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Патент USA US3098885

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Un
States
,
3,098,875
Patented July 23, 1963
1
2
tively more soluble in the gasoline or petroleum prod
3,098,875
Louis Schmerling, Riverside, Ill., assignor to Universal
uct than the deactivators which are prepared in the
PRODUCTION OF SALICYLALDEHYDES
solid state. In addition, salicylaldehyde thus formed may
also be used as an intermediate in the preparation of
acetylsalicylic acid, a well-known medicine, or it may
also be used as an intermediate in the preparation of other
Oil Products Company, Des Plaines, 11]., a corporation
of Delaware
No Drawing. Filed July 5, 1960, Ser. No. 40,511
16 Claims. (Cl. 260-600)
' pharmaceuticals.
Heretofore, it was known that aromatic hydrocarbons
such as benzene could be treated with carbon monoxide
This application is a continuation-in-part of my co
pending applications Serial No. 707,691, ?led January 8, 10 in the presence ‘of a metal halide to form an aldheyde
1-958, and 707,692, ?led January 8, 1958, both now
such as benzaldehyde. This reaction is essentially a
abandoned.
This invention relates to a process ‘for the production
of oxygenated organic compounds and particularly to a
process for the preparation of aromatic aldehydes. More 15
Friedel-Crafts acylation, the reaction being one in which
a formyl halide such as formyl chloride is formed as an
intermediate and condenses with the aromatic hydrocar
bon to yield an aldehyde. However, the present inven
particularly the invention concerns a method for the pro
tion concerns the treatment of a hydroxy substituted com
duction of aromatic aldehydes such as salicylaldehydes,
said salicylaldehydes containing, if so desired, one or
more alkyl substituents.
One object of this invention is to provide a process for 20
pound such as a phenolic compound which may contain
preparing oxygenated aromatic compounds.
A further object of this invention is to provide a process
Hydroxy substituted aromatic compounds ‘which may
be used in the process of this invention include phenol,
for the production of aromatic aldehydes such as salicyl
aldehydes which may contain one or more alkyl substi
tuents on the ring.
One embodiment of this invention resides in a process
for the production of a salicylaldehyde which comprises
heating a phenol, in which at least one carbon atom ortho
to the hydroxy substituent is unsubstituted, selected from
alkyl substituents on the ring, the only requirement which
the starting material must have being that one of the
carbon atoms ortho to the hydroxy substituent be ‘free of
any substituents.
as well as alkyl substituted phenols such as o-cresol, m
25
cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethyl
phenol, o-propylphenol, m-propylphenol, p-propylphenol,
o-isopropylphenol, m-isopropylphenol, p-isopropylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, o-isobutyl
phenol, m-isobutylphenol, p-isobutylphenol, other butyl
the group consisting of phenol and monoalkyl- and di 30 phenols, pentylphenols, hexylphenols, heptylphenols, oc-.
alkylphenols, said alkylradicals containing from 1 to
tylphenols,nonylphenols, decylphenols, undecylphenols,
about 18 carbon atoms, with carbon monoxide and the
dodecylphenols, tridecylphenols, tetradecylphenols, penta
corresponding phenoxide selected from the group consist
decylphenols, hexadeoylphenols, heptadecylphenols, octa
ing of alkali metal phenoxides, alkaline earth metal phen
decylphenols, etc., 2,3-dimethylphenol, 2,4-dimethylphe
oxides ‘and aluminum phenoxides at a temperature in the 35 ncl, 2,5-dimethylphenol, 3,4’dimethylphenol, 3,5-dimeth—
range of from about 100° to about 350° C. and at a
pressure in the range of from about atmospheric to about
300 atmospheres, treating the resultant product with an
acid, and recovering the desired salicylaldehyde.
ylphenol, 2,3-diethylphenol, 2,4-diethylphenol, 2,5-dieth
ylphenol, 3,4-diethylphenol, 3,5-diethylphenol, 2,3-dipro
pylphenols, 2,4-dipropylphenols, 2,5-dipropylphenols, 3,4
dipropylphenols, 3,5-dipropylphenols, etc.
A further embodiment of the invention resides in a 40 i The novel catalysts as used in the present invention
process for the production of a salicylaldehyde which
include aluminum phenoxides such as aluminum phen
comprises heating phenol with carbon monoxide and the
‘oxide, aluminum o-cresoxide (aluminum o-methylphen
oxide), aluminum m-cresoxide (aluminum m-methylphen
sisting of alkali metal phenoxides, alkaline earth metal
oxide), aluminum p-cresoxide (aluminum p-methylphen
phenoxides and aluminum phenoxides at a temperature 45 oxide), aluminum o-ethylphenoxide, aluminum m-ethyl
phenoxide, aluminum p-ethylphenoxide, aluminum o-pro
in the range of from about 100° to about 350° C. and
pylphenoxides, aluminum m-propylphenoxides, aluminum
at a pressure in the range of from about atmospheric to
p»propylphenoxides, aluminum o-butylphenoxides, alu
about 300 atmospheres, treating the resultant product
with an acid and recovering the desired salicylaldehyde.
minum m-butylphenoxides, aluminum p-butylphenoxides,
A speci?c embodiment of the invention resides in a 50 aluminum pentylphenoxides, aluminum hexylphenoxides,
process for the preparation of Semethylsalicylaldehyde
aluminum heptylphenoxides, aluminum octylphenoxides,
which comprises heating p-cresol with carbon monoxide
aluminum nonylphenoxides, aluminum decylphenoxides,
and sodium p-methylphenoxide at a temperature in the
aluminum undecylphenoxides, aluminum dodecylphen
corresponding phenoxide selected from the group con
range of from about 100° to about 350° C. and at a pres
oxides, aluminum tridecylp-henoxides, aluminum tetra
sure in the range of from about atmospheric to about 55 decylphenoxides, aluminum pentadecylphenoxides, alu
minum hexadecylphenoxides, aluminum heptadecylphen—
oxides, aluminum octadecylphenoxides, aluminum 2,3-di
salicylaldehyde.
methylphenoxide, aluminum 2,4-dimethylphenoxide, alu
Other objects and embodiments referring to alterna
minum 2,5-dimethylphenoxide, aluminum 3,4-dimethyl
tive phenolic compounds and to alternative phenoxides
phenoxide, aluminum 3,5-dimethylphenoxide, aluminum
will be found in the following further detailed descrip
2,3-diethylphenoxide, aluminum 2,4-diethylphenoxide, alu
minum 2,5-diethylphenoxide, aluminum 3,4-diethylphen
tion of the invention.
The aromatic oxygenated compounds and particularly
oxide, aluminum 3,5-diethylphenoxide, aluminum 2,3-di
the aromatic aldehydes such as salicylaldehyde which may
propylphenoxides, aluminum 2,4-dipropylphenoxides, alu
contain alkyl substituents on the nucleus which are pre 65 minum 2,5-dipropylphenoxides, aluminum 3,4-dipropyl
pared according to the process of this invention will
phenoxides, aluminum 3,5-dipropylphenoxides, aluminum
2,3-dibutylphenoxides, aluminum 2,4-dibutylphenoxides,
?nd a wide variety of uses in the chemical ?eld. For
example, the alkylsalicylaldehydes may be used as inter
aluminum 2,5-dibutylphenoxides, aluminum 3,4-dibutyl
phenoxides, aluminum 3,5-dibutylphenoxides, aluminum
mediates in the preparation of copper deactivators, which
are additives in gasoline, one advantage of the de 70 2,5- and 3,5-dipentyl-, dihexyl-, diheptyl-, diocty1-, di
nonyl-, didecyl-, diundecyl-, didodecyl-, ditridecyl-, ditetra
activators thus formed being that they are in a liquid state
300 atmospheres, treating the resultant product with a
dilute inorganic acid and recovering the desired S-methyl
rather than in a crystalline state and will thus be rela
decy1-, dipenta‘decyh, dihexadecyl-, diheptadecyl-, diocta
3,098,875
4
3
ployed, suf?cient pressure being used to maintain a por
tion of the reactants in the liquid phase.
It is also contemplated within the scope of this inven
tion that the present process, if so desired, may be effected
decylphenoxides, etc.; alkali metal phenoxides and alkaline
earth metal phenoxides such as sodium phenoxide, lithium
phenoxide, potassium phenoxide, magnesium phenoxide,
calcium phenoxide, sodium o-, m- and p-cresoxide, lithium
o-, m- and p-cresoxide, magnesium o-, m- and p-cresoxide,
in the presence of an inert organic solvent or diluent.
Suitable diluents which may be used include aromatic
hydrocarbons such as benzene, toluene, o-xylene, m
ethylphenoxide, lithium o-, m- and p-ethylphenoxide,
xylene, p-xylene, ethylbenzene, etc.; alcohols such as
potassium o—, m- and p-ethylphenoxide, magnesium 0-, m
methyl alcohol, ethyl alcohol, n-propyl alcohol, etc.; ethers
and .p-ethylphenoxide, calcium o-, m- and p-ethylphen
oxide, sodium o-, m- and p-propylphenoxides, lithium o-, 10 such as dimethyl ether, diethyl ether, dipropyl ether, etc.;
saturated low molecular weight aliphatic hydrocarbons
m- and p-propylphenoxides, potassium o-, m- and p-pro
such as pentane, hexane, heptane, etc.; saturated cyclic
pylphenoxides, magnesium o-, m- and p-propylphenoxides,
calcium o-, m- and p-cresoxide, sodium o-, m- and p
hydrocarbons such as cyclopentane, cyclohexane, methyl
calcium o-, m- and p-propylphenoxides, sodium o-, m
oyclopentane, methylcyclohexane, etc.; or acetone, acetic
and p-butylphenoxides, sodium o-, m- and p-pentylphen
oxides, lithium o-, m- and p-pentylp-henoxides, potassium 15 acid, etc.
o-, m- and p-pentylphenoxides, magnesium o-, m- and
Following the reaction between the phenolic compound,
p-penty-lphenoxides, calcium o-, m- and p-pentylphen
oxides, etc. It is also contemplated Within the scope of
the carbon monoxide and the particular phenoxide the
reaction product may then be treated with Iwater and/or
a diluent acid such as dilute sulfuric acid, dilute hydro
this invention that the rubidium, cesium, strontium and
barium phenoxides and the aforementioned alkyl sub 20 chloric acid, dilute nitric acid, dilute phosphoric acid, etc.,
to decompose the thus formed aluminum, alkali metal or
alkaline earth metal compound and recover the desired
stituted phenoxides may also be employed as well as
the higher molecular weight alkyl substituted phenoxides
salicylaldehyde which has been formed.
such as the alkali metal and alkaline earth metal o-, m
and p-hexylphenoxides, heptylphenoxides, octylphenox
ides, nonpylphenoxides, decylphenoxides, undecylphenox
ides, dodecylphenoxides, tridecylphenoxides, tetradecyl
The process of this invention may be effected in any
25 suitable manner and may comprise either a batch or a
continuous type operation. For example, when a batch
type operation is used a quantity of the hydroxy substi
phenoxides, pentadecylphenoxides, hexadecylphenoxides,
heptadecylphenoxides, octadecylphenoxides, etc. Other
phenoxides which may also be employed include sodium,
potassium, lithium, rubidium, cesium, magnesium, cal
cium, strontium, and barium dialkyl substituted phenox
ides such as sodium 2,3-dimethylphenoxide, potassium 2,3
dimethylphenoxide, magnesium 2,3-dimethylphenoxide,
calcium 2,3~dimethylphenoxide, sodium 2,4-dimethylphen
oxide, potassium 2,4-dimethylphenoxide, magnesium 2,4
dimethylphenoxide, calcium 2,4-dimet-hyl phenoxide, so
tuted aromatic compound and the corresponding phen
oxide is placed in an appropriate apparatus which may
30 comprise a rotating autoclave or other suitable equipment.
The apparatus is sealed and carbon monoxide is pres~
sured in until the desired pressure has been reached after
which the apparatus is heated to the desired temperature
and maintained thereat for a predetermined residence
35 time. At the end of this time the apparatus and contents
thereof are cooled to room temperature, the excess pres
sure is vented, the reaction product may be treated with
water and/or dilute acid to decompose the aluminum, al
dium 2,4-dimethylphenoxide, potassium 2,5-dimethylphen
oxide, magnesium 2,5-dimethylphenoxide, calcium 2,5
dimethylphenoxide, sodium 2,3-‘diethylphenoxide, potas
sium 2,3-diethylphenoxide, magnesium 2,3-diethylphen
oxide, calcium 2,3-diethylphenoxide, sodium 3,4-diethyl
kali metal or alkaline earth metal compound, and the de
40
is separated and recovered by conventional means such as,
fractional distillation, crystallization, etc.
Another type of operation which may be used, which
constitutes the preferred operation of the present inven
phenoxide, potassium 3,4-diethylphenoxide, magnesium
3,4-diethylphenoxide, calcium 3,4-diethylphenoxide, so
dium 3,4-dibutylphenoxides, potassium 3,4-dibutylphen
oxides, magnesium 3,4-dibutylphenoxides, calcium 3,4-di
butylphenoxides, sodium 3,4-dibutylphenoxides, potas
sium 3,5-dibutylphenoxides, magnesium 3,5-dibutylphen
sired salicylaldehyde or alkyl substituted salicyl-aldehyde
45
tion, is a continuous method in which the hydroxy substi
tuted aromatic compound and the corresponding alumi
num, alkali metal or alkaline earth metal phenoxide are
continuously charged to a reaction zone which is main
oxides, calcium 3,5-dibutylphenoxides, etc. It is to be
tained at the proper operating conditions of temperature
understood that the process of the present invention is
not necessarily limited to the alkali metal or alkaline earth 50 and pressure. These reactants may be charged through
separate lines or, if so desired, they may be admixed prior
metal phenoxides hereinbefore set ‘forth, but that other
to entry into said reactor and charged thereto in a single
of said phenoxides may also 'be employed, however, not
necessarily with equivalent results.
stream. In addition, the carbon monoxide is also con
tinuously charged to said reaction zone through a separate
line. After a predetermined residence time in the reac
In a preferred embodiment of the invention the react
ants comprising the hydroxy substituted aromatic com 55 tion zone, which may constitute an unpacked vessel or
pound, the particular phenoxide, either an aluminum phen
coil or which may be lined with an adsorbent packing ma
oxide, an alkali metal phenoxide or an alkaline earth
terial such as dehydrated bauxite, ?re brick, alumina and
metal phenoxide and the carbon monoxide are usually
the like, the reaction product is continuously withdrawn
condensed using an approximately equimolar amount of
and separated from the reactor e?iuent, the latter being
60
each of the phenolic compounds and an excess of carbon
separated and recycled to form a portion of the feed ma
monoxide. However, a molar excess of the phenolic or
terial, while the former is puri?ed ‘by conventional means
hereinbefore set forth.
hydroxy substituted aromatic compound over the particu
The following examples are given to illustrate the proc
lar aluminum-, alkali metal or alkaline earth metal phen
ess of the present invention which, however, are not in
oxide may be employed, the particular phenoxide acting
as a catalyst for the reaction involving the excess phenolic 65 tended to limit the generally broad scope of the present
invention in strict accordance therewith.
compound. The reaction will take place at an elevated
temperature usually in the range of from about 100° to
Example I
about 350° C. or more and preferably in a range of from
A mixture of 100 g. of phenol and 300 g. of aluminum
about 200° to about 300° C. In addition, the reaction is 70 phenoxide is placed in the glass liner of a rotating auto
also carried out at pressures ranging from about atmos
clave. The liner is then sealed into the autoclave and
pheric to about 300 atmospheres or more, and preferably
carbon monoxide is pressed in until a pressure of 100
in a range of from about 40 atmospheres to about 150
atmospheres has been reached. The autoclave and con
atmospheres or more, the particular pressure being de
tents thereof are then heated to a temperature of about
pendent upon the reactants used and the temperatures em 75 200° C. and maintained at this temperature for a period
‘3,098,875
6
of approximately 6 hours. At the end of this time the
contents thereof are heated to a temperature of about
autoclave and contents thereof are cooled to room tem
200° C. The autoclave is maintained at this tempera
ture for a period of about 6 hours at the end of which
time it is allowed to cool to room temperature. The
excess pressure is vented and the reaction product is sub~
perature, the excess pressure is vented and the reaction
product is boiled with water, then ether extracted, and the
extract is subjected to fractional distillation, the cut boiling
at l95-l97° C. at 760 mm. pressure, comprising salicylal
dehyde, is separated and recovered.
jected to fractional distillation, the cut consisting of 5
‘
methylsalicylaldehyde being separated and recovered
therefrom.
Example II
Example VIII
One hundred grams of p-cresol and 30 g. of aluminum 10
A mixture of o-ethylphenol and magnesium o-ethyl
p-cresoxide are placed in the glass liner of a rotating auto
phenoxide is subjected to the same treatment as described
clave which is thereafter sealed into the autoclave. Car
in Example I above. The reaction product resulting from
bon monoxide is pressed in until a pressure of about 150
the reaction is subjected to fractional distillation and the
atmospheres is reached, after which the autoclave and
contents thereof are heated to a temperature of about 15 desired compound, comprising
separated and recovered.
200° C. The autoclave is maintained at this temperature
for a period of about 6 hours at the end of which time
it is allowed to cool to room temperature.
3-ethylsalicylaldehyde is
Example IX
The excess
In a manner similar to that described in Example VII
pressure is vented and the reaction product after being
boiled with water and ether extracted is subjected to frac
tional distillation, the cut consisting of S-methylsal-icylal
dehyde being separated and recovered therefrom.
Example 111
A mixture of o-ethy-lphenol and aluminum o-ethylphen
above a mixture of p-cnesol and potassium p-cresoxide is
subjected to treatment with carbon monoxide at an ele
vated temperature and pressure. The desired product,
comprising S-methylsalicylaldehyde, is separated and re
covered 'by fractional distillation from the reaction prod
oxide is subjected to the same treatment as described in 25
uct.
Example X
Example I above. The reaction product resulting from
A mixture of 100 g. of p-‘butylphenol and 30 g. of
the reaction is subjected to fractional distillation and the
calcium p-butylphenoxide is placed in a rotating autoclave
desired compound, comprising 3-ethylsalicylaldehyde is
which is sealed and carbon monoxide pressed in until a
‘separated and recovered.
30 pressure of 100 atmospheres has been reached. The auto
Example IV
clave is heated to a temperature of about 250° C. and
maintained thereat for a period of about 8 hours. At the
In a manner similar to that described in Example II
end of this time the autoclave and contents thereof are
above a mixture of o-cresol and aluminum o-cresoxide is
cooled to room temperature, the excess pressure is vented
subjected to treatment with carbon monoxide at an ele
vated temperature and pressure. The desired product, 35 and the reaction product is recovered. The reaction prod
uct is subjected to fractional distillation, the cut consisting
comprising 3-methylsalicylaldehy~de, is separated and re
covered by fractional distillation from the reaction prod
of S-butylsalicylaldehyde being separated and recovered
uct.
therefrom.
Example V
A mixture of 100 g. of p-butylphenol and 20 g. of
aluminum p-butylphenoxide is placed in a rotating auto
clave which is sealed and carbon monoxide pressed in
’
40
Example XI
A mixture of 100 g. of p-cresol and 20 g. of sodium
p-methylphenoxide (p-cresoxide) is placed in the glass
liner of a rotating autoclave which is thereafter sealed
until a pressure of 100 atmospheres has been reached.
into said autoclave. Carbon monoxide is pressed in un
The autoclave is heated to a temperature of about 250° C.
til a pressure of about 100‘ atmospheres is reached, after
and maintained thereat for a period of about 6 hours. 45 which the autoclave and contents thereof are heated to a
At the end of this time the autoclave and contents thereof
temperature of about 200° C. The autoclave is main
are cooled to room temperature, the excess pressure is
tained at this temperature for a period of about 6 hours
vented and the reaction product is recovered. The reac
at the end of which time it is allowed to cool to room
tion product is boiled with ‘water, ether extracted and
temperature. The excess pressure is vented and the reac
the extract is subjected to fractional distillation, the cut 50 tion product is treated with dilute sulfuric acid, the result
consisting‘ of S-butylsalicylaldehyde being separated and
ing solution is extracted with ether and the extract is
recovered therefrom.
subjected to fractional distillation, the cut consisting of
Example VI
S-methylsalicylaldehyde being separated and recovered
therefrom.
A mixture ‘of 200 g. of phenol and 200 g. of sodium 55
Example XII
phenoxide is placed in the glass liner of a rotating auto
A mixture of 100 g. of p-dodecylphenol and 100 g. of
clave. The liner is then sealed into the autoclave and
potassium p-dodecylphenoxide is placed in the glass liner
carbon monoxide is pressed in until a pressure of 120
atmospheres has been reached. The autoclave and con
of a rotating autoclave which is thereafter sealed into the
Carbon monoxide is pressed in until a pres
sure of about 100 atmospheres is reached after which the
tents thereof are then heated to a temperature of about 60 autoclave.
200° C. and maintained at this temperature for a period
of approximately 6 hours. At the end of this time the
autoclave and contents thereof are cooled to room tem
perature, the excess pressure is vented and the reaction
autoclave and contents thereof are heated to a temper:
ature of about 200° C. Upon completion of the desired
reaction time which is approximately 6 hours the auto
product is treated with dilute sulfuric acid, ether ex 65 clave and contents thereof are cooled to room tempera
ture. The excess pressure is vented and the reaction
tracted and the extract is subject to fractional distillation,
product is treated with dilute hydrochloric acid. Follow
the cut boiling at l9‘5-l97° C. at 7601 mm. pressure,
ing this the solution is extracted with ether and the ether
comprising salicylatldehyde, is separated and recovered.
extract is subjected to fractional distillation under reduced
Example VII
pressure, the cut comprising S-dodecylsalicylaldehyde be
ing separated and recovered therefrom.
One hundred grams of p-cresol and 20 g. of lithium p~
cresoxide are placed in a glass liner of a rotating auto
clave which is thereafter sealed iIlItO the autoclave. Car
bon monoxide is pressed in until a pressure of about 100
Example XIII
In this example a mixture of p-octadecylphenol and
atmospheres is reached, after which the autoclave and 75 sodium p-octadecylphenoxide is subjected to the same
3,098,875
7
treatment as described in the above examples. The reac
tion product resulting from the treatment with carbon
monoxide at elevated temperatures and pressures is treated
with dilute nitric acid, the solution is extracted with ether
and the ether extract is subjected to fractional distillation,
the desired reaction product comprising S-octadecylsali
cylaldhyde being separated and recovered.
I claim as my invention:
1. A process for the production of a salicylaldehyde
7. A process for the production of a salicylaldehyde
compound selected from the group consisting of salicyl
aldehyde and alkyl salicylaldehydes which comprises
heating a phenol in which at least one carbon atom ortho
to the hydroxy substituent has hydrogen attached thereto,
selected from the ‘group consisting of phenol and mono
alkyl- and dialkylphenols, said alkyl radicals containing
from 1 to about 18 carbon atoms, with carbon monoxide
and aluminum phenoxide at a temperature in the range
compound selected from the group consisting of salicyl
of ‘from about 100° to about 350° C. and at a pressure
aldehyde and alkyl salicylaldehydes which comprises heat
in the range of from about atmospheric to about 300
atmospheres in a proportion and for a su?icient time to
ing a phenol, in which at least [one carbon atom ortho to
selected from the group consisting of phenol and mono
form the desired sallicylaldehyde compound.
8. A process for the production of a salicylaldehyde
the hydroxy substituent has hydrogen attached thereto,
alkyl- and dialkylphenols, said alkyl radicals containing
' compound selected from the group consisting of salicyl-,
from 1 to about 18 carbon atoms, with carbon monoxide
and a phenoxide selected from the group consisting of
ing a phenol in which at least one carbon atom ortho to
alkali metal phenoxides, alkaline earth metal phenoxides
the hydroxy substituent has hydrogen attached thereto,
and aluminum phenoxides, at a temperature in the range
selected from the group consisting of phenol and mono
the range of from about atmospheric to about 300 atmos
pheres in a proportion and ‘for a su?icient time to form
from 1 to about 18 carbon atoms, with carbon monoxide
and sodium p-rnethylphenoxide at a temperature in the
aldehyde and alkyl salicylaldehydes which comprises heat
of from about 100° to about 350° C. and at a pressure in 20 alkyl- and dialkylphenols, said alkyl radicals containing
range of from about 100° to about 350° C. and at a
the desired salicylaldehyde compound, and recovering the
pressure in the range of from about atmospheric to about
last-mentioned compound.
2. A process for the production of salicylaldehyde 25 300 atmospheres in a proportion and for a suf?cient time
to form the desired salicylaldehyde compound, and re
which comprises heating phenol with carbon monoxide
covering the last-mentioned compound.
and a phenoxide selected from the group consisting of
9. A process for the production of a salicylaldehyde
alkali metal phenoxides, alkaline earth metal phenoxides
compound selected from the group consisting of salicyl—
and aluminum phenoxides, at a temperature in the range
of from about 100° to about 350° C. and at a pressure 30 aldehyde and alkyl salicylaldehydes which comprises heat
ing a phenol in which at least one carbon atom ortho to
in the range of from about ‘atmospheric to about 300
the hydroxy substituent has hydrogen attached thereto,
atmospheres in a proportion and for a sufficient time to
selected from the group consisting of phenol and mono
form the desired salicylaldehyde, and recovering the last
alkyl- and dialkylphenols, said alkyl radicals containing
mentioned compound.
3. A process for the production of S-methyl salicyl 35 from 1 to about 18 carbon atoms, with carbon monoxide
and magnesium o-ethylphenoxide at a temperature in the
aldehyde which comprises heating p-cresol with carbon
monoxide and a phenoxide selected from the group con
range of from about 100° to about 350° C. and at a
pressure in the range of from about atmospheric to about
sisting of alkali metal phenoxides, alkaline earth metal
phenoxides and aluminum phenoxides, at 7a temperature 4.0 300 atmospheres in a proportion and for a sufficient time
to form the desired salicylaildehyde compound, and re
in the range of from about 100° to about 350° C. and
at a pressure in the range of from about atmospheric
to about 300 atmospheres in a proportion and for a suf
covering the last-rrrentioned compound.
hyde which comprises heating io-rethylphenol with carbon
the hydroxy substituent has hydrogen attached thereto,
monoxide and a phenoxide selected from the group con
selected from the group consisting of phenol and mono
10. A process for the production of a salicylaldehyde
compound selected from the group consisting of salicyl
?cient time to form the desired 5-methyl salicylaldehyde,
aldehyde and alkyl salicylaldehydes which comprises heat
and recovering the last-mentioned compound.
4. A process for the production of 3-ethyl salicylalde 45 ing a phenol in which at least one carbon atom ortho to
sisting of alkali metal phenoxides, alkaline earth metal
phenoxides and aluminum phenoxides, at a temperature
alkyl- and dialkylphenols, said alkyl radicals containing
from 1 to about 18 carbon atoms, with carbon monoxide
in the range of from about 100° to about 350° C. and at 50 and potassium p-dodecylphenoxide at a temperature in
the range of from about 100° to about 350° C. and at a
a pressure in the range of from about atmospheric to
pressure in the range of from about atmospheric to about
about 300 atmospheres in a proportion and for a suf?cient
300 atmospheres in a proportion and for a su?icient time
time to vform the desired 3-ethyl salicylaldehyde, and re
to form the desired salicylaldehyde compound, and re
covering the llast-mentioned compound.
5. A process for the production of 5-dodecyl salicyl 55 covering the last-mentioned compound.
M. A process for the production of a salicylaldehyde
aldehyde which comprises heating p-dodecylphenol with
compound selected from the group consisting of salicyl
carbon monoxide and a phenoxide selected from the group
aldehyde and alkyl salicylaldehydes which comprises heat
consisting of alkali metal phenoxides, alkaline earth metal
ing a phenol in which at least one carbon atom ortho
phenoxides and aluminum phenoxides, at a temperature
in the range of from about 100° to about 350° C. and at 60 to the hydroxy substituent has hydrogen attached thereto,
selected from the group consisting of phenol and mono
a pressure in the range of from about atmospheric to
alkyl- and dialkylphenols, said alkyl radicals containing
about 300 atmospheres in a proportion and for a su?icient
from 1 to about 18 carbon atoms, with carbon monoxide
time to form the desired 5-dodecyl salicylaldehyde, and
and sodium p-octadecylphenoxide at a temperature in the
recovering the last-mentioned compound.
6. A process for the production of 5-octadecyl salicyl— 65 range of from about 100° to about 350° C. and at a
pressure in the range of from about atmospheric to about
aldehyde which comprises heating p-octadecylphenol with
300 atmospheres in a proportion and for a su?icient time
carbon monoxide and a phenoxide selected from the group
to form the desired salicylaldehyde compound, and re
consisting of alkali metal phenoxides, alkaline earth metal
phenoxides and aluminum phenoxides, at a temperature 70 covering the l-ast-mentioned compound.
12. A process for the production of salicylaldehyde
in the range of from about 100° to about 350° C. and at
a pressure in the range of from about atmospheric to
about 300 atmospheres in a proportion and for a sui?cient
time to form the desired 5~octadecyl salicylaldehyde, and
recovering the last-mentioned compound.
which comprises heating phenol with carbon monoxide
and aluminum phenoxide at a temperature in the range
of from about 100° to about 350° C. ‘and at a pressure
75 in the range of from about atmospheric to about 300
3,098,875
10
atmospheres in a proportion and for a su?icient time to
form the desired salicylaldehyde, and recovering the last
mentioned compound.
13. A process for the preparation of S-methyl-salicyl
aldehyde which comprises heating p-cresol with carbon
15. A process for the production of S-dodecylsalicyl
aldehyde which comprises heating p-dodecyiphenol with
carbon monoxide and potassium p-dodecylphenoxide at a
temperature in the range of from about 100° to about
350° C. and at a pressure in the range of from about
monoxide and 'sodium p-methylphenoxide at a tempera
atmospheric to about 300 atmospheres in a proportion
ture in the range of from about 100° to about 350° C.
and for a sufficient time to form the desired 5-dodecy1
and at a pressure in the range of from about atmospheric
salicylaldehyde, and recovering the last-mentioned com
to about 300 atmospheres in a proportion and for a suf
pound.
?cient time to form the desired S-methylsalicylaldehyde, 10
d6. A process for the pnoduction of S-hexadecylsalicyl
and recovering the last-mentioned compound.
14. A process for the production of 3-ethy1sa1icyla1de
aldehyde which comprises heating p-octadecylphenoi with
carbon monoxide and sodium p-octadecylphenoxide at a
hyde which comprises heating o-ethylphenol with carbon
temperature in the range of from about 100° to about 35 0°
monoxide and magnesium o-ethylphenoxide at a temper
C. and at a pressure in the range of from about atmos
ature in the range of from about 100° to about 350° C. 15 pheric to about 300 atmospheres in a proportion and for
and at a pressure in the range of from about atmospheric
a su?icient time to form the desired 5-octadecylsa1icy1
to about 300 atmospheres in ya proportion and for a suf
aldehyde, and recovering the last-mentioned compound.
?cient time to form the desired 3-ethy1salicylaldehyde,
and recovering the last-mentioned compound.
No references cited.
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