions
original
oil
a dilute
th e
of
solution
water
ether.
layer
and,
layer
The
of
was
ether
after
drying,
off.
was
set
TABLE
6
up
for
fractionation
through
II:
CUT
WT.
n^°D
B.P.
1
2.0
1.3745
40-42
JACKET
46-60
PRESSURE
152
continued
1 ‘1
TIME
CUT
W T.
n SOD
B.^.
8:05
8:35
9 :05
9 : 20
9 :35
9:45
9 50
10 :00
10:10
10:30
12:50
1 :0 5
1: 2 0
1 :30
1: 5 0
2:15
2:30
2 :4 0
2 :5 5
3: 3 0
2
3
4
5
6
7
8
9
1C
11
12
13
14
15
16
17
18
19
20
21
2.2
3.1
1.3
3.0
4.5
4.2
9.3
3.1
0.4
1.5
2.0
3.0
3.0
2.9
5.2
3.6
6.2
2.9
3.4
2.1
1.3759
1 .4118
1.4340
1.4390
1.4395
1.5399
1.4425
1.4466
Solid
Solid
Solid
Solid
3olid
Solid
Solid
Solid
Solid
Sol i d
Solid
Solid
65
102
105
107
107
107
115
118
119
119
119
119
119
119
119
119
119
119
115
123-137
Assuming
cuts
11-1:0
l,l-diraethyl-l-propanol,
56,'fc o T
theoretical
waocy s o l i d
melting
at
on
cooling.
ether,
nortion
the
Arter
one
A
bomb.
1-propanol,
for
chlorine
The
to be
3- c 111 or o-
g . , 0*28
material
moles,
was
a
15:
or C u t
In wa 3
heated
A derivative
melted
at
with
phenyl-
precipitated
from petroleum
78-79°.
Chlorine:
analysis
Calculated
2B.69/o.
33,7
recrystallization
phenylurethan
Analysis
a Baar
Cut
cf
ror rive m i n u t e s .
isocyanate
or
155
153
151
15 3
152
153
153
152
152
152
148
143
148
149
151
150
150
150
150
150
29-31°.
Phenylurethan
A small
a yield
PRESSUKE
1O0
109
n o
n o
112
117
124
127
127
127
123
122
122
123
128
127
128
130
143
176-185
inclusive
obtained.
#as
JACKET
was
run
in
chlorine
for
3 - c h l o r o - 2 ,2 - d i m e t h y l —
Found,
28.51.
the
usual
way
in
1:.>
S U M M A R Y
1) P i v a l l c
acid was
chlorinated
b y m e a n s of
sulfuryl
chloride
in
peroxide*
An
phase
chlorine
with
attempt
2) T h e
pivalic acid
to
was
th e p r e s e n c e
chlorinate
the
acid
yields
of benzoyl
in
the
vapor
unsuccessful.
reaction
yielded
in g o o d
the
of
thlonyl
anhydride
chloride
Instead
on
of
chloro-
the
acid
chloride•
3)
action
of
presence
Chloropivaljfl
sulfuryl
chloride
chloride
was
on p i v a l y l
preoared
chloride
by
in
the
the
of p e r o x i d e s .
4)
C-Chlorotrimethylacetamide
chioropIvaly1 chloride
and
concentrated
was
prepared
aqueous
from
ammonium
hydroxide•
5)
gradation
N o t h i n g was
was
6;
gave
a good
run
A
chloropivallc
the
Curtius
yield
7)
on
of
recovered
aoove
C-chloro
degradation
the
when
of
a Hofmann
amide.
chioropivalyl
C-chloro-t-butyl
Aqueous
sodi.m hydroxide
acid
good
to g i v e
yi elds
de­
chloride
amine.
reacts
with
of h y d r o x y p i v a l l c
acid.
8)
t-amyl
C h l o r o t r i m e tliylacetyl
Grignard
reagent
chloride
was
reduced
to 3 - c h i or o - 2 , h -d Irne thy 1- 1 - p r op a n o 1 •
1GENV I l - O r i G
III
iliVcT
iL'b
DISCUSSION
A.
DEIiY O k
TION
a
When
Stahly,-*-
the d e p o l y m e r i z e d
products
1)
DI-t-BUTYLCARBlNUL.
di-t-butylc&rbinol
isobutylene were
These
uF
obtained
products
Instead
were
explained
of
the h y d r o x y
Removal
di-t__-butylcarbinyl
• •
« V
• •
consequently
•
the
methyl
groups
: c;
«•
3)
the
that
«
a.
M
: c0#:
susceptible
its
neopentyl
electron
pair
is
and
One
of
transferred
:c ;
. **
c * c : c;
♦n •
* ri«
♦
is
•*
>k ..
-> ; c ; c : c / c : c ;
•
tertiary butyl
system,
to r e a r r a n g e m e n t .
a
transfer
group,
but
*
of
-
•
the
without
*
b.
•
*
electron
the
pair
transfer
from
of
group
•
4 *
:c;
4
0
;c-
*^
^
w
|*
; c : c ; c : c ; c : -------- => ; c * : c
"
........... "
0
/“i0 •/>•* •
/’
*« *
• u *
«v *
• *
The p o s i t i v e
its
a positive
: c ; c .
♦* 4 *
a positive
with
There
basis:
•
^
* r\ *
•
following
;c/
* . **
!c ; c
expected nonones•
•
« «
++
doubly
most
the
to g i v e
4
- •4
c
Is
t he
and
*C '
-Mr ' '
i
; c r c ; c
This
trimetliy 1 e t h y l e n e
of
on
dehydrated by
group
•C *
»- * *
2)
was
polymers.
##
•*
«#
tertiary
c —c — c —c
..
•
/-% 0
( v #
i
r
*
vy
»
butyl
fragment
gives
Isobutylene
and
1. 4
The
point
the
in
the
above
reactions
present
theory
important
process
ically deficient
out by
as
in
the
the
without
atom,
transfer
above
the
case,
an
by
nonene
small
amounts
The
one
of
stabilized
transfer
b y
a process
may
be
is
and
explained
by
formed
H
in
terminal
form? tion
of
an
the
up
a proton
The
the
only
Very
were
a proton
is
olefin
c - o —c - c = c
"
none
it
easier
other
to g i v e
m o t h y 1 g r o u p s , an d
/
is
i
i
c c
of
the
concluded
than
the
analogous
c
2,b ,4,4-tetramethyl-2-pentene
that
the
plnacolyl
methyl
group,
c
only
been devised
expels
G
I
C — G — C - C
I
I
The
nair
following process:
above
: c : c : c ;c :
recovered,
has
isobutylene
;#c#: ; #c•; : •c#;
was
or,
C
'*
Since
electron
products.
;*c;
;c
the
carried
group,
2 , 3 , 4 , 4 - te trarne t h y l - 1 - p e n t e n e •
adjacent
the
electron­
its
dehydrated
denolymerized
fragment
the
that
m i g h t be
with
of
i.e.,
the
th e p r o c e s s
t r i m e t h y 1 e t h y 1 ene
nonene
of
electron pair
the
important
group.
the
was
of
The
from
of
recovered
formed.
satisfying
the p r e s e n t w o r k
instead
an
rearrangements,
that
w h e r e b y di-_t- b u t y l c a r b i n o l
nonenes
of
the
and
of
attached
±n
is
Illustrate
reaction
o
k n o w n 4- is
group
gives
However,
a proton,
a proton
in
this
it h a s
easier
Work
loss
of p r o t o n s
Lthyl,
Amyl,
pinacolyl
methyl
from
known•
than
in
group
group
it
is
an
long been
any
th i s
other
Whether
than
it
group
that
group
in
be
it
is
t he
this
shown
is
to
easier
from
the
gives
group
the
following
iVie t h y l , a n d
added
which
up
lose3
studied.
l a b o r a t o r y has
Propyl,
may now
ethyl
known
to d e c r e a s e
Butyl,
group.
this
case
the
ease
of
order:
Neopentyl,
series
after
The
the
to r e m o v e
a proton
neopentyl
group
is n o t
126
B • SYNTHESIS
Recent
cast doubts
and
on
OF METHYL
work
the
derivatives
From
and
reported
th e
bazone
and
derivative
that
the
but
melting
ketone
and
the
properties
other
as
3 emicarbazone
addition,
the
he
oy
these
neohexyl
the p r o p e r t i e s
olefins,
Drake, Klein,
to b e m e t h y l
149— 151°
with
reports
also
of
both
from
was
the
neohexyl
and
172-173°
same
to
semicar—
product,
that
of
Drake,
a 2,4-dlnitrophenylhydrazone
It w a s
concluded,
derivative
different
working
workers.
investigation
and
and
therefore,
of
forms,
methyl
one
melting
70°.
reported
came
two
of
literature.
corresponding
In
ketone
of m e t h y l i s © p r o p y l c a r b i n o l
working
at
that
reports
derivatives
under
at
70-72°.
existed
/)
obtained
he
at
Shabica,^
same
the
2,4-dinitrophenylnydrazone
neohexyl
1499
melting
Mosher,^
Ro3e,
the
L a b o r a t o r y has
of m e t h y l
from
claimed
a semicarbazone
obtained
Klein,
of
th i s
2,4—dinitrophenylhydrazone
derivatives
respectively.
In
dehydration
a oroduct
ketone w h i c h pave
in
Identification
the p o l y m e r i z a t i o n
Kosff^ i s o l a t e d
the
olefins
5 ,3 , 4 — tr irne thy 1 - 2 — p e n t a n o n e
their
at
on
NSOHSXYL KETONE
with
a product
with
the n r e v l o u s
workers,
by
w o r k e r s , but
the
He
the
the
above
the
obtained
In
2,4-dinltrophenylhydrazones
concluded,
same
probably
that
solution,
a mixture
of
since
the
both
product
methyl
127
neohexyl
ketone
and
tiie i s o m e r i c
3 , 3 , 4- tr i m e t h y l -
2 -
pentancne•
It
synthetic
at
material
and
1 7 2 °
70-72P
to
A
Its
pave
did
of
An
the
of
of'
-ret o n e
t
were
m e thyl
of
2
seedinr
ut
in
derivative
were
melt­
melting
tried
in
o
and
the
It
ox
obtained.
with
used
the
appropriate
t he
in
m e ao ce 3 a 2 a 1. .
->roduc t b o i l i r u
1n
Ime
th e
o
a tiidlecJ
by
dhaoica
was
se:nicaroazo..o
melted
has
be-in s h o w n
therefore
L-ruke , n l e i n ,
a mixture
of
order
forma•
range
this
synthesis
:iow e v e " ,
of
tie
rrouuot
40 — 4: ,° th.e 2 , ^ -r.iui trc.-.-h.enylhyci^aZ'''ne m e 1 t u (.; a t
hi,
at
3,3,4— trimethyl-2—pentanone
method
The
different
was
chloride
e t r r:e , .-as
mad -•
two
7 0 - 7 2 °
to j-r-care
same
The
tin? 2 , 4 — d i n i t r o n h e n y l h y d r a z o n e
that
acetyl
ne o h e x y l
dei'initely.
a semicarbazone
Ltlnr
th e
ne - d e :<7/1
d e r i v a ?.! ve3
properties
crystallize
m e
reagent,
o;i' :ret,!y 1
synthesize
methods
attempt
r e a c tion
d'iriitri:
sir-*'l
not
product
t h e
to
2,4-dinltrophenylhydrazone
n r o v '1 c o n c l u s i v e l y
Only
at
a
number
derivative
oy
'ieciUe<l
to d e t e r m i n e
Ketone
ing
.vaa
vnd
hose,
methyl
3 , 3 , 4 — tr i m e t h y l - 2 - p e n t a r o n e •
at
lhb.
end
melted
J.4 b -
o
that
oy
neohexyl
de-
tne
product
Tosher
ketone
and
and
128
G.
Because
B a r t l e t t ^ l n his
Investigate
oxidation
with
a neutral
way
This
took p l a c e
sults
had
al so b e e n
marks
on
vroup
to o x i d a t i o n
the f a c t
altogether
u ni q ue *
foi.lowlo.p- WH3
by
Farmer
C I
I
G-C-G I
C .
I
C = CHr
^ - 9 ^
C
Tills c o m p o u n d
Is
also
as
isolated
In
in a ci d
the
On
solution,
he
a ci d .
No
'Iliese
re­
Bartlett
re­
methylene
as ton I s h in/2; o u t
believed
and
In
1 934,
of a t e r m i n a l
Is
ob­
1,1-dlneo-
o e r m a n r a n a te .
p e r ma .ncra r m te
of
Bartlett
Laboratory©
this
A hydrocarbon
Is o l a t e d
the o x i d a t i o n
dlneopentylacetic
that r e s i s t a n c e
by
bo
identified
with alkaline
found In
decided
Laboratory
this
Butlerow's acid,
oxidr tlon
by
permanganate,
the o l e f i n w i t h d i c h r o m a t e
obtained Alpha
ed
From
w h i c h he
in
obtained
It was
compound had been
and i d e n t i f i e d
oxidizing
results
studies,
alkaline
residue
pentylethylene•
s am e
unusual
the
this w o r k f u r t h e r .
triisooutylene
tained
of
OXIDATIONS
to be
not
one
of
the
but
yield­
*war tin:^
(g h .,)q - c ^
"
I
C.
c
c
1
C -C H 0
2
C
resistant
on o x i d a t i o n w i t h d i c h r o m a t e
of c a r b o n
atoms©
Bartlett
molecular
models,
as a p r s s i b l e
3
to p e r m a n p
late,
an a c i d
the s a m e
of
u-ppr.e s ts , a f t e r
c au s e
for
number
an
inspection
this
behavior
of
the
If 9
c.o :m /1e f e :.i jvi re-,n e e
3t itutefi e t h y l e n e
•;Va. 1 In-
..y MO-'.:
’ 1J ~ j1 . : ,
•
;e ;i t a d
<- -iU|
;a b
m;i
' -i* ■
..■
‘.tl ■ 'Abb
“ ' ■• <•
>r
i'i-i two
,.77,:r n1 :1 i ».e
• ;'•
♦-0
1
to r + I. a r y
!1
. 1
t ' .ia
1
.:
t•
^
1
'.'If/
1a
, •'
t Wfo;
‘ ' t ■
a*.
^ ■ i"
o ' p i.<3■■
■ ] if.--
• ;<r" .•
.
;
e , -.a vc
1: o .vr* 1 ~.i .■ "
' t ■
f3
r,
i‘
1
r
■
•’
y
^
f
;.
”
^
,
+
-v: 1 " * c- 0 .
-1>••;.; .
f *■i
vo
1 f f•p 1.1
Ia
r-j
:1
1
' -j ’.V-i3 1.‘
j h t.3 d
’ ?. ' 3 r‘o r* lor^ b
i
•:f
•.! :
• a ! ::
ale o
*
»*
+■ >
■
f1
fit 1 0 b
3
.,,• v a b y l r . l
.*•.■'■ O
' { 'b e
^ • r r r s
t
■ ; <-•*. .
Ac C C r-1 1 •,y ■”■,
) ''
• *
;
aa-.r-ahal
"
cor-rou. .33 , 1 , I - d t a 6 <”./-erb y]
\ , - r ■.
t: •
V . . . . ’
^*
f* < r •
P ea c fa ■1 o w l v
M;.
a
v; tc
O ’
■- - : - -■r-.. ,;f
I: -
' • •• <-. r
■ ■i• - ■ted
,
*r '1 ">
• t •- .t
t.sl b e
3.1
:. I •. o : l b ! f
of
* ii O
- ; ‘'
■y : '.a <-a
t
••
*1 '
rr.' 1:;! *• .: by
■::. t 7 lot.;, r e ,
r a ^i.fr’
do1 3 r"
I
1 -
•’' -■, Uie a t a !_•a
u . f ■i *_1._■a
•a- a *.t /*! ’>;b q 3
> ■'\ ..•^
e a i ,’ ' *c a 4a:. r +. 1.:•<• ^id
a !T..iJ !’
■a 1.p '-’
u a at b'OX ,r.av b-..
1 3 .
- ‘
\
b
' y 1'■'*
r :■r ■■-jn t_ 1 -'-r
b
■ iiar.b:
' L■
•a P 0 •'"a i-J
This
' ^ acc
of o n y r-yitf'3: t t<". the s u b v
c a r b o n a ton*
Si rc-p t;:<- 1 Irst n ten of
/•
h
tt'/rrt.
r o ■• ■ 1 ; 1 - (
f .• ■;
c
t
! i> t 1
.
;•
c r 1 3^ a-
l.--i
■t i - - ’• r n
, • ' : •• i
’ ’* '
•
{ rb -* .a -
• - '
’b
( •
-r.d-i
'
.•1-'
I/,
fa H u
‘
i*
-p.
-V .-b-
rat- Z or.i e
1 0 O ('i•
It
-
w ' -J c r : B a r i let't r e p o r t s
v id
<•;*..s
decided
te- n 1i e m r t a n
i ; 1;; .'iibs i' .'.oJ
.-.it 1
rc-w * o
s!.‘i
i. ci;i,
r.a
.tii’•*■ ■' t-i -■x• . re - .;ct3
.*:e 1
*'• b
1 tin*;
at
arihyrix»ido
cuiiit
9 7 — 9 1°
id
■-■.":r os -o.. ,
a ■;" ves
:• .
of
.for
1 7 b - 1 7 4°,
s :*•-.
is
nr -■■.
■
.■v
V
low
1 a e vv-jlrr ti
r:o 1 o o
.3,
of
ail
I.’
to
boo
c
wia
recovered.
de-
r* r o v e r e d , I,
a ♦
In
t;ie
'M f- ld b " ’,
w o : 1 at
a
its
and
of
IV,
an
.-n, c a r<:-<r'b d i o x i d e ,
Vi ter
coto'/t.iI
I I I ,
d» —
*•o m p o u i i d ,
n r or. e r tier,
• I v ■ :,
bo .s
-,.r i<
t l t r f 4 } .• r
o bs • r v ed .
v c1d
II
is
was
de~
* •: c O ” p o o n b ,
V,
:
-
•r t
ihiir tr
•
-i' :i.; f .
aril,
1 . . ■;
i
r-.!>•i .**>,
w
vv’
..1 I e
>t
is
r:.v s •;
] '•o !a t.-»* f " 0 ;n t n»*ir d a t a .
if 7 ?.-id 1.^0, «?•»*•-
o i n 1s
a t:irth.;*
ii>iert
x1 :
P •>t s
the
d e c o -e -o d rj;
s
When
other*
i ~.t r: a r> 4 ' <-3 ■-_■ i;r.e'1 Tor
docon^ositior.
. d1
a -’id 7
h
of* s o m e
was
ce.rt qi -a r t e :• !:o!ir,
wi.ic::
since
acid,
.he:; roir.r ooo *’ 1
1 •. , : c c
d
I I ,
s' ,'-w r.o:.,S')U;.i II
i.s J
t.b
known
yl oc-; tic
o x i d r 1 1 o o v; ;
o b t ■'i r e d .
o rs e r v o o. 1 :i t' is
1 t in <3 at.
of
fO b -k .1 0 0 ,
t f h — r7°.
Ci.;i.roii i 1 i o n
+ d v ’ s e 1 i c n c ! :i•
;t, c c
au<- /<-> Ci.ner'-u'ih , p o # 7 4
bee"
oxi.tn t 1 o n
-v- tr vl - t-t> . t.y !
;i.d - r for
co.r.r-...- i i i ' i ' .
has
'-o-'.i
4 o -•> low
fcf
the
e on:—
?s i
;f
e :.
fo w
Th-i.r..
-li^h tnul t-
13 J
E X P E R I 1.1
PURIFICATION
’Vhen 7 0 0 g.
ketone
results
were
were
OF D I I S C P K O P Y L K E T O N E
of E. K.
fractionated
Practical
through Column
diiaonropyl
I,
the f o l l o w i n g
obtained:
TABLE 1
Ti ME
2: 25
3: OO
3: 28
3: bu
4:22
4:50
5:35
6:15
6 :55
7:30
8:03
8:45
9:15
10:15
in ;35
1 1 :00
11: 2o
10 :55
11 :15
12 :05
1:00
2:15
3:00
3: 5o
4:4b
5:50
6:3 0
7:05
7:^5
8: 2b
9:05
9:45
CUT
1
2
3
4
5
6
7
8
9
lb
11
12
13
14
15
16
17
n
D
B .P •
106
1.4075
111
1.4073
113
1.4069
1 13
1.4070
11515
1.4070
114
1.4070
115
1.4070
115.5
1.4070
116
118
1.4064
118
1.4065
118
1.4060
113
1.4060
119.5
1.4053
1.4053
113.5
119
1.4050
119
1.4045
D i s c o n t i n u e d for
18
1.4021
19
1.4041
20
1.4041
21
1.4039
22,23 1.4032
24, 25 1 . 4 0 2 6
26,27 1.4025
28
1 . 4 0 20
29,30 1.4020
31
1.4018
1.4017
32
33
1.4015
34
1.4015
35
1.4015
1.4012
36
JACKET
ll O
114
127
125
7/T .
10.0
6.0
6.6
7.2
7.0
7.2
12.7
1 26
10.6
10.7
9.2
9.2
10.9
11.2
5.0
5 .3
11. 7
12 6
13.9
39veral h o u r s .
125
6.0
124
11 .4
13.5
12.5
21.7
14.7
126
15.1
10.8
18.4
9 .0
9.3
125
lO o 6
10.8
11.3
1 2 .1
continued
7 41 xn.’i
R.R.
12/1
R.R.
12/1
R.R.
12 /1
7 41 m m
R.R.
1 2/ 1
1 52
TABLE
TIME
CUT
10: £c
11:05
11 :43
12:30
1:15
1:55
37
38
39
40
41
42
came
over
continued
B.P*
r 20D
JACKET
1.4012
1*4012
1*4011
1.4014
1 .4013
1.4012
21
a t 1 2 3° ,
n s o D,
dilsoprcpyl
ketone
10.6
9.8
10.5
12.4
11.2
12.0
cuts,
t ot al
weight
1* 4 0 1 0 .
M* p *,
with
2,4-dinitrophenylhydrazone
desired
this
latter
mixed melting point
of
diisopropyl
1 5 5 — 2 57°.
Approximately
when five
liters
of
the s a m e
cr u de
results
ketone were
were
obtained
fractionated
through
HP*
P UKIFICATluN
Stock
through
155-157°:
of
made,
Column
the
all
fraction.
m a t e r i a l w as
ketone,
2 3 0 g*,
This w a s
2 ,4 - d i n i t r o r b e n y l h v d r a z o n e
a known
WT.
125
The n ext
A
1
Column
t o l u e n e was
I,
of s i x l i t e r s ,
OF T O L U E N E .
and
B.p.
dried
over
finally dried
108*5-109
C a C l 0 , 1r a c t 1onated
over
at 7 40 mm ,
3 odium.
n 2 0 D,
A
total
1 * 4 9 6 1 w as
obtained•
PREPARATION
wero
made
molei' .
A
Trie a p p a r a t u s
used
using
of s o d i u m v a r y i n g
amounts
tynlcpl
The
The
OF SOPAAilDK.
outside
run will
sodium
w p s
one-fourth
a l ar g e p i e c e
of s t o c k
Is s h o w n
be
in P l p u r e
from
3*
two
Runs
to five
described*
prepared
for
use
in ch was
sliced
souiurn*
This
off
oxide
as
follows:
all s i d e s
free
of
sodium
133
<o
>s>
,ss**l
*
X '
hi
'jj*-.
,
■
t
«i
*
o
f.*
■**■
jfr
Si
-t
9f
!v.
hO
Q
j
V
LEGEND FOR FIGURE 3
A*
Ammonia
cylinder.
3*
Soda
C.
Mercury back-presaura
D.
Ammonia
E.
Thermometer.
F.
Outlet
G.
Florence
H.
F l a s k c o n t a i n i n g w a t e r to a b s o r b a m m o n i a a n d
i n d i c a t e p a s s a g e of p;as throufrli the s y s t e m .
J.
Cast
lime
tran.
inlet
safety
v a lv e *
tube.
tube.
flask
tran.
Iron reaction
vessel.
15b
w as
weighed,
the m e t a l
tntrl
was
and t r a n s f e r r e d
or 104
4.o moles,
p.,
on b y m e a n 3
p-asket c o a t e d w i t h
ed
e.s the
to the
buboled
bottom
through,
of
the
as p o s s i b l e
of a m m o n i a .
been ad d ed ,
of four* c l e m p s .
the
used.
ammonia
the mo] ten
sodium,
An
When
so
a
the p o t
li d
asbestos
H eating was
inlet
to
started,
tube was
that
the
push­
ammonia
liquid.,
TEMP.
H E .v;AHK3
I S : 30
Started heating
1:00
300°
I n l e t tube t o u c h i n g b o t t o m .
c o m i n g o f f do es n o t bu r n .
1 : SO
S90
E v o l v e d gas
ammonia,
h :SO
S:33
2:45
4:00
4:50
3 SO
335
33 6
350
350
5:50
343
\ o iiif I j.rn ia h le
1 i oia 11 on •
6:4o
350
P u l l e d i n l e t tube out s o that its
e nd was a b o v e the s u r f a c e of trie
molten liquid.
3o 0
D i s c o n t i n u e d heating, but allowed
a m m o n i a to n a n s t h r o u g h ayateiri.
7:00
T he a m m o n i a was
of
the
the m o l t e n
1st't traces
burns.
Also
liquid
of
?ns.
a l l o w e d to p as s
In
sodiuqj.
orderThe
to
comr.
over
GS-aa
od o r of
E v o l u t i o n of i n f l a m m a b l e
slowing down.
•
of
had
s h e l l a c was
sodium melted,
Tlf.E
fac e
quickly
p o t under* an a t m o s p h e r e
fastened
and
as
Some
gas
3 UD -
the s u r ­
let. e the
reaction
so d a ml d o , b e i n g h e a v i e r
136
than sodium,
a layer
of
4. n k s
sodium
The
175
g.
close
as
The
A
to
to
care
was
to
the
a point
b e i tig
again weighed.
culated,
in p u r e
and
corn
retort,
leaving
of
/-ield
some
cannot
of
from
run was
However,
7
the
the
this
be
taken
weight
inlet
was
the
not
solution
of
the
tube.
to
lose
of
the
ratio
was
evaporated
The
solid was
chloride
sublimed,
any
sodium
above
was
weighed.
ammonium
r a tic
rod with
NaNH0 prepared
The
residue
A
g.
th i s
•
of H C 1 •
as
from
176
dissolved
-/here
taker: s o
is
since
quantity
a solution
the
product
theoretical
of N a N H
and
of
yield
to g l a s s
small
dryness,
heated
weight
of p u r i t y ,
due
of
top .
to the
Analy.s 13
added
the b o t t o m
theoretical
e criterion
is
on
total
aoproach
product
to
MaCl.
The
to n i t r o g e n
of' s o d i u m
residue
was
cal­
to n i t r o g e n
NaNH<-o
Wt.
Wt.
Wt .
r e s i n u e Ir e s i d u e III-11
Wt. Na
W t . 13
1 . 61 9 1 g .
0.8879
0.7320
0.3521
0.19.33
Ratio Na/N
25.5/14
T h e o r e t i c a l — 25/14
A s s u m e 9 3# p u r i t y .
This
approximation
trie r e s u l t s
of
method
of
of p u r i t y ,
the
analysis
but
reaction*
is
it d o e s
at
best
giv-*
only
s one
a rough
idea
as
to
13 7
P R E P A H A T I ON O F P E N T A m E T H Y L A C E T O N E
To
liters
of d r y
Isopropyl
5 liter
ketone.
The
The
hours.
added
time
was
Then
slowly
A vigorous
reaction
three
mixture
was
contained were
the
a reflux
heated
turned
moles,
during
took place,
mixture; w a s
hour
after
the
dir.‘et h yl
for
mumonio n hydroxide
added
t h re e
stir
at r o o m
hydrolysis
temperature
of
of w a t e r ’ w a s
the
a very
cbvious
the
excess
of
was
Nothing
washed
and
for
tcluene
successively
the
odor
sodamide
extracted
but
The
dimethyl
added,
was
layer
n-^urs.
of
was
with
thick
two
In
mixture
sulfate.
layers
280
cc
of
was
to
recovered.
water,
5%
evolu­
for
un
added.
cc
of
water
allowed
was
to
complete
s e n a n a ted.
sulfate.
and
an
insure
a m i n o s , formed
w as
hours.
Ar- a d d i t i o n a l
were
total
one h a l f
sulfate
been
of
500
12 h o u r s
other,
and
ref? u x e d
had
a
a
paste.
one h a l f
further
and methyl
with
for
accompanied by
a mixture
coiicen tr a ted
during
and
sulfate
two h o u r s
of
and
10 h o u r s ,
dimethyl
three
The
cooling
of
about
to a
r period
of heatc
After
condenser,
for
of d i -
necked
to r e f l u x l n g
evolved
over
3.2
g. , 2 m o l e s ,
three
th e
tion
all
In
of
was
dropwise
sodamida
necks
the m i x t u r e
c.,
of
the
cooled
420
g.
228
funnel,
mixture
173
added
A m m o n i a was
which
mixture
of
wps
In w h i c h
hours.
during
To
a dropping
stirrer.
38
toluene
flask
attached
of
e suspension
IN T O L U E N E .
probably
The
750
co
There
by
water’
the
extract
fractionated.
ihc
toluene
layer
4C1,
water,
5
was
sodium
138
carfconete,
and
approximately
Toluene
-mill
then
was
about
rinally water.
3 llter3
was
fractionated
700
cc
transferred
of
TIME
2: 45
3:55
4: £5
5 j 55
7; 40
11: lO
11: 55
12:55
8:15
3:15
4: 23
5: 4b
8 : 45
10:10
i l :OQ
11 :35
CUT
drl3d
from
residue
to C o l u m n
TABLE
WT.
The
layer,
over
the
solution
0 *JT
1 1 :00
12: lO
1 :30
2:45
3: 35
4: 50
5: 50
7:00
7 : 25
7:50
8: 15
8 ;3^
19
90
21
22
23
24
o
(wW
26
27
28
29
30
WT .
9o5
13.3
15.5
15.8
9.2
14.7
11.7
11.6
5.9
4.1
4 .2
6.5
carbonate.
through
The
further
n 20D
B.P c
b.p .
133
133
133.3
133.3
133.3
135.5
134
135
136
138
140
14b
u
2° D
was
fractionation.
JACKET
of
Column
residue
2
T h e f i r s t t w o c u t c o n s is t e d
3
1.4238
126
Sol
127
4
5.2
1•4166
5
128
1.5
1.4130
6
8.2
1.4112
130
7
130
1.7
1.4110
A l l o w e d to 3 tw.nd overnight,
8
1.4119
130
1.3
9
4.4
1.4115
131
131.5
10
4.5
1.4105
132
11
1.4099
6.8
132
12
1 .4095
5.5
13
6 .1
132.5
1.4095
132. 5
14
6.3
].4095
1.4091
135
15
16. 1
16
6.2
133
1.403 8
133
7.8
17
1.4086
18
3.8
133
1.4082
Dis cont: inu e d •"'ver:iI p h t •
1 I inlii
oota3slurn
remained.
I fo r
totaling
about
128
131
131
132
132
130
130
131.5
135
131
134
1 33. 5
133
133
134
134
JACKET
1.4085
lo 40 81
1.4081
1.4081
1.4081
1.4081
1.4085
1.4091
1.4105
1.4117
1 . 4 loo
1.4165
ccntinurd
200
{IF
139
TABLE
TIMS
CUT
9 : IQ
9 :50
10 :30
lO : 50
11 :OG
11.05
11:10
31
32
33
34
35
36
37
WT .
a ted
18
to
05
I n c l 'isive ,
through. Colximn S M J :
CUT
TIME
c
l
2
3
4
9 :G O
10:30
11:30
12:30
1 .30
2: 30
3: 30
4 : 30
6
7
5
y/T.
n ?° D
B.P.
3.1
11.5
13.0
12. 4
9.8
11 . 3
1 2 .6
1.4083
1.4079
1.4077
1.4074
i .4074
1.4074
1.4073
1.40^4
130
133
135
135
1 35
135
1 7f,
J.Oo
1Li*
S
>O
Ax' ox line w*»3
1 :i a bo.i’o
oxime
On
foe
130°
In Cuts
be
.a.d
1t
]3
baa la
1°- p v,ob.v b l e
to 13.
t; ie
a c t Ioji o f
case
the
prepared,
all
the
cf
for
m
portion
12 h c n v s .
1 3 0 — 1^-0.
of C u t
Me 3 t i n g
5 above
point w i t h ­
Ml xc-i ;ro 1 t i n g
nolnt with
of rwi'itamethy] a c e t c n e , 1 3 9 — 140.
rel'ractio.’.a cion,
However-,
tc
at
I u d o
r e c r y a t*-«l l.tzatlcr,
a known
In
JACKET
n20D
347.5
1.4200
149
1.^211
149
1.4211
1.4208
149.5
150
1.4205
150
1.4200
150
1.4201
13.5 g •
TABLE
out
con tinued
B.P .
6.1
8 .2
7 .0
8.6
10.8
9.0
4.5
Re s i d u e -
Cu to
2
the
of
the
a yield
of
trio 1 t h e r e
Ordinarily,
23.8/b w a a
Is
p-rnte..i;e t h y lac e t o n e
cbtd. m d »
con.? ide f a b l e
1.3 n o t
j i;b j ec t e d
ir
a net rre t h y 1
obtained
prcduc C
vl e n hexaice tiiyip c e t c m
r e r t iv; e t.hy.l a c e t o n e
; rc-dec t px'*‘--aer:t
> ofia.rlde
-.ontaeetbv]
V noetonn
-u.. .
1 f a ‘ c- .
v;as
1 a ol r ted
to
isol r t ed ,
the*
a u b s e q . n . r.t,
;<o w e v •*r , 1 n
so
is
thc t
<J\
ia
p rcrertles
140
of
t hi s
substance
P RKP AH A T 1 0 N Pg
To
mide
In 3 0 0
1.5 moles,
while
for
Iricr4-u s e
To
1.6
this
stirred
wa s
to
of
the
sodium
tt-en d r i e d
mm
stir
Cclurrr
being
•• p^-ri od
fo r
After
IP
over
I,
for
the
of
two
potassium
product
material
171
mixture
the
g,,
was
held,
of
150**
mixture
all owe d
to
did
to
cooled.
In
cocl.
A
300
'lours •
the
1 ay-u* w a s h e d
and
addled
m i x t u r e w a s t h en
again
ncurs
aoda-
two h o ur s POO g .,
The
and
of
viscosity
was
of
,
temjiereturr
h o u r s , find an
four
d e c a l In
desired
cc
Th e
of
mixture
additional
layers
were
500
.successively with
finally
water.
Column
distillate
II,
The
cc
sepa­
T h e oi l
HC1,
layer
carbonstw.
was
stringed
boiling
from
59°
off
the
to 1 2 5 °
decalin
at
collected©
The
t trougn
ever
a
a m m o n i u m h y d r o old**
carbonate,
The
157
of
at
mixture
two h o u rs ,
cc
added.
water,
through
for
This
although
The
DEC A L I N .
h n;ules
tendency
sulfate.
to
and
no
to s t i r ,
g.,
kelone.
dirretb yi
pdd"d
rated,
was
was
IN
d e c a l i n v.’as
a period
190
allowed
HP
over
150°
war;
of w a t e r
There
added
of
of
vigorously,
c o ns i d e r a b l y •
solution
water
Hh T A 1 E T H Y L A C E T O N S
di isopror-yl
thick
moles,
lit a t e d
w as
of
toe
d e t e r x nl n ed .
of r e d i s t i l l e d
3 0 hcuirs •
become
V
be
a s osr-en3 I o n
cc
being
might
wa3
sot
ur
data
for-
the
for
fractionation
f r a c t i o n a tl on.
141
carried
out
at
atmospheric
TABLE
CUT
TIME
1 2 30
1 15
1 40
2:15
2 50
3: 25
4f 40
5:05
5 :45
11
11
12
12
1
2
O
€■
3
4
4
4
W T.
2.1
9.6
6.4
6.9
5.6
6
12.1
7
5.4
8
4.0
9
6.6
Discontinued
5.1
10
11
6.4
7.1
12
13
6.3
14
6.1
15
6 .2
16
7.0
17
7.4
18
7.4
19
e .o
20
1.3
20
55
30
oo
40
15
oo
25
40
Cuts
54/fe cf
7
to
tifOi'etl cul
<Vhi le
the
w: cii tr < re act: 1 on
ran
run
the
a d van ta/n*
of
the
crude
product
frorc
is
filtered
stripped
and
is
then
5
h ours •
5
75.5
this
ir
toluene,
the
ready
employed
fhe
more
consequently
131
2 31
136
136
136
136
136
137
1 37
1 47
160
5
In
the
temperature
fluid,
5
p.,
run wp3
r e q u l r inp; m u c h
off
124
127
128
127
127.5
130
131
131
131
0.6
moles,
w e r ; c e n t arm-; thylacfttone •
yield
hawe
product
inclusive,
yield,
JACKET
B.P .
112
127
1.4022
128
1.4050
1.4058
12 8.
129
1.4058
1.4062
129.
1.4069
1 31
1.4068
1 31
1.4068
132
f or 36*v y r a l
132
1.4062
1.4066
133
1.4069
133
133
1.4069
1.4068
135
1.4069
133
1.4070
133 .
1.4068
134
1.4078
134
1.4075
136.
120
1.4105
18
follow:
4
r 2° D
1
o
h
3
4
5
00
25
pressure,
solvent.
d e c a l in,
for
this
less
the
method.
the
to
Also,
than
Ices
senarate
desired
d e c s 1 in
mixture
f a c l l l 1 ta t i n e
better
time
After
reuse.
reaction
no
at
remains
a <-1 tatior: •
is
the
biyher
much
14-
PREPARATION
To
in 0 l i t e r s
OF PEXAAIETHYLAGETONE
a suspension
cf
toluene
sen t a m e ttiylace t o n e •
temperature
f or
had
e
assumed
cooled
sulfate
was
mixture,
hour.
very
oOO
The
entire
500
cc. of w a t e r
toluene
cc
mixture
layer
rod
finally
the
tol u e r e
residue
over
'.vac
256
g.,
mixture
was
heated
During
thick,
was
added,
f rac f,ion?. ted
3 :O 5
8:45
9 :30
lO :86
11 :45
12 :50
1 :45
3: 2 O
4 : 20
6:08
C NT
1
2
3
4
5
6
7
a
9
10
n 20D
2 m o l e 3 , of
at
moles,
cool
added
for
300
cc
during
12 h o u r s .
tin? 1 a y e r s
3.3
b.l
5.9
1.4078
8.2
1.407 2
6.1
6.3
5.0
1.407 2
6 .4
1.407 6
7.5
1.40 7 8 10.4
121
127
130
134
134
134
135
135
1 85
1 3 5.5
additional
cf
ammonium
two h o u r s •
Ar. a d d i t i o n a l
sodium
The
carbonate,
r o ta 3 s 1 1-.in c a r b o n a t e
C o l u m n HP •
5
B.P.
The
s ex-ara ted •
HC1 , water,
th^OM-'h
mass h a d
of m e t h y l
an
ch n: u gri iJo ;u m r: I:
WT.
r«=l’l u x i n g
t wo h o u r s .
for
30damide
W h e n the
2.2
dryi: g o v e r
strip p e d o f f
of
t i m e the m i x t u r e
refluxed
was
and
wit:
A f ter
of
again
stir-red
washed
<vat r .
wa s
was
of w a t e r
was
was
v/as
TABLE
TIME
this
consistency.
a period
the m i x t u r e
in
2 moles,
temr.- er a t u r e , 2 7 5 g . ,
still
hydroxide
The
78 g.,
TOLUENE.
added
36 hours.
added
when
was
jelly-like
to r o o m
of
IN
JACKET
140
140
140
140
140
140
140
140
140
141
Th e
1 4o
TABLE
TIME
6 j55
7: 4 5
3; 25
9: 1 5
l O :O O
lO: 35
11: 3 5
11: 50
12: 5 5
1: 3 5
2; 3 5
3 ;lO
3: 30
3: 50
4: lO
4: 30
6: lO
6: 3 5
6: 50
7; 20
7: 55
8: 20
9: 15
lO: 4 5
lO :50
11 : 20
1' :o o
1 :20
*•
m lO
2: 55
3: 30
4: 15
COT
n ^ D
30
to 4 2
i1"ic p e t ic;0 . yi e l d ,
Cut3
*h e
B.P.
JACKET
6 .9
136
11
1.4073
136
7.9
12
1.4073
7.7
136
13
1.4074
136
14
1.4073
8.5
7 .9
15
136.5
1.4073
1
37
6
.8
1
.
4
0
7
3
16
17
1.4078 10.9
137.5
138
18
1.4081
3 .1
39
138
1.4085
3.5
4.8
20
1.4088
138.5
S
.7
1
40
1.4095
SI
148
22
1.4211
5 o1
23
144
1.4 126
2. 9
1.4138
2.7
145.5
24
147
1.4149
2.8
25
149
26
1.4162
3.0
27
149
1.4175
3.3
28
151
1.4183
3.2
1.4189
29
1.8
152
1.4197
152
30
3.3
31
1.4199
4.0
153
*_
7>O
«
....
1.4199
8.7
153
33
1.4200
7.3
153
1.419^ 19.2
34
153
Di s c o n t I r m e d c v e m iph t .
7*• *
t.
3d
1 .419o
155
O
36
1.4197
5.6
153
37
1.4197
7.0
153
38
1.4196
6.6
153
39
7.7
153
1.4196
40
7.9
153
1.4195
41
7 .3
1.4195
153
42
1.4195
153
8.1
Pr*ac tIona.ted to d r y n e s a .
13
p
WT .
5
4
Inclusive,
140
140
140
140
140
140
142.5
144
146
147
149
155
154
154
155
155
158
157
156
156
156
156
155
1 58
3 59
159
159
159
160
160
160
175
84.4
p.,
3<
w o p p h e x a n o t n y 1 a.o e t n a •? 0
to 18
ir. c 1 u m i v e ,
3 ta:*tin >r m a t e r i a l
106
<va a p en t c.rre
gr., 0 . 8
'^ a c e f o
11 7 1
40; 4
144
FrcEPAhATION
H E X A lV,ETIiYLAC R T O N i£ IN
OF
liexamethylacetone
v
c.e t o n e
by
deci’l i n
yields
f.he a ar e
pr^nired. f r o m
93
te ch.nl q u o
‘.nrployed
Instead
of
toluene
was
obtained
by
the
diffej-ent
ap;. '■'eel a b l y , b u t
above
w
3 ri tne
the
two
decalir
o r e r « r dloji
cf
DECALIN .
used
lias
p e n tame t h y 1 —
a b o v e , e x cop t th. a t
as
the
solvent.
methods
did
a;wan t a ^ a
the
Tho
net
differ
mentioned
p o n ta.n*' t h y l a c e t o n e
in
this
s r -1 v--.r t.•
iih'DN C1‘1C N Or
(a)
A t temp tod
To
and
H.
71,
.
f .> O.t
•r.ix turn
T!‘s h r>o
9
was
deduction
a solution
added
cut
is o r m o p y l
1 0 y.
recovered
the
last
f r o ir.
traces
100
cc
‘
A1 uriinuir. I s o o r o i . y l a t e :
of
'Id 'inn I
No
.
dry
is on n o r y l
ketone
In
o p a 1 •.unir:* mi ij •.
"n/rn Ln*>d m b
n 1 con o ] •
was
ith
dl- t-butyl
u-ude"
e r a t •.r e
1
cf
m o l e s , of
laa-c was
t
n^.vA... rT hi Yna.Ce I’e h h
»•?* ^ t.1 .1; t c
? c. t1 Cb
b e 3 nr* ob 1 4 n e d
a 500
by
lor
k n 3 a on ,
by
The
It h o u t o
th ~ boil I n r
'ii x b
cc
or y I a te •
sr.d r a f l v ’x e d
e l , 5°,
t lconcl
noiiL
rbr* I'''tone
f nj. c t i r n a t i or ,
ar.;d if l e d
dis ti llatiorx
.vith d'-r.hlin,
( b ) H e d u c t i or. ’fit!
Into
stirrer
and
cl'
ci r I .-.r
ed
a
y
oO
cc
ecl
a . ♦
• ••
n:
of
t
1
o?i ••• lit'-r
refjuc
e.
s c,l d i d
It:
a
m
f *• y , , n , 4 f
nonzero,
7
Ii-necked
condenser
. t '• I n I ,jO
of
On!
S o d l nr-V.oia t 3 e r r e n e
f IJo
fO ’
w as
n laced
of
v.-a t •»;* o
m e ' -S ,
ftirrib - of
lav ar
f1aak
war,
of
the
5
fitted
wife
a sc I n tier,
do
b
Is
war
1 1 — _t - b e t y I
of
35
y ,
add­
k«-» t o n e
m i x t - u r w a s ad j u.s t-
a r I t ••
3
•
To
t n :« m i xtiu r e
145
a’u s
added,
ove r a p e ’"’i o d
Cf
?o5
moles,
or
iii to
cubes.
Th^
cut
a odium
pot ase i urn c a r b o n s H
was
t.I o n a f i on
, and
at r i p p e d
9:45
11:45
1: 2 5
1 : 40
2: 15
2 :4 5
4:15
6 :O O
CAT
v h
1
2
3
4
5
6
7
r)
>
9
1o
7.4
1.6
3.3
2 .1
6.2
10 . 5
3.0
9.4
11.4
4 .6
C
u ta 4
Ciil'O'liOl , Te 1 t i
to
rHphthalenesulfonic
In
a
200
cc
53
; 1v
A
1’1 a 3 k ,
5 3 g.
on e - e i g h t h
-vc H r ,
inch
layer
dried
ever
fractionation.
The
X;
fur tner
frac-
II:
; e
30-132
105
303
103
112
113.5
113.5
.Ja C K K T
140
109
111
119
131
132
132
732
150
m/n
mm
1 50
154
154
mm
rrun
154
1 14
ir,cli. 3 I re
1 o4
we ro
Id
butyl-
di
Dl-t - h U T Y l C A P b H O L .
OP
Dehydration
g. , 0 . 2 6
set
.Vith l - C h l c r u - 4 -
acid :
moles,
up
flaaK
of
r J i - t -b u ty l
was
edded
(pr*', r,r e d
’■rOos
lol o m u
to tir.’.or. .
•f.••r* e ,\t*-bed
t;;or
of
trio benzene,
Column
1 o4 3 8 5
1.4279
1.4300
3 o 1 id
s ol id
a o 3 id
ao lid
3 nl id
ao 1 1 d
a o.l 1 d
A .u . 3-nBck^d
was
jf
for
d.e.
1O
total
forrr nf
n ^ D
4 - n c p h the ! e n c
j ,'n11 f o n 1 c a c i d
H e
a
1O *
: o i r;t , 4 9- Vr 1
A tttim;- t e d
To
up
thr j u ? h
Column
.
Dii’H Y D p A T I O N
( u)
the
po rtlci.s
sot
oft
th r our, 5
.v&?
co
tablf
TIhh
days,
la "7e r -! Vu ;•e u u -a.r e t e d , a n d
w a u w i- I.a a v;i tJi tw c 50
benzene
four
by
P.
A.
IT,
-H
h
ir to
the os n.ne t ex* me as u r e d
1.3
the
the
carbinol
g.
of
l-chlcoo-
Kurnatr).
utir.,^
liquid
1. . the
tee.:, ‘o a t n e e
of
tae
146
air
bath,
a dry
and
the
ic.e-e.catone
TIM 5
T
IN
8:10
9:00
10:45
11:00
12:45
outlet
of
trap.
The
layers
to
the
tied b e e n
had
been
was
extracted
dried.
Most
mixture
In
sv;
of
ether,
3 tripped
fi'ac tloniitio;.
thr<
r.-f
The
off
cooling.
and
b&3lc
through
200
II.
No
nothing
mixture
tine e t h e r
to a
Column
of w a t e r
flask,
and
transferred
cc
after
trap.
ether
g. , w a s
flask
Ice
cc
the
in 30
reaction
200
obtained:
REMARKS
the
with
to
Started heat
Some moisture,
No reflux. Jacket
t e m p , at 70 °
Discontinued.
NaOH
the
were
T
in
dry
sat
were
3 g • of
the
r e s 1 d u e , 49
for
of
In
of
BATH
connected
data
144,5
159
.141
139
noticed
caught
The
data
AIR
116
122
122
185
added
co1u;nn w a s
following
LIQ.UID
A solution
was
the
solution
Column
cc
flask,
The
II.
and
following
obtained:
Tadl.E 7
TIM
ue
a
’
.VI.
CUT
n ^ D
5: O O
12:55
1 :30
3:10
3:45
4:10
1
n
3
4
5
6
6:0 0
6 :40
7:15
8:0 0
9 :O O
7
8
9
lO
11
lO. f
0.1
0.3
1.7
1.8
1.0
Chan
3 .2
4.3
10.0
5.0
6.0
Cuts
8
to
11
Cuts
4
to
C
a
mixture
of
B.t .
1,4221
1.4252
1.4302
id to 1 5 4
solid
were
33.5
60
74
130
80
140
126
152
142
155
149
156
mm.
Decomposing
89
109
108.5
109
108.5
109
108.5
1 '9.5
109
H O
at
atmospl
3 -lid d i - jt-butyl cc rbirr. 1.
inclusive,
norienes •
JACKET
4.5
were assumed
to
147
A second, r u n
and
conditions,
was
held
kept
No
at
at
1 3 0 — 140°,
decomposition
procedure
was
placed
in
Coluiru: II*
of
regulator,
was
ch
.vac
h e 1d
5
niece
It
after
of
t,e
the
a
3:00 on
bath
of
same
The
technique
in
the
temperature
olefin was
liquid
was
obtained*
remaining
carblnol
3eta-Nar h t h a l e n e s u l f o n i c
runs
The
t
the
column
these
out
severs]
hours
T ’it
cui'Mnol
In
to
flask,
was
in
tc
-1
turr.
each
be
ard
"■ump *
inn.T h e
w: i l e
was
to
.lid'0 *
As
for
case
place
Uler.
more
at
the
ur> u n d e r
was
dry
added*
i c e — a c e ton?
dehydration
a round
of
77d r
off
than
below
it w a s
all
d eh
case
a ores sure
The
trie fe :r rn a te pe
reflux
taxe
to
Acid*
de h v d r a ted
set
two
Path
air-
m i x t.n r e w a s
each
± :i
to
connected
a wntvr
150
to
attached
t e m p e r a tur o d r or - oh
ct<n i;inol *
seemed
made*
do t a — na p h t h a l e n e s ul f on i c a c i d
a 11 o w e d
head
were
two-necked
o 1e f I n - w t t c r
dratlou
' <Cw >
g,
r ♦ a in»-d a t ob'-nt
ret
the
f o i l ows
a t-1 3 0 - 1 3 o°,
-r.pt
whs
with
arid tor n e e
m i ed
If m
as
series ,
In
7*0
separate
The
outlet
traps
the
noticed.
Dehydi'ation
Three
‘The
was
the
the t e m p e r a t u r e
while
Only
using
unchanged*
(bj
was
made
e x c e p t that
1 4 0 — 150°.
recovered
was
*
trie p o t
the
liquid
1on
to "'I:
at
the
several
head*
minutes
tire b e l l i n g
not
1ced
once,
a nd
rmint
th a t d e n y —
only
after
iiea t i n g *
fed
1o w l
1:
To
r::• cur -•* w e
.ru*^ *•» v o I
- the
r h m
i? I
Hur.
43
g.
t o - n a p h f h n 1 ■n e s u l f on ic
cf
eerbincl
uc id •
The
was
audeh
1 g * of
f‘o 1 ’ ow I n w o r ..'ducts
148
wore
collected
substance
Ar.othur
containing
gram
the
agent
/rcite^i c l
obtained
water,
continued
d e h y d r a tior.
hydrating
of
six hours:
wore:
ice
trap , 13.0
and
L.o g .
took
was
had
g ;
another*
place •
added.
boon
low
of
for
a
dehydrated*
4.1 g *
•
To
f o l l o w lug m a t e r i a l s
—o
“
?
t »•*»!-. 1
\s .
.
.
<j o
- £
1
-i. #
o,
g', «
.' n 1
Run
of
w eh«r-;
40 g.
Phe
p
w .re
Y
il O
.
3.
T ■j 34
^
g.
; -. : •V 1
-r : 2 1 • 8
g . of
define
j
All
'■n •
!ned
■•r d
of
of two
de­
hours
all
products
in
of
the
dry
olefin;
~
vvaa a d d e d
9 hourn
at e r i a l
J
c ’ -L •
^ .• ,
of
»•1 1
•. e
t
c* --
2*5
g*
heating
in
-.o
~
f3
1rv
and
id •e nd ove
e
.a ] wr n
a** id .
tf--
r *'
<'
in
olefin;
lr. e a c h
^ e
the
g*
After
'v- •*-■>... Y1
phwd
wa t
off
grer
the
of
the
dry
i,-it'M •i• an *
- J.
—
i f
til ■ ’
w .
-i— *
n.t.her i a l , cclfe^ti.I
te
24.4
art-led
Ye ry
coll e c t e d
o:.-tah.ed;
£ j•
i ng
33 n d
was
lioui‘3 •
total
of carbiriol
~f He t a - n a n h t n v l e n e s u l f o n i c
,
The
ir.a c - r i a.l
i.;-e t a - n n.:h tlla 1 e ns 3 u 1 f1c n i c a c i d .
A. _
net* l e d
a
rebiav;e.
Hon
t «
three
of
58-105°*
acid
Another
In
lolling
2 . 3 g*
boilingpoint,
«'.f H e t a -> sa n d t h ' d e ’- r t s u l f o i d c
•Ki :1 h e a t i n g
little
over* a p e r i o d
dur •n.:- : o a r
v- no
ice
3.4
a /: led- 2 .2. g*
.H C o i n e d :
trs, , 2 . 6
&•
1 O ’.v n o i l —
g ; 3*1
g*
of
"c-lsfin"
i3
of r o 3 Id u a •
c:a en
eoci
in urs
th - w o r d
n i'/e
ox’ w c t e r
token
(n'T\iniho
1■ ■■v e
iri *’ i -'■ir
**r'-1
iv.ylCy,.
s "
f r».*?•
T'e
r
tf n ' t h r e •
Hilt!:,:
o h .
r .*? w e r e
t ,
149
•2
C *
*
was
fractionated
t h r*o u £ vi
TABLE
t
I ;v.
'V-i .
CUT
1 j2 b
2: 50
3: 30
3 :4 0
3: 50
4 :0 5
4 :20
9 : 30
9 : bb
lO :30
1 1:00
11 : 50
7.7
2.6
3.1
5.0
4.4
4 . f=
4.6
4 .4
7.1
7*0
6.2
5.7
R-Vlid V a ,
To
tiit* re:.; H u e
Artec
acid,
twc n o u n s
.vc ad
was
£ . o7
7" ;** 3 La ■-i 1 ] ij ‘ u ‘.v*.a
Coli-.ct,
Ti:
1 m -I
v :30
9 :G O
9 : 25
5 i:i.
c
2-15
r1 Col v, ’r; •V-:;,
L7:0- '
12: 40
can rind
733
out
5r
p s
th-
1
ra.2
.a2
12 6
126
T A B L E 8,
sbova*
at
tr* no
‘•'T
183
133
143
56
g •, w ero
J r*:
2
•a •
n 20D
1
•
t.;
O .5
1 .5
1 . 4 0 42
1 . 4 1 50
:o.n
•P .
8 r7— .O 9
1
'*
-Xr
6->?
REFLEX.
3h/l
C
o r ;
1
the
'lr” r ice
!’*.•«io t i ona tea
.iAC
n/;
<7*■
T
Ion
'Ir* i •5-1 a n d
TABLE
T 1 RE
t> t
£ . ."e.s f a o n 8
1.4725
1.4840
1.4758
'■o'*' K •
inc.,
ct
129
124
124
126
127
177
177
127
130
130
133
13 b
rv -°D
1.6
1 .4
7.0
R-as id ve 9
15
14
15
0 u ts
non
*>
tx.o
i\
-iy t' .vial v.v-tr a o 1 La a t a d
1*0
tx*> f •
AC
v 1 1 ad
a;vi d e v:y l r
10*6
•i
36-1
120
124
176
126
126
126
126
126
126
127
17 4
1.3960
1.4199
.1. 4 2 1 8
1.4 740
1.424 4
i . 474 7
1 .4 7 4 8
1.4232
1.4246
1.4248
1.4850
1.4 7 5 6
1 6 . 5 £.
oo i umr , a n d
oi‘ the
B.F
r.2° D
1
2
3
4
5
«
7
8
o
10
11
12
]a n o s u l f o n i c
8
1
rr.ie d
g
r5
3}
ft
«
ft
JO
o
t-
k
c*
H
X
X
m
10
ft
continued
.1
C.J
•r4.c;
.
to
•
ft
ft
■P
*7 t
r
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Z)
n
c
d
0
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t» .
b.
'I
45
•0
•rH
0
O
rs
OHHC.
ft Cj COo
>
cj ... c .
t^
• • « • • • • • • • • • • • • • • « •
'
H H H H H H r l H H i —»
—
I^
£ -0 o. cr
•0 •
•
0>
* •
HI f’<“■
T’
o ft ft O X H at G X X
• • • • • %• 0 • #
0■
—
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H r**' rj r~i H (
<
r-i
i
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ip d~ co a. c
r—J
S
3
'.0 o ft ft o
ft D
Cl
C
O
rH r - i H r~ , C
v
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jO
JC
>
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••O Cj f t
C
Of t CJ G
•I II II |« ••
H H H H CJ CJ ft
r—
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c
i.4 ft to to CJ ft 02 Nf*r-1
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£,
ft
,~
C-
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ft
Q
C
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*-1
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r
^1
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to
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ft
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>
iJ
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c
0)
£
—<
-p
r**
r"“
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4-j
C.-4
a
cn
'X
r-j
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£
sj
c
ft
CO
CO
ft
s
0
V
H
ft
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• • • «-4
ft c H ce
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—
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V.
m
te '
V,
• * • *
H H H H ft H ft
i 1
£H
^I
O
'W
I‘
X/
-a
E-i
cr
•M
j. .0 o. c; cj o» cj to p „j <m cj cc cj cj cc c. ci oj cj cj o. Zi
• • • • • • • •
.y
».
y.
>
k
r “1
rHrHtHrHrHrHrJrH C H H H r ! H H r
P
iM
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•
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DHr
0
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•
C C'j Ojc to ftftft ft ftoo ftc c c c o c c
h Oj 0 tO cO to CO :jcO cO 'T v ^
<* ^ ^ ^ s) ft ft
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p
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c. ft h
at
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t-*
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p
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ft ij
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cn
9
TAftLp
X
ft
to
ft
to
\
X
H H H H H H H H
H
h
ft
r-i
!> c co o tr. c?. o (jj : a > 0) c C C C C O C O H ' 1 ’j H ij h c
cc c. qj co w Oj c: o: d cc cj to :0 to to to to to to SO to to to fi to. cO
H
0
*»
4.
r~:
j '
ft
D
H
H
ft
fi)
P
r-i
>4
f
C
re!
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d
>
*
M
ta
o
o
■H
t4
t
rf<
|
Cti
I
i
T)
r-i
i-
VJ.
p
L,
C
r:
>**
4*;■
Cc
X
ft
ft
4-1
t
c
«H
v
ft
ft
rH
ft
3}
-ft
0
c
at
I
n
C
«H
rc
t.
x.
a
±1^1
material
wan
to be
0*028
mole3
distillation
eiyht
of
prams
the
of
l o w b o i l I n r; '.nr t e r l a l
t el me th yl e t h y l e n c •
It w a s
h y Ir ol vr. 1 r-<p to r ^ t h y l
The
dibromide
made
25
cc
lever
The
was
cf w a t e r ,
gradually
layers
th is
dry
layer
was
shewn
k n + o ne
that,
t r l m e ti m l •" thy 1 **-*e
C2 .tr
wa y u s i u y
72
sep H T ’\ted.
To
a saturated
forme d
•Vos
:ii.i.1
the
an
upper
th'" nr n e r
formed,
point
with
the
in
f i i p t l l h ’d
n
layer
cf
to
added
lower
formed.
dried.
Part
2,4.— d i n i t r o -
me 1tiny
point,
derivative
If
hoi H o y
her.
of
tr.e^o —
material
was
.
r — 11
of
9
TAbf.o 9,
ol of ir'’ f " ’
t~*n cc
of
solution
•'
we-*
of
rid ti i.» oil
dimetol
fo^maldehydo •
TOO v*.c d i d I T inp
in to a s o l o tier
0.0
':
r er •fane a a th e
the w a t e r
of
c/.ot1I ? ed
and
ti•e us u a l
a ol vent, o
water
layers
added
in w a t i*r’*
A nrn c i p i t f t t e
pel n t , 189— 190°.
'"Then all
f 1ask,
tha
lOO
were
l.yprer w e r e
f c. ••\'--J , th-' mi T f m e wa"1 f** 1 h e r,'-*d.
placed
The
a known
o r i "loo 1 1 nv
to
ketone*
was
layer
to o. s o l u t i o n
a 1 nos t i m.me d i a t o 1 y , i*r I t i n p
d i c ’tol
This
'>a v<-» n 7> d e ->r e s s i o n *
o ;;on 1 d e w a s deeo;m os e<l
The
of
c c
er.d
added
A rijced me 1 t i n y
be'r.
end
the
converting
laopropyl
us ua 1 w a y .
A derivative
1 3 o o r or y 1
by
fro-o
ag.iuned
b.en t -ti to r^fl uxinr;.
wert-* s e p a r a t e d ,
1 16— 118°•
fore
m d
the
disappeared,
phenylhydrazine•
r.eti-yi
in
was
i d e n ti.fi ed
dlbror .1 ;ie a n d
of
iaobutyler.3
materia] recovered
the
to
oT
recovered*
The
be
iacbut.ylene,
'11.13
rr-'Cir-.itute
To e ft 1 tra t** w a s
a n<'i -.bout
cc
five
co
r , 4 — i 1 r i t r m h e :y'1h y d r H ?.ine o
152
The
outlet
surface
of
arm
of
the
phenylhydrazinq
could
be
other
low b o i l i n g
water
layer*
in
tills
the
isolated
To
from
was
a
small
ozonolysis
was
A
to
l O d —1 1 0 0
d e riv a tiv e
o f
known
1 . 1 1 —1 1 . 2 ,
th e re fo re ,
! n
th e
ta ke n
to
recov
added
A
A ll
v/ h j
gave
as
r» p r y
and
above,
including
m e ltin g
9,
above*
in to
Tne
rredominant
material
formed
2,4—dinltro—
103-107°,
th e
m e ltin g
p o in t
w ith
p o in t
a
m a ltin g
o le f in
o z o n iz e d
same
b e s id e s
th is
fo u r
the
o z o n iz e d ,
a , 4 - t e t r a m e t h y l —1 - p e n t e n e •
w ere
In
in
layer
M.p*
o r ig in a l
and
tre a te d
p re c a u tio n s
w ere
f o rm .u ld tth y d e
cane ,
fra c tio n s
TAhLE
tho
9,
were
arul
a ls o ,
the
a i.l
^ e rid u e *
—
concluded
product
of
the
per. t e n e , p o s s i b l v
to g i v e
the
ozonized
fractionation*
3 , 4, 4 — t r i m o t h y l n u n tanorie - 2 w o r e
tetrame thyl— 1
of
a lc o h o l,
Trie
r voduc t s
21-27,
It mus t be
the
r. r e s e n t
oil
no
that
a
o il
3 , 4 , 4 - f r - 3 me t i >y 1 *. e r• t a n o n e - 9 •
Cuts
as
formed,
2 ,3 ,
TABLE
f r a c t i oria t e d
o n ly
was
ti>e
the
No p r e c i p i t a t e
indicating
solution
m ix e d
3 , A , 4 — tr i m e t h y 1r,e n t a n nr-pa—2 *
la ye r*
a
of
d ilu te
m o s tly
14-1B ,
marine r
ke tone
109-112*
c o n ta in e d
same
or
rielow
extended
3 , 4 , 4 — t r i r r i e t b y l n e r >t a n o n e - 2 ,
gave
C uts
solution,
portion
fro m
ra is e d
flask
solution*
preciuitate
r e c r y s ta lliz a tio n
p o in t
ti ls
aldehyde
phenylh.ydrazine •
On
distilling
varying
from
t^apted
Only formaldehyde
recovered*
these
dehydration
ozonolyaia
is
contaminate!
Indices
and
obtained
2
th.at
,3,4,4—
b y
in
some
other
the
free—
io O
tlor.p t l o r
above©
The
dehydrated
n r o d icts
of u n r e a c t o d
were
residuo3
were
di-Jt-butyl
recovered.
from
all
the
combined.
carbinol,
fractionations
From
and
these,
1 . 6 g.
of
£.9
tar
of
g#
154
PREPARATION
(a)
o f
pro; a r a t i o n
.
m e t h y l
n k o h e x y l
k e t o n e
of
Grignaed
r e a g e n t of I - c h l o r o «
the
2 , 2 - d ime t h y l b u t ane :
The
apparatus
consisted
of
the
usual
60
g. , 2 . 5
Irlgnard
ae tuu•
To
m a g n e s iu/n
about
50
the
and
cc
flask
400
of
a
cc
of
In
was
few
'Vlien
with
a
added
dry
solution
2, 2 - d 1 m e t h y l b u t a n e
started
were
ether.
of
300
700
cc
of
cc
of
a c t i v e ethyl
the
reaction
had
started,
chloride
in e t - h e r
was
added
After
was
all
the
allowed
under
base
an
a
400
cc
Gr i g n a r d
ho
the
o
acetyl
over'
several
chloride
^figrar
d
was
total
The
added
reverse
was
of
of
the
It
ishree
mixture
was
filtered
Aft
r atrip; 1ng
r .jd re;! ll-io was
set
un
off
then
with
acid
reagent
moles
of
of
f r a c tior.f t I on
84%.
chloride
neohexyl
the
r
and
Chloride:
acetyl
of
In f i v e
th s e t h
hours.
reaction
t to A c e t y l
addition
norr;r,l e ted
q u a r t r h :crs „
for
1.1
i’p a c t l o n
solution
mcl e.s , of 'rte d i s t i l l e d
wps
1-chloro-
reagent.
Titration
rieuga;';
of
GrJguard
a period
OrIrnnrd
added
moles,
e t h or.
hours.
neoha xy1
The
2 05
beer, a d d e d ,
of
ether
Reagent o
the
nltrocon.
*'
g.,
dry
of
90 g • , 1 . 2
of d r y
had
for
yield
A d d i t io n
To
in
stir
e t-nosphere
shower
(b)
cnlorido
to
'r'o t h i s
m o l e s , of
drignard
and
three
, thf
through
dark
Coluan
II*
15o
TABLE
TIME
CUT
4 :20
6 :2 5
10:10
l O :25
10:40
1 1 :0O
12:00
2: lO
2:50
5: 20
3:40
4:05
5: 55
6:15
6:30
6:40
7:00
7: 25
T.VT.
lO
B.P.
n 2oD
1.3949
40-114
1.4820
84
1.4180
88
1.4163
89
1.4149
89
1.4159
89
1.4159
89
1.4158
89
89
1.4156
89
1.4151
1.4146
38
1.4139
93
1.4178
108
1.4230
116.5
1.4230
116
1.4871
125
1.4330
125
1.4335
130
24.0 £ .
1
2
3
4
5
6
7
8
9
lO
111
12
13
14
15
16
17
18
5.1
2.1
2. 0
2.5
3.0
3.4
2.4
3.3
8.6
5.8
4.5
1.5
3.4
4.2
3.4
3.7
2.6
2.0
R :i3 1 8 . e,
The
i" Is ti 11a tion w a s
d«- 2 i r e >■ K <- tOO * Vi; ii 3 e r■
Ci.ts
on a
ic c
5-10
> V 1*y n
*
Inc.,
2: 2 5
3:00
3 i 40
4 :4 5
2 : 15
3:33
4: 20
4 : 45
5:15
3: 45
CU T
not
PRESS.
135
36
90
90
91
92
S3
93
93
95
104
120
130
133
137
145
175
180
734 m m
100 mm
100
IOO
100
IOO
100
ea.r*^ I e d r n s t tills p 0 3
U k<l:i o f 6 .
Tnr IT-. lO,
v/e r*n s e t
up
for
fruc
12 o sail *i c.c I’in n S
table
TIME
JACKET
.VT.
n'-'^D
ii
B.F-
1.9
1
1 .4105
124-150
2
1 50
1.4155
1 .2
v>
1.4157
1 .5
1 50 . 5
4.2
4
1.A15'7
150 . 5
A l l o w e d it- I'tKiid ov~2 ;*• I pi \I .
C,
1.2
1.4158
151
2.5
1 o4 1 5 7
6
151
1.4157
7
2.5
151
8
3.6 .1.4 1 5 7
151
9
4.0
1.4155
151
1
.
4
1
6
0
10
* oi
80
R e s i d u e , 1.
JACKET
1 60
173
173
171
173
173
171
171
1^1
191
714.8
ran
156
A
made
a
of
I thou t
a portion
C u t 9,
TA3LE
sor'lcarbazone wai
Molting
Cuts
bcilirr
of
r*--or*vs t a 1 11 z a t 1 on w as
A
above•
2 , 4 - d i n l t r o p h f t n y l h y d r & / Jo n e
ncir.t,
4,6,7,
poi r.t w a s
3 o 11 1 rio p o i n t ,
derivative
11,
Tb.o m e l t i n g
was
point
7 5 — 7 6 •5 ° .
r.ado
of
a portion
of
Cut
9
173-174°.
and d
taker,
uh
c crib i n o d ,
1n g
15fi*H-l£3.4°/739
an
Anschut?
>mn.
and
a Cottrell
thermometer*
16"
PRKF A R A T I C H
D ry
OP
PI M E T H Y L IS O P R O P Y L C A R J 3 I N Y L
HC1
was
j assed
t h r c u ^ 1!
cf
PO
din:s tryl i a o o r o p y l c a r b i n o l , n ' D,
of
one
one
and
was
separated
the
oil
had
fo t t c d .
water,
from
h ' y :r.
at - 5 ° ,
then
potassium
the
Aft- r
During
mixture,
two
the
an:l
srd
one
with
260
850
cc
cc
carbonate
before
The
In
again
hours
the
reaction
through
more
had
was
m o le s ,
a period
water
boon
£50
cc
solution.,
cl; 1c r i d e
fracticnating
1 .5
passed,
no
v/ashed ’»i t h
10 %< c e r b o n a ts
of w a te c •
for
formed
HC1
half
£• *
the m i x t u r e
reaction
of
153
1.4170,
The w a t e r
lu.ectl on p.r c d u c t w a s
The
txge In w l th
hours.
half
CHLORIDE.
of
arid t h e n
dried
through
lcept
over
Column
TABI.E IP
TIi.il
9: 50
10:00
10:10
lO : 25
10:35
1C : 40
lO : 56
1 : IP
1:50
r : 10
2: 30
2: 50
3:05
3 : 20
3: 50
r.f":0D
1
At
3
A
5
6
7
n
9
lO
11
12
13
14
1 . 4 IOC'
1 .4161
1 .'Udf
1 .4106
1.4190
1.4109
1.4101
1.4182
1.4196
1.4195
1.4196
1.4197
1.4197
1 .4 127
1.4197
to
-L.iy
t.o
7:45
23
to
1.4199
9-83
J A C K iJT
5 .r .
COT
55-65
67
67.6
68
68
161.0
t n e o r e tl ou 1 w or.? dl :r; thy 1 1 s
189
66
66
67
68
68 • 5
^9 . 5
68
68
69
68
63
68
68
68
63
68
63
63
6R
68
68
68
68
68
68
68
68
63
in c . ,
PRES. i .
£.,
1.09
mm
1 hi m m
189
mm
189
itiin
3 £9
mm
189
mm
moles,
c.gy 1 c r b 1 ug l
73.4 of
oh 1 or i d--> .
II.
1 oo
PHLPAHnTIOI!
OF THF G R I 3 N A H D R E A G E N T
OF
P I L E T R Y L IS O? R OP Y L C A R P I i'iYL C H L O R I D E 0
Tr
F°-
1 • -I molof! , of ^ r- ^r.es I urn in
three— necked
f l a s k was
of d r y
rind 1 3 3 . 0 g.,
ether
carbinyl
ch l oc i ae,
material
wa s
action
diluted
mixture
then
w as
'1F0
t i 1 1 *o,
bas 1 a
of
CO
or
To
44
a period
f.>
dilute
HC1 •
fractionated
ether
and
th
the
re­
one
an
additional
half
four
It h a d
slowly
to
the
boors.
hours,
turned
The
e n d was
quite
thick.
was
t'-- c r.i .1 c t *"■ cam i ] ‘< for* ti t ra t i ny .
On
work,
f h Y L 1 3
was
h u t
(G h i m l , r nOi> y i e l d
Or* H OF
fu T u b
Y L C AH d I u Y L
two
T he
en d
one
quarter
e t t e r was
through
Coiurnn
II.
assumed.
REAGENT
imuro
above
off,
was
added
e solution
chloride
d e c o * p C 3 3<i w i t h
stripped
the
CHLORIDE.
cf r e d l s til led a c e t y l
mixtur>-» was
was
GKI3NAHD
tfje Irirr.crd r o a g e n t n r e p a r ^ d
The
to
this
c M or i rie s o l u t i o n W£3
four
ntll'VI. C.di.CRIDL
of
wita
added
and added
and
cc
of d i m e t h y l i s o n r o p y l *
reaction
of
over;iight.
e1; O r - r
O. O'} m o l e s ,
c f ^ r,y oth'iv*0
tube
of 7 5
t;.n'* O' 1 x L u i • --
Cf
Li 1 L
f
for
to s t a n d
’:"f vious
y
over
a period
filck
.iDl)]Th;k
test
cf d r y
stirred
allowed
Ane
3
over
cc
of a 'solution
Criguard
,nh a i’<■*ir.it3.;id e i* of
.vi or LoO
.uacut).:. i u n
in a
lO cc
1.09 moles,
A smell
a tasted
vessel *
added
e <,-re l i t e r
and
in. l o O
ice
the
of
end
residue
cc
loO
TABLE
15
TIME
CUT
',VT.
n 20D
B.P.
JACKET
PRKS3.
9:50
1
4.7
1.3910
1 .4040
20-22
26
60
88
HO
40
50
150 mm
lO :55
f"
11 :10
3
4
5
11: LO
1 1 :45
ftone
'.vf3 r e c o v e r e d
••
1.0
1.4100
2.1
2 .0
1
of
In
the
the
1.4102
.4139
desired
ebove
103
150 mm
150 mm
1 10
13 2
120
138 »rim
rm.
•3,3, 4 — t*■ime tiiyl — 2— n entancni
f r n c t i o n <itlon.
ATTEMPTED
OXIDATION
OF 1 . 1 - D I N £O P E N T Y L E T H A N E .
The
e p n e r * fc” 3
c one i 3 I . 1 o C
‘' o9
*'1 1.1 o<j wit)
end
level
In
the
n
the
r>V
11
r*r/i.1!1‘ r.::>t h * ,
4 0 ,4
*• d
O t. *
1 rt
1
■.
*' r. .■ f.
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'
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b
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7- j ::r:
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tc
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s 11 p h t
c
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rH *
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f■
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9
1*
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LI.
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9 :30
lO •
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lo ~o
1 1 :30
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i.
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7
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>
•'•
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1 .4 1 9 1
1 * 4 1 91
1 .4 1 9 1
m 4 ^9 1
1 .4191
1 .419 1
11.• 4 1 9 1
1 *4 1 0 1
1 . 1; 1
»1 '> '
m .
11 9
1 :O
1'0
190
1 :0
1 :0
lto
1 90
TOO
1: 0
1 ; ./
1 . 4- 1
1 .O
1
j
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113
110
1 to
1
191
1 91
i: 3
199
1:9
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p
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id
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: • • :*■ .
f;•*• >-ar.ar » C f 3 0o
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'let. 1 'i;;
ae --a**a ted*
‘he a c * d 1 f 1 • ;d 1 a 7 ••r w «-3c x t ” '1d; ted
To
r -1
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ti or. oh
hot.
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of v7..*-f,
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was.f i l t e r e d
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ixt' re w(
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3
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o i■.*I .:♦ I c .! er.it.il till
•s f r a y e d •
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uy-~
r was
extracted
!-•a
e t'.or ,
o 1u m n
tft'-r
II.
,l c
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t
hO
o
a
3' i h
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an
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;
■■
.
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-•
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■
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'
with
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was
rc
The
3 l " l r -T
xt-n
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',
d •/. h
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t hi
f'n r.
1 ♦h
.,.1
o \ i 'h h ' < i•,
No
of
off
e th>; r*»
rlrotal:
ii
c. f
a
t"
-* >
of
w r h e *• ,
hot.
1 ; •• •
• • v/a -
SOo
s o 1 1it 3 o n
s er -r rest * .i f rc-n
• •:t
,
acidified
T p o r - r '* •*•
. * .:i x'h ‘" u w r r. f i ] t e r o d
:JC 1 »
was
f'11 tra te w as
<-c p o r t i o n s
oft-'*
/OS
hydroxide
■i .
th r o ’:- ri
ve r e d .
r - y n i n 1 re*
: •. :i..•v ■'
ll-c
s e p a r a ted.
three
i■ • d r» l
f. t h
•
h e ti!1.ny
r e s i d *’e v; m a
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f !.I c• red .
h-:!•r- dri**d,
3 T hi
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the p o t a s s iuin p e r n m g f i r a t c
1 v t ’ re ’.c o
cId if Ied
f
In w a t e r , a m i S O o
nyi
heated
The
filtrate
tic
fOO
soT-'tion,
co
s : r
portIons
i -■t*r
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v ■*. "h- t *
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\
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’"'ere
ICo
OXIDATION
To
150
311T L F R O W 'S B E T A
OF
ft• , 0 . 7 5
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167
.’s c i p i to tt
din.- c l vc--i
:ro>MCt
Tit. 1 t i n e
in
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re
a c o to no ,
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t aiu.i.
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raised
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water* •
0 . 0 - .• .
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v •_* ,r - r? ‘"it!'
i M
’/ r o d s c t
h v d ?c>l 7 3 l a
far
a
m o l t i ra"
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■ •.■i
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:
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ae
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h-ise
a:.::- -
ita
a ]
the
a o d M
1M
When
>
t-.n
o 1 e c tr* o.r? t r i e
si n c c Me
tid'M t V n
at
is
of
vc I t #=>y e
eurh
v e p;’ s l o w l y .
18h°
in
y f *a ; ■r :
arid.
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■- 1 1-: ■ !.! “
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at
nnteMal
-■.■U-
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9 7 — 9'~<°
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n c r * ’ j h r:cl
a T:= a :a .
1
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. -a -
is
Vh '■* n fr .o
' n o 1 ‘ i;
ti t f ' t i t::e
i'd'i rl t« r a n . l t a
an
i- v 1
point.
>
-'04 — 0 0 6
nod •
o«i
''
at
is
K 91'
* oa
•
of
aaai
97 — 00°
nq..» o • 3
uf
n
-
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el l y ,
o h a t3 n e d .
r* rr r* s o i p i t a t e d
<i3 a s o L v-'M in v, t'>? to,
is
r>*'od •«ct
■a .
wan
.
:: 1 o n
:*"..•3
and
MO-
r_-<-.ina,
s e ;.:i f r O n
1
GO — G4°
i3
--Id
168
melting
at
reanlta.
172-174°
The
after
evolution
tiiis d e c o m p o s i t i o n .
carbon
dioxide
Electrometric
materials
show
the
while
172°
compound
the
of
recrya talllzatlon
185°
material
is
to
from
was
titrations
be
monobasic.
acetone
noticed
of
these
a dibasic
acid,
In
169
?Atc iX : r f\ Qampi vj?M .1'J I ::
i....*W«iy.4/ o£ -ja.r?’
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IJ*
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T~
C C c> afjf /•/
,
:
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42AA
Cr
' '■7 9 9 A/ Mm.-C S-/
171
1 1 Q-cm&jtric
/ /./ r<z. ? /
'JifaJfifi/ c£\£*
cc
0.0999 AT M * O H
1 «'2
SUMMARY
1*
Pdntamethylacetone,
h e x a m e tiiylace t o n e , w e r e
and
methyl
sulfate
2.
3.
with
of
by
the
trlmetnylethylene
the
was
sodium-moist
Di-t-butylcarbinol
product
by
Subsequently
the
action
of s o d a m i d e
on d i i s o n r o p y 1 ketone.
heta—naphthalenesulfonic
nrlncinal
of
nrnpared
H e x a m e t h y l a c e tone
buty1carbinol
and
was
corresponding
and
reduced
benzene
was
to d i - t —
method.
dehydrated
acid.
isobutylene
under
Very
small
were
formed.
vacuum
amounts
The
2 f ,4,4-tetrame thyl-l-pentene.
2 , 2 , 3 , 4 - tetrametbyl— 2—pentene
None
was
form­
ed o
4.
neohexyl
,<.etnyl neoiiexyl
Grignard
5.
none
from
reagent
An
were
and
to
chloride
acetyl
pro rare
and
was
the
synthesized
from
chloride.
3 , 3, 4 -t r i ; e t h y l — 2 — p e n t a *
upnronriate
Grignard
unsuccessful.
6.
and
attempt
acetyl
was
reagent
ketone
attempts
to
oxidize
2,2,7,7-tetramethyloctune
1 , 1 - d l n e o n e n tyle t h a n e
with
alkaline
permanganate
unsuccessful.
7.
butlerow's
permanganate.
covered,
Three
melting
solid
points,
Geta
acid was
oxidation
05-67,°
oxidized
products
1 3 4 — 135°,
and
were
with
re­
209-210°.
alkaline
173
BIBLIOGRAPHY
PART
1.
FI e m i n g ,
(19 3 6)
Ph.
D.
2.
Whitmore
and
co-workers,
3*
Gorianiow,
4.
Markownikow,
5.
Slmonowitsch,
6.
Kizhner,
7.
Van Risseghem,
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8.
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Ann.,
J.
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The
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12.
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14.
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17.
IB.
19.
v
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’
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(8),
Chem.
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A n n 0 , Chim.
Am.
472
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C.
J.
II,
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Livshltz,
J. S e n . C h e m . ,
ibid.,
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1066
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Mulligan,
Chem.
State
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Zentr.,
ibid.,
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Thesis,
I
See.,
Soc.,
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State
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(19 40)
' TS",
( V-38;
-hi,
ixov. 26,
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A n n . , 69, 371; £ 6 , 3 6 5 ( 1 8 5 5 ) :
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20 .
Buckeiaen
and. .'/anklyn, A n n . ,
21.
Schorlemmer,
22.
Silva,
B o r.
23.
Norris
and
2 4•
Young
and
2b .
Carleton,
Ann.,
Am*
Portey,
J.
Schorlemmer,
27.
Grirnshaw,
Ann.,
ibid.,
29.
Just,
Alechin,
31*
Krafft,
32.
Hell
33.
Dootin,
5 4.
Veit,
J.
Soc.,
(1873)
(1833)
?hy s .-Chem.
19, 2 2 2 1 ,
Soc.,
Ann. Chim.,
Soc.,
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bertheloc
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Srdneim,
38.
Talmud,
39.
Huckel
and
40.
Lewis,
iiendricks , arid Y o k e ,
J. A m . C h e m .
Luce,
Rozniki
25,
( 1895)
30.
Ann.
Chem.,
4 1 9,
Chim.
12,
(1901)
e h y s .,
63 1 ,
co-workers,
and
Schulback
44 . o c n l e n k ,
Ber.,
41,
J.
2711,
Ochs , ibid .,
and
Or es,
ibid.,
49,
nrekt.
608,
48,, 294,
8,
27,
55
608,
chem*,
Soc.,
1 4 2 , 207,
50,
1 993,
(1916)
b_, 2 8 8 9 ,
(1916)
( 1856)
(1938)
(1908)
£9,
ibid.,
(5),
(1932)
Acta F h y s i c o c h i m . , J.S.S.R.,
4 /J♦ S c h l e u k
43.
J.,
(1883)
_22, 5 04 , (188 9)
(7), _6, 121,
Chem.
1_5> 175,
(1 8 86 )
michael,
Schorigan,
(1916)
(1872)
3 5.
41.
(1901)
2 2 0 , 1 5 4 , (188 3)
J. C h e m .
and
313,
38, 1 1 2 8 ,
1 6 1 , 2 63 ,
a n d lia/gele, i b i d . ,
Am.
26,
Soc., 1 9 0 0 , 1126
2 2 0 , 1 79 ,
Russ.
Ber.
J.,
Chem.
1 6 6 , 16 3,
Lachowicz, ibid.,
ibid.,
Chem.
Am. Chem.
2 8.
30.
(1 87 2)
Green,
£6.
(i860;
1 4 4 , 1 8 B , (1867)
h>, 9 8 4 ,
J.
1 1 6 , 334,
( 1 9 2 2)
(1935)
(1928)
175
45.
Horn,
Polanyl,
46*
Bachmann
47.
Blum-Herrmann,
48.
M o r t o n a n d c o - w o r k e r s , I b i d . , J, A m . C h e m . S o c .
53 , 2 2 4 4 , 2 7 6 9 , 4 0 2 8 , ( 1 9 3 1 ) ; 5 4 , 1 9 1 9 , ( 1 9 3 2 )
5 5 , 754, 1024, 1697, 2599,
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