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I. STUDIES OF THE ISOPROPYL GROUP. II. SYNTHESIS OF 2,2-DIMETHYL-3-ETHEL 1-PENTANOL. III. STUDIES OF OPTICALLY ACTIVE COMPOUNDS. IV. MISCELLANEOUS STUDIES

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DOCTORAL DISSERTATION SERIES
TITLE I
o f lf e > I s o j ) r o p y ] ( tP o u j>
£ Splhesis cf2,2-Pimeiliyl-j-eiliyl-/-penhnol
£ Sllidiea of Optically Active Compounds
ffi>Miscellaneous Studies_ _ _
AUTHOR
ClyJg Edgar Qeim
UNIVERSITY.
DEGREE
? i .
S
i
d
e
DATE.
C
o
l
l
e
g
e
___________
PUBLICATION NO:
I UNIVERSITY MICROFILMS
ANN A K O t . MICHIGAN
The Pennsylvania State College
The Graduate School
Department of Chemistry
I
II
Studies of the Isopropyl Group
Synthesis of 2 ,2-DImethyl-3-ethyl-l-pentanol
III
Studies of Optically Active Compounds
IV
Miscellaneous Studies
A Thesis
by
Clyde Edgar Gleim
Submitted in partial fulfillment
of the requirements for the degree of
Doctor
of Philosophy
August 1941
1941
Research Professor of Organic Chemistry
1941
Head, Department of Chemistry
ACKNOWLEDGMENTS
The Author wishes to express his most sincere
appreciation to Dean Prank C. Whitmore for his
invaluable assistance and many suggestions given
throughout the course of this work.
Profound thanks are also extended to
Dr. M. R. Fenske and Dr. D. Quiggle for the use
of their fractionating columns, and to Dr. George
H. Fleming and Dr. H. Bernstein for their interest
and advice in this work.
CONTENTS
I
STUDIES OF THE ISOPROPYL GROUP
page
Introduction . . . . . . . .
1
H i s t o r i c a l .............................................
1
D i s c u s s i o n .............................................
2
E x p e r i m e n t a l ............................................
7
A. Description of Apparatus
.......................
7
B. Preparation of 2,2,3 - T r imethyl-1-butano l. . . .
8
1.
Preparation of t-Butylmagnesium Chloride.
.
8
2.
addition of A c e t a l d e h y d e ..................
3.
Dehydration of Pinacolyl A l c o h o l ..............10
4.
Preparation of 2,3 - D i m e thyl-2-chlorob utane. 11
5.
Preparation of the Grignard Reagent
6.
Addition of Formaldehyde
7.
Purification of 2,2,3-Trimethyl-1-toutanol
9
. . . .
13
. . . . . . . . .
15
, 17
C. Dehydration of 2,2,3-TrImethyl-l-butano l. . . .
18
1.
D e h y d r a t i o n .....................................18
2.
Fractionation of O l e f i n s ....................... 19
D. Ozonolysis of O l e f i n s .............................. 21
1.
Ozonolysis of Low Boiling Fractions
. . . .
2.
Ozonolysis of Medium Boiling Fractions.
3.
Ozonolysis
4.
C o n c l u s i o n s .....................................29
of High Boiling Fractions.
. .
. . .
21
26
28
page
£• Preparation of Tetraisopropylethylene Glycol,
1. Purification of Diisopropyl Ketone
.
. . . .
30
30
2. Reaction of Diisopropyl Ketone with
Magnesium A m a l g a m ..............................31
3. Reaction of Diisopropyl Ketone with
Aluminum A m a l g a m ..............................32
4. Reaction of Isopropyl Grignard Reagent with
Diethyl O x a l a t e ........................
33
5. Reduction of Diisopropyl Ketone w i t h Sodium
37
6. Reaction of Diisopropyl Ketone with Sodium.
38
7. Purification of Tetraisopropylethylene
Glycol
.................................... 40
8. Physical Properties of Tetraisopropylethylene
G l y c o l ......................................... 40
F. Dehydration of Tetraisopropylethylene Glycol.
G. Oxalic Acid Rearrangement of the Glycol
.
. . . .
40
42
H. Identification and Physical Properties of the
K e t o n e ......................................... 45
S u m m a r y .................................................. 46
B i b l i o g r a p h y ...................................... ..
II
.
47
THE SYNTHESIS OF 2,2-DIMETHYL-3-ETHYL-1-PENTANOL
Introduction ...........................................
48
H i s t o r i c a l ................................................ 49
D i s c u s s i o n ................................................ 50
Experimental
...........................................
53
A. Preparation of 2,2-Dimethyl-3-ethyl-l-pentanol.
53
1. Preparation of Diethylacetyl Chloride
.. .
53
page
2.
Preparation
of
Methylmagnesium Chloride
. .54
3.
Preparation of 2-Methyl-3-ethyl-2-pentanol •
4.
Preparation of 2-Methyl-3-ethyl-2-chlorop e n t a n e ......................................... 57
5.
Preparation of the Grlgnard Reagent
6.
Preparation of 2,2-Dimethyl-3-ethyl-1p e n t a n o l ................................... €1
7.
A n a l y s i s .................................. 62
. . . .
55
58
B. Preparation of the Methyl Ether of 2-Methyl-3ethyl-2-pentanol. ...... .................... 62
1.
Preparation of theSodium Alcoholate.
.. .
62
2. Reaction of the Sodium Alcoholate with
Methyl Iodide ................................
64
3. Reaction of the Methyl Ether with Hydriodic
A c i d ....................................... 66
C. The Reaction of Sodlum-potasslum Alloy on the
Methyl E t h e r ................................ 67
1.
A p p a r a t u s .................................. 67
2.
Preparation of theSodlum-potas slum Alloy
3.
Reaction of the Alloy with the Methyl Ether
4.
C o n c l u s i o n s ................................ 72
D. Preparation of 4,4-Dimethyl-5-ethyl-l-heptene
1. Preparation of Allylmagnesium Bromide
.
67
68
.
72
.. .
72
2. Reaction of Allylmagnesium Bromide with tAmyl C h l o r i d e ............................ ...
72
3. Reaction of Allylmagnesium Bromide with 2Methyl-3-ethyl-2-chloropentane............ 75
4. Refractionation of 4,4-Dimethyl-5-ethyl-lh e p t e n e ..................................... 76
page
S u m m a r y ..............................................78
Bibliography ...........................................
III
78
STUDIES OF OPTICALLY ACTIVE COMPOUNDS
Introduction ...........................................
79
Historical and Discussion
79
Experimental
..................
.................................
82
A. Fractionation of Refined Fusel O i l ...........
82
1. Fractionating C o l u m n..................... 82
2. Preparation of Fusel Oil for Fractionation.
3. Fractionation
of Refined
83
Fusel O i l ... 83
4. Refractionation of Refined Fusel Oil. . . .
5. Analysis of Fusel Oil
84
.............. 85
B. Preparation of 2 . 2 ,3-Triraethyl-n-valeric Acid
.
86
1. Oxidation of Optically Active 2-Methyl-lb u t a n o l ...................................86
2. Preparation
of Methylethylacetyl Chloride
3. Preparation
of Methylmagnesium Bromide
4. Preparation
of
. 90
• •
91
.2,3- 39iiaethyl-2L-pentanol .
91
5. Preparation of 2,3-Diraethyl-2-chloropentane
92
6. Preparation
92
of the Grignard Reagent . . . .
7. Preparation of 2,2,3-Trlmethyl-n-valeric
acid
......................................... 93
8. Preparation of the Anilide of 2,2,3-Trimethyln-valeric A c i d ...........
94
C. Racemization of Methylethylacetyl Chloride
• .
95
page
D. Preparation of 2,2,3-Triraethyl-l-pentanol • • •
1. Reaction of the Grlgnard Reagent of 2,3Dimethy1-2-chioropentame with Formaldehyde,
Summary
96
96
......... • . . • • ........................... 99
Bibliography . • • • • • • • • . . . . .
IV
Introduction • •
miscellaneous
99
studies
. . . . . . . . . . . .
. . . . . .
100
.............
100
A. Preparation of a New Nonane, 2-Methyl-3-ethylhex&ne
.......... • • • • • •
102
Historical and Discussion. • • • • . .
E x p e r i m e n t a l .............................
1. Preparation of Secondary Butyl Chloride . . 102
2. Preparation of the Secondary Butyl Grignard
R e a g e n t ........... ..
. . . . . . 104
3. Preparation of Methylethylacetic Acid . . .
105
4. Preparation of the Methylethylacetic
C h l o r i d e ......................................107
5. Preparation
ofEthylmagneslum Bromide .
. • 107
6. Reaction ofthe Acid Chloride w i t h Ethylmagnesium Bromide
....................107
7. Dehydration
of4-Methyl-3-ethyl-3-hexanol
8. Ozonolysis and
Identification of Olefins.
• 110
. 110
9. Hydrogenation of O l e f i n s ....................112
10. Purification of the N e w Nonane.
. . . .
11. Physical Constants of the New Nonane.
• • 112
.. .
114
page
B* Preparation of a New Decane, 2-Methyl-5-ethylh e p t a n e ......................................... 115
1* Purification of Dlethylacetaldehyde
2. Preparation of Phosphorus Tribromide
3. Preparation of Isobutyl Bromide
• . • •
115
. . .
115
...........
115
4. Preparation of 2-Methyl-5-ethyl-4-heptanol.
116
5. Dehydration of 2-Methyl-5-ethyl-4-heptanol.
116
6. Purification of the Decenes
. . .............. 116
7. Ozonolysis and Identification of Olefins.
8. Hydrogenation of Decenes
9. Physical Constants.
......... ..
•
117
. *
119
.........................
121
S u m m a r y .................................................. 123
B i b l i o g r a p h y ............................................. 123
I
STUDIES Oi' THE IoOlROiffL OROUP
Introduct ion
Tt was found,
upon making a survey of the literature,
that no information was available concerning the rearrangei-ent of secondary groups,
such as the isopropyl group.
A new alcohol, 2, 2 ,3— trime thyl-l-butc.no 1, containing
an iso^rcp yl rudi ctl was synthesized, and upon dehydx*ation
and su.bseq.uent ident ifioation of the olefins by ozonolysis,
it was found that an isopropyl rearrangement had occurred.
Another new compound, tetraisopropylethylene glycol,
was synthesized.
'.'he glycol,
on treatment with oxalic acid,
underwent a pinacol rearrangement
radical.
A compound,
empirical
involving; the Isopropyl
formula,
CgoH^G,
believed
to be an unim turuted hetone, was isolated from the reaction
products. The compound
is thought to be £, 5-clime thy1-4-
isopropyl-3-hexanone with a double bond , po.vnibatly, in the
4-5 position.
Historical
Oakwood and i’ohland of this laboratory have converted
isoj-ropyl acid amide to isopropyl amine by the Hofmann
method.
The state that apparently nothing
present that could be isolated.
el.e was
2
Miinch prepared dllsopropyl c&rblnol by the sodium
reduction of diisopropyl ketone.
He obtained a small
amount of a heavy oil which boiled at 260° and which he
thought was a p inacol.1
No other information could be
found concerning this glycol.
Discussion
In order to determine if a secondary group would
shift during a rearrangement reaction, the alcohol, 2,2,3
trimethyl-1-butanol, was synthesized and dehydrated.
The
alcohol was prepared by the following series of reactions
C
C-9-CI
C
I
C
t
C-p-MgCl
2*SL
EtgO
II
CH-CHO
o
C-C-CHOHCH3
C
III
HgO
a 12°3
C-C-C=C *
C
C-CsC-C
c=c-c-c
Cl
c-c-<j;-c
c c
C-9-9-M6C 1
c c
V
VI
CHgO
C-C-C-CHo 0H
6 6
8
VII
* The t-butyl ethylene Isomer
was removed by fractionation.
3
Pinacolyl alcohol was pre p a r e d from t-butyl Grignard
reagent and acetaldehyde In a 65% yield.
D ehydration over
activated alumina gave a mixture of t-butylethylone,
and
sym-tetramethyl and unsym-methyllsopropylethylenes in 42
and 58 per cent yields respectively.
The t-butyl ethylene
Isomer was removed b y fractionation.
The other two
Isomers were not separated since b o t h give 2,3-dimethyl-2chlorobutane on the addition of hydrogen chloride.
Constant Index,
constant b o i l i n g t-chloride was ob­
tained in a 64 per cent yield f r o m the unfractionated
olefins,
and in 70 to 72 per cent yields from unsyna-methyl-
isopropylethylene and from 2, 3 - d i m e t h y l -2- b u t a n o l .
latter two compounds were k i n d l y supplied b y Mr,
The
Cook of
this laboratory.
The alcohol,
2,2,3-trimethyl-l-butanol was prepared
in 18 to 23 per cent yields b y the addition of formaldehyde
to the Grignard reagents,
or in 8 to 10 per cent yields
based on the t-chloride.
D ehydration of the carbinol gave
a mixture of isomeric olefins which could not be separated
b y careful fractionation t h r o u g h a column of 50-60
theoretical plates.
However,
b y refractionation,
the
olefins were separated into low, medium, and h i g h boiling
fractions.
Identification of the olefins and estimation
of the yields were accomplished b y ozonolysis.
Isobutyraldehyde,
acetone, formaldehyde, and methyl-
isobutyl ketone were obtained from the ozonolysis of the
low boiling fractions.
The presence of isobutyraldehyde and methylisobutyl
ketone definitely proved that an isopropyl rearrangement
occurred during the dehydration of 2,2,3-trimethyl-l-butaiol.
Theoretically, there are five possible isomeric
olefins which may result from the shift of a methyl or an
isopropyl group during the dehydration of 2,2,3-trimethyll-butanol •
C-C=C-C-C
• i
C-C-C-C-C
i •
c c
c c
II
c-c-c=c-c
I I
c c
III
c-c=c-c-c
c
6
IV
c=c-c-c-c
c
6
v
Compounds I, II and III may result from the shift of a
methyl group, and compounds IV and V may result from a
shift of an isopropyl group.
Since only compound IV gives isobutyraldehyde and
only compound V gives methylisobutyl ketone on ozonolysis,
5
the presence of 2, 4-dime thyl-2-pentene, and 2,4-dimethyl1-pentene has been established.
Acetaldehyde and methyl!sopropyl ketone were found as
ozonolysis products from the ozonolysis of the medium
boiling fractions.
these products.
Ozonolysis of compound III would give
Therefore,
the presence of 3,4-dime thyl-
2-pentene has been established.
This olefin was obtained
through a shift of a methyl group during the dehydration.
Since compound I would give acetone and methylethyl
ketone on ozonolysis, and since these two products were
found to be present as ozonolysis products from the ozon­
olysis of the high boiling fractions, the presence of 2,3dlmethyl-2-pentene has been established.
Ethylisopropyl ketone was not identified as a product
of ozonolysis.
The failure to find this product does not
necessarily prove that the olefin, 2-ethyl-3-methyl-lbutene, was absent, because the presence of a small amount
of ethylisopropyl ketone along with a larger amount of the
isomeric methylisobutyl ketone would be difficult to
separate and detect.
Tetraisopropylethylene glycol was synthesized in order
to further the study of the rearrangement of the isopropyl
group.
An attempt to prepare this glycol from diisopropyl
ketone by the use of magnesium amalgam and b y the use of
6
aluminum amalgam was not successful under the conditions
used.
Neither could the glycol he prepared b y the addition
of an excess of isopropyl Grignard reagent to diethyl
oxalate.
This conclusion is in agreement with that of
Bouveault and Rene who found that when dllsobutyryl was
treated with methylinagneslum iodide, only one carbonyl
2
group reacted and that no pinacol was obtained.
The reduction of diisopropyl ketone with sodium in a
30 % solution of potassium hydroxide, or in an almost
saturated solution of sodium carbonate, gave a
the pure glycol.
yield of
Diisopropyl carblnol was obtained in an
80jg yield b y the reduction of the ketone.
Apparently,
the yield of glycol was not greatly
effected by variation of the rate of the addition of sodium,
for practically the same yields were obtained under all of
the conditions used.
The main product obtained b y the catalytic dehydration
of the glycol over aluminum oxide was the diolefin,
dimethyl-3,4-diisopropyl-2,4-hexadiene.
isolated among the reaction products.
2,5-
No ketone could be
This fact would be
expected since alkaline catalysts favor dehydration.
A pinacol rearrangement was brought about b y heating
the glycol for 25 hours with a 4.5^ solution of oxalic acid
and for 62 hours with & 20^ solution of oxalic acid.
A compound was isolated from the reaction products
which was thought to he an unsaturated ketone, empirical
formula ^11^ 20^*
first,
the compound was thought to
he a ketone which contained three isopropyl groups attach­
ed to a single carton atom. Apparently,
was lost in the rearrangement.
an isopropyl group
This assumption has not
been verified except "by carbon and hydrogen analysis. The
conclusiorB that the compound was a ketone was "based on the
analysis arid on the physical properties of the material.
An attempt to prepare the 2,4-dinitropheny1-hydrazone,
the oemioarbazone, and the oxirne d' rivatives was not success­
ful.
An attempt to oxidise the material with chromic aaid
was also unsuccessful.
small sample of the material was
treated with sodium and ethyl alcohol.
material had a
reatex* index of
he recovered
-e fraction than the original
hetone
'.’he am ourit of active hydrogen,
the method of Aerewininoff.
10.6, was determined by
home audition may have occurred
since 10'- of the Grignard reagent was unaccounted for.
A compound was obtrined from the dehydration of tetraiso;ropylethylene glycol over alumina which was believed to
be a diolefin, 2 ,5-dire t..yl-3, 4-diisogro_ yl-2 ,4-hexadiene . The
structure has not yet been established.
Txperi.wental
A. Descx’iption of Apparatus
columns used
The fract donating
in this work were of the total coneerr.ation vari­
able take-off type.3
*
8
Name
Packed section
1) Column A
1.5 X
2 ) Column B
0.9 X
3) Column C
0.9 X
O
•
5) Column MB
H
4) Column EWJ
X
65 cm
Pac k i n g
Plate value
Single turn
glass helices
14
35 c m
Glass helices
1L
51 cm
3 / 3 2 ” stainless
steel helices
20-25
3 / 3 2 ” steel
helices
35-40
Steel helices
5 0 -SO
100 c m
1.0 X 10O cm
The Cottrell Bolling Point Apparatus was o f the
4
design described b y Qulggle, Fenske, and Tongberg.
A Valentine and a standard Abbe refractrometer was
used for determining the Indices of refraction.
B . Preparation of 2 , 2 , 3 - Trlmethyl-1-butanol
1, Preparatlon o f t-Butylmagneslum Chloride
To 369 grains, 15 moles,
of ma g n e s i u m shavings I n *
12 liter flask fitted w i t h a trident, a m e r c u r y seal
stirrer, a separatory funnel,
and an efficient condenser
to which was attached a sulfuric acid trap, were added a
crystal of iodine,
a cc of methyl iodide,
and 10 cc of
t-butyl chloride diluted w ith 50 cc of ether.
After the
reaction had started, 2450 cc of ether was added directly.
Then the chloride,
1385 g., 15 moles,
diluted w i t h 2 00 0 cc
of ether, was added through the separatory funnel at a
fairly rapid rate.
The addition was complete in 18 ,5 hours.
9
Stirring was c o n tinued Tor three hours.
T i t r a t i o n of a
sample Indicated about an 80# Grignard reagent.
2. Addition of Acetaldehyde
A weighed bottle of Eas t m a n b lue labeled acetaldehyde,
500 g., cooled in an ice b a t h was at t a c h e d t o a m e r c u r y
bubble counter w h i c h led to a tube that e x t e n d e d four
inches b e l o w the surface of the Grignard reagent.
The ice
b a t h was r e p l a c e d b y a w a ter b a t h k e p t at the start at 25°C.
Most of the acetaldehyde d i s tilled over at a nice rate at
25°C ; the addition w a s accompanied b y r a p i d stirring.
Hie
temperature of the water b ath was g r a d u a l l y r a i s e d to 40°C
as the rate of addition slowed down.
r e m o v e d and weighed.
b y difference.
The amount of addition was determined
A n o t h e r bott l e was attached and the addi­
tion continued u n til 657 g.,
14.9 moles, o f acetaldehyde
(2.5 moles excess) had b een added.
17 hours.
The b o t t l e was then
The a d d i t i o n time was
S t irring was c o n tinued for three hours before
the addition compound was decomposed w i t h wate r .
The
u s ual procedure was fo l l o w e d in the d e c o m p o s i t i o n and ex­
traction work.
After washing with a thiosulfate solution,
w i t h a dilute carbonate
solution, w i t h water,
a n d then d r y ­
ing and removing the ether b y means of a 14 inch indented
fractionating head, there remained 1500 cc., 1115 g., of
crude carbinol.
F r a c t i o n a t i o n through a column of 14
theoretical p l a t e s gave 997 g., 9.75 moles,
or a 65# yield
10
r
t
of pinacolyl alcohol, b.p. 68-69.2 C.,
20
(100 inn), nD
1.4141-1.4149.
3. Dehydration of Pinacolyl Alcohol over Activated Alumina
The dehydration of pinacolyl alcohol over acid
catalysts gave tetramethyl, unsym-methylisopropyl, and tbutylethylenes in 61, 31, and
yields respectively.^
The dehydration apparatus consisted of an electrically
heated horizontal glass tube, 24 Inches long and 1 inch in
diameter containing activated aluminum oxide, mesh size
No. 4 - 8, and three thermocouples spaced about eight
inches apart.
To one end of the tube, surrounded by a
layer of asbestus one inch in thickness, was attached a
dropping funnel,
and to the other end, a spiral condenser.
Dry nitrogen gas was passed through the dehydrator heated
to 350°C for an hour before the dehydration was started.
Two receivers were connected to the apparatus.
cooled in a salt-ice bath, and the other,
cooled in a dry ice acetone bath.
the carbinol,
One was
a gas trap, was
The rate of addition of
770 g., 7.4 moles, was about 40-50 drops per
minute, or about 100 g. per hour.
Material balance:
The weight of products recovered
was 758 g . ; the loss in weight during the dehydration was
12 grams; and the weight of the olefins dried over anhyd.
potassium carbonate was 625 grams.
11
Since both tetramethylethylene and unaym-methylisopropylethylene give the desired chloride on addition of
hydrogen chloride, It was only necessary to remove the
lower boiling t-butylethylene isomer b y fractionation*
Fractionation through a column of 14 theoretical
plates gave 265.5 g., 3*1 moles, or a 42# yield of tbutylethylene, b.p. 41-42°C (743 mm) n^° 1.3773-1.3777.
The remainder, 294 g., 3.2 moles, was a mixture of tetra­
methyl ethylene and unsym-methylisopropylethylene.
A 410 g.
4.76 molar quantity of unsym-methylisopropylethylene con­
taining about 5# of tetramethylethylene was kindly supplied
by Mr. Cook of this laboratory.
4. Preparation of 2.3-Dlmethyl-2-Chlorobutane
Run 1.
Dry hydrogen chloride gas, generated by
dropping conc. sulfuric acid onto sodium chloride, was
passed into 163 g., 2 moles,
of olefin mixture (unsym-
methylisopropylethylene, 95#, and tetramethylethylene,
5#)
contained in a 14 x 1.5* test tube cooled by a dry ice
acetone bath.
The extent of the addition of the hydrogen
chloride was followed by determining the increase in weight.
A 70 gram increase (73 g. theoretical) was obtained within
seven hours. The product was washed twice with 50 cc of
cold water, once with 50 cc of a 5# potassium carbonate
solution, and again with 50 cc of cold water.
The product
weighed 215 g. after drying over anhyd. potassium carbonate.
12
Fractionation in vacuo through a column or 14 theoretical
plates over 2 g. or anhyd. potassium carbonate gave 175g.,
1,45 moles, or a 72.5# yield or 2,3-dimethyl-2-chlorobutane,
b.p. 62.5°C (50 mm) n§° 1.4198-1.4202.
Runs 2, 3 and 4.
described above.
These runs were similar to the one
From 338 g., 3.85 moles, or olerin mix­
ture, there were obtained 321.0 g., 1.59 moles, or a
yield or t-chloride, b.p>. 62-63°C (150 mm) n§° 1.4200.
Run 5.
In this run the t-chloride was prepared rrom
an unjfractlonated mixture or unsym-methylisopropyl and
tetramethylethylenes.
F rom 128 g., 1.5 moles or olerin
mixture, there were obtained 117.5 g., 0.37 moles,
or a
64# yield or t-chloride, b.p. 64°C (151 nan) n^° 1.41981.4199.
Run 6.
The t-chloride was prepared directly rrom the
alcohol, 2,3-dimethyl-2-butanol, b.p. 76°C (150 mm)
1.4169-1.4172 which was kindly supplied by Mr. Cook or
this laboratory.
The method dirrered in two ways rrom the
one described above:
1) Only a salt ice mixture was
necessary Tor the cooling bath.
2) The aqueous acid layer,
which generally separated within two or three hours, was
removed and the addition or dry hydrogen chloride was con­
tinued Tor another two or three hours,
prom 325 g . , 3.7
moles, 2,3-dime thyl-2-butanol, there were obtained 315 g .,
2.6 moles,
or a 70.5^ yield or t-chloride.
15
5. Preparation of the Grignard Reagent
To 54 g., 1*4 atoms, of magnesium turnings In a one
liter 3-necked flask fitted with the usual attachments
were added a small crystal of iodine, one cc of methyl
iodide, and 10 cc of anhyd. ethyl ether-hallde solution.
The later was prepared by diluting 170 g., 1.4 mole, of
t-chlorlde with 105 cc of anhyd. ether.
The remainder of
the ether-hallde solution was further diluted with 350 cc
of ether and the solution added dropwise over a 10-hour
period.
The mixture was stirred over night.
Titration of
a 5 cc sample of the clear solution indicated a 0.64 molar
Grignard reagent.
Run 2.
Three similar runs were made.
To 205 g., 1.7 mole of magnesium in a two-
liter round-bottom flask fitted with a trident, a mercury
seal stirrer, a condenser, and a dropping funnel, were
added 10 cc of an anhyd. ether-hallde solution prepared by
diluting 205 g., 1.7 moles, of t-chloride with 125 cc of
ether.
The Grignard reagent of the t-chloride was started
in a test tube containing a few pieces of magnesium turn­
ings, one cc of the t-chloride, two cc of ether, one cc of
methyl iodide, and a crystal of iodine.
This reagent was
added along with the 10 cc of the ether-halide solution.
The remainder of the ether halide solution was diluted with
425 cc of ether, a n d then added dropwise over a 12-hour
period.
The mixture was stirred for five hours after the
14
addition had bean completed•
Titration of a sample
indicated a 46# Grignard reagent*
Run 3*
Again, the Grignard reagent was prepared in a
test tube as described in run 2.
To 110 g., 0.9 mole, of
the t-chloride, was added 68 cc of ethyl ether.
Ten cc of
this solution, along with the reagent prepared in the test
tube, was added to 22 g., 0.9 atoms of magnesium turnings.
The remainder of the solution was diluted with 225 cc of
ether and this solution was added slowly over a six hour
period.
The reagent was stirred for two hours after the
addition was complete.
Titration of a 5 cc sample
Indicated a 35# Grignard reagent.
Run 4.
A small amount of the reagent was prepared in
a test tube b y the following method:
About 0.5 gram of
finely divided magnesium turnings was placed in a test tube
containing a small crystal of iodine and 2 cc of ether.
To this mixture was added one cc of undiluted t-chloride.
The reaction started within a minute.
This reagent was
diluted with a few cc of ether and was added to the twoliter 3-necked flask containing 2.6 g atoms of magnesium.
A solution of 25 cc of a mixture of 315 g., 2.6 moles, tchloride and 190 cc of ether was then added.
The remainder
of the solution, diluted with 625 cc of ether, was added
over a nine-hour period.
A 5 cc sample, on titration,
indicated a 40# Grignard reagent.
15
6. Addition of Formaldehyde to the Grignard Reagent
A glass
U.
tube, 25 x 1.1 cm, was bent In the f o r m of a
The length of the tube after bending was 20 cm*
portion was wound with resistance wire*
This
To one end of
this tube was attached a 500 cc round-bottom flask contain­
ing 35 c. (a 15 g. excess) of powdered paraformaldehyde
dried In a vacuum desiccator for 30 hours over phosphorus
pentoxlde*
The other end of the tube was attached to a
one-11ter 3-necked flask containing a 0*64 molar solution
of the Grignard reagent*
The end of the tube was two
inches above the surface of the ether*
a sulfuric acid
trap was placed on the end of the exit line*
The tri­
polymer was gradually broken down into gaseous formaldehyde
by heating the flask with a free flame*
The resistance was
regulated such that repolymerlzatlon of formaldehyde along
the U tube was Just prevented*
The rate of addition of the
aldehyde was governed by the amount of re fluxing of the
ether*
The addition, accompanied b y vigorous stirring, was
complete In 50 minutes.
The U tube was disconnected and a
5 gram quantity of dry paraformaldehyde was added directly.
Stirring was continued for five hours.
Water was then
added to decompose the addition compound.
The ether solu­
tion was decanted off and the residue extracted twice with
small quantities of ether.
The residue was acidified with
66$ sulfuric acid and was again extracted with ether.
The
ether solutions were combined and washed several times with
16
equal volumes of water to remove some of the dissolved
formaldehyde.
The ether was distilled off through a 14-
inch Indented fractionating head.
The crude alcohol was
refluxed for an hour with a solution of 36 cc of conc.
hydrochloric acid and 50 cc of 95# ethyl alcohol to decom­
pose the acetal present.
Addition of water resulted in
the separation of two layers.
The oarbinol layer was r e ­
moved and washed with a 5% potassium carbonate solution,
and then was dried over anhydrous potassium carbonate.
The alcohol was purified b y fractionation through a column
of 14 theoretical plates.
The yield of 2,2,3-trimethyl-l-
butanol, b.p. 84.5-85°C (50 ram) n|° 1.4330, d|° 0.8466,
mol. refraction calculated 35.93, found 35.51, 2,4-dinitrophenylhydrazone derivative of the corresponding aldehyde
m.p. 145°C, was 17.5 g., a 10.8# yield based on the tchloride,
or a 23# yield b a s e d on the Grignard reagent.
Three similar runs were made.
Run 2.
Seventy-five gram, 2.5 moles,
of paraformalde­
hyde (1.7 mole excess) was vaporised and passed Into a 0.78
molar Grignard reagent in the usual fashion.
mixture was
The reaction
stirred for two hours after the addition had
been completed.
The addition compound was deconposed with
water and worked up as was described in the run above.
Fractionation of the crude material gave 20.4 g., 0.175
moles, or a 10# yield of alcohol, b.p. 84-5°C,
n£
1.4326-1.4328.
Run 3.
To a 0.32 molar Grignard reagent was added
20 g., 0.67 moles, of paraformaldehyde
(10 g. excess).
After stirring the material for two hours,
compound was decomposed with water.
the addition
The ether solution
was dried and the ether was removed by distillation.
The
residue w as worked up In the usual manner which gave 9.4 g.
or a 10# yield of the carbinol, b.p. 84-85°C
(50 mm)
n8° 1.4329-1.4330.
Run 4.
There were obtained on treating a 1.0 molar
Grignard reagent with 100 g . , 3.3 moles,
paraformaldehyde,
22 g.,
(an excess) of
or a 8# yield of carbinol, b.p.
83-84°C (50 rmn) n^° 1.4328-1.4332.
Purification of 2,2,5-Trlmethyl-l-butanol
The high boiling residues obtained from the four runs
were combined and refluxed for three hours with a solution
of 35 cc of conc. hydrochloric acid and 75 cc of 95# ethyl
alcohol.
The ethyl alcohol was removed b y washing with
water and the material was dried with anhydrous sodium
sulfate.
Fractionation of the material along with the low
boiling fractions obtained from previous runs gave 18.2 g.
of carbinol, b.p. 83.8-85°C
(50 mm) n^° 1.4330-1.4332.
The best fractions of the carbinol from the four runs
were combined.
This gave 97.0 grams of alcohol having a
18
b.p. range or 83-85°C
(50 mm) and a refractive Index range
of 1.4521-1.4332.
Purification was accomplished b y fractionation of the
carbinol through a 51 x 0.9 cm total condensation variable
take-off metal packed column of 25 theoretical plates.
Fractionation data:
wt. - 85 8 *
Head
Col.
Temp. Temp.
Press. Frac.
Wt.
112.0
114.0
112.0
93.0
93.0
95.0
81.9
82.6
84.0
50 m m
n
n
1.4
2.4
5.4
1.4329
1.4332
1.4335
112.0
113.5
112.8
115.0
-
95.5
96.0
98.5
98.5
84.0
84.5
84.2
84.8
34.8
84.8
Tl
it
tt
it
n
rt
4 10.0
5 12.9
6 25.7
7 13.9
8
7.5
9
0.5
Residue 1.5
1.4335
1.4332
1.4329
1.4329
1.4328
1.4328
Air
Bath
-
-
-
1
2
3
20
nD
R.R .
Remarks
5/1 Trace of
it
chloride
it Chloride
free
4/1 Good cartdnol
n
—
20
df 0.8466
4/1
4/1
Recovery 82 g.
Loss
3.0 g
Yield of good alcohol, fractions 3-9 inclusive,
76.0g.,
0.66 mole.
B. Dehydration o f 2.2.3-Trlmethyl-1-butanol
1. Dehydration
The apparatus used for this dehydration was described
on page 10.
Dry nitrogen gas was passed through the
apparatus heated to 350°C for an hour before dehydration
was started.
Two receivers were connected to the apparatus.
One was cooled in a salt-ice bath, and the other, a gas
trap, was cooled in a dry Ice-acetone bath.
The temperature
19
of dehydration was maintained between 325-375°C.
The rate
of addition of the carbinol, 75 g., 0.64 mole, was 30-35
<•»
drops per minute, or about 30 g. per hour.
Material balance:
Wt* of alcohol dehydrated was 75 g.
total recovery was 69.5 g; loss was 5.5 g. ; wt. of dry
olefins was 55.0 g.
2* Fractlonation of Olefins
An attempt to separate the Isomeric olefins b y frac­
tionation was not successful.
However, b y two fractiona­
tions through a 100 x 1.1 cm total condensation variable
take-off metal packed column of 50-60 theoretical plates,
the olefins were separated into low, medium, and high
boiling fractions.
Fractionation data:
Lag 1
Lag 3
76.0
78.0
89.0
89.0
89.8
93.0
93.0
93.0
94.0
93.0
94.0
95.0
96.0
98.0
98.0
97.8
98.0
98.0
67.0
78.5
85.0
82.0
85.5
87.0
90.5
91.0
90.5
90.0
90.2
90.5
90.5
90.8
91.5
92.0
92.8
93.0
Head T.
35.0
39.5
63.0
69.0
75.5
79.0
80.0
81.5
82.0
83.0
83.2
83.5
84.0
84.2
84.5
86.5
87.5
88.0
(First fractionation)
Press•
723 m m
tt
M
it
u
it
n
it
tt
it
it
tt
n
tt
tt
it
n
tt
Frac .
Wt.
_20
“d
R.R.
mm
1
0.3
1.3898
30/1
0.5
0.5
45/1
40/1
—
6
1.7
0.3
7
1.0
1.3960
1.4014
1.4049
1.4042
1.4040
1.4040
8
0.5
1.5
1.4035
48/1
1.4042
1.4045
1.4048
1.4057
1.4082
1.4081
60/1
60/1
50/1
2
3
4
5
9
10
11
12
13
14
15
16
0.6
50/1
—
0.8
3.4
2.3
2.5
3.8
1.2
3.3
—
20
Lag 1
Lag 3
97.0
92.8
93.0
91.0
92.0
92.5
—
93.8
94.5
-
97.0
96.5
97.0
98.1
—
102.0
105.0
-
-
Head T.
88.2
88.5
88.8
88.5
89.0
89.5
88.5
88.8
89.2
89.8
Press.
Frac.
Wt.
723 mn
17
18
19
20
21
22
23
24
25
26
Residue
3.5
4.2
3.8
1.5
1.2
2.0
0.5
1.5
1.4
1.5
3.8
it
it
M
tt
tt
tt
tt
It
tt
4°
1.4085
1.4088
1.4085
1.4089
1.4093
1.4098
1.4104
1.4112
1.4118
1.4458
R.R.
...
—
—
35/1
..
40/1
40/1
..
_
—
Recovery 50.1 g.
Lose
4.9 g.
Conclusions:
The first fractionation failed to give much
separation of the olefins.
Refractionation of the olefins:
The first 14 fractions, 19.5 g., were combined and
Lag 3
108.0
105.5
96.5
96.5
96.0
97.0
98.0
99.0
89.0
89.5
90.0
90.0
91.0
92.0
92.0
93.0
Head T.
76.5
78.5
80.0
81.5
83.5
84.0
85.0
85.8
86.8
Press•
Frac .
741.6
tt
tt
tt
tt
tt
733 m m
tt
tt
1
2
3
4
5
6
7
a
9
1.0
1.2
C+
Lag 1
3
•
refractionated through the same column.
2.4
2.8
1.0
2.5
2.7
2.7
1.0
_20
D
1.3852
1.4052
1.4045
1.4045
1.4055
1.4042
1.4041
1.4043
1.4056
R.R.
ee
45/1
45/1
45/1
50/1
..
40/1
40/1
—
Fractionation was stopped at this point and fractions
15 - 21, 18.7 g. were added to the residue In the flask,
and the fractionation continued.
98.0
99.5
99.0
-
90.5
92.0
93.5
-
87.2
89.0
89.5
90.0
90.5
91.0
732 m m
tt
it
tt
tt
n
IO
11
12
13
14
15
0.2
0.2
2.5
4.0
3.6
3.7
3.5
1.4062
1.4102
1.4105
1.4110
1.4112
1.4115
45/1
45/1
21
Fractionation was stopped and fractions 22 - 26 and
the residue, were added (10.7 g.).
The remainder o f the
fractionation was completed through a 51 x 0*9 cm total
condensation variable take-off metal packed column of 25
theoretical plates.
Lag T.
Head T.
91.5
90.5
91.8
106.0
94.0
108.0
110.0
95.0
120.0
96.0
98.0
122.0
111.0
146.0
115.5
122.0
Recovery 42.6 g.
Loss
6.4 g.
Conclusions:
Press•
732.5
ti
it
«
M
n
n
it
tt
Frac.
Wt.
16
17
18
19
20
21
22
23
24
Residue
3.1
1.5
0.2
0.6
0.4
0.2
0.4
0.2
0.2
1.0
“d
1.4128
1.4162
1.4173
1.4200
1.4245
1.4230
1.4230
1.4205
1.4280
1.4405
By two fractionations, the olefins were
separated into three groups:
Group 1, low boiling material,
16.5 g., fractions 2-10 inclusive; Group 2, intermediate
boiling material, 17 g», fractions 11-15 inclusive; and
Group 3, high boiling material, 6.8 g., fractions 16-24
inclusive.
Identification of olefins and estimation of
the yields were accomplished by ozonolysis.
D. Ozonolysis and Identification of Olefins from
Dehydration o f 2.2.5-Trimethyl-1-butanol
1. Ozonolysis of Low Bolling Fractions
A specially treated pentane was used as the solvent
for ozonolysis.
One liter of pentane was vigorously
22
shaken wit h two 200 cc portions of cono.
sulfuric acid,
then w i t h a 5 % solution of p o t a s s i u m carbonate,
with water*
and f i n ally
The pentane was d r ied over anhydrous p o t a s s i u m
carbonate before using.
The u s u a l technique of ozonolysis w a s employed.
solution of 16.5 g.
A
(fractions 1-10 Inclusive) of the
olefins I n 250 cc of pentane was p l a c e d In an ozonolysis
tube cooled In a salt-lce bath.
A d r y Ice acetone b a t h
was attached to p r e v e n t loss of materials.
Oxygen was
passed t h r o u g h the ozonlzer at a rate of 10 - 15 liters
per hour.
T ime r e q u i r e d for the comple t i o n of ozonolysis
was eight hours.
The ozonlde was d e c o m p o s e d b y the zincg
water-catalyst method.
The m a t e r i a l s u sed for the d e ­
composition were 38 g. of zinc dust,
200 cc of water,
a pinch of hydroquinone and sil v e r nitrate.
Time re quired
for the d e c o m p o s i t i o n was 4.5 hours.
The weight
collected,
a n d 225
was 11.4 g.
along w i t h 85 cc of water,
and
of oil
cc of pentane
(14 cc).
F r a c t i o n a t i o n of the oil layer.
Col. T.
52.5
91.0
115.0
H e a d T.
Press.
- 31.0 728 nxn
29.5- 31.0
"
31.0- 80.0
*»
80 . 0 - 1 0 0 . 0
"
1 0 0 * 0 - 105.0
"
105.0- 1 0 8 . 0
"
108.0-109.5
"
109.5- 1 1 0 . 0
"
Frac.
1
2
3
4
5
6
7
Wt.
1.4
0.3
0.2
0.2
0.5
0.9
1.0
on
n^
1.3909
1.3928
1.3943
1.3955
R.R.
Remarks
-0dor-CHr>0
*
7/1
7/1
7/1
25
Head T.
Press •
110.0- 111.0
111.0-111.5
105.0-
728 m m
t>
t»
Col.T.
—
-
Recovery 9*5 g.
Ice trap 2*0 g.
Loss
1*0 g.
Fra a
8
9
10
Residue
20
Wt.
R.R*
“d
1.0
2.0
0.5
1.5
1.3950
1.3950
1.3952
1.3902
Remarks
7/1
7/1
(odor of aldehydes)
Refractlonatlon of the oil layer (Cuts 6, 7, 8 and 9
4.9 g.)
Head T.
Frac.
- 93.0
93 - 96.0
96 -102.0
1
2
Residue
1.3951
1.3950
1.4012
Fractionation of the pentane:
r Bath
Col.T.
65.0
90.0
32.0
32.5
98.0
98.0
105.0
109.0
33.0
33.0
34.0
34.5
Head T.
Press•
Frac.
34.8
35.0
737 m m
tt
1
35.2
35.2
35.5
36.5
t*
ii
it
it
Volume
20 cc
Remarks
odor —
aldehyde
2
15 cc
3
20 cc
4
100 cc
5
50 cc
Residue
20 cc
•
-
—.
65.0
—
76.0
80.0
92.0
93.0
-40.0
56.5-62.0
62.0-68.0
68.0-75.0
78.0-83.0
83.0-87.0
87.0-94.5
95.0-97.5
737 m m
it
it
it
it
N
It
It
1
2
3
4
5
6
7
8
ct
Fractionation of the water layer:
Air
Bat h Col. T.
Head T.
Press.
Frac.
a•
Dry ice trap. 1 cc. odor of aldehydes.
0.2
0.3
0.4
0.2
0.3
0.3
0.9
1.5
n^°
Remarks
Odor CHgO
1.3652
Dace of all
0.1 g. oil
24
Material balance:
Wt. or olefins ozonised 16.5 g. ;
total recovery 15.2 g . ; loss 3.3 g.; wt. of d r y oil 11.4 g.
Identification work:
Acetone, found in the pentane
fraction, cut 1 (amount unestimated) and in the water
fraction, cuts 3, 4, 5, wt. 0.9 g., 0.0155 mole, was
Identified b y its 2,4-dlnltrophenylhydrazone derivative
m.p. and mixed m.p. 122.5-123.5°C
Isobutyraldehyde,
(uncorrected).
identified b y its 2,4-dinitrophenyl-
hydrazone derivative m.p. and mixed m.p. 179.8-180.5°C
(uncorr.) was found in cut 2, oil fraction, wt. 0.3 g.,
and in the dry ice trap (fractionation of the oil layer),
wt. estimated as 1.0 g.
(Total wt. of isobutyraldehyde
was 1.3 g., or 0.0167 mole.)
quantities,
The average of the two molar
0.016, was taken to represent the moles of
2,4-dlmethyl-2-pentene, present in the ozonolysis products
recovered.
The molecular weight of the olefin was 98 grams.
Therefore, 0.016 moles of the olefin corresponds to 1.6
grams, or 12,1% of the 13.2 grams of recovered material.
Since 16.5 grams of material was ozonized,
there would be
(0.121 x 16.5) 2.0 grams of this olefin present in the
16.5 grams of material.
The weight of olefin recovered
from the second fractionation of the original olefin mix­
ture was 42.6 grams.
Therefore, 2.0 grams corresponds
to
25
(2.0/42*6 x 100) 4.7# of the olefin present In the 42.6
grams of material.
The weight of olefins recovered from the first frac­
tionation of the original olefin mixture was 50.1 grams.
Therefore, there was (50.1 x 0.047) 2.35 grams of the
olefin present In the 50.1 grams of material.
However,
the total weight of the olefin mixture before fractionation
was 55.0 grams.
Thus there was (2.35 x 55.0/50.1) 2.58
grams of 2,4-dimethyl-2-pentene present in the 55 grams of
the olefin mix hire obtained from the dehydration of the
carbinol.
Therefore, there was (2.58/55.0 x 100) 5.16^ of
this olefin present in the dehydration products*
Formaldehyde, found in the oil layer, in the water
layer (cut 1) was Identified by its 2,4-dlnitrophenylhydrazone derivative m.p. and mixed m.p. 154-155.5°C
(uncorr.)•
Methylisobutyl ketone, cuts 6, 7, 8, 9 and 10, frac­
tionation of the oil layer, wt. estimated as 5.4 g., 0.05
moles, b.p. 105-111.5°C (728 ram), n^° 1.3943-1.3955, was
Identified by Its 2,4-dinitrophenylhydrazone derivative
m.p. 79-81°C and mixed m.p. 80-82°C (uncorr.).
The
difficulty encountered in purifying this derivative was
probably due to the presence of a small amount of methyl1sopr opyl ke t one.
26
Since the weight of formaldehyde could not be
accurately estimated, the weight of methylisobutyl ketone,
5.4 g., 0.05 moles, was taken as the basis for the calcu­
lation of the per cent 2,4-dimethyl-l-pentene present in
the original olefin mixture.
By going through the same
type of calculations as was shown for 2,4-dimethyl-2pentene, 7.93 g., or a 14.4# of 2,4-dimethyl-l-pentene was
found to be present in the original 55 g. of olefin mixture.
2. Ozonolysis of Medium Bolling Fractions
The medium boiling fractions, cuts 11-15 inclusive,
16.5 g., dissolved in 250 cc of pentane, were ozonized in
5.5 hours.
The ozonlde was decomposed in the usual manner.
Head T.
33.0
37.0
100.0
104.0
104.0
32 - 33
33 - 35
35.0
45.0
45 - 80
80 - 85
89 - 91
91 - 92
92.8
98.0
98 -102
108.0
109 -100
-
105.0
110.0
110.0
-
Press.
Frac.
1
740 mm
n
2
n
3
»t
4
it
5
n
6
it
7
it
8
it
9
it
10
it
11
ti
12
it
13
Residue
S
Col, T.
3
c+
Fractionation of the oil layer.
0.3
2.7
7.5
0.5
0.9
0.4
0.8
1.0
1.2
1.7
0.6
0.4
1.3
1.1
24.5 g.
20
R.R.
D
•
-
6/1
5/1
7/1
Remarks
pentane
pentane
pentane
—
3/1
-
mm
1.3853
1.3875
1.3883
1.3891
-
1.3912
1.3953
7/1
n
—
9/1
it
n
it
Recovery 20.7 g.
Loss
3.8 g.
Conclusions: Fractions 6 - 1 2 inclusive represent
methyl!sopropyl ketone.
MeCOCHMe,
it
n
it
it
it
»t
it
27
Fractionation of water layer.
Col. T.
67.0
71.0
71.0
71.0
82.0
82.0
94.0
Head T.
Press.
45 .0
45 - 57
57 - 65
66 - 70
75 - 79
75 - 79
87 - 95
731.5
it
it
n
it
n
M
-
Material balance:
Frac.
wt.
1
2
3
4
5
6
7
1.0
0.5
0.2
0.4
0.6
1.5
3.0
Remarks
Odor of aldehyde
0.2 cc of oil
Trace of oil
2.0 cc of oil
Water
Wt. of olefins ozonized 16.5 g. ;
total recovery 12.6 g . ; loss 3.9 g . ; wt. of dry oil 9.9 g.
(2.7 g. of oil was recovered from fractionation of the
water layer).
Identification work:
Acetaldehyde,
estimated as 0.5
g., found in the water layer, cut 1, was identified by its
2,4-dinitrophenylhydrazone derivative m.p. and mixed m.p.
146 - 147°C (uncorr.).
Methylisopropyl ketone (oil layer, cuts 6 - 1 2
inclu­
sive, and cuts 3, 4, and 5 oil layer from ozonolysis of
low boiling olefins) wt. 7.0 g., b.p. 89-106°C (740 mm)
1.3853-1.3912, gave a 2,4-dinitrophenylhydrazone
derivative m.p. and mixed m.p. 122-123.5°C (uncorr.).
The
weight of 3,4-dimethyl-2-pentene, based on the ozonolysis
products recovered, was 13.6 grams.
25^ of the original olefin mixture.
This is equivalent to
28
3. Ozonolysis of the High Boiling Fractions
Cuts 16-24 inclusive, 6.8 g., dissolved in 100 cc of
pentane, was ozonized in two hours.
Fractionation of the oil layer.
Col. T.
Head T.
Press.
34.0
60.0
90.0
-
30.0
34.0
35.5
-
734.8
n
n
Frac.
3.8 g*
Wt.
Remai
•
1
0.6
2
0.5
Residue 1.0
peni
Recovery 2.1 g.
1.6 g.
Loss
Fractionation of the water layer •
Col. T.
Head T.
Press•
67.0
38.0
45.0
45 - 51
51 - 56
56 - 58
58 - 68
68 - 74
74 - 77
77 - 80
80 - 85
735 mm
n
1
1
u
it
tt
u
it
-
71.0
71.0
73.0
83.0
—
-
-
Material balance:
n
n
Frac.
wt.
R.R.
1
2
3
4
5
6
7
8
9
0.1
0.1
0.1
0.7
0.1
0.2
0.2
0.1
0.9
4/1
7/1
7/1
5/1
Wt. Of olefins ozonized
total recovery 3.3 g. ; loss 3.5 g.
Identification work:
Acetone, estimated as 0.8 g,
found in cuts 3 and 4 of the water layer and cut 2,
pentane-oil layer, was identified by its 2, 4-dini trophenylhydrazone derivative m.p. and mixed m.p. 122.5123.5°C (uncorr.).
29
Methylethyl ketone, 0.7 g., b.p. 68-80°C (735 mm)
found in cuts 5-9 inclusive, water layer, gave a 2,4dinitrophenylhydrazone derivative m.p. 110.5-112°C and a
mixed m.p. 110.0112.5°C (uncorr.)•
The wt. of 2,3-
dimethyl-2-pentene was estimated as 3.4 g. which corre­
sponds to 5.7$ of this olefin in the original mixture.
Summary:
Four olefins were found to be present as
dehydration products of 2,2,3-trimethyl-l-butanol.
Weight
Yield*
1) 2,4-dlmethyl-2-pentene
2.75 8.
5$
2) 2, 4-dimethyl-l-pentene
8.25 8-
15$
3) 3, 4-dime thyl-2-pentene
13.75 g*
25$
4) 2, 3-dime thyl-2-pentene
3.30 g-
___6$
28.00 8*
51$
Recovery
* The yields were based on the ozonolysis products
recovered.
4. Conclusions
Since only a small amount of formaldehyde was found,
and since the 2,4-dinitrophenylhydrazone derivative of
methyl isobutyl
ketone was very hard to purify, it is
possible that the actual amount of the olefin, 2,4-dlmethyl1-pentene, may be less than the 15$ listed above, the dif­
ference being due perhaps to the presence of some methylisopropyl ketone.
It does not necessarily follow from the
failure to find ethylisopropyl ketone, that the olefin
30
2-ethyl-S-methyl-l-butene was absent*
A
ketone, b.p* 113.8-114°C (745 ran)
20
E thy 11 s opr op y 1
1*4020 Is Isomeric
with methylisobutyl ketone b.p. 117-9°C, n^° 1.3959, and
the presence of a small amount of the former with the
latter w o u l d be difficult to detect*
The presence of isobutyraldehyde and methyllsobutyl
ketone definitely proves that an isopropyl rearrangement
occurred during the catalytic dehydration of the carbinol,
2,2,3- trimethyl-1-butanol at 325-375°C over activated
alumina.
Olefins resulting from the rearrangement of a
methyl group do not give these two substances upon
ozonolysis•
E. Preparation of Tetralsopropylethylene Glycol
1* Purification of Dllsopropyl Ketone
Crude dllsopropyl ketone,
a product of duPont Chemical
Company containing approximately 30# of ethylisopropyl
ketone was purified by careful fractionation through a
column of 13-14 theoretical plates.
A total of 2530 g*,
22 moles, o f pure ketone, b.p. 122-122.8°C (728 mm),
n^
1.3996-1.3998, were obtained from several fractiona­
tions.
31
2 * Reaction o f Dlisopropyl Ketone w ith M a g n e s i u m Amalgam
A modified method of R. Adams and E. W. Adams was
7
use d in this trial run.
A L e l b i g condenser was attached
to a d r y 500 cc r o u n d - b o t t o m f l ask containing 5 g., 0.16
atom, of magnesium turnings and 40 cc of sodium d r i e d
toluene.
A mixture of 5 g. of mec u r l c chloride in 40 g. of
dllsopropyl ketone was added in small por t i o n s with shaking.
No apparent reaction was noticed during the addition which
was completed within fifteen minutes.
The reaction mixture
was then p l a c e d on a s t e a m b a t h and warmed for thirty
minutes.
A f e w bubbles were driven off dur i n g the heating,
but no other noticeable change occurred.
The remainder of the ketone,
20 g., was diluted with
15 cc of dry toluene and added through the top of the con­
denser.
The reaction mixture was heated for one hour at
a temperature which caused considerable b ubbling to occur.
The mixture was finally re f l u x e d for an hour and then,
after cooling down to 50-60°C, was slowly diluted with
10 cc of cold water.
The r e a c t i o n mixture was again heated
for 15 - 20 minutes, and then was filtered while hot.
The
grayish black solid and u n r e a c t e d m a g n e s i u m was shaken with
20 cc of toluene at 75°C to extract any remaining soluble
material.
The toluene solutions were combined and
32
distilled.
Four fractions were taken:
fraction 1, b.p*
1 1 1 . 0 ° C ; 2, 111.0-112.5°C; 3, 112 .5-114.0 ° C ; and 4, 114.0119 . 5°C.
The first three fractions consisted mainly of
toluene, and the fou r t h unreacted dllsopropyl ketone.
No
solid material separated from a n y of the four fractions
on cooling to zero degrees,
so apparently, no reaction
occurred between the magnesium amalgam and the ketone.
3* Reaction of Dllsopropyl Ketone with Alu m i n u m Amalgam
Jozltsch treated diethyl ketone with a luminum amalgam
O
and reported that good yields of the plnacol were obtained^
Approximately the same procedure was used In an attempt to
prepare the plnacol,
tetraisopropylethylene glycol, from
diisopropyl ketone.
To a carefully dried 500 cc round-bottom flask was
added 118 g., 1 mole, dllsopropyl ketone, b.p. 122-123.5°C
20
(728 mm), n^
turnings,
1.4002.
Then a mixture of 12 g. of aluminum
10 g. of mercuric chloride,
and 50 g. of anhy­
drous thlophene free benzene was added rapidly.
was attached to a Lelblg condenser.
tube was attached to the latter.
The flask
A calcium chloride
The materials were
thoroughly mixed b y shaking and the mixture left to stand
at room temperature.
A pink color appeared within five
minutes which gradually changed to r e d over a five-hour
period.
No heat change was noted during this period.
A brownish colored solid had settled out upon standing for
33
about 24 hours and u p o n examining the b o t t o m of the flask,
m etallic m e r c u r y w a s f o und present.
The mixture was
allowed to stand for 50 hours at r o o m temperature bef ore
r e f l u x i n g for three hours.
A f t e r cooling somewhat, 300 co of cold w a t e r was
added slowly w i t h shaking and the solid material removed
by filtering.
The benzene layer was separated off a n d the
water layer e x t r a c t e d w ith 25 cc of be n z e n e .
The benzene
solutions were combined and the e x c e s s water r e m o v e d by
drying over anhydrous p o t a s s i u m carbonate.
The benzene
was d i s t i l l e d off t h r o u g h a 14 i n c h I n d e n t e d f r a c tionating
head and the higher boi l i n g material f r a c t i o n a t e d through
a 14 p l a t e column.
Apparently no r e a c t i o n took place for
p r a c t i c a l l y all of the ketone,
changed.
111 g., was r e c o v e r e d u n ­
The residue, 0.5 g., was p l a c e d in a r e frigerator
and a l l owed to s t a n d for two days, b u t no solid mat e r ial
separated.
4. R e a c t i o n of I s o propyl Grignard R e a g e n t w i t h D i e t h y l
Oxalate
1) P r e p a r a t i o n of Isopropyl B r o m i d e
A small c o n denser was attached to a two-liter roundb o t t o m flask surrounded b y an ice b a t h a n d c o n t a i n i n g 360 g.,
5 moles,
E a s t m a n whi t e label 9 8 - 9 9 ^ Isopropyl alcohol,
630 g. of Baker's U.S.P. grade s o d i u m bromide,
water.
C o n c e n t r a t e d sulfuric acid,
and 3 0 g. of
250 g., was added
34
dropwise through the top of the condenser*
After the
addition was complete, the mixture was warmed on the steam
bath for about an hour, and then distilled up to a
temperature of 135°C*
The distillate was washed three
times with an equal volume of water (to remove unreacted
lsopropyl alcohol), once with dilute potassium carbonate
solution, and again with water*
The crude bromide was
dried over anhydrous potassium carbonate.
Fractionation gave 350 g., 2*8 moles, or a 56.8#
yield of isopropyl bromide b.p* 59-60.5 (739 mm),
20
1.4198-1.4218.
2) Preparation of Isopropyl Grignard Reagent.
A one-llter,
three-necked flask containing 30 g.,
1*5 atom, of magnesium turnings was attached to a condenser.
A dropping funnel and a mercury seal stirrer were also
attached.
The reaction was started in a test tube which
contained a crystal of iodine, a few pieces of magnesium
turnings and a solution of one cc of isopropyl bromide in
two cc of ether.
This reagent was diluted with 25 cc of
ether and was poured into the flask.
was added rapidly.
Then 275 cc of ether
A solution of the bromide 185 g., 1.5
moles, and 100 cc of ether was added over a three-hour
period.
Titration of a 5 cc sample of the clear solution
showed 85# active Grignard reagent.
35
3) Preparation of Diethyl Oxalate.
D r y hydrogen chloride gas generated b y the action of
cone* sulfuric acid on hydrochloric acid and salt was
passed into 800 g.,
10 moles,
of ethanol, cooled in an ice
bath, until a gain of 40 grains in weight was obtained.
The ethanol-hydrochloric acid solution was a d d e d to 140 g.,
1.5 moles,
of oxalic acid
crystals
in a two-liter flask.
The oxalic acid dissolved rapidly on warming.
The solution
was reflu x e d for 12 hours, and then was p o u r e d into 1500 cc
of water.
The h e a v y oil layer was removed and washed with
5% potassium carbonate solution,
with water, and d r ied
over anhydrous po t a s s i u m carbonate.
Two distillations through an ordinary distilling
flask gave 37 g., 0.25 mole,
of diethyl oxalate, b.p. 179°-
1 81°C (735 mm).
4) Addition of Diethyl Oxalate to Isopropyl Grignard
Reagent.
Diethyl oxalate, b.p. 179-181°C ( 740 mm),
35 g.,
0.23 moles, w a s diluted with 35 cc of anhydrous ethyl
ether and the
solution added slowly dropwise
Grignard reagent.
hours.
to the isopropyl
Time required for the addition was four
Some mist formed above the surface of the liquid
where each d r o p of the ester hit.
Gas was liberated
during the addition and the sulfuric acid in trap attached
to the exit line, changed from a colorless to a deep red
36
color.
The sol u t i o n was stirred Tor an hour aft e r the
addition.
vessel*
No solid formation was noticed In the rea c tion
The addition pro d u c t w a s d e c o m p o s e d with wat er
In the usual fashion*
The res i d u e was e x t racted twice
w i t h 200 cc quantities of ether and the e x t r a c t s added to
the m a i n ether solution*
twice w i t h water,
carbonate.
The ether solution was washed
and then was d r i e d over anhyd. p o t a s s i u m
The ether was d i s tilled off thr o u g h a 14 Inch
Indented fr a c tionating head.
W e i g h t of the crude material
was 21.5 g*
Col. T,
H e a d T.
99.0
115.0
125.0
92.0
97.5
105.0
108.0
114.5
114.5
114.5
-
118.0
118.0
118.0
W e i g h t 21.0 g.
Press•
52
50
it
n
48
50
tt
12
n
Frac •
mm
mm
1
2
3
4
mm
5
mm
6
7
mm
8
9
Residue
3
ct
• <
Fractionation data:
0.4
0.4
1.2
0.4
2.0
5.2
7.0
2.0
0.7
2.0
20
R.R.
1.4202
1.4232
1.4230
1.4238
1.4251
1.4285
1.4284
1.4290
4/1
4/1
4/1
4/1
4/1
4/1
Recovery 19.0 g.
2*0 g «
Loss
Conclusions:
1) Some reduction evidently took place,
since a gas
was given off w h i c h colored sulfuric acid red*
2) Fractions 2, 3, 4, 2.0 g.,
diisobutyryl•
pr o b a b l y represents
37
3) Fractions 6, 7 and 8, 14.0 g., probably represent
a ketone-alcohol.
Bouveault and Rene Lecquln round that
diisobutyryl, on treatment with methylmagnesium iodide or
phenylmagnesium iodide, does not give the expected
tertiary alcohol (or glycol), but gives only a simple
alcohol containing one carbinol group and one carbonyl
group.
They obtained 2,4,5-trimethyl-4-hydroxy-3-hexanone
o
by treatment of the diketone with me thylmagnesium iodide.
4) A few crystals formed in fraction 9, which may
have been the expected glycol.
Reduction of Dllsopropyl Ketone with Sodium and 30%
Potassium Hydroxide Solution
Discussion:
Munch prepared diisopropyl carbinol by
the reduction of diisopropyl ketone in a benzene solution
with sodium and water.^
He reported that a small amount
of a heavy oily yellow liquid of a disagreeable odor was
obtained which he assumed to be the glycol.
Experimental:
To a one liter round-bottom flask
fitted with a stirrer and containing 150 g. of benzene
was
added 115 g.,
1 mole, diisopropyl ketone, b.p. 122-123.5°C
(728 mm), n ^
1.4002, and 200 g. of a 30% solution of
potassium hydroxide.
Clean sodium metal, 75 g. (29 g.
excess) cut into small cubes about 1/3 inch on an edge,
was added over a 12-hour period.
added at a time.
From 10 to 20 cubes were
The stirrer, adjusted so that it stirred
38
mainly the top benzene solution, was allowed to run as
slow as possible without stopping.
After adding about
two-thirds of the 75 g. of sodium, the aqueous layer was
siphoned off and another 200 g. quantity of 30# potassium
hydroxide solution added.
(Water may also be added at
this point to cut down the concentration of the alkali.)
After all traces of sodium metal had reacted, 300 cc of
water was added and the benzene layer separated off.
The
benzene solution was washed twice with 300 cc portions of
cold water and then was dried over anhyd. potassium
carbonate.
The benzene was removed by distilling through
a 14-inch indented fractionating head.
fractionated.
Col. T.
133.0
133.0
135.5
137.0
140.0
The residue was
Weight 109 g.
Head T.
Press.
Frac •
20
Wt.
131.0
1
727 mm
1.5
it
131.0
1.2
2
it
132.0
2.0
3
n
4
135.5
3.2
tt
136.0
86.0
5
tt
136.0
6
2.5
(plnacol) residue 6.2
1.4261
1.4215
1.4221
1.4248
1.5252
1.4250
R.R.
5/1
8/1
8/1
4/1
4/1
Yield of carbinol, 91.7 g., 80# yield.
Yield of crude glycol, 6.2 g., 5# yield.
6 . Reaction of Dllsopropyl Ketone and Sodium In a Sodium
Carbonate Solution
This one-mole run was similar to the run described
above except an almost saturated solution of potassium
carbonate was used Instead of a 30# solution of potassium
hydroxide.
Sixty-five grams (10 g. excess) of sodium was
39
added over a 15-hour period.
Occasionally, a little water
had to be added through a pipette in order to dissolve the
solid material which would tend to form and concentrate at
the interface.
Fractionation gave 90.8 g., or an 80}6
yield of diisopropyl carbinol, and 5.5 g. of crude gycol.
Run 3.
Two two-mole runs and one one-mole run were
made in the presence of 25% solution of sodium hydroxide.
Ten hours was required for the addition of the sodium,
60 g., in the one-mole run and 18 hours for the addition
of the sodium, 120 g., for each of the two two-mole runs.
Fractionation of three
292 g., 2.51 moles,
moles of the reduced ketone gave
or an 83/6 yield of carbinol.
No ex­
planation could be given for the failure to obtain the
glycol from these three moles of reduced ketone.
The other
two moles, on fractionation gave 195 g., or an Q5% yield
of carbinol and 14
Run 4.
Three
g.,
of crude glycol.
moles of the ketone gave on reduction
263 g., '15% yield of carbinol and 18.8 g. of crude glycol.
Run 5.
Seven moles of ketone were reduced in two and
in one mole-runs.
Three-liter Erlenmeyer flasks were used
Instead of round-bottom flasks for the reductions.
Frac­
tionation of the seven moles of reduced material gave 45 g.
of crude glycol and 500 g., 67% yield of carbinol, b.p.
137-137.5°C (735 nan), ng° 1.4251-1.4252.
40
7. PurIf1 cation of Tetralsopropylethylene Glycol
The crude glycol, 78.8 g., was purified by crystalliza­
tion from methanol.
The melting point of the pale gray
needle shaped crystals, 60.5 g., was 86-88°C.
A small
sample was recrystallized twice from dilute methanol.
Hie
colorless needles melted at 91-91.5°C.
8. Physlcal Properties of Tetralsopropylothylene Glycol
The pure glycol, m.p. 91-91.5°C, boiled with decompo­
sition at 262-267°C (738 mm).
The molecular weight, as
determined b y the freezing point method, was 227.8 (230
theoretical).
The glycol, which does not form a hydrate
with water, was soluble in alcohol, ether, and benzene,
and Insoluble in water.
F. Dehydration of Te trals opr opyle thylene Glycol
A 24.0 g., 0.1 mole, quantity of the glycol was
catalytically dehydrated over aluminum oxide.
Small por­
tions of the glycol were melted in a separatory funnel
placed on a steam bath.
The melted glycol was added drop-
wise through the separatory funnel.
one portion,
After the addition of
a small stream of dry nitrogen gas was passed
through the apparatus in order to minimize decomposition
of the material in the tube while another portion of the
glycol was being melted.
41
Data:
Batch.
1
2
3
4
Material balance:
Temperature
342
317
330
347
-
Time of addition
345
350
348
365
20
15
25
18
minutes
minutes
minutes
minutes
Weight of glycol dehydrated 24 g.,
total recovery 18.7 g . ; loss 5.3 g . ; wt. of dried products
12.5 g.
Fractionation data.
Col,T.
Head T.
Press.
53.0
55.0
61.0
65.0
55.0
61.8
63.0
71.0
75.5
81.5
85.5
91.5
99.0
105.5
106.0
107.0
734.5
N
It
tt
50 mm
n
tt
145.0
107.8
106.0
108.0
120.0
122.5
122.8
136.0
137.0
..
127.0
49.0
59.0
66.0
-
88.0
98.0
102.0
99.0
105.0
106.0
107.0
107.0
115.0
112.0
114.0
112.0
112.0
119.0
120.0
tm
135.0
145.0
-
Recovery 11.4 g.
it
tt
n
Weight 12.5 g.
20
Frac. Wt.
“D
1
0.3 1.3700
0.7 1.3770
2
0.6 1.3760
3
4
0.2 1.3665
0.1 1.4042
5
6
0.1 1.4180
7
0.1 1.4224
0.1 1.4250
8
9
0.1 1.4289
10
0.2 1.4332
12
0.4 1.4375
13
0.3 1.4358
0.9 1.4349
14
0.3 1.4355
15
16
0.5 1.4362
1.7 1.4362
17
18
19
20
21
22
23
24
25
26
1.7
0.4
0.3
0.1
0.2
0.3
0.1
0.1
0.3
20 m m
27
Residue
1.1
1.1
it
it
1.4360
1.4375
1.4362
1.4480
1.4550
1.4582
1.4578
1.4552
1.4553
R.R.
Remarks
12/1
5/1
5/1
12/1
8/1
8/1
unsaturated
5/1
5/1
liberates HBr
«gg. Br.
0.838
7/1
7/1
7/1
7/1
—
(adds Br2 ;
gives off HBr)
42
Conclusions:
Fractions 11 - 19 inclusive probably
represent the diolefln.
Refractionation of cuts 12 - 20, Inclusive:
Col. T.
Head T.
Press.
107.0
109.0
109.0
109.5
110.0
110.5
110.0
111.2
98.5
101.2
104.5
107.5
108.8
109.2
108.0
105.0
50 mm
it
n
n
n
tt
it
it
Frac
1
2
3
4
5
6
7
8
_20
1.4319
1.4320
1.4332
1.4352
1.4355
1.4355
1.4350
1.4355
Fractions 4 - 8, inclusive, 5.0 g., represent
dime thyl-3,4-di i s opropy1-2,4-hexadi e n e .
G. Oxalic Acid Rearrangement of the Glycol
A 24,0 g ., 0,1 mole,
quantity of the glycol, m.p. 86-
88°C, was placed in a 250 cc distilling flask containing
150 cc of a 4.5# solution (7 g. in 1433 cc water) of oxalic
acid.
The flask was placed under a column and the material
refluxed for 25 hours.
The oil layer solidified on cooling.
A small sample of this solid was removed and was purified
by recrystallization from methanol.
92-92.5°C.
The melting point was
A mixed melting point with the pure glycol
showed no depression.
The concentration of the acid was increased from a 4.5
to a 20# solution by the addition of 23.0 grams of oxalic
acid.
The materials were again heated at the boiling point
43
of the mixture for 15 hours.
fied on cooling.
A sample was removed, purified, and the
melting point determined.
melting point.
The oil layer again solidi­
Ho change was observed In the
The glycol was heated at the boiling point
of the solution for an additional 47 hours, after which
time the oil layer only partially solidified cn cooling to
room temperature.
The remaining solid was melted again,
and the oil layer separated off the hot acid solution.
The unreacted glycol which solidified on cooling, was
filtered off and the liquid, 9.5 g., was fractionated
through a column of 11 theoretical plates.
Head T.
167.0
164.0
164.0
165.0
169.0
169.0
142.0
145.5
150.0
152.5
153.8
154.0
-
-
Press.
Frac.
50 m m
1
“
2
"
3
"
4
"
5
«
6
10 m m
7
Residue
e
Col. T.
Weight 9.5 g.
3
ct
Fractionation data:
(a )
_20
nD
R.R.
4/1
0.5 1.4542
0.5 1.4550
0.9 1*4588
0.8 1.4622
1.0 1.4650
2.0 1.4652
1.3 1.4688
1/1
2.0 (solidified on
cooling)
Recovery 9.1 g.
Los8
0.4 g.
The remainder of the glycol, which failed to react
when heated for 62 hours with a 20# solution of oxalic acid
and 25 hours with a 4.5# solution of oxalic acid, was
treated with a 50# solution of oxalic acid at the reflux
temperature for 38 hours.
44
Fractionation data:
Col. T.
Head T.
168.0
165.5
178.2
153.0
153.0
153.8
153.0
■*
-
•
Weight 10 •1 g.
Press.
50 mm
it
n
tt
it
Frac.
Wt.
1
2
3
4
5
Residue
2.7
0.2
0.8
1.4
1.4
1.1
(B)
20
D
1.4618
1.4650
1.4665
1.4665
1.4682
R.R.
3/1
1/1
Total recovery 8.1 g.
Loss
1.3 g.
First refractionation
Cuts 3, 4, and 5 from fractionation data, B, and
fractions 4, 5, 6 and 7 from fractionation data, A, were
combined and refractionated.
Weight 8.0 g.
Col. T.
Head T.
Press•
Frac.
Wt.
167.0
167.0
167.5
152.5
153.8
153.8
151.0
50 mm
n
it
w
it
1
2
3
4
5
Residue
0.5
1.7
2.1
0.5
1.3
0.2
-
20
nD
1.4617
1.4658
1.4660
1.4660
1.4662
R.R.
2/1
1/1
Recovery 6.7 g.
Loss
1.3 g.
Density of cut 3 was 0 .8934 at 20/4 °C.
Second refractlonatlon
Fractions 2, 3, 4 and 5 from the first refractionation
data, were combined and refractionated through Dr. Fleming^
small fractionating column.
Col. T.
Head T.
175.0
139.0
165.0 mostly 140
158.0
"
140
153.0
140.0
Press•
Frac.
Wt.
28 mm
it
n
it
1
2
3
4
0.4
0.3
0.4
0.5
2°
“d
1.4638
1.4649
1.4650
1.4658
45
Col. T.
Head T.
162.0
162.0
162.0
161.5
161.0
139.0
139.0
139.5
140.5
141.0
Press.
Frac.
5
6
7
!t
8
It
9
Residue
Fract ions , 5-9, were believed to
cl i isopropyl-3-hexanone •
H.
28 mn
n
n
Wt.
n§°
R.R.
0.3 1.4662
0.4 1.4664
0.5 1.4665
0.5 1.4665
1.0 1.4665
0.1 (solid)
be 2 ,G-dimethyl-4,4-
Identification and Physical Properties of the Ketone
An attempt to prepare the oxime derivative in a sealed
tube at 100°C was not successful.
the
An attempt to prepare
semlcarbazone and 2,4-dinltrophenylhydrazone
deriva­
tives was also unsuccessful.
A small portion of the ketone was dissolved in ethanol
and
then sodium metal
ketone.
was added inan attempt to
reduce the
Some material was recovered which had an index of
refraction of 1.4708.
An attempt to prepare a phenyl
urethan derivative from this material was not successful.
An attempt to oxidize the ketone with chromic acid
- and sulfuric acid in an aqueous solution, at room temperao
ture and at 100 C, was not successful.
The material was
recovered unchanged.
The molecular weight, determined by the freezing point
method, was found to be 196.0'(?.). The calculated molecular
weight for 2,.5/-d inethyl-4 ,4-d iisoi>ropyl-3-hexanone is 212.
The material believed to be the ketone,
bromine very slov.ly.
decolorized
46
Active hydrogen, determined "by the Zerewitinoff
method, was found to be 16.6/.
Approximately 10/ of the
Grignard reagent was unaccounted for.
If this unaccounted
amount of the methyl Grignard reagent had reacted with the
ketone, then there was a 10/ addition.
Analysis of the alleged ketone:
By Dr. George Fleming
Caled.*
Sample /7, page 45
/ Carbon
/ Hydrogen
Found
79.2
78.5
13.3
12.0
* The calculated values were based on the alleged ketone,
2 ,5-dime thy l-4T4-diisopropyl-3-hexanone . (
It was
believed,
Cpg IlgQ 0
)
from the results of the analysis,
that an isopropyl group had been lost during the treatment
of the glycol, tetrai3opropylethylene glycol, with dilute
oxalic acid solution.
The calculated values for carbon and hydrogen based on
2,5-dir:ethyl-4-iSOyropyl-Z-hexanone, are as follov;s:
Carbon 7 7.6,! ;
Hydrogen 12.9 /.
These values do not
check with the values of carbon and hydrogen found by the
analysis.
If one as. umes the latter Tetore, 2,5-dimethyl-4-ifoproj.yl-3-hexanone to be uncatuiu ted, i.e., contains one
double b o n d , then the values of e rbon and hydrogen found,
above, agree with the calculated values for this unsatur-.ted
’ 'tone, Oil IlgQ 0, namely, 7o.5,
hp dragen.
for carbon and 11.9/ for
47
Cherefore, the material obtained from the oxalic acid
treatment of t e ’.raisopropylethylene glycol,
item G, paye 42,
is believed to be an uncatur-ted l;e tone, empirical formula,
physical Properties:
The betone, a colorless liquid at
room temperature, has a freezing point ( or m.p.) of 14-15 G
The ketone is insoluble in water, and is soluble in alcohol,
ether, and benzene, 5.p. 153-154
(50mn), or 135 -140 (28mm)
n20l.4GG5(Valentine); d|° 0.5 534.
Junmary
^
nevi alcohol,
2, 2 ,3-trimethy 1-1-butanol has been
prepared and dehydrated.
Dehydrat ion _ave a mixture of four oivfins.
Two of the
olefins were due to an isoj/ropyl shi ft ( 2,4-d imethy 1-2i eitene and 5 ,4-di: .ethyl- 1-pentene ) and two rare due to a
.•ethyl shift ( 3, 4-d im ct hy 1- 2-pen te no and 2, 3-d i: e thy 1-2pentene) •
The ratio of isopropyl shift to methyl shift was
35 to 01 .
The yields
o f
products recovered)
the olefins
(based on the ozonoiysis
obtained from the dehydration of 75 y.,
G.C4 moles, of 2,2,3-trimethyl-l-but? nol, are as follows:
2,4-dime thy1-2—pent ene
2.75 y .
2 ,4-d ir.m: thyl-l-pent ene
G.25 y.
3 ,4 — dime tnyl— 2-peritene
13.75 y.
2 ,3-dimethy 1-2-peiilene
3.3G y.
5y
15,. (?)
25
6>.
47a
A new glycol,
been prepared.
The glycol vias i.:ade to undergo a pinacol
rearrange! .e:it
acid.
The
tetraisopropylethylene glycol, has
her.ting v.’ith a dilute solution of oxalic
constant index 'Material,(page 45, table) was
believed to be an unsaturated ketone
C h H 200.
Thii conclusion v;as based on the following facts:
1). Carbon and hydrogen analysis;
2) Physical properties,
i.e., boiling point, melting point,
density;
, empirical formula,
refractive index,
3) Petern.iiiation of active hydrogen;
and 4) Reaction
with bromine.
The actual struct'.,re of the material believed to be
an u n s e t u m t e d ketone has not been determined.
The material
is thought to be 2,5-dirne thy 1- 4 - iaoi..roiyl-3— hex&none with,
I e r haps, a double bond in the 4-5 ^coition.
B ib 1 io g r c,j..hy
1. i.dinch, u m n . , 1 6 0 , 333
2. houveault and Ren4 , Chemisohes hentralblutt, 2, 1115
(1906)
”
3. Whitmore and Lux,
J. ... C.
>. 5_4, 3448 (1932)
4. Wuigrle,
henske, Tongberg,
6, 466 (19 34)
5 Whitmore,
J. A. C. ... 5_5, 1528
6. W h i t m o r e , Church,
7. Orgcnic Gynthesis,
6
. Jozitsch,
Ind. Eng. Ghem. Anal. Ed.
and heGrew,
(1935)
ibid.
j36, 176
(1934)
Collective V o l u m e J ,page 451.
«J. Russ. ~hy.
Cher;.. 7s. _38, 657
(1906)
48
IX
THE SYNTHESIS OP 2, 2-DIMETHYL-3-ETHYL- 1-PENTANOL
Introduction
Since the original proposed Investigation Involved
the study of an optically active alcohol, 2, 2, 3-trims thyl1-pentanol, and since the starting material (optically
active primary amyl alcohol) was very expensive and diffi­
cult to obtain, a series of reactions, starting with the
reasonably cheap dlethylacetic acid and leading to the
preparation of 2,2-dimethyl-3-ethyl-l-pentanol, was first
undertaken.
(Dlethylacetic acid differs from the optically
active valeric acid only by a methylene group.)
In the latter series of reactions,
some difficulty
was encountered in the attempt to prepare the Grignard
reagent of 2-methyl-3-ethyl-2-chloropentane.
However,
after six unsuccessful attempts, the Grignard reagent was
finally prepared in a 7.l£ yield.
Because of the diffi­
culty Involved in the preparation of the Grignard reagent,
another proposed series of reactions were tried.
This
method involved the preparation of a potassium alkyl com­
pound from which the alcohol could be obtained by the addi­
tion of formaldehyde.
An attempt to obtain the potassium
alkyl compound by the action of sodium potassium alloy on
49
the methyl ether of 2-methyl-3-ethyl-2-pentanol was not
successful under the conditions tried.
Still another method was proposed.
This method i n ­
volved the preparation of 4,4-dimethyl-5-ethyl-1-heptene
by the reaction of allylmagneslum bromide with 2-methyl3-ethyl-2-chloropentane•
The alcohol, 2,2-dimethyl-3-
ethyl-l-pentanol, was to be obtained from the olefin b y a
series of reactions involving oxidation, degradation,
and
reduction.
This investigation was finally given up for work of
a more frui tful n a t u r e .
The original proposed investigation involved the
preparation and the study of an optically active alcohol,
2,2,3-trims thyl-l-pentanol,
in which a rearrangement of
the (secondary) optically active group may occur upon de­
hydration and to determine if an inversion of configuration
occurred during such a rearrangement.
Hi storical
The alcohol,
2-methyl-3-ethyl-2-pentanol, was first
prepared b y L. C l a r k .1
He obtained the alcohol by the
action of methylmagneslum iodide on the ketone, 3-ethyl2-pentanone.
Only the boiling point of the alcohol was
reported in the literature.
50
No information was available In the literature con­
cerning the synthesis of the methyl ether of 2-methyl - 3ethyl-2-pentanol.
No Information concerning the chloride, 2-methyl-3ethyl-2-chloropentane, could be found in the literature.
The corresponding t-iodide, however, was prepared b y
L. Clark .1
No information was available in the literature con­
cerning the preparation a n d the properties of the alcohol,
2,2-dimeth.yl-3-ethyl-l-pentanol•
No information concerning the preparation and proper­
ties of 4,4-dimethyl-5-ethyl-1-heptene was available in
the literature.
Discussion
Mainly olefin and unreacted t-chlorlde was isolated
from the reaction mixtures obtained from six unsuccessful
attempts to prepare the Grignard reagent of 2-methyl-3ethyl-2-chloropentane.
The Grignard reagent was finally
prepared in a 7.1# yield f r o m some of the t-chlorlde which
had stood over anhydrous potassium carbonate for a period
of 8lx months.
51
The usual procedure for the preparation of the
Grignard reagent was followed in the first run.
In the second run, a mixture of the t-ohloride and
ethyl bromide In equal molar quantities was used In an
attempt to prepare a mixture of the two Grignard reagents.
Since difficulty, due to decomposition, was encountered
in the fractionation of some of the t-chloride,
it was
thought that perhaps a trace of hydrogen chloride was
causing the trouble.
So,
a run was made using unfrac­
tionated t-chloride, b u t no Grignard reagent was obtained.
Another attempt to prepare a mixed Grignard reagent,
by a method outlined b y Dr. Wheeler of this laboratory,
was not successful.
A run was also made in a very concentrated solution
of ethyl ether.
The b o t t o m of the reaction vessel was
warmed with a free flame at the start of the addition of
the t-chloride.
The result of the run was that no Grignard
reagent was obtained.
Application of heat was necessary in order to speed
up the reaction of sodium metal on the alcohol, 2-methyl3-ethyl-2-pentanol•
A one mole run was made from which a
67.5% yield of the methyl ether of the alcohol was obtained
by the addition of methyl iodide to the alcoholate.
52
Proof that the material was a methyl ether was ob­
tained from its reaction w i t h constant boiling hydriodic
acid •
Three unsuccessful attempts were made to split the
methyl ether with sodium-potasslum alloy.
runs,
In one of the
the same procedure and technique was followed w h ich
proved to be successful in Dr. H. B e r n s t e i n ’s work on the
splitting of the methyl ether of phenyl ethyl carblnol.
Apparently the reactivity of an ether is greatly affected
by the type and the nature of the groups attached to the
m olecule•
The olefin, 4,4-dimethyl-5-ethyl-1-heptone, was ob­
tained in a 10% yield by a coupling reaction.
Allylraag-
nesium bromide was added to a dilute solution of the t—
chloride.
The olefin could not be obtained entirely free
of a halide impurity b y repeated refractionations.
No
definite chemical p r oof can be offered concerning the
identity of the constant index, constant boiling material
which was assumed to be the olefin on the basis of its
physical properties and its method of attainment.
53
Experimental
A. Preparation of 2,2-Dlmethyl-3-othyl-l-pentanol
1. Preparation of Diethylacetyl Chloride
Seven runs were znade.
A total of 4650 g., 40.0 moles,
of dlethylacetic acid was treated with a 10-20# excess of
thlonyl chloride for 35 to 40 hours to give a total of
4272 g., 31.6 moles, or an average yield of 79# of the
acid chloride, b.p. range 73-78°C (88 mm), nj^° 1.42321.4238.
The b.p. of the pure acid chloride was 73-74°C
20
(88 mm), n^
1.4232.
A typical run:
To a three liter flask containing 875 g., 7.5 moles,
of Carbide and Carbon grade dlethylacetic acid, b.p. 189.9°
20
(732 mm), n^
1.4137, neutral equivalent 116.87,
97.2#, was added 1080 g.
(20# excess)
assay
of thlonyl chloride.
The mixture w a s shaken good, and then, was quickly con­
nected to a condenser, fixed in reflux position,
to w h i c h
there had been attached a calcium chloride tube and a gas
trap.
The endothermlc reaction was considered complete
after standing for 40 hours at r oom temperature.
The
material was fractionated after refluxing for an hour.
Data:
Weight 1120 g.
54
Col. T .
H e a d T.
78.0
77.8
77.8
77.8
53.0
73.2
73.5
74.0
74.0
79.0
79.0
75.5
75.5
Y i e l d 8 4 4 g.,
Press•
Frac .
88 m m
n
ii
it
it
a.
1
2
3
4
Wt.
R.R.
“D
135.0
2.5
2.7
1.5
1.2
Remarks
SOCl*
1.4 2 6 4
1.4252
1.4 2 4 5
1.4239
tt
tt
5
842.8
6
2.5
Res i d u e 120.0
6 .25 moles (83.3#)
5/1
4/1
1.4239
1.4248
good C0C 1
it i»
2. P r e p a r a t i o n of M e t h y l m a g n e s l u m C h l o r i d e
A total
of 2675 g.,
111.5 a t o m s of m a g n e s i u m t u r n i n g s
were t r e a t e d w i t h m e t h y l c h l o r i d e in d i e t h y l e t her
to give
an average y i e l d of 81# m e t h y l m a g n e s i u m chloride.
The
average time r e q u i r e d for the p r e p a r a t i o n of a 7 or 8 m o l e
G r i g n a r d r e a g e n t was f r o m 12 to 15 h o w s .
A t y p i c a l run:
T h e app a r a t u s con s i s t e d of a f i v e - l i t e r r o u n d - b o t t o m
flask c o n t a i n i n g 170 g.,
to which w a s
7.0 moles,
of m a g n e s i u m turnings,
a t t a c h e d a trident and m e r c u r y seal stirrer,
a dropping f u n n e l and an e f f i c i e n t condenser,
38 cm gas i n l e t
o f the flask.
(glass)
tube
and a 0.9 x
that e x t e n d e d to t h e b o t t o m
A s u l f u r i c acid t r a p was a t t a c h e d to a line
leading f r o m the c o n d e n s e r to a window.
To t h e m a g n e s i u m turnings w e r e a d ded 500 cc of d r y
ether,
iodide.
a
small cry s t a l of iodine,
a n d two cc of m e t h y l
The r e a c t i o n s t a r t e d i m m e d i a t e l y .
ch l oride gas,
obtained from a cylinder
sulfuric a c i d bottle,
T h e met h yl
and led t h r o u g h a
tro u g h a tube c o n t a i n i n g f l a k e d
65
sodium hydroxide, and through. & mercury safety v a lve, was
added at a fairly rapid rate until refluxing of the ether
occurred.
Then 2300 cc of ether was added directly through
the separatory funnel.
The addition of the methyl chloride
was continued at a rate which would not cause too vigorous
refluxlng of the ether.
hours.
The reaction was complete in 12.5
Stirring was continued for two hours.
Titration of
a sample of the clear ether solution indicated a 83#
Grignard reagent.
3. Preparation of 2-Methyl-3-ethyl-2-pentanol
The actual yield of the t-carbinol, b.p. 107-108°C
20
(143 mm), nj> 1.434 5, prepared from 3910 g., 28.9 moles of
acid chloride was 1656 g., 12.7 moles.
This yield does not
include the olefin obtained as a result of dehydration of
some of the carblnol during fractionation .
The average
yield of the t-carbinol, b.p. 98-99.2°C (100 mm), for most
of the runs was 55#.
The best yield was 63#.
A consider­
able amount of high boiling material, believed to be the
diketone, was obtained from those runs which gave low
yields of alcohol.
A typical run:
A solution of 336 g., 2.5 moles, of acid chloride in
300 cc of ether was added dropwise to the Grignard reagent
over an 11-hour period,
Stirring was continued for two
hours after the addition was complete.
reagent and the addition compound,
The excess Grignard
cooled in an ice bath,
56
was decomposed b y slowly dropping in Ice*
(Some of the
later runs were decomposed with water under a good con­
denser.)
After the more vigorous reaction had ceased,
water was added w ith shaking until the ether solution
separated from the magnesium compounds.
The ether was
decanted off, and the solid extracted with 300 cc portions
of ether.
More water was added and the extraction con­
tinued until a jel stage was reached.
The ether solutions
were then combined and washed with a 5% solution of sodium
thlosulfate, with a 5% solution of potassium carbonate,
and with water.
The ether solution, dried over anhyd. potassium
carbonate, was distilled through a 1 4 - inch indented frac­
tionating head in order to remove the ether.
The crude
carblnol was fractionated.
Col. T.
He ad T .
Press.
Frac.
Wt.
92.0
94.0
108.0
109.0
114.0
112.0
116.0
117.0
117.0
51.0
52.0
52.0
54.0
97.0
106.0
106.0
107.0
107.2
107.2
107.6
107.8
108.0
108.0
108.0
107.5
145 m m
1
2
3
4
5
6
7
3
9
10
11
12
13
14
15
16
1.9
1.0
0.7
1.4
0.8
3.0
6.1
3.3
7.0
13.0
7.0
13.9
5.7
5.7
2.9
11.8
—
113.0
125.0
115.0
120.0
117.5
118.0
tt
it
143 m m
tt
tt
it
tt
20
nD
1.4202
1.4265
1.4294
1.4295
1.4305
1.4307
1.4309
1.4315
1.4319
1.4315
1.4315
1.4315
R.R.
Remarks
10/1
Carblnol
tt
tt
tt
57
Col. T.
Head T.
Press.
118.0
107.8
-
—
143 m m
n
n
122.0
108.0
Wt.
Frac •
17
18
19
n^
19.6
145.2
2.7
_ _
R.R.
Carblnol
1.4315
1.4315
1.4308
tv
Yield 204*0 g., 63#.
4. Preparation of 2-Methyl-3-eth.yl-2-chloropentane
A total of 1090 g.,
7.34 moles of t-alcohol was
treated with dry hydrogen chloride as d e s c r i b e d below:
A typical run:
by dropp i n g conc.
D r y hydrogen chloride gas, g e n erated
sulfuric acid onto salt wetted w i t h
cone* hydrochloric acid, was pas s e d Into 182 g., 1.4 moles,
of diethylcarbindlmethy l carblnol contained in a 14 x 1.5*
test tube cooled in an Ice-salt bath.
through for s e v e n hours.
The gas was bubbled
The gas was absorbed r a p i d l y at
first and a cloudy color appeared.
This cloudiness
gradually d isappeared and the halide, which se p a r a t e d from
the aqueous acid layer,
was p r a c t i c a l l y colorless.
The
aqueous layer was separated off and hydrogen chloride gas
was passed through f o r another bhree hours.
The halide was then removed,
washed w i t h cold water,
with cold dilute p o t a s s i u m carbonate
then again w i t h water.
solution
(5#), a n d
The halide was d r ied over anhyd.
potassium carbonate.
Some di f f i c u l t y w a s e n c o u n t e r e d in t h e f r a c tionation
of some of the t-chloride.
D e c o m p o s i t i o n would occur at
58
times, even In the presence or a small amount of anhydrous
potassium carbonate*
Data of a successful fractionation
is given below*
Col. T. Head T.
87.0
89.0
90.0
91.0
91.0
90.0
90.0
90.5
90.5
—
it
91.0
91.0
91.0
92.5
65 .5
70.0
76.0
77.6
77.5
77.5
77.8
78.0
77.0
77.5
77.5
-
77.8
78.0
79.5
Press.
50 nan
it
if
if
»
48
50
it
tt
ii
Frac.
1
2
3
4
5
6
7
8
9
ran
mm
10
11
12
13
14
15
Residue
Wt.
0.6
1.2
0.2
1.0
0.7
1.0
5.5
12.7
10.2
11.4
15.7
10.8
11.4
12.5
8.0
3.0
_20
nD
1.4218
1.4248
1.4324
1.4350
1.4352
1.4353
1.4356
1.4354
1.4354
1.4355
1.4358
1.4356
1.4356
1.4356
1.4365
R.R.
Remarks
3/1
4/1
5/1
HC1 odor
n
tt
it
n
odorless
tt
5/1
4/1
5/1
odorless
5/1
5/1
4/1
3/1
odorless
odorless
Fractions 5 to 14 represent good t-chloride.
density of fraction 12 was 0.888 at 20/4°C.
The
The boiling
point of the t-chloride was 77.5-78°C (50 mm).
5. Preparation of the Grignard Reagent of 2-Methyl-5ethyl-2-chloropentane
Six unsuccessful attempts were made to prepare the
Grignard reagent of the t-chloride, 2-methyl-3-ethyl-2chloropentane.
Finally, in the seventh and last attempt,
a 7.1$ Grignard reagent was obtained.
Trial 1.
To 22 g. of magnesium turnings, 50 cc of
dry ethyl ether, and 2 cc of methyl iodide, was added a
solution of 138 g., 0.93 moles, of the t-chlorlde,
59
20
nD 1.4365, in about 300 cc of dry ether.
addition was 4.5 hours.
The time of
Titration Indicated a 28# active
Grignard reagent.
Dry paraformaldehyde, 12 g., was vaporized and passed
In the ether solution.
No carblnol was obtained upon frac­
tionation of the reaction products.
was recovered as olefin.
Apparently,
Most of the t-chlorlde
an error had been
made In the calculation of the per cent Grignard reagent.
Trial 2.
A mixed halide run was made.
A solution of
0.5 mole of t-chloride, kept over anhyd. potassium car­
bonate, and 0.5 mole of ethyl bromide in 100 cc of ethyl
ether were added to 24 g. of magnesium turnings and 350 cc
of ether.
The addition time was 8.5 hours.
The mixture
was stirred for 12 hours and then three 5 cc samples were
titrated.
Titration showed 43# Grignard reagent.
Since
a good grade of ethyl bromide will give a 95# reagent, the
43# Grignard reagent probably all resulted from the reac­
tion of the ethyl bromide.
However, an excess of gaseous
formaldehyde was added to the reagent, but no high boiling
carblnol was isolated among the reaction products.
Trial 3.
t-chloride.
present.
A 0.1 mole run was made using unfractionated
Titration showed that no Grignard reagent was
About 95# of the magnesium was recovered.
60
Trial 4*
Another mixed halide run was made using the
directions outlined by Dr. Wheeler of this laboratory.
Titration of the material indicated a &2% Grignard reagent.
Formaldehyde was added, but no high boiling carblnol was
isolated from the reaction products.
Trial 5*
A Russian chemist found that silicon tetra-
ethylate, Si(0Et)4 , catalyzed certain Grignard reactions
when run in benzene and similar solvents.
No information
was given, however, concerning its use in ethyl ether.
p
A 0.14 mole run was made using three cc of anhyd.
silicon tetraethylate in diethyl ether.
(The silicon tetra-
ethylate was kindly supplied by Dr. Wheeler.)
Results:
No Grignard reaction was obtained.
Trial 6 .
A 0.2 mole run was made in a very concen­
trated solution of ethyl ether.
20
Three cc of a solution of
30 g. of halide, n^
1.4356, was added to five grams of
magnesium turnings.
The bottom of the flask was warmed
for ten minuted with a free flame.
The remainder of the
solution was added over a five-hour period.
Titration
showed that no Grignard reagent was present.
Trial 7.
The preparation of the Grignard reagent.
A few pieces of fine magnesium turnings, a small crystal
of iodine, and five cc of anhydrous ethyl ether were placed
in a clean dry test tube.
Then two cc of t-chloride, which
had stood over anhydrous potassium carbonate for approxi­
mately six months,
was added to the test t u b e •
of head occurred within a minute,
action was taking place.
Evolution
indicating that a re­
As a result of this test,
another run was made.
6 . Preparation of 2,2-Dlmethyl-3-ethyl-j-pentanol
To 6 g., 0.24 atoms,
of magnesium turnings placed in
a 500 cc three-necked flask fitted w i t h the usual attach­
ments, were added one cc of methyl iodide, five cc of a
solution of 34.0 g., 0.25 mole, of t-chloride in 10 cc of
ethyl ether,
tube.
and the Grignard reagent prepared in the test
The remainder of the ether-hallde solution was
diluted with 70 cc of ether and this solution added dropwise over a two-hour period.
the addition of the solution.
Refluring occurred during
Titration of a five cc
sample indicated a 7.1# Grignard reagent.
The reagent
was diluted to 250 cc and five grams of dry paraformalde­
hyde waa added directly.
hours.
Stirring was continued for eight
A slight amount of refluxing occurred just after
the addition of the aldehyde.
The material was decomposed
with wa te r and the residue was extracted with ether.
The
ether extracts were combined and the ether removed by
dl st illation •
Fractionation data:
Weight 29.5 g.
(11 plate column)
62
Col. T.
100.0
103.0
108.0
129.0
96.5
109.0
112.0
113.0
120.0
•
Head T.
101.5
108.5
110.0
115.0
78.5
86.0
85.8
86.5
86.5
87.0
-
-
Press.
Frac •
744.8 mm
1
n
2
tt
3
it
4
50 m m
5
it
6
n
7
n
8
n
9
«
10
it
11
Residue
Wt.
0.2
0.4
12.0
10.5
0.2
0.1
0.1
0.2
0.2
0.3
0.2
3.0
Remarks
—
1.4095
—
1.4281
1.4283
1.4302
1.4311
1.4320
1.4326
1.4325
olefin
olefin
carblnol
carblnol
carblnol
mm
Recovery 24.4 g.
2.1 g.
Los s
Yield of carblnol , cuts 9, 10 and 11, (0.7 gram)
Analysis
by D. Jenkins,
Fraction 11
Calcd.
Found
1st analysis 2nd analysis
Carbon
74.9#
76.4#
73.1#
Hydrogen
14.0#
13.8#
15.1#
A small amount of the phenyl urethan of the alcohol
was prepared.
The melting point appeared to be 138-140°C.
The melting point of a very small amount of the alpha
naphthyl urethan appeared to b e around 95°C.
B. Preparation of the Methyl Ether of 2-Methyl3-ethyl-2-pentanol
1. Preparation of the Sodium Alcoholate of 2-Methyl-3ethyl-2-pentanol
A trial run:
To a 250 cc three-necked flask fitted
with a reflux condenser, a mercury seal stirrer,
and a
63
separatory funnel w a s added 20 g.
(2 g. excess of 0.15
mole) of 2-methyl-3-ethyl-2-pentanol•
A c a l c i u m chloride
tube was fitted to the top of the condenser to prevent the
entrance of moisture.
Metallic sodium 3.45 g., 0.15 mole,
cut in fine pieces was added directly to the alcohol.
slow reaction started.
A
P r o m time to time a little heat
was applied w ith a free flame, but not enough to boil the
t-alcohol.
The stirrer was run intermittently, leaving the
sodium in a v e r y finely divided state.
Hie reaction mix­
ture was allowed to stand over night, and on the following
day just enough heat was applied to remelt the sodium.
The temperature was kept at about 100°C until all of the
sodium had reacted.
A one mole run:
No solvent was employed in this run.
To a 500 cc three-necked flask fitted
with the same attachments described above, was added 130 g.,
1 mole, of anhydrous t-alcohol, b.p. 107-108.2°C (143 ram),
nj^° 1.4314-1.4316.
Twenty-three grams of clean finely cut
pieces of sodium metal was added directly to the alcohol.
After about four hours, 125 cc of sodium-dried thiophenefree benzene was added as a solvent.
The solution acquired a pale yellow color after being
stirred for six hours in the presence of the sodium at room
temperature.
night,
The contents of the flask were stirred over
and on the following day, were slowly brought to the
reflux temperature and refluxed for fifteen hours.
The
64
mixture was
day
the
left
to s t a n d o v e r n i g h t .
solution was
ture a n d w a s
t he d a y .
kept
The
color during
On t h e f o l l o w i n g
a g a i n "brought t o
at t h i s
the r e f l u x
temperature d u r i n g the r e s t
liquid gradually changed
the
course
tempera­
of
to a p a l e r e d
o f the r e a c t i o n .
After five and
one-half days
of r e p e a t e d heating,
and
stirring,
sodium was
c o m p l e t e l y into the
the
converted
f o r m o f the alcoholate.
lO g r a m s
order
of
t-alcohol
to u s e
dried
the e n d
Twenty-two grams
The
following day,
a d ded,
stirring b e i n g continued.
the
brought
The
to boiling
and was
layer was
a n d was
stirred
removed
3 0 0 cc o f b e n z e n e .
and after
of m e t h y l
and
benzene
washing w i t h water,
sodium sulfate
and were
Iodide w a s
The mixture was
there
then
for f i v e h o u r s .
then d i l u t e d w i t h
for five minutes.
The
of
over night,
of m e t h y l
maintained
the aqueous
Iodide,
to 0.15 moles
stirred
five grams
cream-brown colored mixture was
water
wlth Methyl I o d i d e .
solution was
and on the
add a b o u t
of s o d i u m .
calcium chloride was added
sodium alcoholate.
some
o f t h e r e a c t i o n In
the S o d i u m A l c o h o l a t e
trial runs
over
toward
necessary to
up the r e m a i n i n g traces
2. R e a c t i o n o f
A
It w a s
occasionally,
The
top b e n z e n e
layer extracted with
solutions were combined
were d r i e d
fractionated.
over anhyd.
65
Cd. T.
H e a d T.
75.5
8 5. 5
90.0
91.0
90.0
79.5
88.5
92.5
95.0
92.5
95.5
95.0
97.5
Press.
Frac.
752 m m
105 mm
1
it
it
n 6°
R.R.
1.0
1.5
4.5
4.0
2.5
2.4
0.6
2.2
Remarks
benzene
-
2
5
4
5
6
7
8
Residue
it
Wt*
1.4215
1.4216
1.4219
1.4219
1.4256
1.4258
1.4296
1.4508
8/1
8/1
8/1
R e c o v e r y 2 6 . 2 g.
Los s
0 .8 g •
Cuts
ated.
b.p.
5 to 1 0 I n c l u s i v e w e r e c o m b i n e d and r e f r a c t i o n ­
R e f r a c t ion atlon
92.5-95.0°C
gave 8.6 g.
(105 mm),
of product having a
and a refractive
I n d e x of
1 . 4 2 1 6 - 1 . 4 2 1 8 at 20/4°C.
The methyl ether w a s further purified by refluxing
w i t h s o d i u m f o r a n hour,
a n d then r e d i s t i l l i n g .
at 755 m m was
n § ° 1.4217,
1 5 5 - 154°C,
A one mole
run:
good grade methyl
with vigorous
holate.
The
a n d d|° 0 . 8 1 6 5.
A ten p e r cent e x c e s s ,
1 6 0 g.,
of a
iodi d e w a s a d d e d I n s m a l l q u a n t i t i e s ,
s t i rring,
to
one m o l e
a d d i t i o n time was a b o u t
r e a c t i o n m i x t u r e b e c a m e r a t h e r warm,
occurred.
T h e b.p.
The m i x t u r e
of the s o d i u m a l c o ­
o n e - h a l f hou r .
The
b u t no r e f l u x i n g
was s t i r r e d o v e r night.
A large
a m o u n t of s o d i u m i o d i d e h a d f o r m e d a n d s e p a r a t e d o u t over
night.
time,
Stirring was
the
contents
gentle boil
c o n t i n u e d for s i x hours,
of the f l a s k w e r e
after which
s l o w l y b r o u g h t to a
and w e r e r e f l u x e d for two hours.
66
Water was added to dissolve the sodium Iodide*
The
organic layer w a s separated off and washed w i t h dilute
sodium thlosulfate
to remove any free Iodine*
Hie aqueous
layer was extracted with benzene, and the b e n z e n e solution
added to the m a i n portion w h i c h was then w a s h e d w i t h water
and d r ied over anhydrous sodium sulfate at Ice-box
ture*
The benzene
and the excess methyl Iodide w a s removed
b y d i s t i l l i n g through a fractionating head*
gave 97*5 g., or a 67.5# yield
alcohol)
Fractionation
(based on one mole of
of the methyl ether, b.p. 92.4-93.0°C
n§° 1.4216-1.4217,
tempera­
(10O mm),
d^° 0.8153.
3. Reaction of the Methyl E t h e r with Constant Boi l i n g
Hydriodic Acid
A 58 g. quantity of crude hydriodic acid was pur ified
by distilling over
two grams of red phosphorus.
constant b o i l i n g acid was
collected at 124-125°C
The
(735 mm).
To a f l a s k containing 48 grams of (58$) constant
boiling (colorless) hydriodic acid, was added 15 grams of
the methyl ether.
The mixture w a s refluxed for three hours
after w h i c h t h e organic layer w a s separated off, washed
with water,
column*
Data:
and dried and fractionated through an 11 plate
67
Col. T.
Head T.
55.0
66.0
41.2
56.0
Press.
731
lOO
mm
mm
Frac.
Wt.
1
2.9
2
12.0
Residue 1.5
Remarks
methyl Iodide
t-alkyl Iodide
About one-half cc of alcohol separated on saturating
the aqueous layer with sodium carbonate.
(Most of the
methanol was probably converted into methyl iodide b y the
excess hydriodic acid.)
Upon distilling
a few cc of the
t-alkyl iodide at 733 m m pressure, decomposition occurred
at 1 1 5 ° C •
C. The Reaction of Sodlum-p otasslum Alloy
on the Me thy1 Ether
1. Apparatus
The apparatus consisted of a two-liter three-necked
flask,
to w h ich there were attached a gas inlet tube three
inches in length,
a copper spiral,
a one-liter dropping funnel wrapped with
and a condenser.
A rubber tube led from
a one-hole rubber stopper in the top of the condenser to a
two-hole rubber stopper in the funnel; the glass tube,
utilized,
funnel.
extended three inches b e l o w the neck of the
A glass tube was inserted in the second hole of
the stopper to insure an opening.
2. Preparation of the Sodlum-potasslum Alloy
Into the two-liter three-necked flass, were added 0.15
mole, 22.0 g., of methyl ether and 240 cc of dry petroleum
68
ether
(b.p. 60-90°C).
grains
of sodium metal cut Into fine strips and 60 cc of
dry toluene.
In the funnel were placed six
The system was then flushed out w ith d r y
nitrogen gas, dried b y passing through concentrated sul­
furic acid, and through a tube containing flaked sodium
hydroxide.
After passing nitrogen gas through the
apparatus for 15 minutes, 15 g. of potassium metal was
added
to the funnel*
five to one.
toluene.
The ratio of potassium to sodium was
The potassium was weighed out In a beaker of
After obtaining the correct weight of potassium,
the balls w e r e cut Into half size under the toluene and
then quickly transferred with a spatula into the funnel
containing the sodium, toluene and nitrogen gas.
Steam w a s passed through the copper coil around the
funnel and tt» mixture was stirred about every half hour
until the alloy was formed.
about two hours.
A large globule formed in
The alloy was cooled by passing air
through the coil.
3. Reaction of the Alloy with the Methyl Ether
The liquid alloy was m n into the reaction vessel con­
taining 22 g., 0.15 mole of the methyl ether.
The alloy
remaining in the funnel was destroyed b y adding small
amounts of n-butyl alcohol, and then, water.
69
After the addition,
the funnel was replaced with a
mercury seal stirrer and the reaction mixture was stirred
for an hour.
No visible reaction was noticed,
so the
flask was warmed and then was allowed to cool again.
Stirring was continued for five hours at room temperature
and then the reaction mixture was brought to a boil.
A
vigorous evolution of g a s suddenly occurred and a little
of the vapor that escaped through the end of the condenser
ignited spontaneously o n coming in contact w ith air.
After
allowing the mixture to cool down to room temperature,
gaseous dry formaldehyde was added along w i t h a slow stream
of nitrogen gas.
The d r y paraformaldehyde w a s placed in a
500 cc three-necked flask to which there was connected a
nitrogen tube and an electrically heated tube leading to
the reaction vessel.
After the air had been swept out
with nitrogen gas, 20 grams of the aldehyde
(depolymerized
by gentle heating) was slowly driven over into the reaction
vessel.
The reaction mixture became warm as the formalde­
hyde gas was added and the yellow substance, w h i c h had
formed, turned to a reddish-orange color.
Hie mixture was
stirred for three hours and then the excess alloy was
destroyed b y the following procedure:
Wet commercial ethyl
ether was first added in small portions, then a mixture of
ether and
a 3/1 ratio,
ethyl alcohol in a ratio of 4/1,
and then in
then 2/1, and finally 95^ alcohol alone.
After the reaction had stopped,
water was added, and the
70
mixture was stirred until all solid substances had d i s ­
solved.
It was necessary to cool the vessel during the
decomposition.
The organic layer was removed, and the low boiling
materials were distilled off through a fractionating head.
There were obtained from the fractionation of the
reaction mixture,
16.1 grams of the original starting
material, b.p. 93.0°C (100 mm), n|° 1.4214-1.4216.
Apparently no reaction occurred between the alloy and the
ether,
since no high boiling alcohol or residue was
obtained.
Trial 2.
A similar run was made In the same apparatus
with the exception that carbon dioxide was used Instead of
formaldehyde.
No nitrogen gas was added during the addi­
tion of the carbon dioxide.
The carbon dioxide gas, ob­
tained from a cylinder, was dried by passing through
concentrated sulfuric acid.
Approximately 18 grams of the original 22 grams of
starting material was recovered.
residue
Again, no high boiling
(or acid) was obtained.
Trial 3.
This run was supervised b y Dr. H. Bernstein.
The same procedure and technique was followed which proved
to be successful in Bernstein's work with a methyl ether
71
containing a phenyl group.
The quantities of materials used In this trial run
were:
28 g., 0.18 mole, of methyl ether; 17.0 g. of
potassium metal; 7.0 g. of sodium metal; 300 cc of sodiumdried petroleum ether (b.p. 60-90°C) ; and 70 cc of sodiumdried toluene.
The time required for the formation of the alloy was
two hours.
The alloy was in the form of one large gobule.
after cooling, it was run in rapidly.
toluene entered the reaction vessel.
Practically no
The reaction mixture
was stirred vigorously, but no noticeable change w a s noted.
The mixture was then refluxed at the b.p. of the petroleum
ether for seven hours.
During this time some red colored
substance appeared on the sides of the reaction vessel.
The reaction mixture was allowed to cool down to room
temperature and then carbon dioxide gas, passed through a
sulfuric acid bottle, was added at a rate of 2-3 bubbles
per second for four hours.
No heat effect or other
noticeable change was noted during this addition.
The excess alloy was finally destroyed with ether and
alcohol, and the products worked up as previously described.
There were recovered 19.6 grams of the original ether upon
fractionation of the reaction products.
72
4. Conelusiona
The sodium-potassium alloy failed to split the methyl
ether of 2-methyl— 3-ethyl-2-pentanol under conditions
which proved successful for the splitting of a phenyl alkyl
methyl ether prepared by Dr, Bernstein,
D, Preparation of 4,4-Dlmethyl-5-ethyl-l-heptene
1 • Preparation of Allylmagneslum Bromide
The allyl bromide, b.p. 69.7°C
(728 mm) n§° 1.4690,
was purified b y fractionation through a 14 plate column.
To a two-liter three-necked flask connected with a
condenser, a stirrer, and a dropping funnel were added 4.5
moles of magnesium turnings (108 g.),
ethyl ether.
and 300 cc of anhyd.
To 182 g., 1.5 moles of allyl bromide, was
added 860 cc of anhydrous ethyl ether.
This solution was
added to the magnesium and ether at a rate which produced
only a slight amount of reflux.
addition was eight hours.
The time required for the
Titration of a five cc sample
showed 81.0# active Grignard reagent.
2. React!cn of Allylmagnesium Bromide with t-Amyl Chloride
The apparatus consisted of a five-liter flask, a
trident,
a mercury seal stirrer, a dropping funnel, and a
condenser.
The flask was surrounded in an ice bath.
73
The Grignard reagent was filtered into a separatory
funnel by the use of nitrogen gas.
One mole, 110 g., of
t-amyl chloride was placed in the five-liter flask.
After
the t-chior ide had cooled to zero degrees, the addition of
the Grignard reagent was begun.
Hie tes^erature was kept
within a 0 to 5°C range during the addition of the 1.5
moles
(31%) Grignard reagent.
Time required for the addi­
tion was 12.5 hours.
The reaction mixture was
stirred at ice bath tempera­
ture for four hours, then 2.5 hours at room temperature.
The appearance of a solid was noted after stirring for
about an hour at room t e m p e r a t u r e •
Refluxing occurred and
the clear dark liquid gradually became cloudy.
Refluxing
stopped after two hours of stirring at room temperature.
The reaction mixture was then refluxed on the steam bath
for a four-hour period.
by the addition of water.
The excess reagent was decomposed
The ether layer was decanted
off and the residue carefully extracted with ether, water
being added from time to time until a jel was reached.
The extracts were added to the main ether solution and the
whole dried over anhydrous sodium sulfate.
removed through a fractionating column.
Data:
Weight 90 g.
14 plate column.
The ether was
74
Col. T.
56.0
70.0
67.0
75.0
80.0
82.0
85.0
87.0
87.5
88.0
90.0
91.0
92.0
95.0
Head T.
Press.
53.5
51.5
43.0
55.0
58.0
87.0
88.0
92.0
96.0
98.5
101.0
102.5
104.5
105.0
718 m m
n
N
tt
It
It
It
ft
tt
H
tt
tt
tt
Tt
Frac.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Residue
Wt.
2.2
2.6
2.3
3.3
3.4
4.9
1.7
1.2
5.0
4.5
7.8
8.0
9.6
8.0
14.0
20
°D
1.3990
1.4010
1.4005
1.3964
1.4015
1.4146
1.4172
1.4152
1.4152
1.4152
1.4152
1.4140
1.4125
1.4140
R.R.
5/1
14/1
14/1
12/1
8/1
8/1
10/1
9/1
Recovery 81.0 g.
Loss
9.0 g.
Refractionation o f cuts 9 to 15 Inclusive gave 20 g .,
15# yield of a product having a boiling point range of
103.2-104.5°C (735 mm),
1.4146-1.4148 at 20/4°C,
a refractive index range of
and a density of 0.7953 at 20°C.
The physical constants of the expected product, 4,4dimethyl-l-hexene, are as follows:
b.p. 106.2-106.7°C
(742 mm); d|° 0.7198; ng° 1.4102.
The constant index material,
obtained, may be the
expected olefin, together with traces of allyl compounds.
(Allyl alcohol b.p. 97.0°C at 760 mm, n§° 1.4135, d|°
n
20
0.871; allyl bromide, b.p. 69.7°C at 728 mn, nD
20
t-amyl alcohol, b.p. 102°C at 760 mm, d^
1.4690;
20
0.814, njj
1.4052; 1,5-dexadiene, b.p. 59.6°C at 760, n^° 1.4044.)
75
3 . Reaction of Allylmagneslum Bromide with. 2-Methyl-3ethyl-2-chi or op entane .
One mole,
150 g., of the t-hallde was placed In a
three-11 ter flask fitted with the same attachments de­
scribed In the reaction above.
The addition of a solution
of 1.2 moles of active allyl Grignard reagent was started
at a rate of 1 to 2 drops per second after the halide had
cooled to zero degrees.
The temperature was kept between
zero and minus five degrees during the 14 hours of addi­
tion.
During this time, some solid was deposited along
the walls of the reaction vessel.
The reaction mixture
was slowly brought to the reflux temperature of ether and
was refluxed for two hours.
The mixture was then d e ­
composed in the usual w a y and the dried products frac­
tionated.
Data:
Col. T.
80.0
83.0
83.5
95.0
105.0
111.0
111.0
111.0
113.0
113.0
113.0
116.0
116.2
121.0
129.0
100.0
14 p l ate lab. column
Head T.
Press.
Frac.
57.5
83.5
93.5
104.5
108.4
108.6
109.2
109.0
109.4
113.5
112.2
112.5
112.0
112.5
115.0
75.0
733 mm
1
2
3
4
5
6
7
8
9
n
«
ii
tt
it
ii
n
M
It
io
II
11
12
13
14
15
16
tt
II
II
tt
100 mn
Weight 140 g.
20
Wt.
nD
2.2
4.2
1.8
2.3
3.1
5.5
9.9
6.8
9.6
9.1
9.2
10.8
11.0
11.6
9.0
1.4
1.3959
1.4070
1.4104
1.4110
1.4135
1.4145
1.4152
1.4150
1.4155
1.4183
1.4186
1.4219
1.4213
1.4205
1.4221
1.4248
R.R.
8/1
8/1
6/1
10/1
12/1
10/1
10/1
a/i
8/1
8/1
5/1
76
Col. T. H e a d T.
110.0
113.5
116.0
117.0
136.0
100.0
108.0
108.0
109.5
135.0
Press•
Frac.
wt.
100 m m
17
1.6
18
1.4
tt
19
10.0
n
6.1
20
50 m m
21
2.3
2.0
Residue
it
20
°D
R.R.
1.4310
1.4370
1.4388
1.4398
1.4535
5/1
5/1
5/1
1/1
Recovery 132 g.
Fractions 5 to 15 Inclusive were refractionated.
There were obtained 20.4 g. o f material, b.p. 108-109.5°C
on
(728 mm), n£
1.4138-1.4157,
20
d4
0.731.
(The olefin,
2-methyl-3-ethyl-l-pentene, boils at 108-109°C,
20
refractive index of 1.4140, and d4
0.7262.)
and has a
Therefore,
fractions 5 to 15 inclusive, p r o b a b l y were 2-methyl-3ethyl-l-pentene•
4. Refract Ionation of 4,4-Dimethyl-5-ethyl-1-heptene.
Refractionation of cuts 19 to 21 inclusive gave 13.7
grains of material, b.p. 108.2— 108.8°C (100 mm), n^^
1.4384-1.4390.
This 13.7 grams of material was carefully refrac­
tionated.
Data:
11 plate column
Col. T. H e a d T.
118.1
117.5
116.0
118.0
116.5
119.5
107.6
107.4
107.8
108.0
108.2
108.5
108.5
Frac.
Wt.
1
2
3
4
5
6
7
Res idue
0.6
0.3
1.4
2.1
1.4
2.0
2.5
2.0
Press.
101 m m
100
n
it
tt
tt
tt
20
1.4406
1.4390
1.4391
1.4392
1.43 90
1.4392
1.4392
-
R.R.
7/1
7/1
7/1
5/1
5/1
5/1
5/1
R e c o v e r y 12*5 g.
The yield of olefin was about 10#
Density o f fraction 4 was 0.7324 at 20/4°C.
Molecular weight, fraction 5, was 150.4
(Calcd. mol. wt. 154.0)
Molecular refraction calcd. 52.2, found 51.8.
Reaction w i t h B ^ ' C C l ^ s
R a p i d l y d ecolorizes bromine.
Reaction w i t h al c o h o l i c silver nitrate:
slight
p ositive test.
The olefin was again carefully r e f r a c t i o n a t e d in an
attempt
to remove the halogen compound that was present.
R efra c t i o n a t i o n of cuts 2 to 7 inclusive gave 7.0 grams
of material,
1.4393.
b.p.
20
105.5-106.5 C (100 mm), nj>
Result of refractionatin:
The m a terial
gave a slight positive test for halogen.
is almost
1.4392still
Apparently,
impossible t o completely remove the halogen
confound b y fractionation.
it
78
Summary
The Grignard reagent of 2-methyl-3-ethyl-2-chloropentane was finally prepared in a 7.1^ yield after six
unsuccessful attempts.
The methyl ether of 2-methyl-3-ethyl-2-pentanol has
been prepared, and its action v^ith sodium-potassium alloy
has been studied.
The alloy failed to split the methyl
ether under the conditions tried.
A small quantity of the alcohol, 2,2-dimethy1-3-ethyl1-pentanol has been prepared.
A compound which appears to be 4,4-dimethyl-5-ethyl1-heptene has been prepared from the reaction of allyl
Grignard reagent on 2-methyl-3-ethyl-2-chloropentane.
Bibliography
1)
Clarke, L.
Am. Chem. Jour., 39, 574
2)
C. A.
7892 (1939)
32,
79
III
STUDIES OP OPTICALLY ACTIVE COMPOUNDS
Introduction
The purpose of this investigation has already been
discussed in the Introduction of Part II, page 48.
Historical and Discussion
A complete and detailed discussion of the separation
. of optically active primary amyl alcohol,
in a high degree
of purity, from fusel oil by fractionation has been pre­
sented by Dr. J. H. Olewine, Ph. D. Thesis, The Pennsyl­
vania State College, 1938.^
Ihe distillation apparatus was practically Identical
with that used by Olewine In his work.
A total of 55 liters of refined fusel oil, from the
U. S. Industrial Chemical Co. was fractionated, from which
there were obtained 5.9 liters of alcohol having optical
activity.
The best fraction obtained had an observed ro­
tation of -4.67° at 23°C.
This value,
calculated as
specific rotation, -5.9, and using 0.8158 as the density
at 24°C, is equivalent to 97.02# primary active amyl
alcohol.
best cuts:
There were obtained from refractionation of the
3.9 liters of 95-97# alcohol, 0.6 liters of
80
90-95# alcohol, 0.6 liters of 50-90# alcohol, 0.3 liters
of 25—50# alcohol, and 0.5 liters of less than 25# alcohol.
The original sample of the refined fusel oil had an ob­
served rotation of -0.63° at 23°C.
This value, when c a l ­
culated to per cent alcohol is equivalent to 12#.
Primary active amyl alcohol was oxidized to the active
valeric acid in a 69# yield b y the use of potassium di—
chromate in aqueous sulfuric acid solution.
A one mole
run was made using chromic acid in glacial acetic acid
solution.
Only a 40# yield of the active valeric acid
was isolated from the reaction mixture.
covery was 70#.
The total re­
The low yield of the pure acid obtained
in this run was probably due to the difficulties encoun­
tered in separating the active valeric acid from the
acetic acid.
The observed rotation of the pure active valeric acid
(methylethylacetic acid) was plus 16.53° at 28.5°C.
This
value is somewhat higher than the several different values
reported in the literature.
The acid chloride was prepared from the acid and
thionyl chloride by the usual procedure in an 88# yield.
The t-alcohol, 2,2,3-trimethyl-l-pentanol, was obtained
in an 80.4# yield by the addition of the acid chloride to
an excess of methylmagnesium bromide.
The observed
81
rotation of the pur® a l c o h o l was found to be o n l y plus
0.047° at 27°C •
Th® rotation of the t— chi or id®, prepared f r o m the
alcohol b y th® addition of hydrogen chloride, w a s plus
0.03° at 25°C.
The G r ignard reagent of the t-chlarid®
was prepared in 28-30# yields b y th® usual procedure.
The addition of carbon dioxide to the Grignard re ­
agent gave a new acid,
2,2,3-trimethyl-n-valeric acid,
which had a rot a t i o n of minus 0.30° at 2 5 ° C .
The acid
was prepa r e d from the Grignard reagent in a 52# yield.
The anilide of the acid was prepared.
was 68-68.5°C
The melting point
(uncorrected)•
The addition of formaldehyde to the Grignard reagent
gave a new alcohol,
2,2,3-trlmethyl-l-pentanol,
from
which a phenyl urethan derivative, m.p. 137-138°C, was
prepared •
Because
of the low observed rotation values obtained
from some of these compounds,
a study was made to deter­
mine if racemization had occurred.
A study of m e t h y l -
ethylacetyl chloride was undert a k e n because racemization
was most likely to occur in this step, and because the
observed rotation had not previously been obtained.
The
acid chloride was prepared in the usual manner from the
optically active acid and thionyl chloride.
In this run,
82
th© thionyl chloride was removed from the acid chloride at
room temperature by reducing the pressure of the system.
The observed rotation of the acid chloride (in an old two
decimter polarimeter tube) was found to be plus 19.76° at
15°C•
A two-gram sample of this material was heated in a
tube at 100°C for approximately two hours, then the rota­
tion was again determined.
The rotation was found to be
almost zero, thus showing that racemization of the acid
chloride occurred upon heating.
Experimental
A. Fractionation of Refined Fusel Oil
1. Fractionating Column
The nickel column I, Petroleum Refining Laboratory
was used for the fractionation and refractionation of the
fusel oil.
Description:
Column - nickel (No. 20 Stubs
gage wall thickness) ; Diameter - 33 mm (15/16 inches) O.D.
Packing - 3 mm (1/8 inch) single turn rings of No. 26
nickel wire; Packing height - 41 feet; No. of plates 100; H.E.T.P. - 4.9 inches; Maximum throughout - 3.0-3.5
liters per hour; Normal operating through-put - 2.5 liters
per h o u r ; and normal pressure drop - 50 mm.
2. Preparation of PuBel Oil for Fractionation
The refined fusel oil was a product of XJ. S. Indus­
trial Choraleal Co., Baltimore, Md., Serial No. 1736.
The
observed rotation of the refined fusel oil was -0.63 at
23°C.
Three five-gallon cans of the fusel oil was left
to stand for 48 hours at room temperature and 24 hours at
ice-box temperature over three pounds
drous 8odium sulfate.
(per can) of anhy­
The fusel oil was removed from the
ice box and carefully decanted from the sodium sulfate
into d ry ether cans.
The last few hundred cc from each
can was filtered through a
Buchner funnel to remove
suspended sodium sulfate.
3. Fractionation of Refined Fusel O i l .
Run I.
Charged 33,000 cc.
This run required 14
(24-hour) days to fractionate out practically all of the
primary active amyl alcohol.
of condensate
There was collected 14,997 cc
(40# of the total charge), of which 5194 cc
had optical activity.
The fractionation was stopped when
the observed rotation dropped below -1.5°.
The best fractions (360 cc) had an observed rotation
of 4.045, which when calculated as specific rotation
(-4.96) and using the value 0.816 as the sp. gr. of the
alcohol, was equivalent to 84.0# primary active amyl
alcohol.
84
Run II.
Charged 22,000 cc.
This run required 10
(24-hour) days to fractionate off most all of the optically
active alcohol.
Of the 9000 cc of condensate collected,
3000 cc had optical activity.
The best fraction obtained from run II had an observed
rotation of -4.395°, which was equivalent to 91.3^6 primary
active amyl alcohol.
4. Refractlonatlon of Refined Fusel Oil (Optically Active
Alcohol.
Fractions having an observed rotation of -1.86°,
nj^ 1.4040 (toward the beginning of run I) to -0.39, n ^
1.4073 (toward the end of the run) were combined, and
fractions having an observed rotation, Run II, of -2.59°,
n^° 1.4060 (at the start) to -0.45, nj^ 1.4072 (at the
end) were combined to give a total of 8470 cc of optically
active amyl alcohol for refraction.
The same nickel
column was used for the refractionation work.
The following results were obtained from the refrac­
tion of the primary active amyl alcohols
cc alcohol
120
120
720
995
1210
360
360
observed rotation
-4.67 at 23°C
-4.665 at 23°C
-4.66 at 24°C
-4.625 - -4.655
-4.620 at 24°C
-4.61
-4.57
specific rotation
-5.724
-5.720
-5.710
-5.663
-5.660
-5.602
% alcohol
97.02
96.95
96.78
96 - 97
95.98
95.90
94.90
I
85
cc alcohol
605
360
120
120
360
538
observed rotation
specific rotation
-4*32 - -4.52
-4.01 - -4.10
-3.41
—2.82
-1.19 - -1.99
less than -100
-4.19
—3.46
-
# alcohol
90 - 95
83-85
71
58
26-41
less than 20
Therefore, there were obtained approximately:
3.9
0.6
0.6
0.3
0.5
5.9
liters of 95 liters of 90 11ters of 50 liters of 25 liters of
0 liters, total
97# primary active amyl alco
it
tt
tt
it
95#
tt
n
it
tt
90#
it
tt
tt
tt
50#
tt
tt
n
it
25#
The observed rotation of the original sample of re­
fined fusel oil was -0.63° at 23°C, and the specific rota­
tion was -0.772°.
On the basis that the specific rotation
of the pure alcohol is -5.9° (accepted value), and the
density, 0.8158,
at 24°C,
the per cent optically active
alcohol in the fusel oil was 12#.
All the calculations
of the per cent alcohol were based on the accepted values.
5. Analysis of Fusel O i l .
Industrial Alcohol Co.)
1) Normal pentane,
(Serial No. 1736, U. S.
lO cc (Note, the column was dried
with n-pentane)
2) Normal valeraldehyde (?) 0.2#
Semicarbazone,
m.p. 121.0°
3) Normal propyl alcohol, 1.0#; alpha naphthyl urethan
m.p. 77-77.5°, and mixed m.p. 78.5-79°C.
86
4)
m.p.
Isobutyl
alcohol,
25.5#;
alpha naphthyl urethan
103-103.5°C.
5)
Normal butyl
a lcohol,
2 . 5 # ; p h e n y l u r e t h a n m.p.
5 7 - 5 7 . 5 ° C ; a l p h a n a p ht h y l u r e t h a n m.p.
6 ) P r i m a r y ac t i v e amyl alcohol,
7) I s o a m y l a l c o h o l
(Note.
Different
percentage
B.
10.0#.
and h i g h e r b o i l i n g
fusel
of p r o d u c t s
70-70.5°C.
products,
oils w i l l v a r y In t h e n a t u r e
61#.
and
present.)
P r e p a r a t i o n of 2 , 2 . 3 - T r l m e t h y l - n - v a l e r i c A c i d
1. O x i d a t i o n of O p t i c a l l y A c t i v e 2 - M e t h y l - l - b u t a n o l
R u n 1,
Chromic
of o p t i c a l l y a c t i v e
necked flask
14 0 g.,
Add
Oxidation.
alcohol
surrounded by a
1.33 moles,
contained
acid) •
of c h r o m i c
w i t h stirring,
s e cond.
Hie time
(140 g. w a t e r
a t a rate
a n d 1 260 g.
of about
a drop per
r e q u i r e d f o r the a d d i t i o n o f the
alcohol kept between minus
was
hours.
30 hours.
three­
acid d i s s o l v e d in a 9 0 #
to t h e
temperature,
two-liter
The a c i d s o l u t i o n w a s a d d e d t o t he
alcohol,
13
In a
88 g.,
salt-ice bath, w a s added
s o l u t i o n of g l a c i a l a c e t i c a c i d
of acetic
To o n e mole,
T h e m i x t u r e was
and was
five
to p l u s
acid
five d e g r e e s
a l l o w e d t o w a r m up t o r o o m
stirred at r o o m t e m p e ra t u re
The mixture was distilled
through
f or a b o u t
an o r d i n a r y
87
distilling flask —
th® first 300 cc of distillate was sot
(b.p. 92-105°)•
The distillation was continued
until the residual mixture became rather thick.
This gave
900 more cc of distillate, b.p. range 105-112°C.
The residue was diluted with water and then was sub­
jected to steam distillation.
A total of 28 cc of oil and
2500 cc of condensate was collected.
The oil was removed
and the distillate neutralized with a 25# sodium hydroxide
solution.
The alkaline distillate was extracted with
ether and then was evaporated on a steam b a t h to a solid
mass.
The 300 cc of distillate
(b.p. 92-105) was also
neutralized and evaporated to a solid mass.
The 900 cc of distillate was carefhlly fractionated
through a 14 plate column.
This gave 25 g. of crude acid.
The oil layers obtained from ether extraction of the
alkaline distillate were combined w ith the 28 cc of oil
collected on steam distillation,
and the whole refluxed
for a six-hour period with 25# sodium hydroxide.
alkaline
The
layer was removed and evaporated to dryness, and
the alkaline salts combined and placed in a large flask
cooled in an ice-salt bath.
Cold 65# sulfuric a d d
solu­
tion was added slowly, with stirring until the material
was strongly acid.
The oil layer which separated was re­
moved and the acid solution extracted with ether to remove
88
traces
of a c i d •
Hie c r u d e acid was d l r e d o ver a n h y d r o u s
sodium s u l f a t e a n d t h e n p h o s p h o r u s pentoxide.
Fractionation data:
Col. T.
W e i g h t 38 g.
H e a d T.
Press.
110.2
115.0
119.0
119.0
119.5
lOO mm
*
II
It
"
114.5
121.0
123.0
125.0
125.0
Frac •
(11 p l a t e column)
_ 2°
“D
Wt.
1
1.2
2
2.3
3
2.5
4
25.1
2.6
5
Residue
1.0
1.4061
1.4057
1 .4 0 5 8
1.4062
R.R.
5/1
6/1
5/1
5/1
5/1
R e c o v e r y 35 g.
Yield, f r a ctions 3 to 5, 31 g.,
4 0 % b a s e d o n the alcohol.
Total r e c o v e r y f r o m oxi d a t i o n of t h e alc o h o l - 70%.
R u n 2, Dlchrornate Oxidation.
Materials:
320
840
1450
2500
g., 3.6 moles o f 9 3 % p r i m a r y active amyl alcohol
g., 2.0% excess of s o d i u m di c h r o m a t e c y r s t a l s
g., c o n c e n t r a t e d s u l f u r i c acid
g., w a t e r
Method.
The d i c h r o m a t e was d i s s o l v e d in the water,
and the a cid added s l o w l y to the solution.
t emperature h a d d r o p p e d
added s l o w l y w i t h g o o d
to zero degrees,
stirring.
A f t e r the
the a l c o h o l was
The t emperature was
m a i n t a i n e d b e t w e e n m i n u s five to plus t e n d e g r e e s d u r i n g
the addition.
hours.
The a d d i t i o n time was n i n e and o n e - h a l f
T he solution w a s stirred for f o u r hours and t h e n
was b r o u g h t to a boil a n d ref l u x e d for an hour befo r e
steam distil l i n g .
S t e a m d i s t i l l a t i o n was c o n t i n u e d u n t i l
a 5 cc sample of the c o n d e n s a t e r e q u i r e d less than 1 cc of
89
0,1 normal alkali (phenol, lnd«),
a total of nine liters
of distillate was collected.
The oil layer was removed and was shaken with a 10%
solution of sodium hydroxide.
The Insoluble material was
treated with a 50% solution of sodium hydroxide for five
hours at reflux tenperature.
The neutral material was re­
moved and was treated again with a solution of dichromate
from which only 25 g. of neutral prodviets were obtained.
The distillate was made alkaline with sodium hydroxide
and the alkaline solutions combined and evaporated to a
s *mi— solid mass.
Small portions of the semi-solid material
was placed in a two-liter round-bottom flask, cooled in a
salt-lce bath.
Then a 65% solution of sulfuric acid was
added in 10-20 cc portions with vigorous shaking until
the resulting solution was strongly acidic.
The insoluble
acid layer was removed and the aqueous sulfuric acid solu­
tions combined and treated with ether.
An emulsion formed
which would not be broken due to the presence of silicic
acids.
The ether was finally removed by steam distilla­
tion, and the valeric acid layer, remaining, was separated
off.
steam was passed in and two liters of distillate
collected.
This distillate was worked up in a similar
manner and the acid residues combined and dried with sodium
sulfate and phosphorus pentoxide.
90
Fractionation data s
Col. T.
H e a d T.
Press•
116.0 to 100.0
130.0
116.0
122.0
116.5
127.0
118.0
129.0
119.0
126.5
119.0
119.7
127.2
130.0
119.8
130.5
lOO m m
n
W t . 288 g
Frac.
1
2
3
4
5
n
tt
*»
it
6
N
7
8
9
tt
tt
Wt.
14.2
9.8
4.2
2.8
2.8
12.7
99.0
134.6
—
1.3977
1.4027
1.4034
1.4042
1.4052
1.4055
1.4058
R.R.
Remarks
3/1
5/1
5/1
5/1
5/1
5/1
4/1
3/1
wet
dry
2,49 moles,
observed r o t a t i o n of the p u r e acid
at 28.5°C was plus 16.53.
fair l y
g o o d acid
g ood acid
good acid
1 .0
Residue - t a r r y m a s s (about 3 g.)
Yield, c u t s 5-8 inclusive, 252 g.,
The
nD
or 6 9 # yield.
(no solvent)
(All of* the observed r o t a t i o n s
were d e t e r m i n e d in a two-decimeter tube with, a Sch m i dt and
H a e n s c h two-third shadow instrument
Germany.
(No. 8335), Berlin,
A s o d i u m v a p o r lamp was u s e d as a light source.)
2. P r e p a r a t i o n of* M e t h y l e thyl acetyl Chi or lde
To 250 g.,
acetic acid,
2.5 moles,
of optically active methylethyl-
was added a 40# excess of 2.5 moles,
of thionyl ch l o r i d e
(Eastman t e c hnical grade).
was left to stand w i t h an occasional shaking,
Finally,
Th© mixture
for 3 8 hours.
the m i x t u r e w a s slowly b r o u g h t to a boil,
r e f l u x e d for o n e - h a l f hour bef o r e
ation gave 265 g.,
chloride, b.p.
2.2 moles,
68 - 71°C
420 grams
fractionating.
and was
Fraction­
or an 88# yield of acid
(150 ram).
91
3. Preparation of Methylmagnealum Bromide
Materia Is s
H O g., 4.5 moles, magnesium turnings
1 cc of methyl iodide
1800 cc of anhydrous ethyl ether
Cylinder of methyl bromide
The usual apparatus was set up f o r methyl Grignard
preparations.
The methyl bromide gas was passed through
concentrated sulfuric acid and a tube containing sodium
hydroxide.
Time required to prepare the 95# Grignard
reagent was 10 hours.
4. Preparation of
,2.3— Plmethyl-2-pentanol
A solution of 158 g., 2.15 moles, of acid chloride
in 800 cc of ether was added to sun 0.8 mole excess of the
theoretical 4.3 moles of active Grignard reagent.
addition time w a s from 9 to 10 hours.
The mixture was
stirred for an hour before decomposing with water.
the decomposition,
The
After
the ether solution was removed and the
residue extracted with ether.
These solutions were com­
bined and were washed with a 5# solution of sodium thiosulfate, w i t h water, and then dried w i t h a sodium sulfate potassium carbonate mixture.
The ether was removed through
a 14 inch indented fractionating head.
Data:
Weight 236 g.
(14 plate column)
92
Col. T.
77.0
78.0
78.0
81.5
82.0
82.0
8 2.0
82.5
86.0
95.0
Head T.
45.0
59.0
65.0
74.0
78.0
81.0
82.0
83.0
85.0
85.2
86.0
Press.
Frac.
wt
100 m m
1
1.8
it
2
1.7
tt
3
0.7
t»
4
1.9
tt
5
2.5
it
6
1.8
it
7
2.0
it
8
1.8
n
9
4.6
tt
10
9.7
it
11-21 193.6
2.0
Residue
R e c o v e r y 222 g.
Yield, fra ctions 10 - 21 inclusive,
or an 80,4# yield.
The
.
20
R.R.
1.4020
1.3954
1.3990
1.4042
1.4111
1.4163
1.4193
1.4193
1.4237
1.4248
1.4250
5/1
5/1
4/1
4/1
6/1
4/1
201 g., l. 3 moles
observed r o t a t i o n for the pure alcohol
(no
solvent) w a s plus 0 . 0 4 7 ° at 27°C.
5. P r e p a r a t l o n of 2 , 5 - D l m e t h y l - 2 - c h l o r o p e n t a n e
T h e r e were ob t a i n e d f r o m 60 g., 0.5 mole of o p t ically
active
alcohol.
(75 mm),
55 g.,
0.4 mole of t-chloride, b.p. 68-69°C
1.4296-1.4298.
The t-chloride was prepared
b y p a s sing dry hydrogen chloride
through the alcohol.
The
o bserved r o t a t i o n of the t-chloride was plus 0.03° at 25°C.
6 . P r e p a r a t i o n of the G r i g n a r d Reagent
M a t e r 1 als s
0. 4 mole, 5 5 g. of t-chloride
0.4 atom, 9.6 g. of m a g n e s i u m turnings
130 cc of anhydrous ethyl e t h e r
A small crystal of iodine
The procedure used for the p r e p a r a t i o n of the Gr i gnard
reagent w a s identical to that de s c r i b e d in run 2, page 13.
93
The addition time was six to eight hours.
Titration of
a 5 cc sample sho w e d 29# Grignard reagent.
7 * P r e p a r a t i o n of 2,2,3 - T r l methyl-n-valeri c Acid
Pressure ca r b o n a t i on of the Grignard reagent:
thoroughly cleaning and d r y i n g the autoclave,
swept out b y a g u s h of carbon dioxide.
After
the air was
The G r i g n a r d r e ­
agent was p o u r e d in, and the flask was renched w i t h a few
cc of d r y ether.
The valves were closed, a n d the head of
the autoclave s e c u r e l y fastened.
The carbon dioxide bomb
was a t t a c h e d a n d a pressure of 400 lbs per sq. i n c h of
carbon d i o x i d e w a s added.
after an hour,
The apparatus was shaken and
the pressure had dropped to 325 lbs.
The
pressure was a g a i n raised to a b out 400 lbs. and then,
after shaking, w a s left to s t a n d over night.
was 360 lbs.
on the
following day.
opened and the apparatus
The pressure
The valve was s l i g h t l y
slowly allowed to come
to a t m o s ­
pheric pressure.
The mat e r i a l was c a r e f u l l y removed and ice was added
to decompose the a d d i t i on conqpound.
Finally,
the material
was made d i s t i n c t l y a c i d w i t h 65# sulfuric acid.
The
ether solution w a s r e m o v e d and the aqueous solution ex­
tracted w i t h ether.
The ether was removed a n d the organic
material t r e a t e d three
hydroxide.
times w ith a 20# solution of sodium
About 12 g.
the alkaline extraction.
of neutral products r e m a i n e d after
These extracts were acidified
94
with S5% sulfuric acid and then made strongly acidic.
The
Insoluble acid layer was removed and the solution extracted
twice w i t h ether.
The acid obtained f r o m the
tracts was added to the main acid portion.
was dried over phosphorus pentoxlde.
ether ex­
The crude acid
After drying,
the
acid was d e c a n t e d off and the phosphoric acid — phosphorus
pentoxlde res i d u e treated with dry eth y l ether to remove
the last traces of the acid.
(Phosphoric acid is insoluble
in ethyl ether.)
Fractionation data:
Col. T.
152.0
155.0
163.0
168.0
Head T.
146.5
147.0
147.5
147.0
Wt. of dry a c i d 9.0 g.
(11 plate column)
Press.
Frac.
Wt»
n^°
Remarks
55 m m
1
0.8
"
2
0.5
1.4352
"
3
3.7
1.4351
so
"
4
3.5
1.4352 dj 0.9315
Residue - less than 1 g.
Re c overy 8.5 g.
Y i e l d of acid, 8.4 g., or a 52% yield,
ba sed on the 28^ Grignard reagent.
The observed rotation of the acid was minus 0.30°
at 2 5 ° C •
8 . P r e p arat i o n of the Anlllde of 2,2.3-Trlmethyl-n-valeric
Acid
One cc of fraction 4 was placed in a clean d r y test
tube contai n i n g an equal volume of thionyl chloride.
the Initial reaction h a d ceased,
After
th© test tube was warmed
on a steam b a t h until no more gas was liberated.
T hen the
excess thio n y l chloride was removed b y u s i n g vacuum suction.
95
Than aniline was added. dropwise w i t h shaking to the acid
chloride to w h i c h there h a d h e e n added three cc of d r y
benzene.
A solid separated as e ach drop hit the solution.
An e x c e s s of aniline was added,
then w a t e r and a six
normal solu t i o n of hydrochloric acid.
benzene was
added,
About ten cc of
and after shaking thoroughly, the b e n ­
zene solution was separated off.
The solution was washed
again w i t h water, then w i t h d i l u t e sodium carbonate,
water,
The
with
and then dried w i t h anhydrous p o t a s s i u m carbonate.
anllide was obtained by e v a p o r a t i n g off the benzene.
The
colorless anllide, p u r i f i e d b y three r e c r y s talli­
zations f r o m dilute methanol, m e l t e d a t 68-68.5°C.
C • R a c e m l z a t l o n of Me t h y l e t h y 1 acetyl Chloride
In order to d etermine if r a cemlzatlon occurred d u r i n g
the prepara t i o n of the acid chloride or d u r i n g its purifi­
cation b y fractional distillation,
a 0 .15 mole,
15 g.
qu a ntity of optically active acid,
(Obs. rot. 4-16.53 at
28°C) was treated in the cold w i t h a 30# excess of 0.15
mole of thionyl chloride
(30 g.).
The
two materials were
mixed and allowed to stand for four hours at r o o m tempera­
ture.
Then the excess of thionyl chloride was removed at
r o o m te m p e r a t u r e b y pulling about 15 m m of vacuum on the
flask containing
the mixture.
A gas trap was p l a c e d in
the s y stem w h i c h was surrounded b y ice water.
After five
96
hours, p r a c t i c a l l y all of* the thionyl chloride was
completely removed, and most or the acid chloride was
found in the gas trap*
The material considered to he
reasonably pure acid chloride weighed 17.5 grams.
The
acid chloride was placed in an old polarimeter tube and
the observed rotation,
determined at 15°C, was plus 19.76°.
A two gram sample of this acid chloride was heated in
a tube
to a temperature of approximately 1 0 0 °C, for a two
hour period.
Then a w e i g h e d amount, 1.247 g., was diluted
to 18.8 cc w i t h d r y petroleum ether, and then was observed
in the polarimeter.
The r o tation was a l m o s t zero.
There­
fore, racemlzatlon did occur on heating the optically
active acid chloride at high temperature for a period of
time.
Apparently, racemlzatlon does not occur to any
appreciable extent in the reaction of the acid with
thionyl chloride at r o o m temperature.
D . Preparation of 2 ,2 ,3- Trimethyl-1-pentanol
Reaction of the Gri g n a r d Reagent of 2.5-Dlmethyl-2chloropentane w lth Formaldehyde
To 18 g., 0.75 g. a t o m of m a g nesium turnings, was
added 0.72 mole,
98 g.,
of 2,3-dime thy1 -2-chioropentane
(obs. rot. at 25°C, plus 0.03°).
The reaction was started
in a test tube b y adding one cc of the t e rtiary chloride
to three cc of ether,
a crystal of iodine, and a few small
97
pieces of m a g n e s i u m turnings.
This reagent was added alone
with one cc of meth y l Iodide to the m a g n e s i u m In the flask.
Then 10 cc o f a solution of 98.0 g. of the halide In 60 cc
of e t her was added.
The r e m ainder of the solution, diluted
with 180 cc of ether, was a d d e d over a two— hour period.
five cc sample was titrated.
A
The p e r cent Grignard reagent
was 45$.
To the 0.32 molar Grignard rea g e n t w a s added 30 g.,
1.0 mole,
of formaldehyde,
formaldehyde.
the addition
and five g r a m of solid p a r a ­
The mixture w a s stirred for two hours before
compound was deconqposed.
crude dried material,
The weight of the
after refluxing w i t h a solution of
15 cc of c o n c e n t r a t e d hydrochloric acid and 3 0 cc of 95$
ethanol for one-half hour, was 40 grams.
F r a c t i o n a t i o n data:
Col. T.
H e a d T.
Press •
35.0
35.0
51.0
62.0
80.0
110.0
31.0
35.0
32 . 0
40.0
74.5
1 03.0
103.0
108.0
1 10.5
114.0
114.5
114.0
100 m m
n
ii
it
it
—
110.0
112.0
116.0
116.0
117.0
Recovery 32 . 3 6 *
tt
ii
ti
ii
ii
it
it
(11 plate column)
Frac.
Wt.
4.9
1
1.0
2
9.5
3
3.6
4
1.2
5
1.6
6
0.2
7
8
1.1
9
0.2
10
0.3
1.0
11
2.7
12
residue
_ 20
D
1.3972
1.3995
1.3982
1.4017
1.4230
1.4285
1.4338
1.4370
1.4373
1.4378
R.R.
Remarks
4/1
4/1
-
olefin
olefin
olefin
ole fin
carbinol
carbinol
carbinol
98
F r a c t i o n s 7, 8 a n d 9 a n d the r e s i d u e were t r e a t e d
again
with concentrated hydrochloric
at r e f l u x t e m p e r a t u r e
w i t h water,
the
for o n e - h a l f hour.
with dilute carbonate
m a t e r i a l was f r a c t i o n a t e d .
g r a m s more
of the carbinol,
1.4372-1.4378.
After washing
s o l u t i o n and d r y i ng,
Fractionation gave
b.p.
A t o t a l of 5.4 g.
the G r i g n a r d reagent,
acid and 9 5 % ethanol
114.0°
1*4
(100 n m ) , n ^ ° .
(a 12# y i e l d b a s e d on
or a 5 # y i e l d b a s e d on the
t-chloride)
of 2 ,2, 3 - t r i m e t h y l - l - p e n t a n o l was obtained.
One
cyanate.
cc of the c a r b i n o l was t r e a t e d w i t h p h e n y l i s o The phenyl urethan,
at 137-138°C.
after purification,
melted
99
Summary
P r i m a r y acti ve amy l a l c o h o l was obtain ed
d i s t i l l a t i o n of refined
liters
f u s e l oil#
of the o p t i c a l l y a c t i v e
by the
Approximately
four
a l c o h o l v/ere o b t ained w h i c h
had an o p t i c a l p u r i t y of 95 - 9 7 ^
It w a s
the acid
found that racernization oc cur r e d
c h l o r i d e of o p t i c a l l y
A n e w acid,
some
on h e a t i n g
active m e t h y l e t h y l a c e t i c
2 , 2 , 3 - t r i m e t k y l - n - v a l e r i c acid,
o p t i c a l activity,
h as b e e n synthesized,
acid.
having
and its a n i l i d e
d e r i v a t i v e has b e e n p r e p a r e d #
The n e w alcohol,
2 , 2 , 3 - t r I m e t h y l - l - p e n t a n o l , and
nhenylu r e t h a n derivative,
its
has bee n i r e p a r e d .
Bibliography
1).
J. H# Olewine, i-h# I). Thesis,
Ttate College, 1938,
The P e n n s y l v a n i a
100
IV M I S C E L L A N E O U S S T U D I E S
Introduction
A n e w n o n a n e , 3 - m e t h y 1 -4— e t h y 1 - h e x a n e , and
clecane,
a new
2-methy 1-5-ethyl—heptane were synthesized,
thei* physical constants were
and
determined.
H i s t o r i c a l and D i s c u s s i o n
The
s y n t h e s i s o f s e v e r a l n ew h y d r o c a r b o n s h a v e b e e n
undertaken
constants
in t his l a b o r a t o r y ,
on pure h y d r o c a r b o n s
i m p o r t a n t b o t h in p u r e
Th e new n o n a n e ,
was
by
the
C - C - C - O H _______ ^
C
increasingly
in the s t udy
3-methyl-4-ethy1-hexane,
f o l l o w i n g s e r i e s o f reactions:
C - C - C - C l _______± C - C - C - H g - C l
C
6
C02
C - C - CI - C
-OH
M
C O
-
"
''
^
>
excess
OH
C-C-C-&-C-C
» I
c q
are b e c o m i n g
c h e m i c a l r e s e a r c h and
of petroleum.
synthesized
sinoe a c c u r a t e p h y s i c a l
C - C - C• - Ci»- C l
C O
CgH^LIgBr
>
C— C - C - C - C — C
\'
C Q
C
C-C-C-CzC-C
i
C-C-C-C-C-CI I
c c
6
i
°S
101
P r o m the I d e n t i f i c a t i o n of the oz o n o l y s i s products,
it w a s found that no r e a r r a n g e m e n t o c c u r r e d during the
d e h y d r a t i o n of 3 - e t h y l - 4 - m e t h y l - 3 ~ h e p t a n o l .
A large p r o p o r t i o n o f the o l e f i n m i x t u r e was o b t a i n e d
as a result of d e h y d r a t i o n dur i n g the f r a c t i o n a t i o n of the
alcohol.
The r e m a i n d e r of t h e olefin m i x t u r e was o b t a i n e d
f r o m the deh y d r a t i o n
of the alcohol over anhydrous copper
sulfate•
The h y d r o c a r b o n w a s obt a i n e d b y the h y d r o g e n a t i o n of
the olefin m i x t u r e in an Adkins
type shaker bomb.
Raney
nickel was u s e d as a catalyst.
The new decane was prepared by the following series
of reactions.
C - C - C O H _______ ^
i
x
C
C-C-C-Br
•
C
_______ ^
^
-—
C-C-C-MgBr
i
c
(c 2h 5)2chcho
C-C-C-9-C—C-C*
C
OH b
—
c
§
c-c-c-c=c-c-c
•
»
c
c
c-c-c-c-c-c-c
I
I
C
c
c
*The alcohol, 2-methyl-5-ethyl-4-heptanol, was prepared and
dehydrated by Mr. R. S. Thorpe of this laboratory.
102
The dehydration
a l u m i n u m oxide,
The
or the alcohol,
over activated
proceeded without rearrangement.
ol efins,
2-methyl-5-ethyl-3-heptene and 2-methyl-
5 - e t h y l - 4 - h e p t e n e w e r e f o u n d t o be p r e s e n t in a r a t i o of
55 to 45$, b a s e d on
the o z o n o l y s i s p r o d u c t s r e c o v e r e d .
The h y d r o g e n a t i o n of the o l e f i n s w a s c a r r i e d out In
an A d k i n s
type shaker b o m b u s i n g Raney nickel
as a catalyst,
Expe r i m e n t a l
A.
1,
Preparation
of a N e w N o n a n e , 3 - M e t h y l - 4 - e t h y l - h e x a n e
P r e p a r a t i o n of S e c o n d a r y B u t y l
M e t h o d A,
to stand
Py r i d i n e ,
1 . 5 Kg,,
w a s d r i e d b y a l l o w i n g it
over s t i c k p o t a s s i u m h y d r o x i d e for s e v e n days.
To a t h r e e - l i t e r
secondary butyl
f l a s k c o n t a i n i n g 5 2 0 g.,
a l c o h o l and 800 g.,
were attached a reflux
funnel,
Chi or lde
condenser,
A calcium chloride
7 moles,
10 moles,
a s t irrer,
p y r idine,
and a dropping
tube w a s a t t a c h e d to t h e end of
the c o n d e n s e r w h i c h l e d to a gas t r a p a n d a w a t e r
Thionyl chloride,
1 4 0 0 g.
of 2 to 5 d r o p s per
second
The r e a c t i o n m i x t u r e ,
vigorously during
(an e x c e s s )
to the
was
a d d e d a t a rate
a l c o h o l - p y r i d i n e solution.
c o o l e d b y a w a t e r bath,
the addition.
trap.
was
stirred
103
The © v o l u t i o n of s u l f u r d i o x i d e p r a c t i c a l l y c e a s e d
af ter a d d i n g a b o u t t h r e e - f o u r t h s of the t h i o n y l chloride.
Ihe r e m a i n d e r
of the t h i o n y l
The r e a c t i o n m i x t u r e was
another
sti r r e d over n i g h t ,
three h o u r s at 63°C.
w h i c h c r y s t a l l i z e d out w a s
halide
chl o r i d e w a s r u n i n rapidly.
a n d t h e n for
The p y r i d i n e h y d r o c h l o r i d e
f i l t e r e d off a n d the top
l a y e r w a s r e m o v e d and w a s h e d w i t h a 5# s o l u t i o n of
p o t a s s i u m c a r b o n a t e u n t i l a l k a l i n e t o litmus.
d r i e d w i t h anhyd. p o t a s s i u m carbonate,
F r a c t i o n a t i o n gave 2 3 8 . 8 g.,
chloride,
b.p.
R u n 2.
68. 7 ° C
was
2 . 5 8 moles,
(735 ram) n ^
b.p.
considerable amount
67.5-68.8°C
f r a c tionated.
or a 3 7 # y i e l d of
1.3968.
A f i v e m o l e r u n g a v e 200.8 g.,
the chlori d e ,
The halide,
(733 mm),
2 .17 moles,
n ^ ° 1.3967.
of
A
of h i g h b o i l i n g r e s i d u e w a s o b t ained
f r o m t h e two runs.
Organic Syntheses Method.^
To 1 5 5 0 cc.,
c o l d c o n c e n t r a t e d h y d r o c h l o r i c acid
a d d e d 1 5 2 0 g.,
m ixture,
kept
11 moles,
assure complete
(s p . g r . 1.19)
of a n h y d r o u s
in an ice bath,
22 moles,
were
zinc chloride.
was s t i r r e d o v e r n i g ht
solution of all
of
The
to
the zinc c h l oride.
The f l a s k c o n t a i n i n g t h e s o l u t i o n was c o n n e c t e d to
an u p r i g h t c o n d e n s e r a n d the alcohol,
was s l o w l y a d d e d to the s o l u t i o n
condenser.
4 1 0 g.,
5.5 moles,
thr o u g h t h e top of the
The m i x t u r e w a s r e f l u x e d for
8 to 9 hours,
and
104
then after c o o l i n g to r o o m temperature,
was
separated off.
the u p p e r layer
The zinc chloride was r e c o v e r e d from
the aqueous layer b y evaporation.
The
top layer was p l a c e d in a three-liter flask c o n ­
n e cted to a reflux
condenser.
A n equal volume of conc.
sulfuric acid was a d d e d through the top of the condenser.
The mixture was ref l u x e d for one hour before d i s t i l l i n g
through a 14 inch ind e n t e d fractionating head.
of the colorless chloride was 415 g.,
The yield
4.5 moles,
or an
81$ yi eld •
The total w e i g h t of the
67.5-69°C
(735 mm), n ^
secondary chloride b.p.
1.3966-1.3968,
prepared, was 855
g r a m * , 9.24 moles.
2. P r e p ara t i o n of S e c o n d a r y Butyl Grignard R eagent
Two cc o f ethyl b r o m i d e in 10 cc of ethyl ether was
added to 103 g., 4.3 moles
of m a g n e s i u m turnings,
1200 cc o f ether was a d d e d directly.
chloride,
396 g.,
and then,
S e c o n d a r y butyl
413 moles, was added at a rate of 1 to 2
drops per m i n u t e over a 17-hour period.
Titration of a
five cc sample i n d icated a 91$ active G r i g n a r d reagent.
R u n 2, 420 g., 4.5 moles,
gave a 85$ Grignard reagent.
105
3* Preparation of Mothylethylacetlc Acid
Method A:
Pressure Carbonation.
The Grignard reagent*
3,83 molar, was placed in an autoclave, and then gaseous
carbon dioxide from a cylinder was added until a pressure
of 200 lbs. was reached.
The autoclave was then placed on
a roller and rolled for two hours, after which time carbon
dioxide was again added until a pressure of 400 lbs. was
reached.
The apparatus was again rolled for a short time
and then allowed to stand over night.
to 200 lbs. over night.
The pressure dropped
The pressure was Increased to 400
lbs. and left to stand for another six hours.
The pressure
was slowly released and the mixture was removed and worked
up as usual•
There were obtained, on fractionation of the reaction
products, only 135 g., 1.3 moles, or a 29$ yield of acid,
b.p. 117.5°C (100 mm), nj^ 1.4070, based on the secondary
chloride, or a 34$ yield based on the Grignard reagent.
Apparently, pressure carbonation is not very satis­
factory for secondary Grignard reagents.
Method B.
Carbon dioxide gas, obtained from a
cylinder and dried b y passing through a sulfuric acid
bottle, was added at a fairly rapid rate (atmospheric
pressure) to a 3.91 molar Grignard reagent.
106
The gas inlet tube extended to the bottom of the re­
action vessel.
The latter consisted of a three-liter,
three-necked flask, fitted with a mercury seal stirrer and
a condenser to which was attached a sulfuric acid trap.
The temperature of the mixture was maintained between zero
and minus five degrees during the addition.
The addition
complex separated out as the reaction proceeded.
The r e ­
action was considered complete after eight hours, at which
time the gas escaped practically as fast as it entered.
The complex was decomposed with ice, and the top
layer was removed after first making the solution strongly
acid with sulfuric acid.
The ether was distilled off
through a fractionating head.
The acid residue was first
dried with anhydrous calcium chloride and then with
phosphorus pentoxlde.
Fractionation data:
Col. T.
120.0
123.5
122.5
124.5
Weight 335 g.
Head T.
Press.
84.5
112.5
116.0
119.0
100 mm
"
"
"
Frac.
Wt.
1
8.5
2
1.7
3 323.0
Residue 1.5
20
n^
R.R.
- 2/l
1.4068 4/1
1.4062 3/1
Recovery 335 g.
Loss - none
Yield, 323 g., 3.17 moles, or 74# based on the chloride,
or 81# based on the Grignard reagent.
107
4. Preparation of M^thylethylacetyl Chloride
The acid chloride, b.p. 68.8-69.5°C (160 non), njj°
1.4173-1.4175, was prepared In an 80# yield from the acid
and 33# excess thionyl chloride by the usual procedure.
5. Preparation of Ethy lmagneslum Bromide
The usual procedure was used for the preparation of
the Grignard reagent, 93-95#, from 1310 g., 12 moles, of
redistilled Eastman practical grade ethyl bromide, b.p.
37.5-38°C (742 mm).
6. Reaction of Methylethylacetyl Chloride with an Excess
of Ethylmagnesium Bromide
Run 1.
To 324 g., 2.7 moles, of acid chloride, b.p.
69°C (160 mm), n*^ 1.4173, were added an equal volume of
anhydrous ethyl ether.
This solution was added slowly
over an 18 hours period to a 6.65 molar solution of
ethylmagnesium bromide.
Run 2.
A solution of 225 g., 1.88 moles, of acid
chloride, b.p. 68.8-69.5°C (160 mm), n^° 1.4175, in an
equal volume of ether, was added to a 4.65 molar Grignard
reagent In 11.5 hours.
No addition products separated in either of these two
runs.
The liquid, however, became quite viscous toward
the end of the reaction.
The magnesium compounds separated
out on the addition of water.
The ether layers were
108
decanted off and the residues extracted several times with
small quantities of* ether.
The ether solutions from the two runs were combined
and dried with anhydrous sodium sulfate.
The etter was
distilled off through a 14 Inch indented fractionating
head and the residue fractionated through a 14 plate column.
Table A
Col. T.
Head T.
Press.
110.0
115.5
118.0
118.5
50 m m
59.5
tt
59.5
N
62.0
II
61.8
n
62.5
t»
119.0
62.0
i*
118.5
62.5
n
74.0
125.0
n
74.0
1 1 1 . 0
ii
1 1 1 . 0
75.0
tt
92.0
t
t
_
92.0
92.5
Recovery 389 g.
ii
Frac.
Wt.
1
2
3
4
5
6
7
8
9
10
11
12
13
10.1
11.4
9.8
10.5
11.3
10.4
9.1
11.0
74.0
17.2
39.5
60.0
18.0
R.R.
1.4273
1.4271
1.4260
1.4270
1.4270
1.4270
1.4268
1.4268
1.4267
1.4262
1.4283
1.4270
1.4285
8/1
7/1
7/1
7/1
7/1
Remarks
wet
wet
dry
5/1
-
5/1
5/1
4/1
1/1
residue
Table B
Col. T.
70.0
71.0
71.2
71.6
71.0
71.5
75.0
80.0
85.0
95.0
98.5
98.5
Refractionation of cuts 1-10, inclusive
_20
P r e s s . Frac. Wt.
R.R. Remarks
Head T.
nD
57.5
59.2
59.0
59.2
59.2
59.2
59.2
70.5
77.5
77.8
77.8
77.8
50 mm
ii
n
ii
ii
n
n
ii
it
it
it
it
1
2
3
4
5
6
7
8
9
10
11
12
12.0
3.5
3.0
8.5
4.0
6.0
4.0
2.5
1.4283
1.4276
1.4276
1.4276
1.4276
1.4276
1.4277
1.4266
1.4261
1.4258
1.4258
1.4258
6/1
6/1
6/1
6/1
6/1
6/1
5/1
3/1
2/1
5/1
4/1
5/1
dry olefin
alcohol
alcohol
109
Col. T.
98.8
-
Head T.
78.2
78.0
78.4
78.2
78.0
78.0
78.2
78.8
-
-
99.2
99.2
102.5
103.0
-
Press•
Frac.
50 mm
»t
ii
t!
It
tt
tt
tt
It
13
14
15
16
17
18
19
20
21
Wt.
1.4259
1.4259
1.4260
1.4259
1.4259
1.4260
1.4261
1.4263
33.0 1.4278
R.R.
Remarks
5/1
6/1
6/1
5/1
5/1
1/1
Residue
Fractions 3-7, Inclusive, represent 29 g., of olefin,
b.p. 59-59.2°C (50 m m ) , n§° 1.4276-1.4277, d|° 0.7588.
Fractions 9-20, Inclusive, 100 g., represent alcohol,
2<
b.p. 77.5-78.4°C (50 mm), n§°
1.4258-1.4263.
D
Refractlonatlon of cuts 13-18, inclusive, 46 g.,
through a metal packed column of 25 theoretical plates
gave 35.8 g. of alcohol, b.p.
20
75.0-75.2°C (50 ram), n-Q
1.4261, d^° 0.8325.
Refractlonatlon of cuts 11, 12, 13 (Table A), and the
residue
(Table B) through a 14 plate column gave 156.0 g.
of olefin, b.p. 60-61°C (50 mm), n^0 1.4272-1.4279.
Conclusions:
There were
obtained 166 g., 1.32 moles,
of olefin as a result of dehydration of the carbinol
during fractionation.
The yield of carbinol
was 80^.
(olefin calculated as carbinol)
no
7. Dehydration o f 4-Methyl-3-ethyl-3-hexanol
The alcohol, fractions 9, 10, 11, 12, 19 and 20
(54 g.) was dehydrated over 25 g. of anhydrous cupric
sulfate at 200°C.
The alcohol was added at a rate of
about 30 drops per minute.
The olefin and water was
allowed to distill out as the dehydration proceeded.
Fractionation of the dry products gave 19.0 g. of pure
olefins, b.p. 60.8-61°C
(50 ram), nS°
i2C 1.4272-1.4276.
8. Ozonolysis and Identification of Olefins
A total of 185 g., 1,4 moles,
of olefins, b.p. 59-
61°C (50 ram), n^° 1.4272-1.4276, d|° 0.7588, molecular
refraction calcd. 42.73, molecular refraction found 42.73,
was obtained for the hydrogenation and ozonolysis.
A 25 g.,0.2 molar quantity of tie olefins dissolved
in 175 cc of glacial acetic acid was ozonized in 7.5 hours.
The ozonlde was decomposed by the usual technique.
Fractionation of the oil layer:
Head temperature
Press.
Frac.
Wt.
up to 102.0
102.0 105.0
105.0 116.0
116.0 125.0
125.0 129.8
129.8 132.5
132.5 133.0
735 mm
"
11
*
"
”
1
1
1
2
3
4
5
6
7
Re sId ue
0.3
0.2
0.2
0.3
0.8
1.5
3.0
2.5
20
n^
—
1.3958
1.4040
1.4075
R.R.
3/1
3/1
3/1
Ill
Fractionation of the ether from the d r y ice traps
Head temperature
Press•
Frac.
up to 33.5
33.5
33.5
33.5 - 48.0
48.0 - 65.5
65.5 - 75.0
75.0 - 78.0
78.0 - 92.0
92.0 - 115.0
735 mm
n
n
it
n
n
n
it
it
1
2
3
4
5
6
7
8
9
Fractionation of water layer:
Wt.
<■»
0.2
0.2
0.4
0.6
0.8
1.5
Ttere were obtained
1*0 g. of material boiling between 80-9G°C (735 mm).
Material balance:
Weight of olefins ozonized 25.0 g.,
weight of olefins recovered 14.5 g.,;loss 10.5 g.
Identification work:
Diethyl ketone,
fractions 1, 2,
and 3 (0.7 g.) oil layer, gave a 2,4-dinitrophenylhydrazone
derivative, m.p. and mixed m.p. 154.5-156,0°C.
Ethyl sec. butyl ketone, fractions 6 , 7, and 8 (7.0 g.)
was identified by its semlcarbazone m.p. and mixed m.p.
67-67,5°C and b y its 2,4-dinitrophenylhydrazone m.p. and
mixed m.p. 90.0-31.5°C.
Acetaldehyde, found in the water layer, gave a 2,4dinitrophenylhydrazone derivative m.p. and mixed m.p.
159-160.8°C.
Methyl etfryl ketone,fractions 8 and 9, ether layer
(1.4 g.) gave a 2,4-dini trophenylhydrazone m.p. and mixed
112
m.p. 115-116.8°C.
Conclusions:
The amount of* 4-raethyl-3-ethyl-2-hexene,
calculated on the basis of ozonolysis products recovered
was estimated as 53# and the amount of 4-methyl-3-ethyl-3hexene as 12#.
9. Hydrogenation of Olefins
The isomeric olefins, 160 g., 1.25 moles, were
hydrogenated in an Adkins type shaker bomb of one liter
capacity.
Raney nickel was used as a catalyst.
The
temperature of hydrogenation was 125-150°C at 125 atmos­
pheres.
Fractionation of the hydrogenated olefins through
a total condensation variable take-off column of 35
theoretical plates at a high reflux ratio gave 84 g. of
hydrocarbon, b.p. 139-140°C (739 nm), n§° 1.4132, and
48 g. of material, b.p. 137-138°C
(738 mm),
1.4149.
10. Purification of the New Nonane
The 48 grams of low boiling material was rehydrog­
enated at a higher tenperature.
Fractionation of the re-
hydrogenated material gave 32.7 grams of material boiling
at 137-137.5°C (731 mm), n^° 1.4149.
Apparently, re­
hydrogenation was not satisfactory as a method of purifica­
tion of this material.
Sulfuric Acid Treatment of the Impure Hydrocarbon:
This low boiling material, 47 cc, was shaken three times
«
113
with 25 oc portions of concentrated sulfuric acid.
The first
extraction caused the development of some heat, and the acid
turned yellow in color.
There remained 38 cc of material
after the three extractions.
A five oc quantity of material
was reoovered from the aoid by diluting with water.
Fractionation of the 38 o c , 25 g., of material g: ve 16.8 g .
20
of pure nonane, "b.p. 138.5 C (725mm), n D
1,4132.
The 84 g. of hydrocarbon, b.p. 139-140 C ( 739 mm),
20
np 1.4132,
item 9, page llfi, was further purified by
rehydrogenation.
Fractionation data:
Col T.
141.5
143.0
143.0
143.0
142.8
143.0
143.0
143.5
145.0
Head T .
138.6
138.8
139«.8
138.8
139.0
138.8
138.6
138.8
•*
Press.
726 mm
M
M
rt
tt
ti
it
it
Tt
Frac.
1
2
3
4
5
6
7
8
9
10
Residue
Yield of pure hydrocarbon,
.
Wt
2.5
7.5
8.5
9.2
7.0
8.5
7.2
8.4
4.3
5.4
1.0
"D
1.4131
1.4132
1.4132
1.4133
1.4132
1.4132
1.4132
1.4132
1.4132
1.4132
fractions 2-10 inclusive,
67 g.
Conclusions:
a
total of 83 g.
( 67 g. above plus 16.8 g.
from sulfuric acid treatment of the hydrocarbon)
was obtained.
of pure nonane
114
11* P h y s i c a l Constants o f the N e w N o n a n e . 4-Methyl-3ethyl-hexane
The b o i l i n g p o i n t was d e t e r m i n e d in a Cottrell
"boiling point ap p a r a t u s using an Ans c h u t z t h e r m o n e t e r •
Data:
20 cc
T emperature
cc over
138.0
138.3
138.3
138.3
138.3
pressure
2 cc
4 cc
6 cc
8 cc
10 cc
724 m m
n
ti
ii
Therefore, the b o i l i n g point is 138.3°C at 724 m m
pressure•
The ind i c e s of* r e f r a c t i o n were determ i n e d w i t h a
Valentine refractrometer
I-age
113
tt
Tt
Tt
Therefore,
(No. 451,
Industro S c i e ntific Co.).
_20
"d
1.4 1 3 2
1.4132
1.4 1 3 4
1.4134
1.4134
Fraction
6
7
8
9
10
the index of r e f r a c t i o n is 1.4134. at 20* C.
The d e n s i t i e s were d e t e r m i n e d w i t h a Sprengel
p y c n o m e t e r , of 2.079 ml capacity,
20.0°C±.01°
density
0.7 3 8 3
type
at 20* C.
100.0°Fi.01°
0.7245
2 1 0.0°F±.01°
0.6753
114a
E x p e r i m e n t a l data:
Density determinations
fractio n # 5, pag e 113.
V7t.
At.
V.'t.
or p y c n o m e t e r .filled 4.8840
of p y c n o m e t e r empty 3.3491
of liq.u id at 20°C.
175349
Volume
at
at
of p y c n o m e t e r 2.079 ml at
D e n s i t y at 20°C.
faction
Density at 2 0 ° C.
20° G •
20° C.
2 0 ° C.
1 . 5 3 4 9/2 .079 = 0 . 7 3 828 or 0.7383
§ 5, p a g e 113.
D e n sity at 100° F.
o
trial I, 4.8547 atlOO F.
trial H , 4.8568
trial 3, 4.8576
0
Average w t . of p y c n o m e t e r filled
.8563 at 100 F.
v;t. of liquid, 4 . 8 5 6 3 - 3 . 3 4 9 1 = 1.5072
D e n sity at 100° F.
1.5072/2.079 = 0.7249
vrt. of p y c n o m e t e r filled,
F raction # 7, p a g e 113.
V.'t.
Density at 100° F.
of p y c n o m e t e r
filled, trial
I4.8548 at lOO^F.
trial 2
4.8552 at 1 0 0 ° F.
average at 100 F. ,pycnometer filled! .'$550
V/t. Of liouid, 4.8550 - 3.3491 =1.5059
D e n sity at 1 0 0 °F.
1.5059/2.079 =0.7243
Average d e n s i t y
fractions 5 and 7, = 0.7245 at 100
Fraction ■} 7, p'g e 113.
F.
Density at 210°?.
A t . of o y o n o m e t e r filled (avera e of trial 1 and 2)
4.7532 at 210^3.
V.'t.
of p y c n o m e t e r ernj'ty
3.3491 at 20*^0.
At.
of liquid at 2 1 0 °F.
1.4041
D e n s i t y at 210* F. 1.4041/2.079 = 0.G753
E x p e r i m e n t a l data:
Fraction
seconds at 20°C.
V i s c o s i t y v;or1
'} 5* F*
■I1lie con stant
s e c o n d s / c e n t i stoke
113,
Instrument ITo . 11-7*
average
rate
of Floy/ 1.691
for the instrument at 20 G. = 213.8
( fhe constant increases 0,2, for
1141)
every 30 degree
(oentigrade) rise in temperature.)
Viscosity at 20°C.
169.1/213.8 = 0.7507 (centistokes)
Fraction # 7, page 113, Jiveruge rate of flow =168.85
seconds at 2CrC.
Viscosi ty at 20° C.
168.85/213.8 Z
A v erage viscosity at 20°C . =
0.7898
0.7902
(os)
(cs)
f a c t i o n # 5, page 113, Average rate of flow *139.5
seconds at 100° IT.
v iscosity at 100 F.
139.5/ 214.1 - 0 .6519( cent is tokes )
Fraction # 7, page 113, Average rate of n o w =139.7
seconds at 1 Q 0 CF.
(constant- 214 .l3ec,/c£)
Viscosity at 100°F.
139.7 / 214.1 = 0.6525
c
Average v iscosity at 100 F. =
(cs)
0 .6522(oentistokes)
Fraction ii 7, i ge 11S, Average rate of flow *85.1
leconds at 210*^. ( constant = 2 14.l l s e c,/cs)
Videos tty at 210° F .
Correction factors,
hexane:*
At 20 C
&C.
At 100 F.
At 2 1 0 °F.
the true viscosities
65.1/ 214.11 * 0 .3975 (centistokes)
instrument £ M-7,
correction
—
11
"
for 3-methyl-4-eti:pl-
-0.10C
-- i
-0.15,1
—0,41/
(in centistokes)
after making these
corrections are as follows: 0.7894 centistokes, Q.C512 cs.,
c
0
<and 0.3959 cs. at 20 C, 100 F and 210 F. respectively.
Viscosities (in centipoise units) a:re as follows:
0.4718, and 0.2*7? at 20*0, 1 0 0 *F, and 210 F.
0.3888,
115
* T h e v i s c o s i t i e s were
O s t wald viscometer,
de t e r m i n e d w i t h a m o d i f i e d
i n s t r u m e n t No. M-7,
similar
to Pig.
2
s hown b y and d e s c r i b e d b y Cannon and P e n s k e .2
20°C±.01°
100°F±.01°
Viscosity
0.5828
(centipoise units)
B.
2 1 0 ° F ± .01°
0.471®
0.2674
P r e p a r a t i o n of a N e w D e c a n e , 2 - M e t h y l - 5 - e t h yl-heptane
1. P u r i f i c a t i o n of D i e t h y l a c e t a l d e h y d e
Diethylacetaldehyde,
a product of Carbide and C a r b o n
C h e m i c a l Corp., was p u r i f i e d by f r a c t i o n a t i o n t h r o u g h a
column of 15 th e o r e t i c a l pla t e s .
the aldehyde,
116°C
1281 g.,
The boiling p o int of
20
1 2 . 8 moles, n D
1.4025, was 114-
(732 ram).
2. P r e p a r a t i o n o f P h o s p h o r u s Trlbromlde
A r u n was made u s i n g
F l i n n .3
the d i r e c t i o n s d e s c r i b e d b y
D i s t i l l a t i o n g a v e 2150 g.,
the p r o d u c t h a v i n g a b.p.
R u n 2.
T h i s r u n was
170-172°C
(732 ram).
the same as the one above
except 500 g. of ph o s p h o r u s
D i s t i l l a t i o n gave 2450 g.,
or a 77# y i eld of
and 870 cc o f b r o m i n e was used.
or an 82# y i e l d o f the product.
3. P r e p a r a t i o n of I s o b u t y l B r o m i d e
I s o bu t y l bromide,
(140 rum), n§° 1.4360,
1760 g.,
12.87 moles,
b.p.
41-43°C
was p r e p a r e d f r o m i s o b u t y l alcohol
116
by the method of Whitmore and L u x .4
4. Preparation of 2-Methyl-5-ethyl-4-heptanol
The carbinol was prepared In yields of 38-41# b y the
addition of diethylacetaldehyde (a total of 12.5 moles)
to lsobutylmagneslum bromide.
The Grlgnard reagent was
prepared In 90-94# yields by the usual procedure.
A
typical run Is exemplified by the addition of one mole of
the aldehyde to the Grlgnard reagent prepared from one
mole of the bromide.
The best fractions from four runs were combined to
give 810 g., 5.1 moles, of carbinol, b.p. 98-100°C (30 ram),
n^° 1.4345.
Hie alpha naphthyl urethan derivative melting point
and mixed melting point was 88-90°C.
5. Dehydration of 2-Methyl-5-ethyl-4-heptanol
The carbinol,
710 g., 4*5 moles, was catalytlcally
dehydrated over activated aluminum oxide at 320-370°C.
Three 1.5 mole runs were made.
80 drops per minute.
The rate of addition was
The apparatus used for the dehydra­
tion was described on page 10.
6 . Purification of the Decenes
The crude olefins were fractionated through a 0.9 x
51 cm total condensation variable take-off metal packed
117
packed column of 20-25 theoretical plates into low,
medium, and high boiling fractions*
These three fractions were each carefully refrac­
tionated, and the best cuts combined for ozonolysis and
hydrogenation.
Combination of the best cuts gave 145 g.,
1 mole, of olefin mixture having a b*p. 147-148°C (723 mm),
and a n£v 1.4186-1.4195.
The Cottrell boiling point of one of the best cuts
was 147*5° (735 mm), and the density was 0.7362, and
refractive index 1.4195 at 20/4°C.
Identification of the olefins was accomplished by
ozonolysis.
7* Ozonolysis and Identification of Olefins
A 22.0 g., 0.15 molar quantity of the olefins, dis­
solved in 125 cc of glacial acetic acid, was ozonized in
eight h o u r s •
The ozonlde was decomposed by the zinc5
water-catalyst method.
Fractionation of oil layer:
Head temperature
92
102
113
116
119
177
- 102
112
- 115
- 118
- 176
- 193
10*5 g.
Press.
Frac.
Wt.
735 mm
it
w
it
it
it
1
2
3
4
5
6
Residue
3*8
0.2
2.0
2.5
1.0
0.3
0.2
118
F r a c t i o n a t i o n of a q u e o u s
Head temperature
00
to
•
0
1
.. 78.0
- 82.0
86.0
- 88.0
- 92.5
- 94.5
— 97.5
- 98.0
- 97.5
layer:
Press.
Frac .
Wt.
733 m m
it
it
it
it
it
t»
n
«*
1
2
3
4
5
6
7
8
9
1.4
0.6
1.2
1.1
1.5
1.7
1.9
0.4
2.5
D i s t i l l a t i o n of t h e ether
from the d r y ice trap:
F o u r g r a m s of l i q u i d w i t h an aldehyde odor r e m a i n e d after
the ether w a s removed.
M a t e r i a l bal a n c e :
W e i g h t of mat e r i a l
o z o n i z e d 22 g.;
total r e c o v e r y 1 7 . 5 g. ; loss 4.5 g.
I d e n t i f i c a t i o n work:
oil layer,
3.8 g., was
hydrazone
zatlons,
sample
a n d m i x e d m.p.
oil layer, g a v e
at 1 3 6 . 5 - 1 3 7 ° C .
1 2 1 - 1 2 2 . 5°C.
a 2,4 - d i n i t r o p h e n y l -
d e r i v a t i v e w h i c h melted,
of the
fraction 1
i d e n t i f i e d b y its 2,4 - d i n i t r o p h e n y l
h y d r a z o n e d e r i v a t i v e m.p.
F r a c t i o n 3,
I s o v aleryl aldehyde,
after three r e c r y s t a l l i
T h e mixed m.p. w i t h an a u t hentic
corresponding derivative
of d i e t h y l a c e t a l d e -
hyde w as 1 3 7 - 1 3 7 . 5°C.
F r a c t i o n 1, w a ter layer,
r e c o v e r e d f r o m the d r y ice
a n d the 4 grams
trap, g a v e
of m a t e r i a l
2,4 - d i n l t r o p h e n y l -
h y d r a z o n e d e r i v a t i v e s w h i c h m e l t e d at 181.5-182°.
No
119
d e p r e s s i o n In m.p,
o c curred when mixed w ith an authentic
sample of the 2,4-di n i t r o p h e n y l h y d r a z o n e derivative of
ls o b u t y r y l aldehyde.
D i e t h y l ketone,
fractions
5, 6 and 7, aqueous layer,
w as I d e n t i f i e d b y Its 2 , 4 - d i n i t r o p h e n y l h y d r a z o n e d e r i vative
m.p.
and m i x e d m.p. 1 5 5 - 1 5 6 . 5°C.
Conclusions:
0.07 moles,
Fractions 3, 4 and 5,
oil layer,
i
was i d e n t i f i e d as d i e t h y l a c e t a l d e h y d e •
5 g., 0 . 6 5 mole of the r e c o v e r e d p r o d u c t s
a n d 1 g. f r o m fraction 1, water
1 sobutyraldehyde.
Therefore,
6.0 g.,
About
(4 g. f r o m ether
layer) was identified as
there w e r e 0.06B m o l e s or
55# of 2 - m e t h y l - 5 - e t h y l - 3 - h e p t e n e p r e s e n t In the olefin
mixture•
A b out 4 grams
of the oil layer,
I d e n t i f i e d as isovaleryl aldehyde.
i s o v a l e r y l aldehyde
recovered,
f raction 1, was
On the b a s i s of the
there was 3 9 # of 2-methyl-
5- e t h y l - 4- h e p t e n © p r e s e n t in the o r i g i n a l mixture.
Therefore,
there was about a 5 5 - 4 5 # m ixture of the
two olefins p r e s e n t f r o m the d e h y d r a t i o n
8 . Hydrogenation
of Decenes
An A d ki n s type shaker b o m b was u s e d
123 g.,
of the alcohol.
0.88 moles,
of olefin mixture.
u s e d as the catalyst,
to h y d r o g e n a t e
R a n e y nickel was
a n d the temper a t u r e of hydro g e n ation
120
was 125-15 0 ° at 125 atmospheres*
F r a c t i o n a t i o n Data:
Col. T.
112.0 g.
H e a d T.
Press•
Frac •
155.0
151.4
151.8
151.5
1 5 4.0
154.5
155.2
157.0
1 5 7.0
158.0
158.0
15 9.0
fl o oded
15 8.0
157.5
15 7.0
147.0
150.0
150.2
151.2
153.0
154.5
156.0
157.2
158.0
158.0
159.0
160.0
158.0
156.8
157.0
1 5 7.8
739 m m
1.9
1
2
1.4
2.0
3
4
1.1
1.8
5
6
2.1
7
2.4
8
2.6
9
5.5
10
3.4
3.6
11
10.8
12
13-14 22.2
1 5 7.0
157.5
158.5
159.2
157.8
157.8
157.8
157.2
tt
n
it
it
n
it
it
n
it
n
it
it
it
-
it
it
15
16
n
-
17
18
19
20
Residue
it
tt
it
Wt.
Column E.M.J,
20
R.R.
D
1.4079
1.4103
1.4101
1.4101
1.4107
1.4110
1.4113
1.4115
1.4117
1.4118
1.4118
1.4119
1.4119
30/1
30/1
_
9.7
16.8
1.4120
1.4127
6.1
7.9
2.5
1.6
1.9
1.4127
1.4127
1.4128
1.4129
at 20°C
at 21°C
(1.4119 at 23°C)
at 21°C
at 21°C
at 21°C
R e c o v e r y 107.0 g.
5.0 g*
Los s
Cuts 7 to 20,
9 3.0 g., were r e c o m b i n e d Tor r e h y d r o ­
ge n a t i o n •
Fractionation
W e ight 84.0 g.
Col.
T.
156.2
157.0
156.5
156.2
157.5
157.0
of r e h y d r o g e n a t e d decane:
Column E.M.J.
H e a d T.
Press•
Frac •
Wt.
154.9
156.0
156.0
156.9
157.2
157.5
743 m m
1
2
3
4
5
6
0.9
1.6
2.9
2.4
4.1
10.5
it
tt
n
tt
it
20
nD
1.4119
1.4130
1.4131
1.4130
1.4131
1.4132
R.R.
30/1
30/1
121
Col.
T.
Head
157.2
157.2
157.5
158.2
159.0
T.
P r ess .
157.8
158.0
158.0
158.2
159.0
Frac •
Wt.
7
8
9
742 m m
10
it
11
Residue
11.9
16.5
15.9
12.6
0.7
1.3
743 m m
II
tl
**>
1.4132
1.4133
1.4133
1.4133
1.4 1 3 3
1.4139
R e c o v e r y 8 1 . 3 g.
Loss
3.0 g .
F r a c t i o n 9,
d ? ° 0 .7356.
9. P h y s i c a l
Constants
of 2 - m e t h y l - 5 - e t h y 1 - h e p t a n e
T h e C o t t r e l l b o i l i n g p o i n t was d e t e r m i n e d w i t h an
..
Anschutz
^r/i
therometer.
Data:
20 cc
Temperature
cc over
pressure
158.3
158.4
158.4
158.4
158.4
158.4
2 cc
4 cc
6 cc
8 cc
10 cc
735 inn
"
"
"
n
"
Therefore,
t h e b o i l i n g p o i n t is
1 5 8 . 4 ° at 735 m m
pressure•
The indices
of r e f r a c t i o n wore d e t e r m i n e d w i t h a
Valentine refractrometer
Page
120
121
ti
it
Therefore,
(No. 451,
Fraction
6
7
8
9
10
Industro Scientific
Co.),
D
1.4132
1.4132
1.4133(4)
1.4134
1.4134
the i n d e x of r e f r a c t i o n is 1 . 4 1 3 4 a t
20° C.
122
The densities were determined with a Gprengel type
pycnometer,
o
of 2.079 ml capacity at 20 C.
inaction £ 8, page 121;
Mt. of pycnometer filled at 20°C = 4.8775 (trial
V/t. of pycnometer
filled at 20° C s 4.8786 (trial
V/t. of pycnometer filled at 20° C = 4.8385 (trial
Average wt. of pycnometer filled
4.8732
ft. of pycnometer
empty at 2 0 °C.
3.3491
1)
2)
3)
Wt. of liquid 4.8782 - 3.3491 = 1.5292 ml
Density at 20°C.
1.5232/ 2.079 = 0.7356
Fraction £ 9, page 121:
Average wt. of pycnometer filled = 4.8496 at 100 F.
V.rt . of pycnometer emnty at 20** O’ = 3.3491
V/t.
of liquid at 100* F.
1.500 5“
Density at 1 0 0 ^F. 1.5005 / 2.079 - 0.7218
Fraction § 10, page 121;
..t.
'./t.
■ft.
of pycnometer filled
at
lOO^F
4.8505
of pycnometer empty at 20^0.
3.3491
Of liquid at 100 F.
1.5014
'Density at 1 0 0 ® F. 1.5014 / 2.079 - 0.7221
average density at 1QQC F .
0.7220
Fraction £ 10, page 121;
ft. of pycnometer filled
(trial 1 and 2)= 4.7488 at
2106F.
V/t. of pycnometer empty fit 20 G .
Wt. of liquid at 210 ° F.
Density at 210* F.
1.3997 / 2.079 *
= 3.3491
1.3997
0.6732
The temperatures were.maintained within ±lus or minus 0.01 degree
Viscosities:
Dxpjeri mental data:
122a
Inaction # 8, page 121, Average rate of flow = 220.6
seconds at 20PC.
(Constant for instrument LI-7 » 213.8 sec./
certist6kes)
Viscosity at 20° C.
220.6/ 213.8 « 1.0318
(centistokes)
inaction if 10, page 121, Average rate of flow ■ 221.78
seconds at 20° C.
Viscosity at 2,0^0.
221.78 / 213.8 - 1.0377
Average g&aeoslt.y at 2 Q ° C . « 1.0348
fraction
8, page 121,
average rate of flow * 177.8
seconds at 100° I*’. ( constant at 1G0°F = 214.1)
Viscosity at 100 F.
177.8/ 214.1 -
0.8304
(centistokes)
fraction
10, page 121, average rate of flow • 178.47
econds at 100s 7.
178.47 / £14.1
•
o
II
Viscosity at 100? F .
..ver.age visco sity at 1 0 0 r F. = 0 .832
-.vex*age rate of f lov;
A a c t i c n / o,pl21,
at 210 - 7 ,
fraction , 9, page 121, _.v. rate of flow
210
'F.
at
Fraction ,/ 10, page 121, Av. rate of f 1 ow
at 210 c?.
o
»*
The average rate of flow for the oecane at 210 F. = 100.8
seconds.
(constant at 210 CF for instrui:;ent f-7 =814.11)
Viscosity at 2 1 0 ° F. =
100.0 / 214.11 * 0 ,4723(centistokes)
Correction factors (in centistokes) for the viscosities o f
8-methy 1-5-ethyl-heptane are as follows:
At 2 0 CC, -O.OGp;
At 100 ° F. , -0.08 5,'*, ^
210 rF., -0.29;. ®
The viscosities
in certi
ois units for 2-rnetky 1-0-ethy 1-
1.ej tone are as follov.'s: 0.7C08 at 20 C.; 0.6001 at 100 V . ;
and 0.3170 at 210 n.
( Temperature r a g e
^ lus or air as 0.01
)
123
Summary
A n o w nonane,
thesized,
3-methyl—4-ethyl-hexane,
and t h e p h y s i c a l
A n o w decane,
lias bee n
syn­
constants determined,
2-methyl-5-ethyl-heptane,
has b e e n
thesized and the physical constants determined.
Two
new alcohols,
4 - m e t h y l - 3 - e t h y l - 3 - h e x a n o l and
2- m e t h y l — 5 - e t h y l - 4 - h e p tan ol , h a v e b e e n s y n t h e s i z e d .
Bibliography
1) O r g a n i c S y n t h e s e s ,
C o l l e c t i v e Volume
2) C a n n o n a n d F e n s k a ,
Ind. E ng,
3) F I i n n ,
T h e s i s , page 179,
C o llege, 1935,
4) W h i t m o r e a n d L ujc , J. A.
5) W h i t m o r e ,
Church,
The
C h e m . , I Q , 279
(1938)
Pennsylvania State
C, S,,
a n d McGrew,
X, p a g e 131,
54,
Ibid.
3448
56,
(1932).
171
(1934).
syn­
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