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Патент USA US2082459

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ratented June 1, 1937
UNITED STATES. PATENT’ OFFICE
'
Joseph B. Nioaoi-rnr'ookiyn, N. v.
No Drawing. Application Mai-oh 29, 1933. .
Serial- No. 683,427
mm
-
(01260-110)
This invention relates to a‘ method of produc
I
i
"
'
phenolic aliphatic acids by reacting‘v an
urated aliphatic acid with a phenolic compound
ing substituted aliphatic acids, and more particu
larly to a method of producing phenolic aliphatic i in the presence of a kationoid} condensingagent,
acids either by reacting an unsaturated ‘aliphatic. ' ~
_1Another ‘object of this invention is to produce
_
5 acid with a phenolin the presence of a kationoid "phenolic aliphatic'acids ‘by intramolecularrear- '
condensing agent or by intramolecular rearrange rangementiof a phenoxy aliphatic acid to'the
ment of the isomeric vpher'ioxy aliphatic .acid; in vcorresponding isomeric‘ phen'olic aliphatic acid
the presence of a kationoid catalyst.
' , _--in they presence of .a kationoid catalysti -
' I? "
‘
"v
Hitherto it wasv not possible to produce vphenolic ~ A further object of _ this invention is the useof'.
_
aliphatic acids by either of the ‘above -methods.-.'_ a. mixture or glacial ‘acetic ; acid.‘ and c'oncen-. 10
It has been found that'phenolic aliphaticlacids.‘ tratedsulfuric acid ‘as’ kationoidage'nt in which .
10
of the general formula
'
.
_
RcR."'HcR"-<xoma"
are readily obtainedjeither
.
,
a
-
__ '
_
-_
of‘ glacial acetic acid any-other .'
'may'beused.~
solvent for one or all ‘ of'the
'
reacting
'
‘compounds
-'
.,
an un-‘m
Still another object of this invention consists
saturated aliphatic acid .of thegeneral formula ,‘ ‘_ .' in the preparation of soaps containing a phenolic _
‘group in their molecule which products
.
valuable pharmaceutical properties. '
with o. phenol in the presenceof a llationoid'. an: '. very'
'. A‘ further object is the production of chaulv
-. densing agent or by intra'molecular rearra'nge- '
. ment ofa phenoxy aliphatic acid oi." the general 7 \moogric; acid and its'ihomologues and substitution.
51.20
products containinggajphenolic group‘ in their
> molecule-which ‘compounds have very remarkable _
-
'
'
-.
,
,
.
.
,
I
.
,
_
-
in In
thepresence
thesev formulas
of a kationoid
R represents
catalyst.
hydrogen
'
or '1a
saturated or unsaturated acyclic oralicylic rad;
ical which may contain one orfmore‘substituents
such as a hydroxyl, carbonyl‘, 'carboxyli'sulfo- or
therapeutical
properties.‘
‘another object of this ‘invention is‘ the use
1.‘ of_ Still
the products obtained according to the above
‘described, methods "in _ pharmaceutical prepara '26...‘ i
, tions, salves, ointments, creams and thelike,
_ thereby including substances in these prepara
tions which combine the phenolic characteristics
. _ nitro- group or a halogen atom; ‘R'frepresents.
.a carboxyl group, R" and R’" hydrogen or a sat;
withf'those of the aliphatic acids and esters and
30 urated or unsaturated acyclic'or 'alicyclic radical.
. which may contain one or more substituents such‘
so-
theirder'ivatives within one and the same mole-'
as a hydroxyl, carboxyl, carbonyli' Sl?fo- of _
nitro- group or a halogen atom.
with. the above and other objects ‘in view, all
-I-. ‘of which will'fully'appear in the following de-‘
’
X represents
or anyaother
phenyl,
arylnaphthyhtetrahydro'i
radical ‘whichjmayfbez scription and claims; the present-invention will ‘ 35
03 Li naphthyl
,jl'i'ereinafter be more fully described in the fol
substituted by any aryl, alkyl or 'aralkyl group}.
.lowing examples;- '
.
=
_
_'
unsubstituted or substituted by a mum-halogen‘, ' Example 1.'-'-Addition of oleic acid to meta-creed
vor hydroxyl, carbonyl, carboxyl, azo, and sulfo. ' Equimolecularmixtures of oleic acid and meta
group.
40
40
The terms “kationoid condensing agenti’land. ’ cresol are mixed under cooling with sulfuric acid.
“kationoid catalyst” are used-herein audit! the
The mixture is allowed to stand for several days
until the entire mass has become viscous. The
claims appended hereto in the sense of the recent] mass
is‘then poured into cold water, washed until
electronic postulations of Robert Robinson, com
the sulfuric acid is removed, dissolved with alkali,
?ltered, reprecipitated with acid and ?nally dis 45
tilled in vacuo. The product obtained is of a
tionen”, Verla'g Ferdinand Enke, Stuttgart, 1932,_ pleasant,
thymol-like odor and shows the charac
a pare for instance his book on “Versuch einer
Elektronentheorie organisch-chemischer Reak
especially page 16. Such agents are for instance
substances possessing latent valences, such as
50 acids, metal atoms which are able to form co-v
ordination systems with. water or ammonia, sulfur
from sulfur trioxide; sulfuric ‘acid, acid sodium
sul?te, atoms and free; radicals with incomplete
electron
55
shells.
' ‘
_
Thus, one objectof this invention is
produce
teristics oi’ a fatty acid as well as of a phenol.
Itsmelting point is about 37° C. In place of the
m-cresol shown in this example phenol may be 50
used in which case the product is 10 (p-hydroxy
phenyl) stearic acid.
'
- _ Example 2.—_Addition of erucic acid to phenol"
llquimoiecular amounts of crude acid and
55
a
'
v
phenol are dissolved in four times their amount Example 8.—Additioa of elaidic acid to pyro
of glacial acetic acid.v Then the same amoimt
aallol
of concentrated sulfuric acid is added to make a
Equimolecular amounts :of elaidic acid and
sulfuric acid-acetic acid mixture in the propor
pyrogallol are dissolved in glacial acetic acid and
l 'tion of 1:4, and the mass is heated for several dry hydrochloric acid is introduced into thesolu
hours to 120° C. Thereafter, the mixture is cooled tion while boiling under 're?ux. ‘After ‘several
and diluted with water while cooling. The acid hours. the reaction product is isolated and puri
is puri?ed as described in Example 1 by_dis-' ?ed according to Examples 1 and 2.
solving in alkali. reprecipitation and vacuum
10 distillation or it is’
from alcohol. [sample Dee-Addition oluchaahsoocric acid to 10
.
‘mm 3-M%W.
to
Equimolecular amounts-of elaeoetearic acid
.
4
t
I
1
"Eauimolecular amounts of chaulmoogric told
and guaiacol .are dimolved in glacial acetic acid
and heated with zinc chloride imder re?ux. After
15, and phenol are dissolved in ten times their 1. several hours the reaction product is isolated 15
amount of glacial acetic acid and a current of dry. Y and
to Examples 1 and 2.
ofriclnole'ic acid to tetra
hydrochloric acid‘ is introduced into the
- temple
The
temperature
is
kept
at
about
100°’
water.
'Ricinoleic acid
are 20
2° c. The mixture is then poured into water and
the product is isolated and puri?ed according suspended in saturated aliphatic hydrocarbons,
to the methods described in Examples 1 and-2. such as hexanesaand, after addition of concen
trated sulfuric acid. is heated under reflux while
The product obtained contains stillanother tin
saturated group and can be‘ subjected to further" stirring vigorously. After several hours the re
25 reaction with phenol in a mixture of glacial acetic action is complete and the reaction product is
acid and concentrated sulfuric acid according isolated by distillation with steam to remove the
hexanes and puri?ed according to Examples 1
to Example 2.
.
Y
‘
until a viscous mass is obtained on dilution with
Example L-Addition of sorbic acid to :cglenol
30
Sorbic acid and a mixture of xylenols are dis
solved in glacial acetic acid and to this solution
aluminum chloride is added. The resulting-mi»
ture is then heated under a re?ux until'thelcon
35 densation is complete. The product is isolated
and puri?ed as described in Examples 14' and 2..
Example say-seamen of chaulmoooric
to
and 2.
_
Example 11.—Addition_of olein to salicylic acid
Equimolecular ‘amounts'of olein and salicylic
acidaredissolvedwhilecoolinginamixtureof
- sulfuric acidand glacial acetic acid (proportion
1:5),_.then heated'gently for ‘several hours at
‘50' to 60° .C. 'lhe reaction product is isolated'and
puri?ed in-the- manner described in the preceding
-‘examples._-
-
,.~
-- EmanipleJfL-dddi?o? oltcaetor oil to paaillin
with twice its weight of castor oil is
Equimolecular amounts of chaulmoogric acid ‘
40 and phenol are dissolved in the same amount of dissolved in a mixture of equal parts of acetic
concentrated sulfuric acid and care is taken‘ that
the temperature does not exceed 80' C. .- After
acid anhydride and
acetic acid. To this
concentrated sulfuric acid is added while
vigorously. and keeping the- temperature
allowing the mixture‘ to stand for several hours '
24; to'_ 481 hours standing at
at room temperature the condensation is co'm-.~
the reaction mixture is worked
‘5 pleted, the reaction mixture is'diluted with water
while cooling and the reaction product is isolated ‘fupa'inqthemanner described in the preceding
and puri?ed according to Examples 1 and 2.
examplesr-f
_
_‘
Example 6.-_Addition of the ethyl ester of had->1 j Erample>13.—iiddttion ol'tiuia oil was to phenol
50
nocarpic acid to resorcinol
The ethyl ester of hydnocarpic acid is dissolved ' Tung oil‘ acid and a mixture of 'equimolecular
in ?ve times its weight of glacial acetic acid. amounts offormaldehyde, dimolved in acetic acid,
To this solution a mixture of the equimolecular ‘and phenol,‘ are heated with a mixture of glacial
55 amount of resorcinol in a mixture of glacial acetic acetic acid and concentrated sulfuric acid and
after several hours precipitated by addition of
acid and concentrated sulfuric acid in the pro
water. The product obtained is a modi?ed
portion of 5:1 is added while stirring vigorously. phenol-formaldehyde resin' with very valuable
The mixture is then heated under re?ux for glopertitses whichlis soluble in various organic
several hours and the reaction product isolated
00 and puri?ed according to the Examples 1 and 2.
It is also possible to esterify the acids obtained _E'xample14.—y1teananm't of creamy stearlc
u
according to these examples with alcohols in the
presence of sulfurb'acid, instead of starting with
'
tom,» obtained from oleic tom
7 by the addition of :h'ydrobromic acid, is reacted
65 the esters.
'
'
'
with pot?siumimeta-creeolaie. The latter is
trample 7.—Addittlon of oleic acid to hydro
heated at about 100° C(in a mixture of glacial‘
quinone
. I
ven
Equimolecular amounts or oleic acid and hy
.
-
:
'
acetic acid and sulfuric acid (0:1) for several
hours.’v Thereby a rearrangement takes place
drcquinone are introduced gradually into fused ' ' yielding the 10-(2-hydroxy semethyl phenyl)
70 toluene sulfonic acid.
The reaction mixturev is
diluted with water after cooling, and extracted
stearic ‘acid. This acid can also be obtained ac
oordingto'hxample ,1.
with ether. After evaporation of the ether, the‘
I
"
phem
15.--Ream1l0ement
. in! chaulmoooric
ofacid
m
oleic acid-hydroquinone condensation product is . i Example
75 puri?ed by vacuum distillation. _
The
.
salt of para-chlorophenol and
I.
3
2,082,469
bromo chaulmoogric acid are reacted with each
other to form para chlorophenoxy chaulmoogric
acid which latter then is rearranged to the cor
responding
l-hydroxy-?-chlorophenyl
chaul
moogric acid by heating in glacial acetic acid
in the presence of aluminum chloride. The reac
tion mixture is worked up in the manner de
scribed above.
Example 16.—Rearmngement of thymoxy stearic
10
acid
_
In a suspension of thymoxy stearic acid, ob
tained from bromostearic acid and the sodium
salt of thymol, in staurated petroleum hydrocar
15 bons, boiling between 100° and 120° C., a cur
rent of dry hydrochloric acid is introduced while
stirring vigorously and keeping the temperature
at the boiling point of the solvent. After several
hours the rearrangement is completed and the
20 reaction mixture is steam distilled in order to
remove the petroleum hydrocarbons. The reac
tion product may be puri?ed by recrystallization
from alcohol.
Although specific examples have been given,
products of these acids may be employed, for in
stance their halogeno, their sulfo, their hydroxy
and the like derivatives. The high molecular oxi
dation products of petroleum, petroleum wax,
brown coal tar and the like which are easily ob
tained by catalytic oxidation of the above men
tioned raw materials and which possess very re
markable disinfecting properties, which is in
creased considerably by the combination with
10
the phenolic compounds, are also very useful.
The temperature may vary from 0° to 150° C.,
according to the reactivity of the reactants. The
heating may also be carried out under pressure.
When sulfuric acid is used, its concentration
is preferably 96%; however, monohydrate or any 15
other suitable concentration of the sulfuric acid
may be employed. The duration of the reaction
depends upon the temperature, the reactivity of
the reactants and the kationoid agent selected
and can be varied according to the requirements.
The methods of isolating the reaction product
and purifying them can be varied in accordance
with the properties of the reactants and reaction
products. These and other changes may be made
tions may be made by.those skilled in the art in
in the invention within the spirit and scope
thereof.
accordance with the principles set forth herein.
Instead of glacial acetic acid, other liquids may
above described methods may be used as such,
only one of the'reactants while the other is
merely suspended in the solution. 0r liquids
1. A method of producing phenolic aliphatic
acids by reacting an unsaturated aliphatic acid
25 the invention is not limited thereto as modi?ca
The compounds obtained according to the
or in the form of their salts or esters as con
be used as solvents for the reactants, such as sul
stituents
of soap preparations, especially phar
furic
acid
itself,
or
the
homologues
of
acetic
30
acid, such as propionic or butyric acid, or alkyl maceutical ones, shaving creams, tooth pastes
sulfates or mixtures of solvents with each other and various other toilet preparations. Or they
and with non-solvents, or other solvents which I may be used in the treatment of diseases, as for
are not readily attacked by sulfuric acid such instance the products obtained from chaulmoo
gric acid for the treatment of leprosy and the like.
Q: Ll as saturated petroleum hydrocarbons, hexane
What I claim as my invention is:
and the like. The solvent may be a solvent for
may be used which are not solvents for the re
actants but in which the latter are merely sus
pended in very finely comminuted form. Varia
tions in the proportion of solvent to reactants
and condensing or rearranging agent may also
be made. Instead of sulfuric acid and the other
mentioned kationoid agents, other compounds
may also be used, such as for instance phosphoric
acid, benzene sulfonic acids, boron tri?uoride,
acid reacting salts,lsuch as acid. sodium sulfate,
sodium monophosphate and the like, chlorosul
with a phenol in the presence of a mixture of
glacial acetic acid and concentrated sulfuric acid. 40
2. As a new product, '10(p-hydroxyphenyl)
stearic acid.
-
3. As a new product, hydroxy-phenyl dihydro
chaulmoogric acid.
4. A method of producing saturated phenolic 45
organic acids containing a free phenolic hydroxyl
group in the molecule, by condensing a phenol
having an available reactive unsubstituted nu
clear position, withan acid of the group consist
ing of unsaturated aliphatic acids and singly un
fonic
acid,
alkyi
sulionic
acids»
and
many
other
,
50
acid-reacting agents. A mixture of kationoid saturated alicyclic fatty acids, in the presence of
a mixture of concentrated sulfuric acid and gla
agents may be employed advantageously.
Instead of the phenols mentioned, other phe; cial acetic acid.
5. A process for preparing hydroxyphenyl di
nols, such as e. g. xylenols, naphthols, tetra
hydronaphthois, hydroxy diphenyls.‘ or phenol
derivatives, such as nitrophenols, chlorophenols,
the sulfonic acids of these phenolic compounds,
the esters of salicylic acid, such as the methyl
and the phenyl ester, phenol ethers, phenol alde
hydcs, such as salicyclic aldehyde, and many
others may be reacted with the aliphatic acids.
Instead of the unsaturated aliphatic acids
mentioned, other acids. such as linoleic acid, or
di~ and tribasic acids, such as muconlc acid,
" citrnconic acid. may be added to the phenol,
while their corresponding saturated acids may be
hydro chaulmoogric acid which comprises con
densing phenol with chaulmoogric acid in the
presence of concentrated sulfuric acid.
6. A product prepared by the condensation of
oleic acid with a phenol in the presence of a
mixture of sulphuric acid and glacial acetic acid. 60
7. A saturated hydroxyphenyl carboxylic acid
obtainable by condensing a phenol with an acid
of the group consisting of unsaturated aliphatic
acids and singly unsaturated alicyclic fatty acids
in the presence of a mixture of concentrated sul
furic acid and glacial acetic acid.
used in combination with the phenol for the re
arrangement reaction.
Likewise the substitution _ _,
'
JOSEPH B. NIEDERL.
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