JPS63122644A - Production of 3,5,5-trimethylcyclohex-2-ene-1,4-dione - Google Patents

Abstract

PURPOSE:To industrially and advantageously obtain the titled compound in high yield, by oxidizing 3,5,5-trimethylcyclohex-3-en-1-one with molecular oxygen or a molecular oxygen-containing gas in the presence of an organic base and specific cobalt complex catalyst. CONSTITUTION:3,5,5-Trimethylcyclohex-3-en-1-one (beta-isophorone) is oxidized with molecular oxygen or a molecular oxygen-containing gas is the presence of an organic base and a cobalt catalyst expressed by the formula [R<1>-R<4> are H, 1-4C hydrocarbon group, further R<1>-R<3> are 1-4C alkoxy, halogen or NO2; X is 2-15C bifunctional hydrocarbon group of 4-10C bifunctional hydrocarbon group having NR<5> (R<5> is H or 1-7C hydrocarbon group) therebetween; Y is halogen, OH, 4-15C tertiary alkoxy, 4-15C tertiary alkylperoxy, 1-5C acyloxy, etc.] to advantageously afford the aimed compound useful as perfumes, etc., with suppressed formation of hardly separable by- products by polymerization or side reaction of the beta-isophorone.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is highly evaluated as a flavoring agent for foods, cosmetics, tobacco, etc., and is also useful as a raw material for manufacturing pharmaceuticals such as carotenoids and vitamin E, and fragrances. 3,5,5-trimethylcyclohex-2-ene- useful as
The present invention relates to a method for producing 1,4-dione.

[Conventional technology]

Conventionally, various methods for producing 3,5,5-trimethylcyclohex-2-ene-1°4-dione have been proposed. 3,5.5- in West German Patent No. 2,356,546
Trimethylcyclohex-2-en-1-one (hereinafter α
-inphoron) was oxidized with chromium oxide in a mixed solvent of acetic acid and acetic anhydride to give a yield of about 50% of α-inphoron (3.5.5-)dimethylcyclohex-2- Synthesizing ene-1,4-dione.

This method has a low conversion rate and yield, has the risk of explosion due to the use of a large excess of chromium oxide relative to α-inphorone, is expensive to produce, and requires a large amount of chromium wastewater treatment. The disadvantage is that it requires a lot of effort. Furthermore, in West German Patent No. 457,158, α-inphorone was oxidized with oxygen in the gas phase in the presence of a vanadium catalyst to obtain a yield of about 30% compared to α-inphorone.
．． 5.5-trimethylcyclohex-2-ene-1,4
-Diones are synthesized. This method has low conversion and yield, but only 45.5-dimethyl-3-formylcyclohex-2-en-1-one. What is 4-dione? It has the disadvantage that the same amount is produced as a by-product. Furthermore, in West German Patent No. 2,459,148, α-inphorone is oxidized with oxygen in the active phase in the presence of an iron acetyl or cobalt catalyst and a rhodium (I) tristriphenylphosphine chloride catalyst. 3.5.5-trimethylcyclohex-2-ene- with a yield of about 30%.
1°4-dione is synthesized. This method has the drawbacks of poor selectivity and yield. Furthermore, JP-A-61-
In No. 191645, 3.5.5-trimethylcyclohex-2-ene was obtained in about 50% yield by oxygen-oxidizing α-inphorone in the presence of an alkali metal or aromatic amine and phosphomolybdic acid or silicomolybdic acid. -1,4-dione is synthesized. In this method, the conversion rate and yield are low, and the 3,5.5-t! It has the disadvantage that the reaction product contains approximately the same amounts of J methylcyclohexane-2-ene-1,4-dione and α-inphorone, which is a raw material that is difficult to separate.

Next, in French patent 2.25λ730, 3,5,5-trimethylcyclohex-3-en-1-one (hereinafter β-
Inphoron (hereinafter referred to as inphoron) was oxidized with oxygen in the presence of a tertiary amine and a copper (Il) salt of pyridine in an alcoholic solvent in a yield of approximately 30% relative to β-inphoron.
．． 5.5-trimethylcyclohex-2-ene-1,4
-Completely synthesizes dione. This method has low yield and β
- It has the disadvantage that a polymer of inholon is produced as a by-product. Also, in the West German patent 2.457°157, β
- Inphoron Q β-Inphoron is subjected to oxygen oxidation for about 35 hours in the presence of an acetylacetonate complex catalyst derived from a transition metal such as vanadium, chromium, copper, manganese, iron, cobalt, or nickel. 3.5.5-)riftylcyclohexane with the highest yield of 55%
Synthesizing 2-ene-1,4-dione. This method has the disadvantage that the reaction time is long and the yield is low.

[Issues that the invention attempts to violate]

The object of the present invention is to provide an industrially advantageous method for producing 3.5.5-trimethylcyclohex-2-ene-1,4-dione gold by overcoming the disadvantages or deficiencies of the prior art as described above. It is in.

[Means to solve the problem]

The present invention combines 3,5,5-)limethylcyclohex-3-nin-1-one (β-inphorone), an organic base, and the general formula (
1) (However, in the formula, R1, R2 and R3 may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom or a nitro group. , R4 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X represents 2 having 2 to 15 carbon atoms.
valent hydrocarbon group, or a divalent hydrocarbon group having 4 to 10 carbon atoms with -NR8- (R5 represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms), and Y is ,
Halogen atom, hydroxyl group, tertiary alkoxy group having 4 to 15 carbon atoms, tertiary alkylperoxy group having 4 to 15 carbon atoms, acyloxy group having 1 to 5 carbon atoms, trifluoroacetate group, trifluoroethoxy group, or 3,5.5-) Samethicine-lohexa-2-2-2-1, which is characterized by being oxidized with molecular oxygen or molecular oxygen base gas in the presence of a cobalt catalyst represented by l), which represents a trichloroethoxy group. .4-Dione production method.

By using the method of the present invention, compared to the conventional method,
Polymerization and side reactions of β-inphorone are suppressed, 3,5.5
-) IJ methylcyclohex-2-ene-1,4-dione and by-products that are difficult to separate are not produced and the yield is 3.5.5.
-) IJ Methylcyclohex-2-ene-1,4-dione can be produced industrially and efficiently.

β-inphorone used in the present invention can be synthesized by distilling α-inphorone in the presence of P-toluenesulfonic acid (US Pat. No. 3,385,902).

Furthermore, the cobalt complex catalyst used in the present invention has the general formula (1
) Essentially any compound can be used as long as all the compounds are satisfied.

In general formula (1), examples of R1, R2, and R3 include hydrogen atoms, alkyl groups such as methyl, ethyl, and propyl;
Alkoxy groups such as methoxy and ethoxy, chlorine, fluorine,
Examples of R4 include hydrogen, alkyl groups such as methyl, ethyl, and chlorovir, and X includes linear alkylene groups such as ethylene, fluoropyrene, butylene, and hydrogen of alkylene groups. Substituents whose atoms are substituted with an alkyl group such as methyl or ethyl or a cycloalkyl group such as cyclohexyl are bonded together to form a ring structure such as a cycloalkyl group or an aromatic group, or even in an alkylene group. -NR5- (R11 is hydrogen or an alkyl group such as methyl or ethyl) is present. Examples of these R1, R2, R3, R4, and X, and examples of Y are illustrated in Table 1 along with the compound names. The compound names shown in Table 1 are described as cobalt complex catalyst groups.

The method for synthesizing the cobalt complex catalyst used is well known (Ch
emistry Letters, 1715~l
754.1983). For example, tertiarybutylbaroxycobaltsalen is produced by a method in which N,N'-salicyalethylenediaminecobal) (Il) (hereinafter referred to as cobaltsalen) is reacted with tertiarybutylperoxide in a methylene chloride solution at room temperature. can be synthesized.

Tertiary butyl peroxycobalt salen is produced by a method of carrying out a triphenylphosphinde reaction with tertiary butyl peroxycobalt, and hydroxycopal to salen is produced by heating tertiary butyl peroxycobalt salen at 40 to 50°C in the presence of air in methanol. It can be synthesized by the following method.

Chlorocobalt salen can be synthesized by reacting tertiary butyl peroxycobalt salen with a salt powder, and acetyloxycobalt salen can be synthesized by reacting tertiary butyl peroxycobalt salen in methylene chloride with acetic acid.

The amount of cobalt complex catalyst to be used for the reaction is preferably 10"' to 0.2 times mole per mole of β-inphorone. Particularly preferably 10" to 0.08 times mole.The selectivity of the reaction is Other molar ratios can be used as long as they do not interfere.The reaction is carried out in the presence of an organic base, but
Organic bases include alkylamines, especially dimethylamine,
Secondary or tertiary amines such as trimethylamine, diethylamine, methylethylamine, triethylamine, dibutylamine, diimpropylamine, ethylbutylamine are preferred. The amount of organic base used is 0.02 to 20 times the mole of β-inphorone, especially 0.
．． 1 to 5 times the molar amount is preferred.

Although the reaction can be carried out in the presence of only an organic base,
It is preferable to carry out the reaction in the presence of other solvents. Reaction solvents include hydrocarbon solvents such as hexane, benzene, toluene, and xylene, diethyl ether, diimpropyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, Ether solvents such as tetrahydrobilane, ketone solvents such as acetone, methyl imbutyl ketone, methyl ethyl ketone, methyl butyl ketone, monochloroethane, dichloromethane, chloroform, carbon tetrachloride,
1. Halogenated solvents such as 2-dichloroethane, alcoholic solvents such as methanol, ethanol, butanol, propatool, carboxamide solvents such as dimethylformamide, dimethylacetamide, diethylformamide, N-methylpyrrolidone, acetonitrile, propiosol, etc. Examples include nitrile-based solvents such as nitrile and butyronitrile, water, and mixed solvents consisting of arbitrary combinations thereof. In particular, the addition of water has the effect of accelerating the conversion rate of β-inphorone. Reaction time is 0.3-6
0 hours, especially 0.5 to 36 hours is preferred. The reaction temperature is preferably -30 to 80°C, particularly 0 to 50°C. The reaction can be carried out at normal pressure or under elevated pressure.

After the reaction is completed, for example, the solvent and organic base are recovered under reduced pressure, and then subjected to steam distillation or poured into a peroxide deactivator such as an excess sodium sulfite aqueous solution, ferric sulfate aqueous solution, or ferric chloride aqueous solution, followed by suitable extraction. Extract with a solvent such as ethyl acetate, benzene, toluene, diethyl ether, carbon tetrachloride, chloroform, dichloroethane, etc., collect the solvent layer, and wash with saturated hydrogen carbonate solution, saturated brine, etc. By drying with a drying agent such as magnesium sulfate and distilling and recovering the solvent, λ5,5-)dimethylcyclohex-2-ene-1,4-dione can be obtained.3. a5-Trimethylcyclohex-2-ene-1,4-dione can be purified by vacuum distillation, column chromatography, recrystallization, etc., if necessary. explain.

Example 1 3.147 f (12
8x10-2 mol), ethylene glycol dimethyl ether 28-, tri 1fk7 mi 71.00? (9,8
8X 10-3 mol), tertiary butyl peroxycobalt salen 0.307f (7,41X 10-' mol)
were mixed, and oxygen was blown into the mixture at a rate of 70 liters per minute at 25 to 30° C. for a total of 9 hours with stirring. Next, diethylene glycol dimethyl ether and triethylamine were recovered under reduced pressure, and 100 de of ethyl acetate was added. Washed with 201Rt of 10T sodium sulfite aqueous solution, 10tnt of saturated sodium bicarbonate aqueous solution, and 20ml of saturated brine in this order, the organic layer was dried over anhydrous magnesium sulfate, filtered, and after recovering ethyl acetate, a liquid residue of 3.526y was obtained. Ta. This product was subjected to simple distillation under reduced pressure to obtain a fraction of 3.059f. This fraction was collected by gas chromatography (FFAP2m, 70
As a result of analysis at ℃~200℃, 5℃/m1n), 3.5
．． 5-1! jMethylcyclohex-2-ene-1,4-
It contained 84.2% dione (yield 74.4%).

Example 2 β-Inphoron Z92 was added to the reaction apparatus described in Example 1 above.
1P (2,11XI O""2 mol), ethylene glycol dimethyl ether 26.4-, triethylamine 0.87? (8,61X10-3 mol), water 1.063
d, tertiary butyl peroxycobalt salen 0.3
5Or (8,45 x 10-' moles) were mixed, and oxygen was blown in at a rate of 70-'/min for 2 hours at 27-32°C under stirring. Next, perform the reaction treatment described in Example 1.3.
15 El of liquid residue was obtained. This product was subjected to simple distillation under reduced pressure to obtain a fraction of 2.700 f. As a result of analyzing this fraction by gas chromatography (conditions described in Example 1), 3,5,5-trimethylcyclohexa-2
It contained 87.0% of -ene-1°4-dione. (
Yield: 73.0%) Example 3 2.9 g of β-inphorone was added to the reaction apparatus described in Example 1 above.
16F (2,11×10-” moles, 26.4 d ethylene glycol dimethyl ether, 0.8 d triethylamine
72f (8,63X10-3 mol), water 1.056d,
cumin bar oxycobalt salen 0.35(1(7,3
4 x 10-' mol) and 1
Oxygen was blown at a rate of 70°/min for 2 hours. Next, the reaction treatment described in Example 1 was carried out to obtain 3.312 tons of liquid residue. 3. This product is subjected to simple hydraulic distillation.
A fraction of 033f was obtained. This fraction was analyzed by gas chromatography (conditions described in Example IK) and the results were 3.5.
It contained 84.2% of 5-trimethylcyclohex-2-ene-1,4-dione. (Yield 79.5%) Example 4 2.9% of β-inholone was added to the reaction apparatus described in Example 1 above.
13F (2,11 x 10-" mole), triethylamine 0.87 F (8,61
4X 10”” moles) and stirred at 29-31°C.
Oxygen was blown in at a rate of 70° per minute for a total of 16 hours.

Next, 500 g of hexane was added. The organic layer was washed with 10 sodium sulfite aqueous solution 20-1 saturated sodium bicarbonate 5-1 saturated brine 30 fnt, and the organic layer was dried and filtered over anhydrous magnesium sulfate. After recovering hexane, a liquid residue of 3.028 f was obtained. . By subjecting this product to simple distillation under reduced pressure, 2. A fraction of 711f was obtained. This fraction was analyzed by gas chromatography (conditions described in Example 1) and the results showed that 3,5.5-)dimethylcyclohex-2-ene-1,
It contained 66.2 units of 4-dione. (Yield 55.6
h) Example 5 β-inphorone 2.9 was added to the reaction apparatus described in Example 1 above.
21? (112X 10-" mol), Trier fk7: 10.82? (8,12 7
. The reaction treatment described in Example 1 was then carried out to obtain a liquid residue of 4.6211. By distilling this product under reduced pressure, 4
．． A fraction of 069F was obtained. The results of analyzing this fraction by gas chromatography (conditions described in Example 1) were 3 and 5.
．． It contained 51.4 units of 5-trimethylcyclohex-2-ene-1,4-dione. (Yield: 65.0%) Example 6 2.9 g of β-inholone was added to the reaction apparatus described in Example 1 above.
22F (12X10-”mol), ethylene glycol dimethyl ether 22-, triethylamine 0.879
(8,61
10-'mol) were mixed and oxygen was blown into the mixture at a rate of 70 ml per minute at 27-30° C. for 17 hours while stirring. Next, the reaction treatment described in Example 1 was carried out to obtain a liquid residue 2 of 3.143 f. By distilling this product under reduced pressure, 2.79
89 fractions were obtained. Analysis of this fraction by gas chromatography (conditions described in Example 1) resulted in 3,3.5-
) It contained 817 units of samethylcyclohex-2-ene-1,4-dione. (Yield 71.9%) Example 7 2.925 β-holon was added to the reaction apparatus described in Example 1 above.
f<zizxio-”mol), ethylene glycol dimethyl ether 26.4 m/, triethylamine 0.84
y (8,32 x 10-” moles), water 1.056 m
, 0.34 of lutosulfene (9,93 x 10'-' mol) were mixed, and oxygen was blown in at a rate of 70 m/min for 2 hours at 27-30°C with stirring. Next, The reaction treatment described in Example 1 was carried out to obtain a liquid residue of 3.238F.This fraction was analyzed by gas chromatography (under the conditions described in Example 1) and the result was 3.5°5-! It contained 84.0% of J methylcyclohexate-2-ene-1,4-dione.

(Yield: 70.0%) Example 8 β-inphoron z91 was added to the reaction apparatus described in Example 1 above.
9t (zizxio” mole), 26.4d ethylene glycol dimethyl ether, 0.87r triethylamine
(8,61X10-3 mol), water 1.075m, hydroxycobalt salen 0.34Of (9,93X10-
'mole) and 70 molar in 1 min at 27-32°C under stirring.
Oxygen was blown at a rate of - for 25 hours. Next, the reaction treatment described in Example 1 was performed and the result was 3.33! A liquid residue of M was obtained. By simple distillation of this material under reduced pressure, 2.951f
A fraction was obtained. Analysis of this fraction by gas chromatography (conditions described in Example 1) revealed that λ5.5-trimethylcyclohex-2-ene-1,4-dione'i84
．． It contained 0. (Yield: 77.1 h) Example 9 β-inphoron z91 was added to the reaction apparatus described in Example 1 above.
9r (2,,12xxo-'' moles), diethylene glycol dimethyl ether 26.4fnt, ) ethylamine 0.97f (9,60X 10''-'' moles), water 1.
076F, acetoxycobalt salen 0.330f
(8,59 x 10'-' moles) and under stirring 27~
Oxygen was blown at a rate of 70 parts per minute at 30°C for 2 hours. Next, the reaction treatment described in Example 1 was performed, and 3.239
A liquid residue of 2 was obtained. This product was subjected to simple distillation under reduced pressure to obtain a fraction of 1823F. This fraction was analyzed by gas chromatography (conditions described in Example 1) and the results were 3.5.5-tri)f-cyclohexar-2-ene-1,
It contained 86.11 4-dione. (Yield 75.6
%) Example 10

Claims (1)

[Claims] 3,5,5-trimethylcyclohex-3-ene-1-
ion as an organic base and the general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) (However, in the formula, R^1, R^2, and R^3 may be the same or different, and each is a hydrogen atom. , represents a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or a nitro group, and R^4 is a hydrogen atom or a nitro group having 1 to 4 carbon atoms.
~4 hydrocarbon group, X is a divalent hydrocarbon group having 2 to 15 carbon atoms, or 1NR^5- (R^5 represents a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms) Y represents a divalent hydrocarbon group having 4 to 10 carbon atoms, and Y represents a halogen atom, a hydroxyl group, a tertiary alkoxy group having 4 to 15 carbon atoms, or a tertiary alkyl group having 4 to 15 carbon atoms. oxy group,
It represents an acyloxy group, trifluoroacetate group, trifluoroethoxy group, or trichloroethoxy group having 1 to 5 carbon atoms. ) 3,5,5-trimethylcyclohex-2-ene-, which is oxidized with molecular oxygen or molecular oxygen-containing gas in the presence of a cobalt complex catalyst represented by
Method for producing 1,4-dione.