United States Patent (19) 11 Patent Number: 4,471,140

All 45 Date of Patent: Sep. 11, 1984

(54) PREPARATION OF AROMATIC
OTHER PUBLICATIONS
ALDEHYDES
75 Inventor: Andrew T. Au, Needham, Mass. Eley et al., Advances in Catalysis, vol. 25, (1976),
272-339, 390-413.
73 Assignee: The Dow Chemical Company,
Midland, Mich. Primary Examiner-Bernard Helfin
(21) Appl. No.: 409,748 Attorney, Agent, or Firm--Douglas N. Deline
22 Filed: Aug. 19, 1982 57) ABSTRACT
(51) Int. Cli.............................................. CO7C 45/28 Aromatic aldehydes are formed by the liquid phase
(52) U.S. C. ................................................... 568/.432 reaction of molecular oxygen with methyl-substituted
58) Field of Search ................ ... . . . . . . . . . . . . 568/431, 432 aromatic compounds in the presence of base, a cobalt,
(56) manganese, chromium or nickel salt catalyst and an
References Cited easily removable amine.
FOREIGN PATENT DOCUMENTS
0012939 7/1980 European Pat. Off... 13 Claims, No Drawings
 4,471,140
1. 2
pound. Examples include alcohols, ethers, halogenated
PREPARATION OF AROMATICALDEHYDES hydrocarbons, dimethylformamide, dimethylsulfoxide,
etc. The solvents may be employed in combination or
BACKGROUND OF THE INVENTION singly. Preferred solvents are alcohols such as metha
The present invention relates to an improved process nol, ethanol, isopropanol, butanol, tertiary butanol,
for the oxidation of methyl-substituted aromatic com ethylene glycol, etc.
pounds. More particularly, the present invention com Bases suitably employed include alkali metal or alka
prises an improved liquid phase catalyst system for the line earth metal hydroxides, alkoxides or amides. Pre
preparation of aromatic aldehydes, especially p-hydrox ferred for their ready availability and low cost are so
ybenzaldehyde. 10 dium or potassium hydroxide. The amount of base em
In U.S. Pat. No. 4,113,782, formylated phenoxy com ployed is from about 1 to about 20 equivalents per
pounds are prepared by air oxidation of methylated equivalent of methyl-substituted aromatic compound,
phenoxy compounds such as p-methoxytoluene in the preferably from about 2 to about 4 equivalents.
liquid phase in the presence of co-catalysts comprising The oxidizing agent is oxygen which may be used
lower fatty acids or anhydrides and at least one soluble 15 singly or mixed with other inert gases. Air is the pre
salt of cobalt, manganese, chromium or nickel. ferred oxygen-containing gas. The amount or concen
In EP No. 12,939 to Sumitomo Chemical Company tration of oxygen is not particularly limited and may be
Ltd., p-cresol is oxidized in the liquid phase by an oxy suitably determined by due consideration of safety and
gen-containing gas in the presence of base and a cobalt convenience. Pressures from 1 to about 100 atmo
compound or metallic cobalt. Cobalt porphyrin com 20
spheres are suitable.
plex was disclosed as a suitable catalyst at page 7, line 4. The reaction temperature is suitably from about 0°C.
Amines were taught to be suitable solvents, however, to about 300 C. and preferably from about 25° C. to
later research has indicated that amines in general are about 100 C.
not suitable solvents. The metal salt catalysts employed are soluble salts
25
SUMMARY OF THE INVENTION having either organic or inorganic anions. Suitable are
According to the present invention, the catalytic halide, organic acid, oxide, hydroxide or inorganic acid
oxidation of methyl-substituted aromatic compounds salts of cobalt, manganese, chromium or nickel. Initially
under basic conditions in the liquid phase by the action the metal may be added in any available valence. Exam
of an oxygen-containing gas in the presence of soluble 30 ples of the metal salt catalysts of the invention are fluo
cobalt, manganese, chromium or nickel salts is im ride, chloride, bromide, iodide, acetate, oxalate, stea
proved and advanced over previously known liquid rate, naphthenate, nitrate, sulfate, carbonate, oxide or
phase processes by additionally adding to the system an hydroxide salts of the above metals. Preferred catalysts
easily removable amine. are divalent or trivalent cobalt salts.
The amount of soluble metal salt employed is not
35
DETAILED DESCRIPTION OF THE critical. Suitably from about 0.001 to 1, and preferably
INVENTION from about 0.01 to 0.1 equivalents of metal salt per
Methyl-substituted aromatic compounds that are se equivalent of methyl-substituted aromatic compound
lectively oxidized according to the present invention may be employed.
are those previously known and taught in the art. Suit Additionally present according to the instant process
able compounds are those of the formula is an easily removable amine. By the term "easily re
movable' is meant amines that may be removed from
R the resulting product by volatilization, e.g., low boiling
easily distillable amines, or those that are removed by
45 treatment with aqueous acid.
CH3 Suitable amines are primary, secondary or tertiary
aliphatic, cycloaliphatic or aromatic amines, or di
amines of up to about 12 carbons. Examples of suitable
wherein R is hydroxyl or C1-4 alkoxy, R' is halo, lower 50 easily removable amines include ammonia (either sup
alkyl or hydrogen. Specific examples of suitable meth plied as free ammonia or an ammonium salt such as
ammonium hydroxide), trimethylamine, trietylamine,
yl-substituted aromatic compounds for use according to dimethylamine, dicyclohexylamine, ethylenediamine,
the invented process are p-cresol, 2,6-dichloro-p-cresol, tetramethylethylenediamine, piperidine, pyridine, dime
2-bromo-p-cresol, 2,4-xylenol, 3,4-xylenol, 2,6-di-tert thylaminopyridine, etc. Preferred easily removable
butyl-p-cresol, p-methoxytoluene, 4-methoxy-2,6- amines are dialkylamines, trialkylamines, tetraalkyl-sub
dichlorotoluene, etc. 55
Preferred methyl-substituted aromatic compounds stituted ethylenediamines and cycloaliphatic amines.
are cresols, especially p-cresol, which is converted by Most preferred amines are piperidine, ammonia, tri
the instant oxidation to p-hydroxybenzaldehyde. The methylamine and triethylamine.
aromatic aldehyde products of the instant process are Because such easily removable amines may be dis
known compounds having utility as intermediates in the 60 tilled from the product or otherwise removed by acid
preparation of pharmaceuticals, agricultural chemicals, washing, they are easily separated from the reaction
polymeric resins and other industrial chemicals. products and reused if desired. The prior art catalyst,
The process is conducted in the liquid phase. While cobalt porphyrin, is not easily removable by either acid
the methyl-substituted aromatic compound may itself washing or distillation and is therefore present as a
form the liquid phase, it is preferred to add a liquid 65 contaminant of the desired aromatic aldehyde or lost as
solvent. Suitable liquids are organic compounds that are part of the reaction tars. Considering the initial expense
inert under the reaction conditions employed and capa of porphyrin chelants compared to the present easily
ble of dissolving the methyl-substituted aromatic com removable amines, their subsequent loss is a consider
 4,471,140
3 4.
able economic waste. Therefore, the present invention 1. A process for preparing aromatic aldehydes com
offers a greatly improved method for preparing aro prising contacting a methyl-substituted aromatic com
matic aldehydes. pound corresponding to the formula:
The amine is employed in minor amounts sufficient to
form complexes with the metal salt. A preferred amount R
is about a stoichiometric amount or a slight excess
thereover up to about a 10 percent excess of a stoichio CH3
metric amount based on the complex formed.
SPECIFICEMBODIMENTS 10
Having described the invention, the following exam wherein R is hydroxyl or C14 alkoxy, and R is halo,
ples are provided as further illustrative and are not to be lower alkyl or hydrogen, with an oxygen-containing
construed as limiting its scope. gas at a pressure from about 1 to about 100 atmospheres
15
and a temperature from about 0° C. to about 300 C. in
EXAMPLE 1. the presence of base, a metal salt catalyst selected from
A mixture of 21.0 g of p-cresol, 24.0 g of crushed the soluble organic or inorganic salts of cobalt, manga
sodium hydroxide and 1.0 g of cobalt dichloride hexa nese, chromium and nickel, a liquid solvent and a minor
hydrate in 125 ml of methanol containing 20 drops of amount sufficient to form a complex with the metal salt
piperidine is stirred rapidly between 60° C.-65C. while 20
of an easily removable amine.
oxygen is bubbled into the mixture. After 18 hours, gas 2. A process according to claim 1 wherein the easily
chromatograph results indicate almost total absence of removable amine is a primary, secondary or tertiary
p-cresol. The mixture is then cooled, neutralized with aliphatic, cycloaliphatic or aromatic amine or diamine
dilute HCl, saturated with NaCl and extracted with of up to about 12 carbons.
3. A process according to claim 1 wherein the easily
ethyl acetate. The extract is washed with saturated 25
removable amine is selected from the group consisting
sodium chloride solution, dried over magnesium sulfate of ammonia, trimethylamine, triethylamine, dimethyl
and concentrated to a brown solid (22.4 g). When crys amine, tetramethylethylenediamine, piperidine . . and
tallized from a 50/50 volume mixture of chloroform dimethylaminopyridine.
/hexane, 14.7 g of the desired parahydroxybenzalde 30
4. A process according to claim 1 wherein the metal
hyde is collected on a filter (62.7 percent yield). This salt catalyst is a metal hydroxide or a metal salt of an
material is in every way identical to an authentic sam organic acid or inorganic acid.
ple. 5. A process according to claim 1 wherein the metal
EXAMPLE 2
salt catalyst is a cobalt salt.
35
6. A process according to claim 1 wherein from about
The reaction conditions of Example 1 are substan 0.001 to 1 equivalent of metal salt catalyst per equiva
tially repeated employing the easily removable amines lent of methyl-substituted aromatic compound is pres
further identified in Table I. In the tests 3.0 g of p ent.
cresol, 3.6 g of NaOH, 25 ml of methanol, 0.4 g of 7. A process according to claim 1 wherein a solvent is
CoCl2.6H2O and the indicated amine ae combined and 40
additionally present,
stirred while O2 is bubbled through the reaction mix 8. A process according to claim 7 wherein the solvent
ture. Conversion is determined by gas chromatograph is an alcohol, ether, halogenated hydrocarbon, or mix
ture thereof.
analysis after the indicated time period. Results are 9. A process according to claim 8 wherein the solvent
contained in Table I. is methanol.
45
TABLE I 10. A process according to claim 1 wherein the meth
% Conversion. After yl-substituted aromatic compound is p-cresol and the
Amine Amount 6 hours 10 hours aromatic aldehyde formed is p-hydroxybenzaldehyde.
None 25 55 11. A process according to claim 1 wherein the tem
(conc) NH4OH -0.2 ml 52 95 50
perature is from about 25 C. to about 100 C.
tetramethylethyl- -0.2 ml 66 12. A process according to claim 1 wherein the
enediamine amount of easily removable amine is from about a stoi
dicyclohexylamine
4-dimethylamino-
-0.2 m
0.15 g
50
50
--- chiometric amount based on the complex formed to
pyridine about a 10 percent excess thereover.
13. A process according to claim 1 wherein the sol
vent is an alcohol.
What is claimed is: k s

65