JP3216268B2 - Epoxide manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxide represented by the general formula (2). The epoxide is an important compound as a synthetic intermediate when producing various products including fragrances, medicines, agricultural chemicals, liquid crystals, resins, and the like.

[0002]

The conversion of olefins to the corresponding epoxides using peracids such as peracetic acid and m-chloroperbenzoic acid is well known (Some Modern Methods of Organic
Synthesis 3rd ed. P370-373). However, since peracids have high impact sensitivity and explosive properties, they cannot be said to be an advantageous production method from an industrial viewpoint. In order to solve such a problem, oxygen oxidation is carried out using a catalyst containing a soluble praseodymium compound in the presence of an aldehyde (JP-A-59-231077) or a soluble nickel catalyst (Chem. Lett., 1991, 1). A method has been developed. However,
Since it is a homogeneous catalyst, the separation of the target product epoxide from the catalyst and the recovery of the catalyst become complicated, and if the catalyst is not recovered, the load on the wastewater is large. It is hardly enough.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an advantageous process for producing epoxides by oxygen oxidation of olefins using a catalyst which is easy to obtain and recover and has a low drainage load in the presence of an aldehyde. It is in.

[0004]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems, and have reached the present invention. That is, the present invention relates to the general formula (1) (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom (C ₁ -C ₂₀ ) alkyl group, (halogen, hydroxy, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, Or a phenyl group substituted with phenoxycarbonyl)
Phenyl group (substituted with halogen, alkyl, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, or phenoxycarbonyl), phenylalkyl group, (halogen, alkyl, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, or phenoxycarbonyl A phenylalkyl group, an acyl group, an alkoxycarbonyl group, or a phenoxycarbonyl group, wherein R ¹ and R ² or R ¹
And R ³ may be mutually bonded to form a ring, or R ¹ , R ² and R ³ may be simultaneously bonded to form a condensed ring. ) And oxygen in the presence of aldehydes as metal catalysts such as Fe and Fe ₂
General formula (2) characterized in that the reaction is performed in the presence of only one or more metal-based catalysts selected from O ₃ , Cu, Cu (OH) ₂ , Cu ₂ O, and CuO. (Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above).

In the present invention, examples of the olefin represented by the general formula (1) used as a raw material include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and pentadecene. Eicosene, methylbutene, methylpentene, methylhexene, methylheptene, methyldecene, methyltetradecene, dimethylbutene, dimethylpentene, dimethylhexene, dimethylheptene, dimethyldecene, trimethylnonene, ethylpentene, ethylhexene, ethylheptene, n-propylnonene, Tetramethylnonene, tetramethyldecene,
Ethyl-n-propyldecene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclododecene, methylcyclopentene, methylcyclohexene, ethylcyclohexene, ethylcyclooctene, dimethylcyclohexene, norbornene, pinene, allyl chloride, allyl bromide, crotyl chloride, bromide Crotyl, 1,
4-dichlorobutene, pentenol, cyclohexenol, terpineol, methylpentenyl ether, cyclohexenylethyl ether, cyclohexenylphenyl ether, pentenyl acetate, cyclohexenyl acetate,
Pentenone, hexenone, heptenone, methyl hexenoate, ethyl oleate, phenyl hexenoate, phenyl oleate, styrene, methyl styrene, ethyl styrene, stilbene, p-chlorostyrene, m-chlorostyrene, p-methylstyrene, p-ethyl Styrene, p-
Methoxystyrene, p-ethoxystyrene, methylisoeugenol, m-phenoxystyrene, p-acetoxystyrene, p-acetylstyrene, p-methoxycarbonylstyrene, p-phenoxycarbonylstyrene,
Phenylbutene, phenylpentene, phenylhexene, phenyloctene, p-chlorophenylbutene, m
-Chlorophenylbutene, p-methylphenylbutene,
p-ethylphenylbutene, p-methoxyphenylbutene, p-ethoxyphenylbutene, m-phenoxyphenylbutene, p-acetoxyphenylbutene, p-acetylphenylbutene, p-methoxycarbonylphenylbutene, p-phenoxycarbonylphenylbutene, Examples include cyclohexenone, methyl cinnamate, methyl p-methoxycinnamate, phenyl cinnamate, cholesterol, cholesteryl acetate and the like. In addition, the substitution position of the olefin is arbitrary and includes the geometric isomer.

The epoxide which is the object compound of the present invention is
By using the olefin, it can be obtained as an epoxide represented by the general formula (2), for example, ethylene oxide, propylene oxide, butene oxide,
Pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, undenene oxide, dodecene oxide, pentadecene oxide, eicosene oxide, methylbutene oxide, methylpentene oxide, methylhexene oxide, methylheptene oxide , Methyl decene oxide, methyl tetradecene oxide, dimethyl butene oxide, dimethyl pentene oxide, dimethyl hexene oxide, dimethyl heptene oxide, dimethyl decene oxide, trimethyl nonene oxide, ethyl pentene oxide, ethyl hexene oxide, ethyl heptene oxide, n- Propyl nonene oxide, tetramethyl nonene oxide, tetramethyl decene oxide, ethyl-n
-Propyldecene oxide, cyclopentene oxide,
Cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, cyclododecene oxide, methylcyclopentene oxide, methylcyclohexene oxide, ethylcyclohexene oxide, ethylcyclooctene oxide, dimethylcyclohexene oxide, norbornene oxide, pinene oxide, epichlorohydrin, epichlorohydrin Bromohydrin, 1-chloro-2,3-epoxybutane, 1-bromo-2,3-epoxybutane,
1,4-dichloro-2,3-epoxybutane, epoxypentanol, epoxycyclohexanol, terpineol oxide, epoxypentyl methyl ether, epoxycyclohexylethyl ether, epoxycyclohexylphenyl ether, epoxypentyl acetate, epoxycyclohexyl acetate, epoxypentanone , Epoxyhexanone, epoxyheptanone, methyl epoxyhexanoate, ethyl epoxyoctadecanoate, phenyl epoxyhexanoate, phenylepoxyoctadecanoate, styrene oxide, methylstyrene oxide, ethylstyrene oxide, stilbene oxide, p-chlorostyrene oxide, m- Chlorostyrene oxide, p-
Methylstyrene oxide, p-ethylstyrene oxide, p-methoxystyrene oxide, p-ethoxystyrene oxide, 1- (3 ′, 4′-dimethoxyphenyl)
-1,2-epoxypropane, p-acetoxystyrene oxide, p-acetylstyrene oxide, p-methoxycarbonylstyrene oxide, p-phenoxycarbonylstyrene oxide, phenylbutene oxide, phenylpentene oxide, phenylhexene oxide, phenyloctene oxide, p-chlorophenylbutene oxide, m-chlorophenylbuteneoxide, p-methylphenylbuteneoxide, p-ethylphenylbuteneoxide, p-methoxyphenylbuteneoxide, p-
Ethoxyphenylbutene oxide, m-phenoxyphenylbuteneoxide, p-acetoxyphenylbuteneoxide, p-acetylphenylbuteneoxide, p-methoxycarbonylphenylbuteneoxide, p-phenoxycarbonylphenylbuteneoxide, epoxycyclohexanone, 3-phenylglycide Methyl acid, 3-
Examples thereof include methyl (4-methoxyphenyl) glycidate, phenyl 3-phenylglycidate, 5,6-epoxy-3-cholestanol, and 5,6-epoxy-3-cholestanyl acetate.

[0007] Metal-based catalysts are iron-based catalysts and copper-based catalysts. Examples of iron-based catalysts include Fe or Fe ₂ O ₃ . Examples of copper catalysts include Cu, Cu (OH) ₂ , C
u ₂ O or CuO. Further, a mixture of these, or a catalyst in which these catalysts are supported on heteropolyacid, silica gel, carbon powder, polymer, or the like may be used. The amount used is not particularly limited, but usually,
It is in the range of 0.01 to 120 mol%, preferably 0.1 to 10 mol%, based on the olefin.

The aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal, decanal, 2-methylpropanal, 2-methylbutanal, cyclohexanecarboxaldehyde, isovaleraldehyde, benzaldehyde, m -Chlorobenzaldehyde, p-chlorobenzaldehyde, p-tolualdehyde, p-anisaldehyde, pivalaldehyde and the like. In the case of no catalyst, 2-methylpropanal,
2-Methylbutanal, isovaleraldehyde, pivalaldehyde are preferred. Although the amount of use is not particularly limited, it is usually in the range of 1 to 30 mole times, preferably 1 to 10 mole times with respect to the olefin.

[0009] The addition of a proton source is particularly effective when the transition metal catalyst is a simple substance. As the proton source, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, trifluoroacetic acid, propanoic acid, butyric acid, heptanoic acid, decanoic acid, benzoic acid, p
-Toluene sulfonic acid, hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid,
Water and the like are preferred, and acetic acid and benzoic acid are preferred. Although the amount of use is not particularly limited, it is usually in the range of 1 to 100 moles per mole of the iron-based or copper-based catalyst.
However, when the iron-based or copper-based catalyst has water, a proton source is not particularly required.

In the present invention, a solvent may be used. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, chloroform and ethylene dichloride, esters such as ethyl acetate, nitriles such as acetonitrile, benzene and toluene. , Xylene, monochlorobenzene, dichlorobenzene, and other aromatic hydrocarbons.

As the oxygen used in the present invention, air may be used in addition to oxygen, and the supply method thereof is not particularly limited, but it may be blown, in an oxygen atmosphere or the like, and may be at normal pressure or under pressure. The method of charging is not particularly limited, but when Fe ₂ O ₃ is used, it is preferable to charge the olefin last. The reaction temperature is generally in the range of 0 ° C. to the reflux temperature of the reaction mixture, and preferably in the range of 20 ° C. to 80 ° C. The reaction time is not particularly limited, but the reaction mixture may be analyzed by GC or the like, and the time when the production rate of the target epoxide reaches a plateau may be determined as the reaction end point, and is usually in the range of 1 to 48 hours.

In the present reaction, the aldehyde used becomes the corresponding carboxylic acid, and can be easily separated from the desired product. After the completion of the reaction, for example, after filtering and recovering the catalyst, the filtrate is washed with an aqueous sodium hydrogen carbonate solution, and then concentrated.
If necessary, the desired epoxide can be obtained by operations such as rectification.

[0013]

According to the present invention, an iron-based or copper-based catalyst which can be easily obtained and recovered in the presence or absence of a proton source in the presence or absence of an aldehyde, and has a small drainage load, is used to convert the corresponding epoxide from an olefin with oxygen. Is an industrially excellent production method which can obtain under moderate conditions.

[0014]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Examples 1 and 2 A solution of 914 mg of heptanal in 2 ml of dichloromethane was added to a mixture of 164 mg of cyclohexene, 1 mol% of catalyst (based on cyclohexene), 1.2 mg of acetic acid and 10 ml of dichloromethane at 25 ° C. under an oxygen atmosphere for 1 hour. Over and dripping,
The mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC, and the results shown in Table 1 were obtained.

[Table 1] ^{* 1} vs. cyclosexene

EXAMPLE 3 281 mg of 1-decene, 1 mol% of catalyst (based on 1-decene), 1.2 mg of acetic acid, 685 mg of heptanal and 1 part of dichloromethane
0 ml of the mixture was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 2 were obtained.

[Table 2] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 4 to 9 A mixture of 281 mg of 1-decene, 1.1 mg of Fe, 1.2 mg of acetic acid, 6 mmol of aldehyde and 10 ml of dichloromethane was prepared.
The mixture was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 3 were obtained.

[Table 3] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 10 to 14 281 mg of 1-decene, 1.1 mg of Fe, 1 mol% of acid (based on 1-decene), 685 mg of heptanal and 10 parts of dichloromethane
The ml mixture was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 4 were obtained.

[Table 4] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 15 to 17 A mixture of 281 mg of 1-decene, 1.1 mg of Fe, 2.4 mg of benzoic acid, 685 mg of heptanal and 10 ml of a solvent was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. The reaction mixture was analyzed by GC and the results shown in Table 5 were obtained.

[Table 5] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 18 and 19 A mixture of 281 mg of 1-decene, 1.1 mg of Fe, 2.4 mg of benzoic acid, heptanal and 10 ml of dichloromethane was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. G the reaction mixture
Analysis by C gave the results shown in Table 6.

[Table 6] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 20 to 22 A mixture of 281 mg of 1-decene, 2.4 mg of Fe, benzoic acid, 685 mg of heptanal and 10 ml of dichloromethane was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. G the reaction mixture
Analysis by C gave the results shown in Table 7.

[Table 7] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 23-30 2 mmol of olefin, 1.1 mg of Fe, 2.4 mg of benzoic acid,
A mixture of 685 mg of heptanal and 10 ml of dichloromethane was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. The reaction mixture was analyzed by GC and the results shown in Table 8 were obtained.

[Table 8] ^{* 1 for} olefins, ^{* 2 for} olefins, Figures in parentheses are for olefins consumed.

Examples 31-35 Instead of 685 mg of heptanal, 517 mg of pivalaldehyde
The results shown in Table 9 were obtained in the same manner as in Examples 23 to 30 except for using.

[Table 9] ^{* 1 for} olefins, ^{* 2 for} olefins, Figures in parentheses are for olefins consumed.

Examples 36 to 39 A mixture of 272 mg of α-pinene, 1.1 mg of Fe, 2.4 mg of benzoic acid, 6 mmol of aldehyde and 10 ml of dichloromethane was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 10 were obtained.

[Table 10] ^{* 1} vs. α-pinene. ^{* 2} vs. α-pinene. Figures in parentheses indicate consumption α-pinene.

Example 40 561 mg of trans-5-decene, 2.2 mg of Fe, 2.4 mg of acetic acid
And a mixture of 20 ml of dichloromethane under an oxygen atmosphere 2
At 5 ° C, a solution of 1.83 g of heptanal dissolved in 4 ml of dichloromethane was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC with the following results. Conversion: 87% Trans-5-decene oxide yield: 84% (vs trans-5-decene) 97% (vs trans-5-decene) cis-5-decene oxide Yield: 3% (vs trans- 3-decene) 3% (to trans-5-decene consumed)

Examples 41-51 A mixture of 637 mg of benzaldehyde, 3.2 mg of Fe ₂ O ₃ and 12 ml of benzene was stirred vigorously at room temperature under an oxygen atmosphere, followed by the addition of 2 mmol of olefin over 0.5 hours. After the addition was completed, the mixture was further stirred at the same temperature for 17 hours.
The reaction mixture was analyzed by GC and the results shown in Table 11 were obtained.

[Table 11] ^{* 1} vs. olefins, ^{* 2} vs. olefins, Figures in parentheses indicate olefins consumed, ^{* 3} Isolation yield.

Examples 52 to 54 A solution prepared by dissolving 897 mg of cyclohexanecarboxaldehyde in 2 ml of dichloromethane was added to a mixture of 164 mg of cyclohexene, 3 mol% of a solvent (based on cyclohexene), 1.2 mg of acetic acid and 10 ml of dichloromethane at 25 ° C. under an oxygen atmosphere. The mixture was added dropwise over 2 hours, and the mixture was further stirred at the same temperature for 15 hours. The reaction mixture was analyzed by GC and the results shown in Table 12 were obtained.

[Table 12] ^{* 1} vs. cyclohexene

Examples 55 and 56 A mixture of 281 mg of 1-decene, 1 mol% of catalyst (vs. 1-decene), 637 mg of benzaldehyde and 12 ml of dichloromethane was stirred under an oxygen atmosphere at 25 ° C. for 17 hours. The reaction mixture was analyzed by GC and the results shown in Table 13 were obtained.

[Table 13] ^{* 1} : 1-decene, ^{* 2} : 1-decene, and figures in parentheses are consumption 1-decene.

Examples 57-62 2 mmol of olefin,
A mixture of 1.0 mg of Cu (OH) ₂ , 673 mg of cyclohexanecarboxaldehyde and 12 ml of dichloromethane is obtained.
The mixture was stirred at 25 ° C. for 17 hours under an oxygen atmosphere. The reaction mixture was analyzed by GC and the results shown in Table 14 were obtained.

[Table 14] ^{* 1 for} olefins, ^{* 2 for} olefins, Figures in parentheses are for olefins consumed.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-95079 (JP, A) JP-A-47-39016 (JP, A) JP-A-5-112549 (JP, A) 221391 (JP, A) JP-A-48-15808 (JP, A) JP 50-31125 (JP, B1) US Patent 4,483,998 (US, A) US Patent 3,327,716 (US, A) US Patent 3,337,873 (US, A) UK Patent Application Publication 1308380 (GB, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 301/00-301/06

Claims (3)

(57) [Claims] 1. The general formula (1) (Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom (C ₁ -C ₂₀ ) alkyl group, (halogen, hydroxy, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, Or a phenyl group substituted with phenoxycarbonyl)
Phenyl group (substituted with halogen, alkyl, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, or phenoxycarbonyl), phenylalkyl group, (halogen, alkyl, alkoxy, phenoxy, acyloxy, acyl, alkoxycarbonyl, or phenoxycarbonyl A phenylalkyl group, an acyl group, an alkoxycarbonyl group, or a phenoxycarbonyl group, wherein R ¹ and R ² or R ¹
And R ³ may be mutually bonded to form a ring, or R ¹ , R ² and R ³ may be simultaneously bonded to form a condensed ring. ) And oxygen in the presence of aldehydes as metal catalysts such as Fe and Fe ₂
General formula (2) characterized in that the reaction is carried out in the presence of only one or more metal-based catalysts selected from O ₃ , Cu, Cu (OH) ₂ , Cu ₂ O and CuO. (Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above). 2. An olefin represented by the general formula (1) is reacted with oxygen in the presence of an aldehyde, in the presence or absence of a proton source, and in the presence of a metal catalyst. A method for producing the epoxide represented by the general formula (2) according to claim 1 . Wherein aldehyde is 2-methylpropanal, 2-methylbutanal, isovaleric aldehyde or method according to claim 1 or 2 wherein the pivalaldehyde.