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STUDIES IN THE CONDENSATIONS OF ALDEHYDES WITH PHENOLS

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IlcCoy, John Spalding, 19161942
Studies in the condensations of alde.112
ftydes with p h e n o l s .
New York, 1942,
4p.l.,144 typewritten leaves,
diagrs.
29cm..
Thesis (Ph.D.) - New Yorl: university,
Graduate school, 1942.
Eibliography: p.142-144.
A84676
r
Xerox University Microfilms,
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Ann Arbor, Michigan 48106
T H IS D IS S E R T A T IO N HAS BEEN M IC R O F IL M E D E X A C T L Y AS R E C E IVE D ,
STUDIES IN THE CONDENSATIONS OF ALDEHYDES
WITH PHENOLS
By
\ * A
o*'
John S a -McCoy
Submitted in partial fulfillment of the requirements
for the decree of Doctor of Philosophy at
New York University
June, 1942
Acknowledgment
I wish to express my sincere gratitude to
Professor Joseph B. Niederl who initiated this
problem and without whose helpful assistance and
constant encouragement this research would not
have been completed.
To the Rev. Richard 3. Schmitt, S.J., whose
inspiration and advise through many years has been
of untold importance, I respectfully dedicate this
thesis.
TABLE OF CONTENTS
SCOPS OF RESEARCH..................................
1
PART
IDIRECT PHENOL - ALDEHYDE CONDENSATIONS...
2
INTRODUCTION.....................................
3
DISCUSSION.......................................
10
Condensation of Phenol with Aldehydes........
10
Condensation of Cresolswith Aldehydes.........
14
Condensation of " Unblocked " Xylenols with
Aldehydes...........................
15
Condensation of " Blocked " Xylenols with
Aldehydes...........................
15
CONCLUSIONS......................................
PART
II
18
INDIRECT PHENOL -ALDEHYDE CONDENSATIONS. 19
INTRODUCTION......................................
20
DISCUSSION.......................................
22
I
II
III
Attempted synthesisthrough p-Nitrotoluene.
22
Attempted synthesisthrough p-bromphenetol. 25
Condensation of Dimethylol-p-cresol with
Various Phenols.....................
CONCLUSIONS . ...................................
28
37
EXPERIMENTAL
PART
I DIRECTPHEIJOL-ALDEHYDE CONDENSATIONS. ..
.
38
3.4-Xylenol-Aldehyde Condensations
39
2.5-Xylenol-Aldehyde Condensations.............
53
3.5-Xylenol-Aldehyde Condensations.............
65
2,4-Xylenol-Aldehyde Condensations...........
79
2.6-Xylenol-Aldehyde Condensations.............
96
PART
I
II
III
II INDIRECT PHENOL-ALDEHYDE COMJti,3ATI0iSS. . 109
Condensation of p-nitrotoluene with
formaldehyde, etc............
110
Condensation of p-bromphenetol with
formaldehyde,etc.........
122
Condensation of Dimethylol-p-cresol with
Various Phenols..............
131
SUMMARY.........................................
3IBLIG3RAPHY
I39
142
SCOPE OF RESEARCH
The object of this InvestigatIon is the study of
11 blocking effects " in direct ( Part I-) and indirect
( Part II ) phenol-aldehyde condensations. Thus, phenols
possessing one or two ortho positions, one ortho and
one para position, two ortho and one para position, and
one para position alone, were systematically subjected
to condensation with representative aromatic and
aliphatic aldehydes ( direct condensation ) and with
certain phenolic dl-alcohols ( indirect condensation ).
The physical and chemical characteristics of the
resulting condensation products were ascertained and
examined for structural generalizations..
PART
I
DIRECT PHENOL - ALDEHYDE CONDENSATIONS
INTRODUCTION
In 1872, A. Baeyer ( 1 ) condensed phenols ( phenol,,
naphthol, resorcinol, pyrogallol, etc. } with aldehydes
( formaldehyde, benzaldehyde, etc. } for the first time
and obtained reddish-brown resinB. It was possible to
Isolate some crystalline products, but no structural
formulas were given at that time.
Emil J&ger ( 2 ) showed that in the condensation of
thymol with chloral a dlphenylmethane type of compound was
obtained, ter Meer ( 3 ) carried this type of condensation,
a little further by the condensation of anisol with
formaldehyde using concentrated sulfuric acid as the
condensing agent to obtain a compound of the following
structural formula:-
R. Fablnyi ( 4 ) and A. Steiner ( 5 ) did further
work on these condensations using various phenols and
aldehydes and also various condensing agents. In each
case a dlphenylmethane type of compound of the following
structural formula was obtained as the main product:
O
H'
— <D>
OH
S = Alkyl, aryl
or hydrogen
During the intervening years this type of
condensation was investigated thoroughly and practically
every phenol and aldehyde was condensed, the product
isolated and identified.
However, the reaction of aldehydes with phenols is
not as simple as would be expected, as shown by the fact
that, according to the conditions of the condensation.and
of the molar ratio of reacting materials, very different
results may be obtained, so that compounds, unlike in
chemical a physical properties can be isolated. Some
of the condensation products are crystalline while others
are amorphous and resin-like.
Baekeland ( 6 ) was the first to propose a definite
formula for that type of compound obtained by the use
of high temperatures and pressures on a mixture of
phenol and formaldehyde. ( Baekeland calls this type of
compound M infusible, insoluble resin ". )
-
5
-
Baekeland ( 7 ) also gives a formula, based on
carbon and hydrogen values, of i104H93°l6
for th8
condensation of formaldehyde and phenol. He also claims
to have prepared the same compound by condensing
saligenin with phenol in a molar ratio of 14 to 1 to
give a compound of the same formula, ^ 104.^92° 16 *
14 0J1QC>
7 8 2
+
C-H OH
65
=
13 H O
2
+
C
104 92 16
J. W. Aylsworth ( 8 ) has condensed phenol with
formaldehyde in a ratio of three molecules of phenol
with two molecules of formaldehyde, without the use of
a condensing agent, and assumes the constitution, to be :
.0 H °
6 4
CH
X
C.H.O
6 .4
However, outside of the relative proportions of the
ingredients used, there is no Justification for the
formula.
The dlphenylmethane compounds perhaps play some
-
6
-
role in the formation of these resins, since.Baekeland
( 7 ) has isolated from his resins considerable amounts
of paradioxydiphenylmethane.
Haschig ( 9 ) is of the opinion that some resins
are mixtures of three isomeric dloxydiphenylmethane
compounds, mixed with the excess phenol used in the
reaction. However, this opinion is not substantiated
by the physical property of the large solubility
of
dioxydiphenylmethanes in hot water.
Haschlg ( 9 ) has also taiten up the subject from
quite a different point of view. In the case of phenol,
the dialcohol may be formed and this can react further
with phenol { with the loss of formaldehyde ) to give
dlphenylmethane compounds which may farther condense
as follows
2
ch2
OH
ch2
When a larger portion of formaldehyde is present,
the following might result:OH
OH
HOHoC / N c h
o8OH2°^/S 3H oOH hoh
A
CH
OH OH
Y
CH
A
H0H2
CH^OH
SH OH HOH C
2
2
20g0H ■
Wohl t 10 ) has advanced the theory that these
bodies are polymerization products of methylene derivatives
of the tautomeric phenol.
H
H
.c = c
CH
lc = 0
= 0
H
H
Baekeland and Bender ( 11} offer the following
course of reaction in the formation. of polymers in
production .of a resin of the phenol-formaldehyde
R<
‘C=0
R>^
+
H0C,H,_
6 5
X 0H
. A
**
n o o 6h 5
the
type..
Rearranges v
----
R.
,0H
N C
R^
R
+
6 4
Rearranges
\
sometimes
^
C-H OH
6 -5
=
r
SC
D
*' SC JT'OH
6 4
R . ^O^Hj.OH
'</
r
Y
6 A
vC , H fOH
6 4
A polymerization reaction then would take place
as follows
Hv
0 = 0
+
Hx
2 C _.H OH ---- *
6 5
Hn ,00 H,
0.
6 5
h ' s 06H4OH
,00 H
C = C' 6 5 ----- ^
H'
C^H,OH
6 4
+
Hv
'0=0
H'
Hs
( 0 ,H 0 )
14 12 2 n
From the above diagram, it seems that Baekeland proposes
that the reaction takes place as follows
1)
Condensation takes place between the hydroxy
hydrogen of the phenol and the oxygen of the aldehyde..
2)
The resulting phenoxy compound rearranges to a
para-hydroxy compound.
3)
Condensation takes place between.the resulting
alcohol and the hydroxy hydrogen of another phenol molecule.
4)
The mixed phenoxy compound sometimes rearranges
to a diphenol.
Since it becomes utterly impossible to separate and
identify all the chemical compounds present in such
resins as mentioned above, even if these products could
be Isolated by fractional crystallization, precipitation
or distillation* provided they were not already colloidal
bodies, Intermixed with each other in solid solution,
some other method of approach must be used.
According to the theory of ortho and para substitution,
any condensation must take place on positions ortho or
para to the hydroxy group of the phenol. Since the
resins either are formed by polymerization after
one position of the phenol has been substituted
as
according to Baekeland { 10 ) or are formed by further
reaction of the other unsubstituted ortho and para
positions, the obvious reactions to determine what
happens would be to condense aldehydes with the xylenols
which, in some cases, offer only one ortho or the para
position for condensation.
DISCUSSIGN
Phenols may he divided into two main groups
in
regards to their reaction with aldehydes under the
influence of dry hydrogen chloride as a condensing agent.
In 3-roup I may be placed all those phenols which
tend to give resins when the proportion of aldehyde to
phenol is greater than one mol of aldehyde to two mols
of phenol and would include the following phenols - - phenol, o—, m-, and p-cresol, and 2 ,5- 3*4- and 3 ,5-xylenol.
In 3-roup II may be placed those phenols which do
not
give resins when the proportion of aldehyde to
phenol is greater than one mol of aldehyde to two mols
of phenol. These phenols would Include 2,4-xylenol and
2 ,6 -xylenol; in other words, those phenols which have
available for condensation only one ortho or only
the
para position to the hydroxyl group.
3R0UP I
CONDENSATION OF PHENOL WITH ALDEHYDES
In the course of studies on condensations of the
aldehydes with phenol, only alkylidene diphenol types
of condensation products involving one mol of aldehyde
with two mols of phenol has been exhaustively studied
( 12, 13, 14, 15, 16 ). A one to one ratio condensation
has been described by J..B. Nlederl and coworkers C 17 )
in which phenol and the three cresola were condensed
with various aldehydes in a one to one ratio to give
compounds of undetermined structure in high yields.
In the case of the condensation of unsaturated
aldehydes with phenol, the following results were obtained
1)
The condensation product weighed much more than
the theoretical yield could account f o r. .
2)
The carbon and hydrogen analyses varied,,
depending on the method of condensation, the solvent
used in the condensation reaction and
the treatment
of the compound before analysis.
3)
Polymers v/ere obtained in all cases, Irrespective
of the molar ratio of the aldehyde to phenol.
For Instance,
the condensation of phenol with
crotonaldehyde, 70 grams ( 1.0 mol ) of crotonaldehyde,
when condensed with 94 grams ( 1.0 mol ) of phenol In
400 cc. of glacial acetic acid, using hydrogen chloride
gas as a catalyst, gave a grey amorphous powder on
pouring the reaction mixture into water. .
After washing thoroughly with water and allowing
to dry for one week, an amorphous powder remained which
weighed 250 grams ( theoretical - 148 grams ). The
powder had not decreased in volume, the odor of acetic
acid had been removed completely, and the sample was
apparently dry. On standing for a few months, the
weight had decreased slightly. The excess weight could
be attributed only to the addition of the solvent, in
this case acetic acid, to the condensation product.
Under the same conditions, using propionic acid as
a solvent for the condensation reaction, a grey amorphous
powder weighing 344 grams was obtained ( theoretical 148 grams ). The condensation was also perforoied using
butyric acid, oleic acid, ether, alcohol and water as
the solvent, respectively. In each case, when it was
possible to obtain the condensation product in the
solid state ( in some cases it was possible to obtain
only an oil ) the same conditions prevailed - - - a
large increase in weight over that calculated
for
the reactants used.
That the solvent must have entered the reaction
is illustrated by the following table, showing the
carbon and hydrogen values for the crotonaldehyde phenol condensations, using different solvents in
the condensation reaction
TABLE
I
ANALYSIS
SOLVENT
Acetic Acid
C, .76.12; H, 7.21
Propionic Acid
C, 67.42; H ,;6 .63
Butyric Acid
G, 64.34; H, 7-90
Oleic Acid
C, 71.75; H ,.7 •90
Ether
0, 69.34; H , 7 . 4 0
Ethyl Alcohol
0, 70.09; H, 7.01
The same effect of the solvent was obtained
on
condensing cinnamic aldehyde under the same conditions
with phenol.
For instance, 24 grams ( 0.25 mol ) of phenol
condensed in butyric acid with 44 grams ( 0.25 mol )
of cinnamic aldehyde yielded 122 grams of dry
condensation product ( 53 grams - theoretical yield ).
Table II shows the effect of the solvent on
the analyses for the condensation of cinnamic aldehyde
with phenol.
TABLE
SOLVENT
II
ANALYSIS
Acetic Acid
C, 81.77; H, 5.68
Propionic Acid
G, ,79.40; H , .5.82
Butyric Acid
C, 80.21; H, 5.84
These condensation products were treated with
various reagents; for instance, refluxed with acetic
acid and zinc dust, or refluxed with Claisen solution,
but In all cases the same type of results were obtained
- - - no constant analyses.
All of these compounds have no definite melting
points, decomposing on heating with the evolution.of
a gas. They cannot be crystallized from any common
solvent and can be obtained in the solid state only by
dissolving in some water-miscible solvent and pouring
into a large volume of water.
The cresols were not Investigated a3 thoroughly
as the phenol condensations since the same amorphous
powders have been obtained by J. B. Niederl and
coworkers ( 17 )• However, the same types of compounds,
with abnormal yields ( at the very least, the theoretical
yield ) were obtained in each case.
The xylenols are of particular Importance in these
condensations because of the wide variety of structural
relationships represented. They have been investigated
fully in regard to alcohol formation ( formaldehyde
and a basic catalyst, such as sodium hydroxide J by
Auwers ( 18 ) and F . S . Granger ( 19 J.
Of the xylenols, the 2,3 -xylenol was unavailable
for investigation. However, this
compound falls
into
the same claS3 as the 3,4-xylenol and the 2 ,5-xylenol.
OH
OH
OH
2 ,3-xylenol
2 ,5-xylenol
3,4-xylenol
These phenols all contain two positions available
for condensation, either both ortho, or one ortho and
one para to the hydroxyl group. It is possible to
obtain amorphous powders under the proper conditions
of condensation. However, the conditions in these
experiments do not seem to be strong enough, in the
case of the 2 ,5-xylenol, to give the usual resin
and
only crystalline dlphenylmethane types of compounds
were obtained. On the other hand, 3,5-xylenol is similar to phenol
OH
3 ,5-xylenol
or meta cresol, having all three active positions
available for condensation and will give the usual
resin or dlphenylmethane type of compound depending
on the molar ratio of reactants.
It should be noted here that the halogenated
benzaldehydes, o-chlorobenzaldehyde and p-chlorobenzaldehyde
or of such a nature that they do not give the usual
resins under the conditions of the condensation, reaction..
GROUP
II
BL03KED COMDEMSATIONS OF ALDEHYDES AND PHEHOLS
£ince no consistent results could be obtained on
condensing phenol, the eresols and the xylenols already
mentioned with aldehydes, it was decided that it would
be necessary to condense with representative aldehydes
those phenols which would not form polymers. The phenols
best suited for this purpose are 2,4-xylenol ( one
ortho position available for condensation ) and
2 ,6-xylenol ( one para position available for condensation J.
OH
2 ,4-xylenol
OH
2 ,6 -xylenol
-
17
-
It may be stated that, as a general rule, the
type of condensation product obtained in condensation
reactions involving phenols and aldehydes depends on
the molar ratio of the aldehyde to the phenol. When
the ratio of aldehyde to phenol Is one to one ( molar )
a polymeric compound should be obtained while if the
molar ratio of the aldehyde to phenol is one to two,
a dlphenylmethane compound should be obtained..
However, In the case of 2,4-xylenol and 2,6xylenol, irrespective of the molar ratio of aldehyde to
phenol, crystalline dlphenylmethane derivatives only
could be Isolated from the reaction mixture. On
condensing these xylenols with aldehydes in a ratio
of one to one the same compounds were obtained, as
shown by the analyses of the compounds themselves
and their acetates and also by the
rnlxed melting
points of the.se products with the compounds obtained
by condensing the same aldehyde and xylenol in a molar
ratio of one to two.
These facts lead to the following conclusions:-
CONCLUSIONS
1)
When aldehydes are condensed with properly
blocked phenols having only one position in the ring
available for condensation, only dlphenylmethane type
of condensation products can be obtained..
2)
In order to obtain a polymer in the condensation
of an aldehyde with a phenol, it is necessary to have
available for condensation at least one ortho and
the para position or two ortho positions to the hydroxyl
group.
3)
The results obtained when multimolar quantities
of the aldehyde are used Indicate that the resinuous
character of a Bakelite type of compound ( page 8 )
is not due to anti- or posterior polymerization of
the aldehyde, but is due to multiple dlphenylmethane
types of linkages.
4)
All linkages, connecting phenol rings in
sidehyde-phenol condensation products, are of the
dlphenylmethane type.
PART
II
INDIRECT PHENOL - ALDEHYDE CONDENSATIONS
PART
II
INDIRECT PHENOL - ALDEHYDE CONDENSATIONS
INTRODUCTION
Of the various structural formulas suggested for
the phenol-aldehyde condensations obtained by condensing
phenols with aldehydes directly In either acidic or
alkaline medium as outline in Part I of this thesis,,
the Raschig ( 9 ) sixteen-membered ring formula appeared
to be worthy of further studies. .This is particularily
so since Nlederl and Vogel ( 20 ) in their publication
regarding a probable structure of the crystalline
products of certain
resorcinol - aldehyde condensations
have suggested a similar ring structure.
A crystalline condensation product of acetaldehyde
and resorcinol has been reported by several investigators
but statements relative to the constitution of this
compound are conflicting. The conventional alkylidenediphenol structure ( 21 ) as well as the acetal
structure ( 22 ) have been advanced. However, quantitative
elementary analysis of the crystalline water-free
acetates and propionates Indicate an equimolar ratio
of reactants. molecular weight determinations show
that the ratio of the reactants is 4:4. The condensation
products do not appear to undergo hydrolysis upon
refluxing with alcoholic sulfuric acid C absence of
acetal linkages ) nor with hydroiodic acid ( absence of
ether linkages ). Further work on the same type of
condensation products involving the absoption spectra
of the compounds by 1. Schwarts ( 23 ) ana A. Berntsen ( 24
indicate that the bonds are all of the diphenylmethane
type.
Ring structures possessing four times the same
molecular aggregates are widely encountered in the
heterocyclic series ( porphyrins, hemln, chlorophyll,
etc. ) . A similar type of structure for the aldehyde
resorcinol condensation products would be in harmony
with the properties of the compounds. This type of
structure would Involve
the simple reaction.mechanism
of a four-fold self condensation through intermolecular
dehydration
as shown
HO
OH
OH
DISCUSSION
It was decided to synthesize such a slxteenmembered ring directly by Independent methods. The
methods that were considered are as follows :I.
CONDENSATION OF p-NlTROTOLUENE WITH FORm ALDEHYDE,
REDUCTION OF THE CONDENSATION.PRODUCT TO THE
DIAMINE, DIAEOTIZATION AND A CRI3NARD REACTION
ON THE DI-HALIDE
( Flow Sheet I ).
Formaldehyde was condensed with p-nltrotoluene to
give 2,2'-dimethyl-5,5'-dinitrodiphenylmethane in 81>»
yield ( nitrobenzene gives less than 5% yield in the same
reaction J according to the procedure of H. Weil ( 25 ).
2,21-dimethyl-5,5'-dinitrodiphenylmethane was
reduced with stannous chloride and hydrochloric acid to
give the corresponding diamine in good yield.
On diazotization of the diamine, the theoretical
amount of nitrous acid was taken up by the compound but
on treating the diazotized solution with potassium
iodide under various conditions only black tars,
containing free iodine and some nitrogen, could be
obtained. These tars could not be purified or transformed
into the corresponding di-iodide compound by any
means.
known
On treating the diazotized solution of the diamine
with cuprous bromide or chloride, solid amorphous
complex copper salts were obtained. They were extremely
stable and could be decomposed only by the method of
Heinz-Werner Schweckten ( 26 ) which consists of the
distructlve distillation of the complex copper compound
with an equal weight of sodium bromide or sodium
chloride to give small amounts of the corresponding
di-bromide or di-chloride. However, the yield of
these compounds did not Justify pursuing this course
of synthesis any further.
- 24 -
Flow Sheet
I
OH
CH
CH
NO
HNO
KI
CH
CH
CH
CH
CH
.CH
H
CH
CH
II
CONDENSATION OF p-3R0MPHENETOL WITH FORMALDEHYDE
AND A URI3NARD REACTION ON THE CONDENSATION
PRODUCT ( Flow Sheet II )
p-Bromphenetol can be condensed with formaldehyde
using concentrated sulfuric acid as a condensing agent
according to the procedure of Diels and Bunzl ( 27 J with
slight modifications to give 2 ,2 *-diethoxy-5 ,5 1-dibromdiphenylmethane.
This compound, however,, could not be made to react
with magnesium, although many of the known methods of
starting the reaction were tried ; for example, the
use of a " cleansing reagent " as described by
V. 3-ri.gnard ( 28 ).
There is no doubt that dl-halogen compounds
in
the benzene series will react with magnesium to form
the corresponding di-magnesium compounds since many
of these are reported in the literature ( 29, 30,
31, 32 ). However, in the case of the compound in
question, no reaction was observed..
C. Emschweller ( 33 ) has reported that two
molecules of magnesium will react with methylene
iodide to give the corresponding
dl-magnesium
compounds. The fact that magnesium will react with
methylene iodide has been verified in this laboratory
but no quantitative measurements were made on the
completeness of the reaction. However, no reaction
will take place between this dl-magnesium compound
and 2,2'-diethoxy-5,5'-dlbromdiphenylmethane so this
method of synthesis of a sixteen-membered ring had to
be abondoned.
- 27 -
Flow Sheet
00 oH
00 H
Br
Br
II
00
OH
CH I
OH
OH
CH
CH
H
2
‘
4
Ill
CONDENSATION OF DIMETHYLOL-p-CRESOL WITH
VARIOUS PHENOLS
The syntheses employed consist of condensing a
well-known crystalline phenolic di-alcohol ( 1,3,5-trimethyl1',2,3'-trihydroxybenzene ), the condensation.product
of p-cresol with two mols of formaldehyde in basic
solution ( 34 )t with
A)
phenols ( p-cresol and p-bromphenol ) each of
which has two ortho positions available for reaction
( Equl-molar condensation ) and
3)
a blocked phenol ( 2,4-xylenol ) having only
one ortho position available for condensation ( Blocked
condensation }.
The condensation products resulting from (A) may
be either " cyclic " or '* open chain " in structure,
but the blocked condensation in ( B ) allows only an
" open chain " structure.' By a comparison of the
*
physical properties of the original condensation
products of ( A ) and ( B J
similarities or dissimilarities
of structure may be concluded, and by quantitative
elementary analysis of the crystalline water-free
acetates obtained from ( A ) the detection of terminal
hydroxyl groups, the presence of which would favor the
- 29 -
open chain and the absence of which would favor the
cyclic structure, may be made..
In the equimolar condensations ( A ) p-cresol as well
as p-bromphenol were condensed with equimolar quantities
of the dimethylol-p-cresol In the presence of dry
hydrogen chloride. The high melting condensation products
precipitated from the reaction mixture and were recrystallized
from ethyl alcohol. However, In the blocked condensation.
( B ) when two mols of 2,4-xylenol v/ere condensed
with one mol of dimethylol-p-cresol under identical
conditions, no precipitate was obtained..The solution
separated into two layers on standing for one week.
The upper layer was decanted, the lower layer dissolved
in ether, washed with water, dried, the ether removed
by evaporation and the residue taken up In ethyl alcohol.
The condensation product could be obtained In the solid
state by pouring the alcoholic solution into water.
There is a wide variation in melting points In the
two types of condensation products, the p-cresol and
p-bromphenol compounds melting at 215°C and 210°C
respectively, while the 2,4-xylenol compound melts
at 116°C.
- 30 -
PROPOSED REACTION MECHANISM AND STRUCTURE
Reaction
OH
A
OH
HOH C / \ C H 2GK
OH
2 HCHO
NaOH
CH
CH
CH
CH
CH
Ac
R
OH
OAc AcO
OAc
OH
CH
CH
CH
CH-
PROPOSED REACTION
a ECHANISH
Reaction
AND STRUCTURE
B
OH
OH
2HCHO
NaOH
H
3
HC1
OH
OH
OH
CH,
CH,
CH,
H-
It can be seen from the above flow sheet that,
using 2,4-xylenol, it is not possible to obtain a
compound, with a earbocyclic structure. There should
be a difference in physical properties between this
dibenzyl-phenyl compound and those obtained by using
M unblocked 11 phenols. The melting points illustrate
this very well, that of the dioenzyl-phenyl compound
being about one hunared degrees lower than those of
the carbocyclic compounds.
However, the analyses of these compounds, as
was the case In all compounds of this type, are functions
of the treatment of the compounds before analysis ( time
and temperature of drying,etc. ) as shown in the
following tables.
TABLE
III
DIMETHYL0L-P-GRE30L AMD o-CRESOL_______
Analysis before drying
0, 77.54; H,6,72
0, 77.51; H,6.99
Analysis after drying
{ 12 hrs. at 105°C. in vacuum )
0 , 7 6 .16; H,6 .59
3 .31$; 3.44$
Volatile matter at 105°0•
TABLE
IV
DIMETHYLOL--0-CRE3QL AND n-BROMPHENOL
Analysis before drying
0, 5 3 *6 6 ;H, 4.24;Br, 31.96
3, 53.59;H, 3.98;Br, 32.22
Analysis after drying
0, 5 5 .1 0;H, 3.60
( 12 hrs. at 105°C. in vacuum )
Volatile matter at 105°C.
3.60$
According to Nlederl and Vogel ( 20 ) it is
necessary to make the acetates of these compounds in
order to obtain intelligible and consistent results in
regard to carbon and hydrogen analyses, 3ince the free
-
33 -
phenolic compounds show a great tendency to retain
solvents in varying amounts. Therefore, calculation
are made on the basis of the analyses of the acetates.
The condensation of p-bromphenol with diqjethylolp-cresol allows the introduction of a 11 tracer " element.
The differences in the theoretical carbon and hydrogen
values and also in the percentages of bromine in
straight chain compounds and cyclic compounds are
correspondingly larger because of the large weight of
the bromine atom as shown in the following tables
TABLE
V
ACETATE OF PIMETHYLOL-p-CRESOL AND p-ORESOL CONDENSATION
FOUND :
C, 73-85; K » 6.12
CALCULATED FOR STRAIGHT CHAIN
One dimethylol-p-cresol and
two p-cresol ( triacetate )
C, 73.42; H, 6.33
Two dimethylol-p-cresol and
C, 73-68; H , 6 . 2 7
three p-cresol ( pentaacetate )
Three dimethylol-p-cresol and
four p-cresol(heptaacetate)
C, 73-79; H, 6.24
TABLE
VI
ACETATE OF DIMETHYLOL-p-ORESOL AND p-BRQMPHENOL CONDENSATION.
FOUND :
C, 59.09; H, 4.62; B r t 20.11
CALCULATED FOR STRAIGHT CHAIN
One dimethylol-p-cresol and
two p-bromphenol (triacetate)
C,53.64;H,3.97»Hr,26.49
Two dimethylol-p-cresol and
0.55*56;H,4.l3;Br,24.17
three p-bromphenol (pentaacetate;
Three dimethylol-p-cresol and
C,56.44;H,4.19;3r,23-16
four p-bromphenol (heptaacetate)
It will be noticed that the condensation of
dimethylol-p-cresol is not conclusive in its analytical
results since the calculated values for a straight chain
compound are close to those actually found and also to
those for a Bixteen-membered ring. However, in the
condensation of dimethylol-p-cresol and p-broiiiphenol this
is no longer the case since the values calculated
for
the straight chain compounds and the values actually
found vary widely. One other type of compound is of
Interest in this consideration; namely, that in which
a terminal hydroxy ( primary alcohol ) group could
exist. Tables VII and VIIl show the calculated values for
straight chains containing terminal hydroxyl groups
for condensations involving dimethylol-p-cresol and
p-bromphenol respectively.
- 35 -
TABLE
VII
ACETATES OF DlMETHYLOL-p-CRESOL AMD n-CRESOL CONDENSATION
FOUND :
C, 73,85; H, 6.12
CALCULATED FOR STRAIGHT CHAIN WITH T E R M U A L HYDROXY 3A0UP3
One dimethylol-p-cresol and
one p-cresol ( triacetate )
C,
68*75; H, 6.25
Two dimethylol-p-cresol and
two p-cresol ( pentaacetate J
C,
71*19; H, 6.21
Three dimethylol-p-cresol and
three p-cresol ( heptaacetate )
C,
72.09; H, 6.20
TABLE
VIII
ACETATES OF DIMETHYLOL-p-CRESOL AND p-BROMPHENOL CONDENSATION
FOUND :
C, 59.09; H, 4.62; 3r, 20.11
CALCULATED FOR STRAIGHT CHAINS WITH T E X T U A L HYDROXY CROUPS
One dimethylol-p-cresol and
C,5o.l2;H,4.67;Br,17»82
one p-bromphenol (triacetate)
Two dimethylol-p-cresol and
C.57.28;H,4.53;Br,19«09
two p-bromphenol (pentaacetate)
Three dlmethylol-p-cresol and
G,57.70;Ii,4.48;Br,19*56
three p-bromphenol (heptaacetate)
It can be seen that these values are not in
concordance with the values actually found. Thus
there
remains only the sixteen membered rings, the quantitative
elementary
analytical values of which agree on
the
analysis of the crystalline water-free acetates tooth
in the case of the p-cresol xompound and also in the
case of the p-bromphenol compound.
PROPOSED STRUCTURES OF EQUIMOLAR CONDENSATION PRODUCTS
CH
•Ac
OAc
H
Ao(
0H
CH
■CH
CH-
Calcd. for
( 648 )
0, 74.07; H, 6.17
Found:
0, 75*85; H, 6.12
3r
CH
CH
OAc
H
OAc
Ac
H.
OAc
CH
Calcd. for
Found:
C^H^OgBr
( 778 )
C, 58.61; H-., 4.36; 3r.20.56
0, 59.09; H, 4.62; Br,20.11
Since this type of structure resembles a pointed
cross, the name " cruci-phenols " ( simple and mixed
11 crucilytes " J has been suggested for these types
of conuensation proaucts ( 35 )•
CONCLUSIONS
Quantitative analytical studies of the crystalline
acetates of both simple and mixed equimolar condensation
proaucts of iimethylol-p-cresol favor a porphyrin type
of carbocyclic structure ( sixteen-aiembered ring J.
A new open chain dibenzyl-phenyl type of conuensation
product has been prepared.
PART
I
EXPERIMENTAL
3,4-XYLENOL - ALDEHYDE CONDENSATIONS.
PROPOSED REACTION MECHANISE AND STRUCTURE
3,4-XYLENOL - ALDEHYDE COND-ilNSAT ION S
CH,
CH
JH
3
CH
CH
HO
HO
CHOH
0ii
C-H
I
R
CH
OH
HO
CHI
CONDENSATION OF 3,4-XYLENOL WITH ACETALDEHYDE ( RATIO 1:1 )
A solution of 30.5 grams ( 0.25 mol ) of 3,4-xylenol
dissolved in 50 cc. of glacial acetic acid was cooled
an Ice bath and 11.0
In
grams ( 0.25 mol ) of acetaldehyde
was added. Dry hydrogen chloride was passed in until
the solution was saturated. On standing, no precipitate
formed, so the solution was poured into water. A white
amorphous solid was obtained which was filtered off
and v/ashed thoroughly with water. The solid v/as
dried
thoroughly and analyzed. It could not be crystallized
from any common solvent. The yield of the amorphous
powder was quantitative.
lieltlng point :
Softens at 132°C., viscous liquid at
148°C., forms a meniscus at 154°C.
Analysis:
Since the solid was amorphous and had
no sharp melting point, no theoretical value is advanced.
Found:
C, 77.64; H, 5 .60
(
Sample dried for 18 hours
at 105°C., in vacuum }
ACETATE OF 3>4-XYLEW0L-ACETALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product ( Ratio 1:1 )
was refluxed for three hours with 50 c c . of acetic anhydride.
The solution was poured into water and the white amorphous
precipitate filtered off and dried thoroughly.
Lelting point:
Softens at 78°C., forms a viscous liquid
at 35°3., forms a meniscus at 92°C.
Analysis:
Since the solid Is amorphous and has no
sharp melting point, no theoretical value is advanced.
Found: C,78.06; H, 6.48
CONDENSATION OF 3,4-XYLEN0L WITH ASETALDEHYDE
( PATIO 2:1 )
Two and four tenths grams ( 0.02 mol ) of 3,4-xylenol
was dissolved in 10 c c . of glacial acetic acid and
the solution was cooled in an ice-bath. Four tenths of a
gram ( 0.01 mol ) of acetaldehyde was aaaed and dry
hydrogen chloride gas passed in until the solution was
saturated. A crystalline precipitate was obtained
which
was filtered off and recrystallized from ethyl alcohol,
welting point
149°0.
2,2'-dihyaroxy-4,4'-5,51-tetramethyldlphenyl»ethane
Anal.
Found:
Calcd. for ^13^ 22^2
^
^
^ * 80.00; H, 8.15
0, 79.86; H, S.33; m.w.274
ACETATE OF 3,4-XYLENOL-ACETALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product ( Ratio 2:1 )
was refluxed with 50 c c . of acetic anhydride for two
hours. The solution was poured into water and the white
crystalline precipitate filtered off and recrystallized
from ethyl alcohol.
Kelting point
Anal.
Found:
l6l°C.
Calccl. for
0^26°^
* 354 *
c » 74.58; H, 7.34
C, 74.44; H, 7.24
got!d :-::t c a t t o ^
op
3 ,4 -xylen o l
r e ! tp a l d t ! k y p e
( r a t io
One and two tenths grarn of 3,4-xylonol ( 0.01
i: i
mol )
was dissolved in 10 oc. of glacial acetic acid and one
grar ( 0,01 mol ) of bens ale el:yde added. The solution
was cooled in an ice-hath and dry hydrogen chloride
passed in until the solution was saturated• Or. standing
nothing precipitated out of tie solution so it was
poured into water tin.'' the v/hite colid f :*liored cff
and dried thoronyhly. Since it could not be crystallized
from any common col vent, it was analyzed without
crystallization, ’'he yield was cuantitative.
Pelting point:
colored
Analysis
M-puld,
:
Starts to soften at 130°0., amber
o
very vlsccua
at 145
G., me n i s c u s
at
b
150 C.
Since the c o m o u n d Is amorphous and has
no sharp melting point, no theor-d.leal vaiuo Is advanced.
Pound, :
C, 82.42; I!, P.03
{
Sample dr?ed fcr twelve
hours at 105 C., in vacuum )
)
ACETATE OF 3,4-XYLEi\fOL-BEK Z.ALOEH YUE COM Oh* SAT ION PRODUCT
One gram of the condensation product ( Aatio 1:1 )
was refluxed with 20 c c . of acetic anhydride for five
hours. The solution was poured Into water and the
white solid filtered off. It could not be recyystallized
from any common solvent.
Melting point :
Starts to soften at 60°C., forms a
meniscus at 65°C.
Analysis:
Since the solid is amorphous and has no
sharp melting point, no theoretical value is advanced.
Found :
0, 80.41; K, 6.31
G01ID2K3ATICH OF 3 , 4-X Y L2H 0L WITH 3EII4ALDEHYDE
( RATIO 2 :1
J
Two and four tenths grams ( 0.02 mol ) of 3»4— xylenol
was dissolved In 10 cc. of glacial acetic acid and one
gram
( 0.01 mol ) of benzaldehyde was added. The solution
was cooled in an Ice-bath and dry hydrogen chloride
passed in until the solution was saturated. A crystalline
precipitate formed which was filtered off and recrystallized
from ethyl alcohol.
-■■-elting point
170°0.
2,2*-dlhydroxy-4,4',5,5'-tetramethyltritane
Anal.
Found:
Galcd. for
c23ll24°2
^ 332 }
33*13; H f 7.23
0, 63*lo; H, 7.50
- 47 -
ACETATE OF 3,4-XYLEN0L-BENZ ALDEHYDE CONDENSATION PRODUCT
One gram of the condensation product ( Ratio 2:1 ),
was refluxed with 20 cc. of acetic anhydride for two
hours. The solution was poured into water and the
crystalline precipitate filtered off and recrystallized
from ethyl alcohol.
belting point
162°C.
Anal. Calcd. for c;27H 28°4
Found :
^
^
C, 7 7 .8 8 ; H, 6.73
C, 77*62; H, 7 .08
- 48 -
CONDENSATION OF 3,4-XYLENOL WITH p-CHLOROBENZALDEHYDE
Two and four tenths grams ( 0.02 mol J of 3,4-xylenol
was dissolved in 10 grams of glacial acetic acid and
1.4 grams ( 0.01 mol ) of p-chlorobenzaldehyde added.
The solution was cooled in an ice-bath and dry hydrogen
chloride gas was passed in until the solution was
saturated. On standing In the ice-box for one week, no
precipitate had formed so the solution was poured Into
200 cc. of water. The white solid that
formed was
filtered off and crystallized from ethyl alcohol.
On condensing these two compounds in a ratio of
one aldehyde to one xylenol the same condensation product
was obtained, as ascertained by the fact that there is
no depression of the mixed melting point.
melting point
197°C.
2,2' -dlhyaroxy-4,4* ,5*5' -tetramet,hyl-4' '-chlorotritane
Jx.tkf'* 1
AGITATE OF 3,4-XYLENOL - p-GHLOROBEM GALDEHYDE CON DEN SATION.
PRODUCT
Two grams of the condensation product
was refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the crystalline precipitate
filtered off and recrystallized from ethyl alcohol.
The acetate of the condensation product obtained
by condensing one mol of the aldehyde with one
mol
of the xylenol is the same as the product mentioned
above, as ascertained by the fact that there was no
depression of the mixed melting point.
Melting point
Anal.
Found:
148°C.
Galcd. for
C^^O^Cl
( 450 ) G, 72.00; H, 6.00
G, 71.56; H,.5.98
CONDENSATION OF 3,4-XYLENOL WITH o-CHLOROBENZALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 3,4-xylenol
was dissolved in 10 c c . of glacial acetic acid
and
1.4 grams ( 0.01 mol J of o-chlorobenzaldehyde
added.
The solution was cooled in an ice-bath and dry hydrogen
chloride gas passed in until the solution was saturated.
On standing in the ice box for one week, no precipitate
had formed so the solution was poured into 200 cc. of
water and the white solid filtered off. This was
recrystallized from ethyl alcohol.
On condensing these two compounds in a ratio
of one aldehyde to one xylenol, the same condensation
product was obtained, as ascertained by the fact
that there is no depression of the mixed melting point.
Melting point
o
234 0.
2,2'-dihydroxy-4,4',5,5*-tetramethyl-2'’-chlorotritane
ACETATE OF 3,4-XELENOL - o-CHLOROBENZALDEHEDE CONDENSATION
PRODUCT
Two grams of the condensation product was refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the
crystalline
precipitate filtered off and recrystallized from
ethyl alcohol.
The acetate of the condensation product obtained
by condensing one mol of the aldehyde with one
mol
of the xylenol is the same as the product mentioned
above, as ascertained by the fact that there was no
depression of the mixed melting point.
Melting point
Anal.
Found:
149°G.
Galcd. for
Cg^H^O^Cl ( 450 ) G, 7 2 .fl>0; H, 6.00
C, 71.99; H, 5.86
3,4-XYLENOL - ALDEHYDE
CONDENSATIONS
SUMMARY
ALDEHYDE
RATIO
M. P.
ANALYSIS
Acetaldehyde
Acetate
1:1
154
92
0 , 77.64; H, 5.60
0 , 78.06; H, 0 .48
Acetaldehyde
Acetate
2:1
149
161
0 , 79.86; H, 8.33
0 , 74.44; H, 7.24
Benzaldbhyde
Acetate
1:1
150
65
0. 82.42; H, 6.03
0, 80.41; H, 6.31
Benzaldehyde
Acetate
2:1
170
162
0, 83.16; H„ 7'*50
0, 77.62; H,. 7.08
p-chlorobenzaldehyde
Acetate
1:1
or
2:1
197
148
0, 71.56; H,. 5-98
o-chlorobenzaldehyde
Acetate
isl
or
2:1
234
149
0, 71.99; H. 5.86
2,5-XYLENOL - ALDEHYDE CONDENSATIONS
PROPOSED REACTION MECHANISE AND STRUCTURE
2,5“XYLENOL - ALDEHYDE CON DEWSATIOHS
JH.
- 54 -
CONDENSATION OF 2,5-XYLENOL WITH ACETALDEHYDE
Two and four tenths grains ( 0.02 mol ) of 2,5-xylenol
was dissolved in 10 c c . of glacial acetic acid and
the solution was cooled in an ice-bath. Four tenths of
a gram ( 0.01 mol ) of acetaldehyde was added and dry
hydrogen chloride passed into the solution until it
was saturated. A crystalline precipitate was obtained.
This was filtered off and recrystallized from ethyl alcohol.
On condensing the same aldehyde with the xylenol
in a molar ratio of one aldehyde to one xylenol, the
same condensation product was obtained, as ascertained
by the fact that there was no depression in the mixed
melting point.
Melting point
205°C.
4,4'-dihyaroxy-2,2',5*5'-tetramethyldiphenyl«ethane
Anal.
Found:
Calcd. for
C_0H 0 O
-LO dd d
( 270 )
0, 80.00; H, 8.15
C, 80.52; H, 8.44
ACETATE OF 2,5-XYUJtfOL-ACETALDEHYDE CONDENSATION PRODUCT
One gram of the condensation product was refluxed
with 20 cc. of acetic anhydride for two hours. The
solution was poured into 200 cc. of distilled water and
the crystalline precipitate filtered off. It was
recrystallized from ethyl alcohol.
This acetate is the same as the acetate as
obtained
from the condensation of the aldehyde and xylenol
In a molar ratio of one to one as ascertained by the
fact that there was no depression in the mixed melting
point.
Melting point
105°C.
Anal. Calcd. for
Found:
022H2604
* 354 ^
°» 74.58; H, 7.54
C, 74.57? H, 7.34
CONDENSATION OF 2,5-XYLENOL WITH BENZALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 2,5-xylenol
was dissolved in 10 c c . of glacial acetic acid and
one gram ( 0.01 mol ) of benzaldehyue added. The
solution was cooled in an ice-bath and dry hydrogen
chloride passed in until the solution was saturated.
A crystalline precipitate was obtained. This was poured
onto a porous tile and allowed to dry. It could be recrystallized
from ethyl alcohol.
This product is the same as the product obtained
by condensing the alaehyde and xylenol in a molar
ratio of one to one as ascertained by the fact that
there is no depression In the mixed melting point.
Melting point
224°C.
4,4'-dlhydroxy-2,2', 5>5'-tetramethyltritane
Anal.
Found:
Calcd. for
( 332 )
C, 83-13; H, 7.23
C, 32.41; H, 8.06
ACETATE OF 2,5-XYLENOL-BENZALDEHYDE CONDENSATION PRODUCT
One gram of the condensation product was refluxed
with 20 c c . of acetic anhydride for two hours. The
solution was poured into 200 cc. of distilled water
and the crystalline precipitate filtered off and
recrystallized from ethyl alcohol.
This acetate is the same as that obtained
the condensation of the aldehyde and xylenol in
from
a
molar ratio of one to one, as ascertained by the fact
that there is no depression in the mixed melting point.
Melting point
Anal.
Found:
Calcd.for
174°C.
Cg^KggG^
( 416 J
0, 77*88; H, 6.73
C, 77-71; H, 6.62
CONDENSATION OF 2,5-XYLENOL WITH CROTONALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 2,5-xylenol
was dissolved In 10 c c . of glacial acetic acid and
1.4 grams ( 0.02 mol ) of crotonaldehyde aoded. The
solution wa3 cooled in an ice-bath and dry hydrogen
chloride was passed in until the solution was saturated.
On standing for one week, nothing had crystallized out
so the solution was poured into water. A white solid
was obtained which was recrystallized from ethyl alcohol.
The same product was obtained on condensing the
aldehyde and xylenol in a molar ratio of one to two
as ascertained by the fact that there was no depression
in the mixed melting point.
Melting point
195°^•
4,4*-dihydroxy-2,2 1,5,5'-tetramethyldiphenyl-3-chlorobutane
Anal.
Found:
Calcd. for
-2oH 25°2G1
( 332 ^
G * 72.29; H, 7-53
C, 7 2 .27; H, 7-88
ACETATE OF 2,5-XYLENOL-CROTONALDEHYDE CONDENSATION PRODUCT
One gram of the condensation product was refluxed
with 20 cc. of acetic anhydride for two hours.,The
solution was poured into water and the crystalline
precipitate filtered off and recrystallized from
ethyl alcohol.
This acetate is the same as the acetate obtained
from the condensation product of the aldehyde and
xylenol in a molar ratio of one to two as ascertained
by the fact that there was no depression in the
mixed
melting point.
Melting point
Anal.
Found:
119°3.
Calcd. for
024H29°401 ^
^
G » 69*23; H, 6.25
C, 69*32; H, 7.04
CONDENSATION OF 2,5-XYLElIOL WITH p-CKL0A032NZALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 2,5-xylenol
was dissolved in 10 cc. of glacial acetic acid and
1.4
grams { o.Ol mol ) of p-chlorobenzaldehyde added..
The solution was cooled in an ice-bath and dry hydrogen
chloride passed In until the solution was saturated.
The solution was placed in an ice-box for one week but,
since no precipitate formed, it was poured into water.
A white crystalline precioitate was obtained which was
recrystallized from ethyl alcohol.
This product is the same as that obtained on
condensing the aldehyde and xylenol in a molar ratio
of one to one as ascertained by the fact that there is
no depression in the mixed melting point.
Melting point
208°C.
4,4’-ulhydroxy-2,2 1,5,5*-tetramethyl-41'-chlorotritane
Anal.
Found:
Calcd. for
C^^^C^Cl
( 366 J
C, 73.41; H, 6.39
C, 73.62; H, 7-39
ACETATE OF 2,5-XYLENOL-p-CHLOROBENZALDEHYDE CONDENSATION
PRODUCT
One gram of the condensation product was refluxed
for two hours with 20 c c . of acetic anhydride. The
solution was poured into water and the white crystalline
solid filtered off and recrystallized from ethyl alcohol.
This acetate is the same as that obtained
from
the condensation product of the aldehyde and xylenol
In a molar ratio of one to one as ascertained by the
fact that there is no depression in the mixed melting
point.
Melting point
Anal.
Found:.
187°G •
Calcd. for
fl27H o70AG1
di 2 Y
^ ^5° ^
72.00; H, 6.00
C, 71*35? H, 5.95
CONDENSATION OF 2,5“XYLENOL WITH o-CHLOROBENZALDEHYDE
Two and four tenths grams of 2,5-xylenol ( 0.02 mol )
was dissolved in 10 cc, of glacial acetic acid
and
1.4 grams ( 0.01 mol ) of o-chlorobenzaldehyde added. 'The
solution was cooled in an lce-bath and dry hydrogen
chloride gas passed In until the solution was saturated.
The solution was placed in an ice-box for one week but,
since no preclpitation had occured, the solution was
thrown into water. The white precipitate was filtered
off and recrystallized from ethyl alcohol.
This product is the same as that obtained
on condensing the aldehyde and xylenol in a molar
ratio of one to one as ascertained by the fact that there
is no depression in the mixed melting point.
Melting point
Above 275°C•
4,4*-dihydroxy-2,2 ', 5»5*-tetramethyl-2* *-chlorotrltane
Anal. Oalcd. for
Found:
G 23H 23°2C1
^
^
°» 75*41; H, 6 .39
C, 75*28; H, 6.25
ACETATE OF 2,5-XYLEN0L-O-CKL0R03ENZALDEHYbE CONDENSATION
PRODUCT
One gram of the condensation product was refluxed
with 20 cc. of acetic anhydride for two hours. The
solution was poured into water and the crystalline
precipitate filtered off and recrystallized from ethyl
alcohol.
This acetate is the same as that obtained
the condensation product ofthe aldehyde
from
and xylenol in
a molar ratio of one to one as ascertained by the fact
that there Is no
depression in the mixed melting point.
Melting point
206°C.
Anal.
Found:
Calcd. for
Cg^H^O^Cl
( 450 )
C, 72.00; H, 6.00
C, 71.74; H, 6.42
- 64 -
2,5-XYLENOL - ALDEHYDE CONDENSATIONS
SUMMARY
ALDEHYDE
RATIO
M .p.
Acetaldehyde
Acetate
1:1
205
105
C, 30.32; H, 8.44
C, 74.57? K, 7*52
Benzaldeh3rde
Acetate
1:1
or
2:1
224
174
0, 82.41; H, 8.06
C, 77*71; H, 6 .62
Crotonaldehyde
Acetate
1 :i
or
2:1
195
119
o, 7 2 .2 7 ; H, 7-53
0, 69-32; H, 7.04
p-8hlorobenzaldehyde
Acetate
1:1
or
2:1
208
187
C, 75-62; H, 7.39
C, 71.35; H, 5.95
o-Qhlorobenzaldehyde
Acetate
1:1
or
2:1
275
206
0, 75.28; H, 6.25
0, 71.74; H, 6.42
or
2:1
ANALYSIS
3,5-XYLENOL - ALDEHYDE CONDENSATIONS
PROPOSED REACTION fcECHANISM AND STRUCTURE
3,5-XYLENOL - ALDEHYDE CONDENSATIONS
OH
H,C
OH
CH
OH
CH
0
CHiOH
0
H
C-H
I
R
OH
C
3
OH
■OH
3
I
a
CH
- 66 -
3OND2NSATI0M OF 3,5-XYLilNOL WITH AUTALDBHYDm ( RATIO 1:1 )
A solution of
30.5 grams ( 0.25 *aol ) of 3 ,5-xylenol
dissolved in 50 c c . of glacial acetic acid was cooled
in an ice bath and 11.0 grains ( 0.25 010I ) of acetaldehyde
added. Dry hydrogen chlDDide was passed in until the
solution until it was saturated. On standing, no precipitation
occured so the solution was poured into water. A
white
amorphous powder was obtained which was filtered onto
a Bdchner funnel and washed thoroughly with waier.
The solid wa3 dried and analyzed. The yield wa3 quantitative.
The white solid coula not be recrystallized from any
aomi.ion solvent, giving, on evaporation, an oil which
could be resolidified by dissolving in ethyl alcohol
and pouring into water.
i'-elting point:
Softens at 13Q°J., forms viscous liquid
at 138°0., meniscus at 142°C.
Analysis:
Since the 3olid is an amorphous powder and
has no sharp melting point, no theoretical value is advanced.
FoCLnd*.
0, 77*56; H, 7.00
-
67 -
ACETATE OF 3,5-XYLmdOL-ACETALDEHYDE COi^aiiSATICN PRODUCT
Two grams of the conaensation proauct was refluxed
with 20 c c . of acetio anhydride for two hours. The solution
was poured into water and the white solid filtered
off anu dried. It could not be recrystallized from
any common solvent.
Melting point :
Analysis:
Softens at 77°^•» forms meniscus at S4°G .
Since the solid is amorphous and has no
sharp melting point, no theoretical value is advanced.
Found:
3, 77*74; H, 7*04
CONDENSATION OF 3,5-XYLENOL WITH ACETALDEHYDE( RATIO 1:2 )
A solution of 4.88 grains ( 0.04 mol ) of
dissolved in 10 c c . of glacial acetic acid was
3,5-xylenol
cooled
in an ice-bath and 1.12 cc. ( 0.88 grams, o.o2 mol )
of acetalaehyde was added. Dry hydrogen chloride gas
was passed in until the solution was saturated. On
standing for two days a white crystalline solid had
precipitated and was filtered off and recrystallized
fi-om ethyl alcohol.
Melting point
147°C.
4,4*-dihyaroxy-2,2*,6,6*-tetramethyldlphenyl»ethane
Anal. Oalcd. for
Found :
ClgH 2202
( 270 )
C, SO.00; H, 8.15
0, 7 9 .27; H, 7.59
3 OK DiiiC3 AT I OK OF 3, 5-XYLEUOL WITH BENYALDmHYDE
( RATIO 1:1
To a solution of o.l j;rame ( 0.05 uiol ) of 3i5-xylenol
dissolved in 10 cc. of glacial acetic acid was added
5*5
c c . ( 5*4 grains, 0.05 aiol ) of benzaldehyde. The
solution was cooled in an ice-bath and dry hydrogen
chloride passed in until the solution was saturated..
The solution was allowed to stand for two days in an
ice-box . The acetic acid was decanted from the semisolid perclpitate that had formed and the precipitate
was dissolved in 10 c c . of ethyl alcohol. A white
amorphous powder was obtained on pouring this alcoholic
solution into water. This was filtered off and dried
thoroughly. The yield was quantitative.
heltin.5 point:
Analysis:
o
°
Softens at 142 3., forms meniscus at 159 3
Since the solid is amorphous, ana has no
sharp melting point, no theoretical value tos advanced.
Found:
0, 82.52; H, 5.88
( Sample dried for 15 hours
at i.05°C • > in vacuum )
ACETATE OF 3 ,5-XYLENOL-BENZALDEHYDE CONDENSATION PRODUCT
Two grains of the condensation product was refluxed
with 20 cc. of acetic anhydride for five hours. The
solution was poured into water and the white amorphous
precipitate filtered off. It could not be recrystallized
from any common solvent.
belting point :
Analysis:
Softens at 17o°C., forms meniscus at 187
Since the solid is amorphous and has no
sharp melting point, no theoretical value is advanced.
Found:
C, 30.26; H, 6.73
(
Sample dried for 18 hours
at 105° C ., in vacuum
)
CONDENSATION OP 3 ,5 -XYLENOL WITH BENZALDEHYDE
( RATIO 2:1 J
To a solution of 61.1 grams ( 0.5 mol ) of 3j5-xylenol
dissolved in 50 cc. of glacial acetic acid was added
54 grams ( 0.25 mol ) of benzaldehyde. The solution., was
cooled in.an ice-bath and dry hydrogen chloride passed
in until the solution was saturated. After standing
for one hour, a semi-solid mass began to precipitate.
On standing in contact with petroleum ether for one day,
the semi-solid mass formed crystals which could be
recrystallized from ethyl alcohol.
Ilelting point 244°C.
4,4'-dihydroxy-2 ,2 ',6 ,6 '-tetramethyltritane
Anal.
Found:
Oalcd. for
^23H24°2
* 332 ^
83-13; H, 7.23
C, 82.96; H, 6.77
ACETATE OF 3 ,5 -XYLENOL-BENEALDEHYDE CONDENSATION PRODUCT
Two grains of the condensation product was
refluxed
with 20 c c . of acetic anhydride for two hours and
then poured into water. The white crystalline precipitate
was filtered off and recrystallized from ethyl alcohol.
Melting point 110°G.
Anal.
Found:
Calcd. for
( 416 )
0, 77-88; H, 6.73
0, 77-91; H, 6.52
CONDENSATION OF 3,5-XYLENOL WITH p-CHL0R03£NZALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 3»5-xylenol
was dissolved in
10 cc. of glacial acetic acid and
1.4 graais ( 0.01 mol ) of p-chlorobenzaldehyde added.
The solution was
cooled in an ice-bath and dry
chloride gas was
passed in until the solution
hydrogen
was
saturated. On standing in the ice-box for one week,
no precipitate had formed so the solution was poured
into 200 cc. of water. The white solid was filtered
off and recfystallized from ethyl alcohol.
This product
Is the same as that obtained by
condensing the aldehyde and xylenol In a molar ratio
of one to one as ascertained by the fact that there
is no depression in the mixea ^eltlng point .
Melting point
129°3.
4,4'-dihydroxy-2,2 1,6 ,6 1-tetramethyl-4'*-chlorotritane
Anal.
Found:
Calcd. for
0 Cl
23 23 2
( 360 )
C, 75-41: H, 6.39
C, 74.62; H, 6.60
ACETATE OF 3 ,5-XYLENOL-p-CKLQRO BENZALDEHYDE CONDENSATION
PRODUCT
Two grains of the condensation, product was refluxed
with 50 cc. of acetic anhydride for two hours.
The
solution was poured Into water and the crystalline
precipitate
filtered off and recrystallized
from
ethyl alcohol.
Melting point
Anal.
Found:
Calcd. for
Cg^Hg^O^Cl
( 450 ) C, 7 2 .0 0 ; H, 6.00
C f 71-70: H, 5.48
CONDENSATION OF 3 ,5 -XYLENOL WITH o-CHLOROBENZALDEHYDE
Two and four tenths grams ( 0.02 mol J of 3»5-xylenol
was dissolved In 10 co.of glacial acetic acid
and
1.4 grams ( 0.01 mol ) of o-chlorobenzaldehyde added.
The solution was
cooled in an ice-bath an~ dry
chloride gas was
passed in until the solution
saturated.
hydrogen
was
After standing in the ice-box for one
week nothing had precipitated so the solution, was poured
into 200 cc. of water. The white precipitate was filtered
off and recrystallized from ethyl alcohol.
This same product may be obtained by condensing
the aldehyde and xylenol In a molar ratio of one to
one as ascertained by the fact that there is no
depression in the mixed melting points.
Melting point
160°0.
4,4'-dihydroxy-2,216,6*-tetramethyl-2'*-chlorotritane
Anal.
Found:
Calcd. for
G23H 23°2G1
^
^ G » 75-41; H, 6.39
C, 75-56; H, 7-59
ACETATE OF 3,5-XYLEN0L-O-CHLQR03ENZALDEHYDE CONDENSATION
PRODUCT
Two grams of the condensation product were
refluxed with 50 cc. of acetic anhydride
for two
hours. The solution was poured into water and the
crystalline acetate filtered off and recrystallized
from ethyl alcohol.
Melting point
Anal.
Found:
Calcd. for
124°C.
°27*?27°40:l ^ 450 ^ °» 72.00; H, 6.00
C, 7 1 .8 3 ; H, 5.93
3,5-XYLEHOL - ALDEHYDE 00NDEU3ATI0HS
3U1£-IARY
ALDEHYDE
AI'IALYSIS
IATIO
Acetaldehyde
Acetate
1:1
142
84
o, 77-56: H, 7.66
^ » 77*74; H, 7.04
Acetaldehyde
Acetate
2:1
147
o, 79.27; H, 7.59
Benzaldehyde
Acetate
l:i
158
187
c. 8 2 .5 2 ; H, 5.88
^ » 8 0 .26; H, 6.73
Benzaldehyde
Acetate
2:1
244
110
0 , 82.96; H, 6.77
0 , 77.91; H, 6.52
p-chlorobenzaldehyae
Acetate
1:1
or
2:1
129
74.62; H, 6.60
0 , 71.70; H, 5.48
o-chlorobenzaldehyde
Acetate
1:1
or
160
124
w » 75-56; H, 7-39
C, 71.83? H, 5.93
2,4-XYLENOL - ALDEHYDE CONDENSATIONS
PROPOSED REACTION iyi£GHANI3M AND STRUCTURE
2,4-XYELNOL - ALDEHYDE CONDENSATIONS
3H
OH
OH
HO
0
tt
C-H
i
R
CH
H'
CH
OH
CONDENSATION OF 2,4-XYLENOL WITH ACETALDEHYDE
( RATIO 1:1 )
Thirty one grains ( 0.25 mols } of 2,4-xylenol was
dissolved in 50 cc. of glacial acetic acid and the
solution cooled in an ice-bath. Fifteen cc. ( 11 grams,
0.25 mol ) of acetaldehyde was added.
Dry hydrogen
chloride was passed in until the solution was saturated.
The precipitate that formed was filtered off,
washed thoroughly with water and dried. It was
recrystallized from ethyl alcohol.
Welting point
133° C .
2 ,2 '-dihydroxy-3 ,3 ',515'-tetramethyldlphenylethane
Anal.
Found:
Calcd. Cor
g i q H 2202
^ 2^° ^
80.00; H, 8.15
C, 80.63; H, 7.47
ACETATE OF 2,4-XYLFNOL-ACETALDEHYDE CONDENSATION PRODUG!
Two grams of the condensation product was
with 20 cc. of acetic anhydride for two hours.
refluxed
The
solution was poured into water and the crystalline
product filtered off and dried. It was recrystallized
from ethyl alcohol.
Melting point
Anal.
Found :
84°C.
Calcd. for
J22H26°4
( 354 *
74t8°* H * 7.37
C, 74.35; H , 7*31
- 82 -
CONDENSATION OF 2,4-XYLENOL WITH ACETALDEHYDE
(.RATIO
2:1 J
Two and four tenths grams ( 0.02 mol ) of 2,4-xylenol
was dissolved In 10 cc. of glacial acetic acid and
the solution cooled in.an ice-bath. Four tenths of a
gram ( 0.01 mol ) of acetaldehyde was added and
dry
hydrogen chloride passed into the solution until it was
saturated..A crystalline precipitate was obtained. This
was filtered off and recrystallized from ethyl alcohol.
The mixed melting point with the compound obtained
by the condensation of 2,4-xylenol with acetai.deh.yde
in a molar ratio of one to one showed no depression;
therefore, the compounds are the same.
Welting point
131°G.
2 ,2 '-dihydroxy-3,3 r,5,5*-tetramethyldlphenylethane
Anal.
Found:
Calcd. for
ci8H22°2
^ 270 ^
C, 80.00; H, 8.15
C, 79-70; H, 8.65
ACETATE OF 2,4-XYLENOL - AGETALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was
with 50 cc. of acetic anhydride for two hours.
refluxed
The
solution was poured into water and the crystalline
product filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
84°C.
Calcd. for
Found :
C
H 0,
22 26 4
( 354 )
0, 74.80; H, 7.37
C, 74.55; H, 7.39
CONDENSATION OF 2,4-XYLENOL WITH BENZALDEHYDE
( RATIO
1:1
Thirty one grams ( 0.25 mol ) of 2,4-xylenol was
dissolved in 50 cc. of glacial acetic acid and twenty
six grains ( 0.25 mol ) of benzaldehyde added. The solution
was cooled in an ice-bath and dry hydrogen chloride passed
in until the solution was saturated. The solution turned
into a semi-solid mass on standing over night. The
solid
was filtered off on a suction filter and washed with
petroleum ether. The crystals were extracted in a
Soxhlet extractor with petroleum ether and then
recrystallized from ethyl alcohol. The condensation
product is soluble in hot Jlalsen solution.
Melting point
163°C.
2,2*-dihydroxy-3„31,5,5'-tetramethyltritane
Anal.
Found:
Calcd. .for ^23li2h°2
( 352 ^
33-13; H, 7-23
C, 83-26; H, 7.35
ACETATE OF 2,4-XYLEHOL - BENEALDe HYD e CONDENSATION PRODUCT
Two grams of the condensation product was
refluxed
with 50 cc. of acetic anhydride for two hours.. The
solution was poured into water and the crystalline
product filtered off. It was recrystallized from
dilute ethyl alcohol.
Melting point
Anal.
Found:
155°C.
Calcd. for
C^H^O^
( 417 J
C, 77-69; H, 6.95
C, 77-43; H, 7 .01
CONDENSATION OF 2,4-XYLENOL WITH BENZALDEHYDE
( RATIO
2:1
Two and four tenths grains ( 0.02 mol / of 2,4-xylenol
was dissolved in 10 c c . of glacial acetic acid and
one gram of benzaldehyde ( 0.01 mol ) added. The solution,
was cooled in an ice-bath and dry hydrogen chloride
passed In until the solution was saturated. A precipitate
was obtained which was filtered off and recrystallized
from dilute ethyl alcohol.
The mixed melting point with the compound obtained
by condensing 2.4-xylenol with benzaldehyde in a molar
ratio of one to one showed no depression; therefore,
the compounds are the same.
Welting point
165°C.
2 ,2 '-dihydroxy-3 ,3 ’,5 ,5 *-tetramethyltrltane
Anal.
Found:
Calcd. for
^2^ 2k°2
< 332 )
C, 83-13; H, 7.23
C, 83.26; H, 7-50
ACETATE OF 2,4-XYLEKOL-BENZALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was refluxed
with 50 cc* of acetic anhydride for two hours.. The
solution was poured into water and the crystalline
product filtered off and dried. It was crystallized
from ethyl alcohol.
Melting point
Anal.
Found:
155°C.
Calcd. for
C27H 29°4
( 417 J
°* 77*69; H, 6.95
C, 77*63; H, 6.67
CONDENSATION OF 2,4-XYLENOL WITH CROTONALD^HYDE
Twelve and two tenths grams ( 0.10 mol
( RATIO 2:1 )
of 2,4-xylenol
was dissolved In 100 cc. of glacial acetic acid. Three
and one half grams ( 0.05 &ol ) of crotonaldehyde was
adaea. With vigorous stirring, 20 c c . of concentrated
hydrochloric acid was added and the solution allowed
to stand for two days. A crystalline precipitate was
obtained which was filtered off and washed with small
amounts of glacial acetic acid and then recrystallized
from benzene. This compound gives a positive
test for halogensbut no test is obtained
Beilsteln
on boiling
with sodium hydroxide, acidifying with nitric acid
and adding silver nitrate.
Melting point
152°C.
2 ,2 '-dihydroxy-3 ,3 1,5»5'-tetramethyldiphenyl-3-chlorobutane
Anal.
Calcd. for
Found :
G2oH2 5 °2 G1
^332
)
2, 7 2 .29 ; H, 7.53
C, 72.46; H, 7.52
ACETATE OF 2,4-XYLENOL-CROTNALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was
refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the crystalline
product filtered off and recrystallized from ethyl
alcohol. ( This compound forms an oil on standing
for a short time. )
Melting point
Anal.
Found:
48°C.
Calcd.•for
G24H 2904Gl
* 416 ^
6 9 .23; H, 6.25
C, 69-55; H, 6.20
CONDENSATION OF 2,4-XYLENOL WITH CROTONALDEHYDE ( RATIO 1:1 )
Twelve and two tenths grams ( 0.10 mol ) of 2,4-xylenol
was dissolved in 100 c c . of glacial acetic acid
and
7*0 grams ( 0.10 mol ) of crotonaldehyde added. With
vigorous stirring, 20 c c . of concentrated hydrochloric
acid was aided and the solution allowed to stand for
one week. After this time a crystalline condensation
product had precipitated. This was filtered off and
washed with small amounts of glacial acetic acid.
The compound wa3 recrystallized from benzene.
The mixed melting point with the compound obtained
by condensing 2,4-xylenol with crotonaldehyde in a
molar ratio of two to one showed no depression.
Melting point
152°C.
2 ,2 '-dlhydroxy-3 ,3 *,3 ,5 *-tetramethylaiphenyl-3-chlorooutane
COHDENSATIOH OF 2, 4-XYLENOL WITH p -CHLORO3ZiitALDmHYD£
Two and four tenths grams { 0.02 mol J of 2,4-xylenol
was dissolved In 10 cc. of glacial acetlo acid and
1.4 grams ( 0.01 mol ) of p-chlorobenzaldehyde added.
The solution was cooled in an ice-bath and dry hydrogen
chloride gas passed in until the solution was saturated.
On standing for a few days in the ice-box a crystalline
precipitate was obtained which was plaeea on a
porous
tile and allowed to dry. It was recrystallized from
ethyl alcohol.
This product is the same as that obtained
by
condensing the aldehyde and xylenol in a molar ratio
of one to one as ascertained by the fact that there
was on depression in the mixed melting point.
belting point
164°0.
2,2*-dlhydroxy-3,3',5»5'-tetramethyl-4'1-chiorotrltane
Anal.
Found:
Calcd. for
C._H 0 01 ( 366 )
23 23 d
C, 75.41; H f 6-39
0, 74.93: H, 5.96
ACFTATE OF 2,4-XYLMMOL-p-OHLOROBENEALDi^HYDL CONDENSATION
PRODUCT
Two grams of the condensation product was
refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the crystalline
product filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
Found:
Calcd. for
135°0.
C
H
O^Cl
( 450 ) C, 72.00; H, 6.00
0, 71.49; H, 6 .13
CONDENSATION OF 2,4-XYLENOL ‘WITH o-CHLOROSEN4ALDEHYDE
Two and four tenths grams ( 0.02 mol ) of 2,4-xylenol
was dissolved in 10 cc. of glacial acetic acid
and
1.4 grams ( 0.01 mol ) of o-chlorobenzaldehyde added.
The solution was
cooled in an ice-bath and dry
hydrogen
chloride gas was
passed in until the solution was
saturated. On standing In the Ice-box for two days
a crystalline precipitate was obtained which waB
filtered off and dried on a porous tile. It was
recryspalliaed from ethyl alcohol.
This compound is the same as that obtained by
condensing the aldehyde and phenol in a molar
ratio
of one to one as ascertained by the fact that there
was no depression in the mixed melting point.
melting point
193°C.
2,21-dihydroxy-3 ,3'»5,5 '-tetramethyl-2 ’1-chlorotritane
Anal.
Found:
Calcd. for ^2^ i2302G1
* 366 ^
7 5 *4l; H » 6 ‘39
C, 75-43; H, 6.13
ACETATE OF 2,4-XYLENOL-o-CHLOrlCSEKZALDrliYDE CONDENSATION
PRODUCT
Jwo grams of the condensation product was
with 50 cc. of acetic anhydride for two hours..
refluxed
The
solution was poured into water amd the crystalline
product filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
Found*.
160°C.
Calcd..for
c27ii27°4C1
* ^5° ^ °> 72.00; H, 6.00
C f 71-85; H, 6.12
2,4-XYLENOL - ALDEHYDE CONDENSATIONS
SUMMARY
ALDEHYDE
RATIO
M.t>-.
ANALYSIS
Acetaldehyde
Acetate
1:1
133
84
0 . 8 0 .6 3 ; H, 7.47
o, 74.35; H, 7.31
Acetaldehyde
Acetate
2:1
130
84
c, 79.70; H, 8.65
o, 74.55; H, 7-39
Benaaldehyde
Acetate
1:1
163
155
o, 8 3 .2 6; H, 7.35
o * 77-43; H, 7.01
Benaaldehyde
Acetate
2:1
165
155
0,
Orot onaldehyde
Acetate
1 :l
or
2:1
152
48
72.46; H, 7.52
0
-t, 69-55;
H, 6.20
p-chlorohenaaldehyde
Acetate
1 :1
or
2:1
164
135
0,
74.93; H, 5-96
71.49;
H, 6.13
0,
o-chlorobenaaldehyde
Acetate
1:1
or
193
160
o,
0 , 8 3 .26; H. 7-50
77.63; H, 6.67
rt
*
75.48; H, 6.13
» 7 1 .8 5 ; H, 6.12
-XYLENOL - ALDEHYDE CONDENSATIONS
PROPOSED REACTION MECHANI3h AND STRUCTURE
2 ,6 -XYLENOL - ALDEHYDE 0OH DEii3AT ION 3
3H
H „ C / r \ OH.
0
II
C-H
I
a
OH
CH
CH
CONDENSATION OF 2,6-XYLEHOL WITH ACETALDEHYDE
(RATIO l:l)
Thirty one grama ( 0.25 mol J of 2,6-xylenol was
dissolved in 50 c c . of glacial acetic acid and
11 grams
( 0.25 mol J of acetaldehyde added. The solution was
cooled in an Ice-bath and dry hydrogen chloride gas
passed In until the solution was saturated. A solid
crystalline condensation product precipitated and
was filtered off, washed with small amounts of glacial
acetic acid and dried. This was recrystallized from
50^ ethyl alcohol.
Eeltlng point
131°C.
4,4'-dihydroxy-3 ,3',5,5’-tetramethyldiphenylethane
Anal.
Found:
Calcd. for
^18H 22°2
^ 2^° ^
8°*°°; H, 8.15
C, 80.17; H, 7.86
ACETATE OF 2,6-XYLENOL-ACETALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was refluxed
with 50 c c . of acetic anhydride for two hours. The
solution was poured into water and the crystalline
product filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
Found:
148°C.
Calcd. for
G22H 26°2
* 354 ^
G ’ 7 4 *80; H »
C, 75-05; H, 7.24
CONDENSATION OF 2,6-XYLENOL WITH ACETALDEHYDE
( RATIO 2:1 }
Two and four tenths grams ( 0.02 mol ) of 2,6-xylenol
was dissolved, in 10 c c . of glacial acetic acid and
0.5
gram ( 0.01 mol ) of acetaldehyde added. The solution
was cooled In an ice-bath and dry hydrogen chloride
passed in until the solution was saturated. A crystalline
precipitate was obtained which was filtered off and
recrystallized from dilute ethyl alcohol.
The mixed melting point with the compound obtained
by the condensation of the xylenol and aldehyde in a
molar ratio of one to one showed no depression; therefore,
the two compounds are the same.
melting point
13l°J .
4,4'-dihydroxy-3»3',5»5*-tetramethylalphenylethane
Anal.
Found:
Calcd. for
G l8H 22°2
* 270 ^
80.00; H, 8 .15
C, 79-52; H, 7.86
ACETATE OF 2,6-XYLENOL-ACETALDEHYDE CONDENSATION PRODUCT
Two gram3 of the condensation product was refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the crystalline
product filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
Found:
Galcd. for
148°G.
^22H 26°4
( 354 ^
0 » 7 4 *S 0 *
‘ H * ?*37
G, 74.98; H f 7.06
CONDENSATION OF 2,6-XYLENOL WITH BENZALDEHYDE
( RATIO 1:1 )
Thirty one grams ( 0.25 mol ) of 2 ,6-xylenol was
dissolved In 50 c c . of glacial acetic acid and 27 grams
( 0.25 mol ) of benzaldehyde added. The solution was
cooled In an lce-bath and dry hydrogen chloride passed
in until the solution was saturated. On standing over­
night a crystalline mass had formed. This was filtered
off and washed with small portions of glacial acetic
acid. The condensation product could be recrystallized
from dilute ethyl alcohol solution.
Melting point
143°C.
4,4*-dihydroxy-3 ,3 ',5,5*-tetracethyltritane
Anal.
Found:
Galcd. for
Sg3H 24°2
( 332 )
C, 83*13; H, 7.23
0, 82.84;; H, 7 .20
ACETATE OF 2,6-XYLENOL-BENZALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was
refluxed
with 50 c c . of acetic anhydride for two hours.. The
solution was poured into water and the crystalline
product filtered off and recrystallized from dilute
ethyl alcohol.
Melting point
Anal.
Found:
111°C.
Calcd. for
C27H 29°4
* 417 J
77.69; H, 6.96
C t 78.01; H, 0.67
CONDENSATION OF 2,6-XYLENOL WITH BENZALDEHYDE
( RATIO 2:1 )
Two and four tenths grams ( 0.02 mol ) of 2,6-xylenol
was dissolved In 10 c c . of glacial acetic acid, and
one gram { 0.01 mol ) of benzaldehyde added. The solution
was cooled in an ice-balh and dry hydrogen chloride
was
passed In until the solution was saturated. A crystalline
precipitate was obtained which was filtered off ai.d
recrystallized from dilute ethyl alcohol.
The mixed melting point with the compound obtained
by the condensation of 2 ,6 -xylenol with benzaldehyde
In a molar ratio of one to one showed no depression;
therefore the compounds are the same..
Melting point
142°d.
4,4’-aihydroxy-3 ,3 ',5,5*-tetramethyltritane
Anal.
Found:.
Calcd. for
c23H 2h°2
* '532 ^
C ' 83-13; H, 7.23
0, 83.08; H, 7-1S
ACETATE OF 2,6-XYLENOL-BENZALDEHYDE CONDENSATION PRODUCT
Two grains of the condensation product was
refluxed
with 50 cc. of acetic anhydride for two hours.. The
solution was poured into water and the crystalline
product filtered off and recrystallized from dilute
ethyl alcohol.
Melting point
Anal.
Found:
111° C .
Calcd. for
C 27H 29°4
( 417 )
7 7 *6 9 } H,
6.9o
C , 78.07; H, 7 .09
CONDENSATION OF 2,6-XYLENOL WITH CROTONALDEHYDE
( RATIO 2:1 )
Six and one tenth, grams ( 0.05 mol ) of 2,6 -xylenol
was dissolved in 50 cc. of glacial acetic acid
and
2 grams ( 0.025 mol ) of crotonaidehyde added.
The
solution was cooled in an ice-bath and dry hydrogen
chloride gas passed in until the solution was saturated.
The solution turned deep purple in color but no
precipitate was obtained. After standing over-night
in the ice-box the solution was poured into water
and the solid precipitate filtered off. This could be
recrystallized from carbon tetrachloride to give
brown colored crystals. These crystals were recrystallized
from benzene and then ethyl alcohol.
Melting point 199°C.
4,4'-dihyoroxy-3,3* »5»5'-tetramethyluiphenyl-3-chlorobutane
Anal.
Found:
Calcd. for ^20H 25°2Gl
( 332 J
°» 7 2 -29;H ,T-53:^1,10.54
0 , 72.19;H,7,60;C1,10.98
ACETATE OF 2,6-XYLENOL-CROTONALDEHYDE CONDENSATION PRODUCT
Two grams of the condensation product was
refluxed
in 50 cc. of acetic anhydride for five hours. The
solution was poured into water and allowed to stand
for two days. The aqueous solution was extracted with
ether, the ether extract washed with water and
dried
over anhydrous sodium sulfate. The ether was removed
by evaporation and , on standing, the residue crystallized.
This was recrystallized from ethyl alcohol.
Melting point
Anal.
Found:.
Calcd. for
110°C.
G24H 29°401
C,69.23;H,6.25;Ulp8.4l
C,6 9 .17;H,6.35;C1,8.40
CONDENSATION OF 2,6-XYLENOL WITH CHOTONALDSHYDE ( Ratio 1:1 )
Twelve and two tenths gram3 ( 0.10 mol) of 2 ,6 -xylenol
was dissolved in 100 c c . of glacial acetic acid and
7.0 grams of crotonaldehyde ( 0.10 mol ) added, rtlth
vigorous stirring, 20 cc. of concentrated hydrochloric
acid was added and the solution allowed to stand for a
few weeics.
During this time, a crystalline mass had
formed.
This was placed on a porous tile and allowed to dry.
The compound was recrystallized from ethyl alcohol.
The mixed melting point with the compound
obtained
by condensing the xylenol and alaehyde in a molar
ratio of two to one showed no depression.
Melting point
197°C.
4,4'-dlhydroxy-3,31»5,3'-tetramethylaiphenyl-3-chlorobutane
- 108 -
2 ,6-XYLENOL - ALDEHYDE SONILKSATIONS
SUMMARY
ALDEHYDE
RATIO
M .o . .
ANALYSIS
Acetaldehyde
Acetate
1:1
131
148
8 0 .1 7; H, 7.86
o, 75.05; H, 7.24
Acetaldehyde
Acetate
2:1
131
148
0 , 79.52; H, 7.86
C, 73-98; H, 7.06
Benzaldehyde
Acetate
1:1
143
111
C, 82.84; H, 7.20
78.01; H, 6 .67
Benzaldehyde
Acetate
2:1
142
111
3, 33.06; H, 7.19
0 . 78.07; H, 7.09
Grot onaldehyde
Acetate
1:1
or
2:1
199
110
7.60*
0,
i 72.19; H, 6 .35**
w » 69.17; H,
* 01, 10.98; **-Gl, 5.40
PART
II
EXPERIMENTAL
CONDENSATION OF p-NITAOTOLUEKE rflTH FORMALDEHYDE,
REDU CTION OF THE J O N 3ATION PRODUCT TO THE
DIAMJJE, DIACOTIZAT ION AND A SRISHARD REACTION
OF THE DI-HALIDE.
CONDENSATION OF p-NITROTOLUENE WITH FORMALDEHYDE,
REDUCTION OF THE CONDENSATION PRODUCT TO THE
DIAMINE, DI AZOTIC AT ION AND A OR U N AID REACTION
ON THE DI-HALIDE
( Flow Sheet I )
Synthesis of 2,2'-dimethyl-5*5'-dinitrodiphenylmethane
To a solution of 234 grams ( 1.7 mols J of
p-nitrotoluene dissolved in 1000 grams ( 545 cc. ) of
concentrated sulfuric acid was added, with vigorous stirring
90 cc. ( 36 grams, 1.2 mols) of an aqueous 40# formaldehyde
solution. The reaction mixture was kept helow 15°C by
Immersion In an ice bath. After standing at room temperature
for two days, precipitation took place. The precipitate
was filtered off through a fritted glass filter and
washed with water. The solid was steam distilled
to
remove unreacted p-nitrotoluene. One hundred and ninety
seven grams of 2 ,2 1-dimethyl-5 ,5 1-dinltrodiphenylmethane
was obtained along with 33 grams of p-nltrotoluene ( 12 grams
of p-nitrotoluene not accounted for
Melting point 153°C.
Yield 81#
-
5# ) •
REDUCTION OF 2,2'-DIM3THYL-5,5*-DIHITRODIFHENYLMETHANE
One hundred and ten grams ( 0.4 mols ) of
2,2 '-dimethyl-5,5 '-dlnitrodiphenylmethane was added to
a solution of 560 grams ( 2.5 mols ) of technical stannous
chloride { hydrated ) dissolved in 600 c c . of concentrated
hydrochloric acid and 200 cc. of 95# ethyl alcohol.
The solution was heated on a water bath for one hour at
60 - 70°C and then refluxed until complete solution
had taken place.
The solution was transferred to a three liter, three
necked round bottom flasked equipped with a mechanical
stirrer and a separatory funnel. The solution was cooled
in an ice bath and 900 grams ( 22.5 mols ) of 3odium
hydroxide dissolved In 900 cc. of water was added slowly
through the separatory funnel with vigorous stirring. The
temperature was kept below 20°0. The solution was diluted
with three liters of water and extracted with one liter
of ether in small portions. The ether extracts
were
combined, washed thoroughly with water and dried over
anhydrous sodium sulfate. The ether was removed by
distillation on a water bath. Seventy grams of thick
oil was obtained.
This oil was dissolved in 150 cc. of glacial acetic
acid and diluted with 450 c c . of distilled water. The
solution was boiled with bone-black and filtered. The
clear filtrate was neutralized with dilute ammonium
hydroxide solution, keeping the temperature below
o
20 C. The solution was extracted with ether, the ether
extract washed with water, dried over anhydrous sodium
sulfate and the ether allowed to evaporate. A solid
crystalline product was obtained.
Melting point 98°C.
Yield
61#
( 53 grams )
Analysis of Dihydrochloride of Diamine
Calcd. for
Found :
C15H 20W 2C12 ( 293 ) C, 60.40; H, 6 .7I
0 , 60.39; H, 6.74
- 113 -
THE DIAZOTIZATION OF 2,2'-DIMETHYL-5,5*-DIAMINODIPHENYLMETHANE
Number I
To a solution of 5 cc. of concentrated hydrochloric
acid In 500 cc. of distilled water ( 1 # solution ) was
added 2.26 grams ( 0.01 mol ) of 2 ,2 *-dimethyl-5>5 *diaminodiphenylmethane. The solution was heated on a
water bath until everything had dissolved. This
was
placed in a one liter, three necked round bottom
flask
equipped with a stirrer, thermometer and separatory
funnel. The solution was cooled to 5 - 10°C and
1.40 grams ( 0.02 mol ) of sodium nitrite dissolved in
200 cc. of distilled water was added slowly until
diazotlzatlon was complete as shown by a positive test
with starch-potassium Iodide paper. Urea was added
to remove excess nitrous acid and then the dlazotized
solution was added slowly and with vigorous stirring to
3.5 grams ( 0.02 mol ) of potassium iodide dissolved in
300 c c . of distilled water containing 10 cc. of
concentrated hydrochloric acid. As soon as the last of
the diazotized solution had been added the solution
was filtered. A red amorphous powder was obtained. On
standing in contact with the atmosphere for about one
half hour, decomposition.took place, leaving a black,
semi-solid mass. This was dissolved in.ether, washed
with water and sodium thiosulfate solution, dried over,
anhydrous
sodium sulfate and the ether allowed to
evaporate. A black oil, which could not be crystallized,
was obtained. .
Number II
To a solution of 10 cc. of concentrated, hydrochloric
acid in 500 cc. of distilled water was added 2.26 grams
( 0.01 mol ) of 2,2*-dlmethyl-5,5'-diaminodiphenylmethane.
The solution was cooled to 5 - 10°C and a solution,
of 1.4 grams { 0.02 mol J of sodium nitrite dissolved
in 200 cc. of distilled water was added with vigorous
stirring. One hundred and eighty three cc. of the
sodium nitrite solution was added before a positive test
with starch- potassium iodide paper was obtained.
( This
corresponds to 1.28 grains of sodium nitrite and shows
complete diazotization of both amino groups, within the
weighing error. J
The diazotized solution was poured
immediately into a solution of 3.5 grains of potassium
Iodide dissolved in 300 c c . of distilled water
which also
contained 200 cc. of ethyl acetate I Density = 0.906 )
which was to be used as a solvent for the organic compound.
The reaction proceeded smoothly and the ethyl acetate
removed the organic compound as it was formed. The
ethyl acetate layer was removed and washed with 500 cc.
of distilled water. The solution turned black within ten
minutes. After drying over anhydrous sodium sulfate, the
ethyl acetate was allowed to evaporate. A black oil, which
could not be crystallized, was obtained.
Number
III
To a solution of 10 cc. of concentrated hydrochloric
acid in 500 cc. of distilled water was added 2.26 grams
( 0.01 mol ) of 2 ,2 '-dimethyl-5 »5 *-diamlnodiphenylmethane.
The solution was cooled to
5 - 10°C and, with vigorous
stirring, 1.4 grams ( 0.02
mol J of sodium nitrite in
200 c c . of distilled water
was added slowly. ( 180 cc. of
this solution was added before
a positive test was obtained
with starch-potasslum iodide paper. ) The diazotized
solution was placed in the ice-box over night and
then
poured into a solution of 3.5 grams ( 0.02 mol ) of
potassium iodide dissolved in 300 cc. of distilled
water containing 200 cc. of carbon tetrachloride ( density 1.59 ). The carbon tetrachloride was
kept in contact
with the solution until the reaction wa3 complete, about
four hours during which time the organic compound was
extracted as the complex was decomposed. The carbon
tetrachloride layer was separated and dried over
anhydrous
sodium sulfate. There was not much sign of decomposition
and the slight color could be removed by washing
with
sodium thiosulfate solution. However, on removing the
carbon tetrachloride, decomposition of the compound occured
and nothing crystalline could be obtained from the
reaction.
Number
IV
To a solution of 10 c c . of concentrated hydrochloric
acid in 500 cc. of distilled water was added 2.26 grams
( 0.01 mol ) of 2 ,2 *-dlmethyl-5 »5 '-dlaminodiphenylmethane..
o
The solution was cooled to 5 - 10 0 and, with vigorous
stirring, 1.4 grams ( 0.02 mol ) of sodium nitrite
in 200 cc. of distilled water was added until a positive
test was obtained with starch-potassiuin iodide paper.
Sodium acetate was added and the solution made slightly
basic with 33 % sodium hydroxide solution. It was then
poured into a solution of 3.5 grams ( 0.02 mol )
of
potassium iodide dissolved in 300 cc. of distilled water..
A brown solid precipitated out which was filtered off.
It had no melting point and was insoluble in methyl alcohol,
ether, toluene, dioxane, ethyl acetate and diisobutylene.
The powder was placed with 60 cc. of concentrated
hydrochloric acid and refluxed for three hours. There
was no reaction and the original was recovered. Since
it could not be comverted into a compound soluble in
organic solvents, it had to be discarded..
Number
V
To a solution,
acid
of 10
in 500 cc. of water
oc. of concentrated hydrochloric
was added 2.26grams ( 0.01 mol J,
of 2,2'-dimethyl-5,5*-dlaminodiphenylmethane. The solution
was cooled to 5 - 10°C and 1.4 grams ( 0.02 mol ) of
sodium nitrite in 200 cc. of distilled water was added*.
The solution was allowed to stand overnight in the ice
box. After standing for twelve hours, the te3t with
starch-potasslum iodide paper was negative..
Solid cuprous
In 48/i> hydrobromlc
bromide was preparedand dissolved
acid,
diluted to 200c c . with
distilled
water and the diaaotiaed solution added. A brown solid
was precipitated and a large amount of nitrogen evolved.
The solution was heated to 70°1 to remove the remaining
nitrogen and the brown 3olid filtered off. This was
dried and ground up.
That a copper salt had been obtained could be
ascertained by heating a portion of the precipitate on
a porcelain spatula. One and one half grams of the
amorphous powder was refluxed with 20 cc. of concentrated
hydrochloric acid and 30 c c . of water. There was no
reaction and the original compound was recovered, which
still gave the test for copper.
- 119 -
Number
VI
To 550 c c . of 2 % hydrochloric acid aolution was
added 2.26 grams ( 0.01 mol ) of 2 ,2 '-dimethyl-5,5 1diaminodiphenylrnethane. This was cooled to 4°C and
1.4 grams ( 0.02 mol J of 30dium nitrite dissolved
In
200 c c . of distilled water was added with vigorous
stirring. The solution was allowed to stand for
two
days in the Ice-box at 4° C .
Solid cuprous bromide was prepared and dissolved
in 48 % hydrobromic acid. The solution was diluted with
200 c c . of distilled water and the diazotlzed solution
added Immediately. A brown solid precipitated. The
solution was heated to 70°^ on a water bath to remove
the nitrogen and the solid matter filtered off and
dried.
The brown amorphous powder was refluxed with 100 cc.
of glacial acetic acid for six hours. Some insoluble matter
was filtered off and the acetic acid solution diluted
with 5°° cc. of distilled water. The solution was
extracted with ether, the ether extract washed with
water and dried over anhydrous sodium sulfate. On
evaporation of the ether a black tar was obtained which
could not be recrystallized from any common organic solvent.
Number
VII
To a solution of 250 cc. of 10 ^hydrochloric acid
was added 11.3 grams ( 0.05 mol ) of 2,2 '-dimethyl-5 ,5 1diaminodiphenylmethane. The solution was diazotized with
7 grams ( 0.10 mol ) of sodium nitrite in 200 cc. of
distilled water, the temperature being kept below 5° G*
Cuprous bromide was prepared and dissolved in
50 cc. of 48 % hydrobromic acid. This was added
250 c c . of distilled water and the diazotized
to
solution
added immediately. There was an evolution of nitrogen
and a brown amorphous powder precipitated. The solution
was heated on a water bath to 70°C until the evolution
of nitrogen had ceased. The brown solid was filtered
off and washed thoroughly with water.
After drying
in a desicator for two days, the weight was 20.3
grams.
( The theoretical yield, based on the formation of
2 ,2 '-dimethyl-5 ,5 '-dibromdiphenylmethane, is 17-7 grains )
Ten grams of this brown solid was ground up
with
20 grams of sodium bromide. The mixture was placed in an
8 Inch test tube equipped with a cork and bent tube
leading to another small test tube immersed in ice. All
volatile matter was distilled out and a red oil
was
obtained. This was dissolved in ether, washed with water
and dried over anhydrous sodium sulfate. On evaporation,
of the ether a crystalline solid was obtained.. It was
recrystallized from ethyl alcohol, kelting point 82°C.
The yield on this method of preparation of the
di-halogen compound of diphenylmethane was so small
that the method was discarded.
Anal.
Calcd. for
Found :
G 15H 14flr2
( 354 >
C » 50.85; H, 3-93
0, 50.97; H, 3.75
CONDENSATION OF p-3ROPiPHENETOL wITH FORMALDEHYDE,
AND 3-RIJNARD REACTION OF THE GOwur.NSATIOK
TiVITH .-.ETHYLENE IODIDE.
PRODUCT
CONDENSATION OF p-BROJMPHENETOL WITH FORMALDEHYDE,
AND 3-R13-NARD REACTION OF THE CONDENSATION PRODUCT
WITH METHYLENE IODIDE ( Flow Sheet II )
Synthesis of p-bromphenetol
Two hundred grains of phenetol, dissolved in
500 cc. of carbon disulfide saturated with water, was
placed in a two liter, three necked round bottom flask
equipped with a stirrer, separatory funnel and an
out-let tube leading to a trap containing sodium, hydroxide
solution. The solution was cooled In a water bath and
270 grams ( 85 c c . ) of bromine was added slowly over
a period of one hour with vigorous stirring. The solution
was allowed to stand until the color of bromine had
disappeared and then was placed in .a separatory funnel
and washed with water, 10% bodium carbonate solution,
and with water again. Without drying, the carbon disulfide
was removed by distillation from a water bath. The
residue was fractionated and 250 grams of p-bromphenetol
was obtained. ( Boiling point
Yield 76%
227-230°C.)
SYNTHESIS OF 2,2 ‘-DIETHOXY-5,5'-DIBROMDIPHEiM YLMETHANE
Note
Special precautions must be observed in
this synthesis since, if the temperature of the reaction
mixture is not maintained at at least - 10°C.f two
reaction occur which prevent the formation of the
desired compound. ( 1 ) ihe p-bromphenetol reacts with
the concentrated sulfuric acid to form a stable white
crystalline compound,.soluble in water without
the
evolution of heat, and ( 2 ) a brown, amorphous
polymer
soluble in.all common solvent..Therefore, the following
procedure was followed.
Two hundred grams of p-bromphenetol ( 0.5 mol )
was dissolved in 250 cc. of concentrated sulfuric acid
which had been cooled in a carbon-dioxide-acetone
mixture. With vigorous stirring, 20 cc. of formaldehyde
( 40 % ) { 0.27 mol ) diluted with 30 cc. of distilled
water was added drop-wise over a period of one hour. The
solution became semi-solid ( both because of the freezing
of the sulfuric acid and also the precipitation
of
the reaction product which formed on the addition of
the first few cc. of formaldehyde solution. ) Although
there Is a large amount of heat evolved during the reaction,
- 124 -
the temperature was maintained at - 12°C. After the
addition of the formaldehyde the solution was maintained
at a temperature of 4°G for twelve hours. The solution was
thodV, poured onto ice and allowed to stand until the Ice
had melted. The white solid that formed was filtered
off and dried. It was recrystallized from acetic acid
and then from ethyl alcohol. Melting point 145°G.
Anal.
Found:
Galcd. for
0i7H i30 2Br2 * 414 J
G » 49.27;'; H, 4.34
G , 49*72; H, 4.28
A, ^
i
C GRFETT8AT TOF OF 2 ,2 »-D T F T It OXY-5 ,5» -D7.IVR01,H I PTTETIYLL1ETIIA1TF
'VfrnT;
TT
^ T ^}TvtrV"r)T^
Twelve and one half grama of 2,2 *-riIothoxy-5,5dj.hrcmdiphonylmethane was placed in 100 cc. of concentrated
o
sulfuric acid and cooled to 4 0. in an ice-hath. To this
was addod, with vigorous stirring, 4.5 grams ( iwice the
theoretical amount ) of 40 percent fcrmald^hpde solution
diluted to 7 cc. with water. The temperature
above 10°0*
The solution wa3
ice and a? lowed to come t
O ' 5.
not go
poured into two liters of
room tenperat-xre * The brown
solid that nreci,->'.tatod war filtered off and washed
thoroughly with water• Felting ~oInt
Anal.
Found
Calcd. for ( C ^ O B r ^
210°C.
C, 50.70; TI, 4.22
C, 50.09; H, 4.02
Since a solvent could not be found for this
compound, a molecular weight could not be performed*
THE GRIQ-NARD REACTION WITH 2 ,2 *-DIETHOXY-5,5' -DIBROMDIPHENYLMETHANE
Number
I
The magnesium used in this experiment was
powdered
magnesium washed with dilute hydrochloric acid, water,
acetone, ether and then absolute ether, twice.
Two grains of magnesium was placed in a 500 c c .
three necked, round bottom flask, equipped with a reflux
condenser and a dropping funnel. A solution of 4.14 gpams
( 0.01 mol ) of 2 ,2 '-diethoxy-5 ,5 '-aibromdlpbenylmethane
dissolved in 100 cc. of absolute ether was added along
with a drop of methyl iodide and a crystal of iodine.
The solution was refluxed for two hours, and then 2 cc.
of methylene iodide ( 6.65 grams, 0.03 mol ) was added.
The solution was refluxed for ten hours without
any
sign of a reaction having taken place. Water and dilute
hydrochloric acid, was added to the solution, the ether
spearated and dried over anhydrous sodium sulfate. The
ether was allowed to evaporate and 4 grams of
2 ,2 '-dlethoxy-5 ,5 '-dibroradlphenylmethane was recovered,
melting point 145°C.
- 127 -
Number
II
Two grama of magnesium turnings was washed
with
dilute hydrochloric acid, water, acetone, ether and
anhydrous ether. This was placed in a 500 c c . three necked
round bottom flask equipped with a reflux condensed and
dropping funnel. Two c c . of methylene iodide ( 6.65 grams,
0.03 mol ) was added and the solution refluxed
for
one hour.
On standing over-night, the magnesium had
reacted
and the solution formed two layers. Two grams of
2 ,2 '-diethoxy-5 ,5 *-dibromdiphenylmethane dlssolvd in
100 cc. of anhydrous ethyl ether was added. On
refluxing
the solution for five hours, a white solid precipitated.
This was decomposed with dilute hydrochloric acid and
dissolved in ether. After drying over anhydrous
sodium
sulfate, the ether was allowed to evaporate and
the
solid residue extracted with ethyl alcohol. The residue
from the extraction melted at 145°G ( original J.
On fractional crystallization of the alcohol
extract, the melting point could be lowered to
138°G but no compound other than the original
be obtained from the solution.
could
Number III
Two grams of magr.esium, washed with dilute
hydrochloric
acid, water, acetone, n-butyl ether, and then with
anhydrous n-butyl ether was placed with 100 c c .
of
anhydrous n-butyl ether in a 500 cc. three necked, round
bottom flask equipped with a reflux condenser and
dropping funnel. Iwo c c . ( 6.65 grams, 0.03
) °f
methylene iodide was added. On refluxlng ( temperature 146°G.)
the solution became cloudy. Two grams of 2 ,2 '-diethoxy5 ,5 1-dibromdiphenylmethane dissolved in anhydrous
n-butyl ether was added and the solution refluxed for
five hours. Dilute hydrochloric acid was added, the
ether layer removed and dried over anhydrous sodium
sulfate. On evaporation to dryness a solid residue was
o
obtained, melting at 140.5 0 and on subsequent crystallization
from ethyl alcohol at 143°G ( original ).
Number
IV
Magnesium turnings ( 1.85 grams, 0.074 mol J washed
with dilute hydrochloric acid, water, acetone, n-butyl
ether and anhydrous n-butyl ether was placed in. a 500 cc.
three necked round bottom flask equipped with
areflux
condenser and dropping funnel. Fifty cc. of anhydrous
n-butyl ether was added to the magnesium and then
16 grams ( 0.038 mol J of 2,2 '-diethoxy-5 ,5'-dibromdiphenylmethane dissolved in 100 cc. of anhydrous
n-butyl ether was introduced into the flask. No reaction
occured on refluxing for five hours, so two drtops of
ethyl iodide wa3 added. On continued refluxing
for
thirty-two hours a small amount of brown precipitate
had formed but not all of the magnesium had
reacted.
Three cc. ( 10 grams, 0.04 mol ) of methylene iodide
was added and refluxing continued for ten hours.
Dilute hydrochloric acid was added to the
solution
and the ether layer removed, washed with water, and
dried over anhydrous sodium sulfate. The ether
was
removed by evaporation. The residue was recrystallized
from ethyl alcohol, first fraction, m.p. 136°0 ,
subsequent fractions with progressive high melting
points up to 145°D. No material, other than the
could be isolated.
original,
- 130 -
Number
V.
Two grams of magnesium turnings, washed with dilute
hydrochloric acid, water, acetone, isopropyl ether,
and then with anhydrous isopropyl ether was placd in a
500 c c . three necked, round bottom flask equipped with
a reflux condensed and dropping funnel. Three cc.
( 10 grams , 0.04 mol ,) of methylene Iodide, along with
a small crystal of loaine was added and the solution
refluxed ( temperature 60°G ) for two days. After
this time, not all of the magnesium had dissolved .
The ether solution was decanted from the unreacted
magnesium and two grams of 2 ,2 '-dlethoxy-5 ,5 *-dibromdiphenylmethane was added. The solution wa3 refluxed for
three days. Dilute hydrochloric acid was added and the
ether layer separated, washed with water and dried over
anhydrous sodium sulfate. The ether was removed
by
evaporation and the residue fractionally crystallized
from ethyl alcohol. Melting point of all fractions - 143°C. ( original J.
CONDENSATION OF DIMETHYL0L-p-GAE30L WITH
VARIOUS PHENOLS .
- 13 1 -
CONDENSATION OF DIMETHYLOL-o-CRESOL WITH
VARIOUS PHENOLS
SYNTHESIS OF DIMETHYLOL-p-CRESOL
To a solution of 108 grams ( 1 mol ) of p-cresol
dissolved in 200 c c . of 20 % sodium hydroxide
was
added 215 grams of 35 % formaldehyde solution ( 2 mols )
according to the procedure of Ullman and Brittner ( 34 ).
The solution was allowed to stand for four days during
which time precipitation of the sodium salt occured. This
was filtered off and washed with a saturated sodium
chloride solution. The sodium salt was dissolved in
500 c c . of boiling water and neutralized with a
dilute
acetic acid solution. The di-alcohol precipitated and
was recrystallized from ethyl alcohol.
Melting point 132°C.
Yield
91 %
CONDENSATION OF DIMETHYLOL-p-CRESOL
WITH p-CRESOL
One tenth of a mol ( 16.8 grams ) of dlmethylolp-cresol was dissolved In 50 cc. of glacial acetic acid
and 0.1 mol ( 10.8 grams)of p-cresol added. Dry hydrogen
chloride was passed in until the solution was saturated.
Seventeen grams of precipitate was obtained on standing.
Nine grams more
of the same
by diluting the
acetic acid filtrate with water.
Melting point
Yield
-
material could be
obtained
215° C .
A total of 26 grams of material was obtained.
This corresponds to an equimolar condensation.of reactants,
accounting for all the reactants ( dimethylol-p-cresol
and p-cresol )
Analysis:
used.
This compound shows a loss of
3*36 % of
its weight on performing a " water " determination at
105°C.
Calcd.for
Found:
a32R32°4
(
430 * G ' 8 0 *00; H »
6 '67
C, 76.16; H f
6.59
ACETATE OF DIMETHXLOL-p-CRESOL AND p-CRESOL CONDENSATION
Fifteen grams of the condensation..product was
refluxed with 75 cc. of acetic anhydride for two hours.
The solution was poured Into water and the crystalline
precipitate filtered off and recrystallized from ethyl
alcohol.
Melting point 125°C.
Anal.
Calcd. for
Found :
C40K400q
( 648 )
C, 74.07; H, 6.17
C, 7 3 .85; H t 6.18
Molecular weight
^32
CONDENSATION OF DlEETHYLOL-p-CRESOL WITH p-BROMPHENOL
One tenth of a mol ( 16.8 grama ) of dimethylolp-cresol wqs di33olved in 50 cc. of glacial acetic acid
and 0.1 mol ( 17.3 grams ) of p-bromphenol was added.
Dry hydrogen chloride was passed in until the solution
was saturated. No precipitate was obtained on standing
so the solution was poured Into water. Thirty grams
of material was obtained which was recrystallized
from ethyl alcohol.
Melting point
Yield
-
210°C.
Thirty grams of condensation product corresponds
to a 93^ yield based on a one to one molar condensation.
However, this still contains 3.60/S of volatile matter
that Is removed at 105°C.
Analysis:
Found:
Calcd. for
C3oH2604Br2 ^ 610 ^
59.01; H, 4.26
C, 55.10; H, 3.7 6
ACETATE OF DIKETHYLOL-p-CRESOL AND p-BROKPHENOL CONDENSATION
Ten grams of the condensation product was refluxed
with 50 cc. of acetic anhydride for two hours. The
solution was poured into water and the white crystalline
precipitate filtered off and recrystallized from ethyl
alcohol.
Melting point
Anal.
111°C.
Calcd. for
Found :
G38H 34°8Br2 f 778 * 0*58.61 ;H,4.37;Br,20.56
C ,59.09;H,4.62;Br,20.11
Molecular weight
806
-
136
-
CONDENSATION OF DIMETHXLOL-p-CHESOL WITH 2,4-XYLENOL
Five one-hundredths of a mol ( 8.4 grams)of
dimethylol-p-cresol was dissolved in 20 cc. of glacial
acetic acid and 0.1 mol ( 1.22 grams ) of 2,4-xylenol
added. Dry hydrogen chloride was passed into the
solution .until it was saturated. On standing for one
week, the solution separated into two layers. The upper
layer, consisting mostly of acetic acid, was
decanted
and the lower layer dissolved in ether, washed with
water and dried. The ether was evaporated and the
residue taken up in ethyl alcohol.A white solid was
obtained on diluting the ethyl alcohol solution with
water. The yield was quantitative .
Melting point 116°C.
Analysis:
Found:
Calcd. for
C
H 0
( 370 )
25 2o 3
C, 79.78;
H, 7.44
C,
H, 7.28
77.74;
ACETATE OF DIMETHYLOL-p-CRESOL AND 2,4-XYLENOL CONDENSATION
Two grains of the conaensation product was refluxed
with 20 c c . of acetic anhydride for two hours. The
solution was poured into water and the white crystalline
precipitate filtered off and recrystallized from
ethyl alcohol.
Melt ins point 143°C.
Anal. Calcd. for C ^ H ^ O g
Found :
( 502 )
0, 74.10; H,6.77
C, 74.03; H,6.39
- 138 -
SUMMARY
SUMMARY
PART
l)
I
Phenols with only one ring position available for
reaction were condensed with eqbi- and multimolar quantities
of saturated, unsaturated and aromatic aldehydes.
Crystalline condensation products of the alkylldenedi-phenol type were obtained exclusively in all cases.
2J
When aldehydes are condensed with properly
blocked phenols having only one ring position, available
for reaction, no Bakelite types of condensation products
are formed, Indicating that the formation of such
condensation.products requires at least two
available
ring positions in the reacting phenol. In blocked
phenols, the possibility for the formation of ether
types of condensation products definitely exists, yet,
9ince no such products were formed, it appears that in
aldehyde-phenol conaensation formation of oxygen-carbon
linkages Is not favored. The results obtained
when
multimolar quantities of the aldehyde were used,, indicate
that the resinous character of Bakelite is not due to
ante- or posterior polymerization of the aldehyde, but
Is due to multiple dlohenvlmethane types of linkages.
3)
In the case of the condensation systems involving
an unsaturated alaehyde, the catalyst partook in the
reaction, a fact never before observed In this type
of condensation.
4)
Material taken from Part I of this thesis was
published in the Journal of the American Chemical
Society,63, 1731 ( 1941 ).
- 141 -
PART
1}
II
Indirect phenol-aldehyde condensations were
carried out by first condensing a suitable phenol with
two mol equivalents of formaldehyde and then condensing
the resulting phenolic-dlalcohol with various phenols.
This type of Indirect condensation enables the
production of simple and of mixed phenol-aldehyde
condensation products, and the extension of the
" blocking effect " in phenol-alaehyde condensations
to include the production of open chain aiDenzyl-phenyl
types of condensation products.
2)
Quantitative analytical studies of the crystalline
acetates of both the simple and mixed equlmolar condensation
products favor a porphyrin type of carbocyclic structure.
Since this type of structure resembles a pointed cross,
the name 11 cruci-phenols 11
( simple ana mixed
"erucilytes 11 )
has been suggested for these types of condensation
products.
3)
Material ta=<en from Part II of this thesis has been
accepted for publication in tne Journal of the American
Chemical Society.
BIBLIOGRAPHY
- 143 -
BIBLIOGRAPHY
1)
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2)
E.
3)
ter Meer, Ber., 2*
4)
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283 ( 1887 )
5)
A. Steiner, Ber., 11,
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6)
L. Baekeland, J. Ind.
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7)
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8)
J. W. Aylsworth, U. S. Patent, 1,020,593
9)
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24)
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1941
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