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Патент USA US2109015

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Patented‘Feb. 22, 1938 -
‘ 2,109,015
Joseph B. Nicderl and Victor Niedcrl,
New York, N. Y. ‘
Application July 5, 19.35.
' I
Serial No. 29,318
(on. 260E154)
This invention relates to a process for the pro
hydes, p-dicarboxylic acids and "El‘aldehydo acids.
duction 01' polycyclic phenolic condensation'prod
These may be represented by theiollowing general
ucts, more particularly to such condensation proc
esses which involve certain aliphatic, oxygen
containing compounds and various phenolsrf It
relates further to new- bicyclic phenolic (com
pounds which may be obtained by these processes.
The aliphatic oxygen-containing compounds
are those in which there are two reactive hydroxyl
10 groups, either or both of which may be an alco
holic hydroxyl. group or one which results from an
enol transformation of a carbonyl group present
in an aldehyde, acid, ketone or ester. In general
these two hydroxyl groups are attached to carbon
15 atoms which are in the p position with relation
to each other but in some cases they may be at
tached to adjoining carbon atoms.
:a-oo-omooon, ‘n-od-oin-ono,
/ono, mo\/O0OH' , Rio
a-oo-om-oo-n, a,-o\ '
respectively, in which R is an alml 'group or
In the case of the aldehydes and ketones the
condensation may take place with the enol form.
In the case of acids either the free acid or any of
its esters may be condensed with a phenol. One I5
mol. of a compound of these classes may be con
densed with one or with two mols of a phenol ac- .
cording to the conditions of condensation and the
Since, at the time these oxygen-contain
ing compounds condense with the phenol, they all -products desired. All of these products have
20 have hydroxyl groups present either an alcoholic valuable properties as such and also as interme 20'
diates for the preparation of condensation prod
hydroxyl or one resulting from an enol trans
ucts with formaldehyde etc. and of other com
formation, _they will be designated in the ap
pounds. On account of their phenolic character
pended claims as p-dihydroxy compounds gener
they are valuable asinsecticides, germicides etc.
A great many phenols may be condensed with 25
These compounds may be divided into three
the oxygen-containing» compounds oi the classes
general classes as follows:
A. ?-dihydroxy compounds of which typical described above. Such phenols must have one
examples are the glycols such as 1.3-butanediol, reactive hydrogen atom, either ‘ortho or para to
2.4-pentane diol, 1.3-propane diol and others of the hydroxyl group, available for condensation.
30 like structure and the a-dihydroxy compound Mono or polynuclear phenols may be used or
their nuclear substituted derivatives including
' B. ?-hydroxy carbonyl compounds. This class halogen derivatives, alkyl phenols such as the
includes p-hydroxy carboxylic acids“ and their
esters, p-hydroxy ketones and p-hydroxy alde
35 hydes and the acetals of these ketones and alde
hydes. These compounds have the general for
drogen. Typical examples. of these compounds
45 are p-hydroxy butyric acid, s-hydroxy butalde
C. p-dicarbonyl compounds in which the two
‘ carbonyl groups are attached to the same carbon
atom. This
class includes
tertiary carbon atom. The naphtholsiare also
group such for instance as the mono-alkyl ethers
v respectively in which R is an alkyl group or hy
the phenol attached to a primary,“secondary or
ethers containing one free phenolic hydroxyl
Ra-C (0H) CH2CO—R
hyde and diacetone alcohol.
octyl and higher alkyl phenols in which the alkyl
group may be a straight or branched chain ‘and
suitable for these condensations as are phenolic
R's-C (OH) CHa-—-COOH,
cresols, ethyl, propyl, butyl, amyl, hexyl, heptyl,
acids, p-keto-aldehydes, p-dilretones, p-dialde
of resorcinol, hydrcquinone etc. and the di-alkyl
ethers of the trihydroxybenzenes. Di-alkyl phe
nols such as the xylenols, thymol, carvacrol and
tri-alkyl phenols are likewise suitable for conden
sation with the oxygen-containing compounds
described abovek.
Examples of speci?c p-dihydroxyv compounds
have been listedunder A abovebut others of the
same type are also suitable. ?-hydroxy carbonyl
compounds which may be used include diacetone
intermolecular hydrogenation and dehydratlo?
. alcoholpdiacetophenone alcohol,._and their homo
logs, p-hydroxy-butyricacid and_its esters, and
to form the corresponding indene and a resinous
other similarly constituted compounds. The p
mass. The indane thus formed is identical with '
v' dioarbonyl compounds include malonic acid and
its mono-or dilalkyl esters, aceto acetic acid and
its esters andother compounds.
that obtained from one mol. each of phenol and
In many of the condensations there is tormed
The condensation of the phenol and any of the
in addition to the type of product described above
some p-tertiary butyl phenol and some p-isopro
penyl phenol, the latter usually in the form of a
oxygen-containing bodies may take place in two
distinct steps.
The ?rst step is a simple con
10 densation as exempli?ed by the following general
polymeric resinous material. These are formed 10
by a scission of the initial condensation product
(OHI)!O—R+CIHIOH -> (03030-3
as follows:
om-d-j-om-ooom "15
in which R is —CH2COCH3, —-C&CH(OH) CH4! or
-C(0H),(CH3):. ‘when one mol. of each of the
20 reactants is used the condensation can go one step
'farther forming a. ?ve-membered carbon side
p-terdary butyl phenol
ring on the phenol. Thus with an alpha or beta
dihydroxy compound an indane derivative is
formed and with diacetone alcohol reacting in~its
enol form a derivative of indene is produced which
upon pyrolysis also forms an indane derivative as
furic, hydrochloric, phosphoric etc. and metal
vary over a very wide range depending princi
pally on the number of mols of water to‘ be re
1,3,8-trimethyi-6-hydroxy indane
moved during the condensation. Generally the
amount 'of condensing agent will vary between‘
one-halt and two mols per mol. of phenol taking 35
part in the reaction.
gin-on; H:
1,8,3-trimethyl-6-hydroxy indene
In producing the indanes from the reaction
between 2-methyl-pentanediol-2,4 the process is
45 carried out in a single operation so that the ?nal
product contains both these compounds.v From
pinacol and phenol
The following examples will serve to illustrate
the invention. In these examples only one phe
nol, viz: phenol itself, and three of ‘the oxygen
' containing compounds, viz: vdiacetone alcohol, 40
pinacol and '2-methyl-pentane-diol-2,4 are
shown. It is understood, however, that any of
the oxygen-containing bodies or the type de
scribed above and any phenol having available
reactive hydrogen atoms, either ortho or para to 45
the hydroxyl group, can be substituted for those
speci?cally shown in the examples.
i951")?! \
an m
penyl phenol
salts such as the halides of aluminum, boron,
copper, magnesium, tin, zinc etc. The relative
amountsot reactants and condensing agent may 30
0 (CH2):
' . polymeric p-isopro
_All 01’ these condensations are carried out in
the presence of a condensing agent having an
acidic reaction. These include acids such as sul
is. shown by the iollowing equations:
/ “Cm
1,1,Hrlmethyl-6-hydroxy indano
From diacetone alcohol and phenol
l 1,3-trlniethyl-5-hydroxy
indene polymer
C (011:):
l l 3-tl'im8thyl-54i drory
The 1,3,3-trimethyl-5-hydroxy indene, how
ever, polymerizes readily under the conditions of
The temperature at which the reaction is car
ried out depends among other things on the con
the condensation and yields a resinous material. densing agent. When sulfuric acid is used, the
II On distillation the polymeric material undergoes reaction is usually carried out at relatively low
temperature, for example 0°—40° C. in order to
avoid sulfonation of the phenol or the product.
When metal halides such as zinc chloride, mag
nesium chloride, copper chloride etc. are ‘used,
the temperature is preferably high, say l50°-250°
C. When the sulfuric acid is diluted with a
solvent such as acetic acid, the temperature may
be raised to 70° C. or higher. With gaseous hy
drogen chloride high temperatures, preferably
about 40°-100° 0., are employed. These tempera
tures can of course be varied depending on the‘
reactants and the product desired.
Example 1
To a mixture consisting of equimolecular quan
titles of 2-methyl-pentane-diol-2,4 and phenol
one mol. of powdered anhydrous zinc chloride is
Any alkyl phenol or the naphthols mayybe
condensed with pinacol in a similar manner.
To a mixture‘ of one mol. each of diacetone ale
cohol and‘ phenol, one-half mol. of concentrated
sulphuric acid diluted with three parts by‘weight
of glacial acetic acid is added. This mixture is
then allowed ‘to stand at room, ‘temperature or
heated on a steam bath to a temperature not ex 10
ceeding 70° C. for several hours. ‘While still
warm the mixture is poured into water and the
oil which separates is washed several times with
water in order to remove the acids and any other
water-soluble materials.
Example 4 '
added and the mixture is quickly heated to the
boiling point, about l90°-200° C. and is allowed
Dry hydrogen chloride gas is passed slowly
puri?ed by extracting?rst with alkalies or with
Claisen’s solution (50% potassium hydroxide so
lution and an equal volume of methyl alcohol)
and after separation from this solution by acidi?
cation either with hydrochloric or sulfuric acids
the resulting oil may then be subjected to a frac
tional distillation. The product resulting from
this condensation is 1,3,3-trimethyl-6-hydroxy
indane. It melts at 120° C., boils at 260°-265° C.;
the dinitro derivative melts at 112° (2., the di
bromo derivative at ‘74° C. and the monobromo
derivative of its methyl ether melts at 78° C. It
is 2-methyl-2-(p-hydroxy phenyl) pentanone-‘l.
through a mixture of one mol. each of diacetone
to reflux for two hours. While the mixture is alcohol and phenol at room temperature or at a
still warm, it is poured into water slightly acidi
?ed with hydrochloric acid whereupon an oil eral hours the reaction mixture is poured into
separates. This oil is repeatedly washed with water whereupon an oil separates. This is
water and puri?ed. The puri?cation may be. washed several times with water in order to re 25
move the acid and any ‘water-soluble materials.
carried out by direct distillation either at at
mospheric or reduced pressure. It may also be One of the products obtained by this procedure
is insoluble in water but soluble in alkalies and
most organic solvents. It is best crystallized
from the lower aliphatic hydrocarbons particu
larly petroleum ether of di-isobutylene.
There is always formed as a by-product some
of the - isomeric l,3,3-trimethyl-5-hydroxy in
vu dane. These compounds have phenolic proper
ties and therefore can undergo any of the usual
reactions and processes of the phenols in which
the acidic hydrogen or the aromatic nucleus is
involved, such for instance as condensation with
formaldehyde, acetone and'other aldehydes and
ketones. They may also be suli'cnated and m
trated in the usual manner in order to produce
various derivatives such as amino, diazo com
pounds etc. ‘
On account of their phenolic nature (phenol
‘coe?icient about 23). they may be used as bacte
ricides and germicides. They also exhibit oestro
genic properties. In exactly the same manner
any alkyl phenol or the naphthols can be con
densed with the 2-methyl-pentane-diol-2,4.
Example 2
Example 5
A mixture of equal mols of diacetone alcohol
and phenol is diluted with an equal volume of
p-cymene and this mixture is refluxed in an at
mosphere of hydrogen with not more than one
mol. of anhydrous zinc chloride for two hours.
The reaction mixture is'allowed to cool, is washed
with water slightly acidi?ed with hydrochloric
acid. The p-cymene may be removed by dis
tillation or the reaction products may be extract- '
ed with the Claisen mixture and subsequently
recovered by acidi?cation and further washing 40
with water.
Example 6'
A mixture of one mol. each of diacetone alco
hol, phenol and powdered anhydrous zinc chlo 45
ride is heated rapidly‘to 180° and re?uxed for
90 minutes at this temperature. At the end of
this time the mixture is poured into water slight
ly acidi?ed with hydrochloric acid and the oil
which separates is thoroughly washed with water
to remove acid and any other water-soluble con
Example 7
To a mixture of one mol. each of diacetone al
cohol and phenol one mol. of ?nely powdered an
hydrous magnesium chloride is added and the
mixture is heated on an oil bath to 180° C. for
several hours. After cooling it is poured into
water slightly acidi?ed with hydrochloric acid.
The oil which separates is thoroughly washed
with water in order to remove all water-soluble
The products obtained according to Examples
To a mixture consisting of one mol. of pinacol
and two mols of phenol, two mols of powdered
anhydrous zinc chloride is added and the mix
ture is slowly heated to boiling, about l70°-180°
C. The mixture is re?uxed for about a day pref
erably in an atmosphere of dry hydrogen chloride.
While still warm it is poured into water slightly
acidi?ed with hydrochloric acid and the oil which
separates is puri?ed as described in Example 1.
3 to 7 inclusive contain several compounds in-.
cluding, the phenolic indenes, indanes and sub 65
stituted phenols such as p-tertiary butyl phenol,
p-isopropenyl phenol and phenylol ketones such
as 2-methyl-2-(p-hydroxy phenyl) pentanone-A.
These compounds may be separated by fractional
distillation at reduced or atmospheric pressure. 70
In many cases it is advantageous‘ to dissolve the
The product obtained is 1,1,2-trimethyl-5-hy
droxy indane melting at 120° C. and boiling at
and then to extract it with Claisen’s solution
from which the products can be recovered by
260-265° C.
product in toluene or_other similar hydrocarbon
acidifying with hydrochloric or sulfuric acid. 75
The resulting oil is then dried and subjected to
vacuum distillation.
indanes and indenes obtained according to the
foregoing examples may be oxidized‘ to yield
On vacuum distillation several fractions may
be collected as follows: At a pressure oi’ 2-3 mm.
acid which may be further oxidized to form 4
of mercury up to 90° C. a blue colored liquid of
unknown constitution and unreacted starting
materials distill over. A second i'raction from
91-! 30° C. ‘at the same pressure consists oi’ p
tertiary butyl phenol and 1,3,3-trimethyl-6-hy
droxy indane.
A third fraction boiling at about
180°—185° C. at ,2-3 mm. pressure contains a
?rst (4-hydroxy-2-acetyl phenyl) dimethyl acetic
hydroxy-Z-acetyl benzoic acid. This product
may also be further oxidized to yield a-hydroxy
phthalic acid or it maybe distilled whereupon it
loses carbon dioxide and forms m-hydroxy
We claim:
1. The process of preparing 1,3,3-trimethyl-6- ‘
resin which is a polymer of p-isopropenyl phenol.
hydroxy indane which comprises reacting on 2
A fourth fraction at 210°-2l5° C. at the-same
pressure contains‘ a resin ‘resulting from the
polymerization of 1,1,3-trimethyl-5-hydroxy in
dene. The distillation may also be carried out
at atmospheric pressure under which conditions
the following fractions may be obtained: Up to
methyi-pentane-diol-2,4 with phenol in the pres
220° C. unreacted starting materials and some
ence of a condensing agent.
2. ‘The process of preparing 1,1,3-trimethyl-5- 1
hydroxy indene polymer which comprises react
ing on diacetone alcohol with phenol in the
presence of a condensing agent.
3. Phenols having an alkylated ortho-con
p-tertiary butyl phenol; the second fraction from
220°-250° C. contains p-tertiary butyl phenol and
densed, ?ve-membered carbocyclic side ring.
4. Polymeric 1,1,3-trimethyl-5-hydroxyindene.
the third fraction boiling i’rom 250°-280° C. con
. 5. 1,3,3-trimethyl-6-hydroxy indane.'_
tains 1,3,3-trlmethyl-6-hydroxy indane.
The indane products obtained from diacetone
25 alcohol and the cresols have strongly aromatic,
pleasant, thymol-like odors. The new phenolic
6. 1,3,3-trimethyl-5-hydroxy indane.
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