JPH01190647A - Production of aldehyde and epoxide compound - Google Patents

Abstract

PURPOSE:To efficiently produce both the title compounds, by oxidizing a compound containing an olefinic carbon-carbon double bond with H2O2 by using at least one of a heteropoly acid and salts thereof as a catalyst and a magnesium sulfate as a dehydrating agent. CONSTITUTION:A compound (e. g. cyclopentene or cyclohexene) containing an olefinic carbon-carbon double bond is oxidized with hydrogen peroxide in the presence of at least one of a heteropoly acid and salts of the heteropoly acid (especially hetero atom is P, A, S, B or Ge, poly atom is Mo, W, Nb or W and metallic salt of group I, II, III or VIII of the periodic table or organic salt of ammonium or amine is preferable) and magnesium sulfate to give an aldehyde and an epoxide compound (e.g. glutaraldehyde and cyclopentene oxide). The reaction rate can be improved under a mild condition and preparation of high-boiling diol as a by-product can be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a method for preparing a heteropolyacid compound containing an olefinic carbon-carbon double bond and hydrogen peroxide in the presence of at least one heteropolyacid salt and magnesium sulfate. The present invention relates to a method for co-producing a corresponding aldehyde and epoxide compound by reacting the same.

Conventional technology Aldehydes are important intermediate raw materials for various chemical products.
Certain aldehydes, such as glutaraldehyde, are also used in applications such as disinfectants, leather tanning agents, and microcapsule hardening agents, and there is a desire to develop inexpensive and efficient production methods.

Conventionally known methods for producing aldehydes include a method of synthesizing L2-diol from an olefin and oxidizing it with an oxidizing agent, or a method of obtaining an oxirane compound (for example, cyclopentene oxide) from an olefin and oxidizing it. Research has also been carried out on gummise directly produced from olefins in consideration of simplification of the reaction route, improvement of the aldehyde ratio, safety, etc. That is, as a method for producing aldehyde using a compound having an olefinic carbon-carbon double bond as a raw material, a method using hydrogen oxide using a boron compound and a molybdenum salt as essential components (Japanese Patent Publication No. 51-28606), A method in which a tungsten compound is added as an essential component and hydrogen oxide is used next week (Japanese Patent Application Laid-open No. 57-95921.), periodic table 4. A method using alkylidene peroxide using one or more compounds of elements of Group 5 and 6, Group 5 and 6, ■b, vb, ■b, ■b, and ■ group elements (Japanese Unexamined Patent Publication No. 145826/1982), etc. be.

In addition, the present inventors have also developed a method using hydrogen peroxide containing as an essential component a heteropolyacid or a compound of a heteropolyacid and an element selected from boron, phosphorus, arsenic, antimony, and bismuth (Japanese Unexamined Patent Publication No. 61-289051). No. 62-19548).

On the other hand, epoxides are also important intermediate raw materials for the synthesis of alcohols, alcohol amines, polyethers, etc., and along with aldehydes, it is desired to develop inexpensive and efficient production methods.

A conventional method for producing epoxides is a method in which olefins are reacted with hydrogen peroxide in a two-phase system in the presence of 12-molybdophosphoric acid, a phase transfer catalyst such as cetylpyridium chloride, and anhydrous magnesium sulfate ( Asahi Glass Industrial Technology Promotion Association Research Report 44.77~
81, 1984), a method using a phase transfer catalyst as at least a part of the catalyst and a reaction between olefins and hydrogen peroxide (Japanese Unexamined Patent Publication No. 156475/1984).

When a boron compound is used as a cocatalyst in the above method for producing aldehydes using a compound having an olefinic carbon/carbon double bond as a raw material, a large amount of boron compound is required,
There are problems in that the catalyst activity is significantly lowered due to moisture in hydrogen peroxide used as an oxidizing agent or moisture generated by the reaction, and there are many by-products such as 1,2-diol and carboxylic acid. On the other hand, the method of using alkylidene peroxide as an oxidizing agent solves the above problems such as moisture to some extent, but the oxidizing agent is more expensive than hydrogen peroxide, so it is not necessarily advantageous in industrial production. .

In addition, the method using 1 m or more of a heteropolyacid or a heteropolyacid and a compound selected from boron, phosphorus, arsenic, antimony, and bismuth significantly increases the reaction rate and selectivity, but produces a high-boiling point diol as a byproduct. This makes the separation and purification operation of aldehyde complicated.

On the other hand, in the above-mentioned method for producing an epoxide, a compound having an olefinic carbon/carbon double bond is used as a raw material.
When the present inventors tried again to synthesize an epoxide compound using the method disclosed above, they found that the reaction rate was extremely slow and the result was far from the industrial level.

Unfortunately, there has been no known method for co-producing aldehydes and epoxide compounds from compounds with olefinic carbon-carbon double bonds through hydrogen peroxide oxidation.

Ninth Means to Solve the Problem Summary of the Invention The present inventors have discovered that the production of diols can be suppressed by continuously removing water produced by the reaction from the reaction system using a heteropolyacid or a heteropolyacid salt. In addition, we thought that the reaction rate would be improved, so we conducted the reaction in the presence of various dehydrating agents. Go nine. As a result, the presence of magnesium sulfate in the system not only has the effect of suppressing the production of diols and increasing the reaction rate, but also allows the co-production of useful aldehyde and epoxide compounds. Accordingly, the present inventors have discovered that, for example, if a phosphomolybdotungstic acid catalyst is used, it can be controlled by changing the ratio of molybdenum to tungsten, thereby completing the present invention.

That is, in the present invention, a compound having an olefinic carbon-carbon double bond, particularly one in the molecule, is treated with hydrogen peroxide in the presence of at least one heteropolyacid or a heteropolyacid salt and magnesium sulfate. The present invention relates to a method for producing aldehydes and epoxide compounds characterized by oxidizing them with.

Catalyst The first component of the catalyst used in the present invention comprises at least one type of known heteropolyacid or heteropolyacid salt. Particularly preferred heteropolyacids have heteroatoms such as P, As,
BL, B or t) G・ and the poly atom is Mo, W, Bib
, V and their mixed coordination species, the Keggin structure, or their analogs, are heteropolyacids. In addition, heteropolyacids are listed in the periodic table of heteropolyacids mentioned above! Family, Group ■.

Group M, Group II metal salts, and ammonium.

It may be a salt of an organic base such as an amine or a partial salt.

Heteropolyacids and heteropolyacid salts can be prepared by known methods. For example, a heteropolyacid with a Keggin structure is an oxyacid of a poly atom such as sodium molybdate and a simple oxyacid of a heta atom, and is it an acidic aqueous solution containing the salt? Obtained by heating.

12 Na, MoO4+ Na, 810. +26B
OA → H48tMo,, o411 + 26 N &
The OA+j I Hl O heteropolyacid salt is obtained, for example, by neutralizing a free heteropolyacid with a predetermined amount of base.

Examples of the base include alkali metal carbonates, monobicarbonates, alcoholades, and organic bases such as pyridine and triethylamine. Examples of heteropolyacids and heteropolyacid salts include the following.

Phosphomolybdic acid, arsenic molybdic acid, silicomolybdic acid, germanomolybdic acid, boromolybdic acid, phosphomolybdotungstic acid, phosphomolybdovanadate, phosphomolybdoniopic acid.

Phosphorus molybdo tungstoniobate, phosphorus molybdo tungst vanadate, arsenic molybdo tungstic acid, arsenic molybdovanadate, arsenic molybdoniobic acid, arsenic molybdo tungston niobate, arsenic molybdo tungst vanadate, silicon molybdo tungstic acid, silicon Molybdotungstoniobate, Keimolybdotungstovanadate,
Germanomolybdotungstic acid, germanomolybdotungstoniobate, germanomolybdotungstovanadate, bomolybdotungstic acid, bomolybdotungstovanadate, bomolybdotungstoniobate,
Phosphotungstic acid, arsenic tungstic acid, silicotungstic acid, germanotungstic acid, borotungstic acid, phosphotungstovanadic acid.

Linkungestniobic acid, arsenic tungstovanadate,
Arsenic tungstoniobate, silicotungstovanadate,
Silicotungstoniobic acid, germanotungstvanadate, germanotungstoniobic acid, borotungstvanadic acid, borotungstoniobic acid, phosphorpanadic acid, arsenic vanadic acid, civanadic acid, germanovanadic acid,
Bovanadic acid, phosphorusniobic acid, arsenic niobic acid, keiniobic acid, germanoniobic acid, boronibic acid and their lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, beryllium salts, magnesium salts, calcium salts, strontium salts, barium salts , copper salt.

Silver salts, zinc salts, cadmium salts, iron salts, conocult salts, nickel salts, ruthenium salts, rhodium salts.

Examples include metal salts such as palladium salts and platinum salts, and organic base salts such as ammonium salts, trimethylamine salts, triethylamine salts, and pyridine salts. When a heteropolyacid salt is used as a catalyst, it can be prepared separately in advance from a heteropolyacid and a base, or it can be used as a heteropolyacid salt in the reactor by adding the heteropolyacid and a base to the reaction system. .

Although the heteropolyacid and the heteropolyacid salt may be used while containing water of crystallization, it is preferable to use them after removing some or all of the water of crystallization by heating or the like. The amount of the first component of the catalyst of the invention can vary widely, but generally:
For 1 mole of the raw material compound having an olefinic carbon-carbon double bond, 1. OX 1 '0-6~1.0X
10-' mole, preferably 1.0X10-4 to 1.0X
It is in the range of 10-1 mol.

Compounds of elements selected from boron, phosphorus, arsenic, antimony and bismuth, which are also used as two components, are, for example, as follows.

Boron compounds include boron oxide, boric acid, borates, boric esters, boron halides, boron phosphates, and boron complex compounds, including boric anhydride, metaboric acid, orthoboric acid, sodium orthoborate, and boron complexes. sodium acid, magnesium orthoborate, magnesium metaborate, calcium orthoborate, zinc orthophosphate, aluminum orthoborate,
Trimethylboric acid, triethylboric acid, triphenylboronic acid, triethylboroxine, triethylboroxine,
Tributylboroxine, boron trifluoride and their dimethyl etherate, diethyl etherate, Fe1
Examples thereof include boric anhydride, metaboric acid, orthoboric acid, and boron trifluoride.

Phosphorus compounds include phosphorus oxide, phosphorus oxygen salts, phosphorus oxygen acid salts and esters, no-logogenated phosphorus, phosphides, and phosphorus complex compounds, including phosphorus pentoxide, phosphorus dioxide, orthophosphoric acid, birophosphoric acid, and metaphosphoric acid. , dish phosphoric acid, pyrophosphorous acid, polymetaphosphoric acid, polymetaphosphorous acid, monosuperphosphoric acid,
Disuperphosphate, sodium orthophosphate, sodium birophosphate, sodium metaphosphate, sodium phosphite, magnesium orthophosphate, magnesium birophosphate, magnesium metaphosphate, magnesium phosphite, calcium orthophosphate, calcium birophosphate, calcium metaphosphate, Examples include calcium phosphite, bismuth orthophosphate, zinc orthophosphate, aluminum orthophosphate, trimethylorthophosphate, triethylorthophosphate, trimethylphosphine, triethylphosphine, triphenylphosphine, phosphorus pentachloride, etc. Phosphorus pentoxide, Particularly preferred are phosphorus trioxide, orthophosphoric acid, and pyrophosphoric acid.

Arsenic compounds include arsenic oxide, arsenic acid, arsenate and esters,
Arsenic halides, arsenides, arsenic complex compounds, etc.
These compounds include arsenic dioxide, arsenic pentoxide, arsenous acid, arsenic acid, sodium arsenite, sodium formate, magnesium arsenite, magnesium arsenate, calcium arsenite, calcium arsenate, trimethyl arsenate, triethyl arsenate,
Particularly preferred are trimethylarsine, triethylalkune, triphenylarsine, arsenic trichloride, arsenic dioxide, arsenic pentoxide, arsenous acid, and arsenic acid.

Antimony compounds include antimony oxide, antimonic acid,
Antimony salts and esters, antimony halides, antimonides, antimony salts, and antimony complex compounds, and these compounds include antimony trioxide, antimony tetroxide, antimony pentoxide, antimonous acid, antimonic acid, and antimony suboxide. sodium acid, sodium antimonate, magnesium antimonite,
Magnesium antimonate, calcium antimonite, calcium antimonate, antimony trifluoride, 57
Antimony tsuride, antimony trichloride, antimony pentachloride, antimony arsenite, antimony arsenate, puntimony phosphate, tetramethylbistivine, tetramethylbistivine, triphenylstibine, tetramethylbistivine, etc. Particularly preferred are antimony oxide, antimony tetroxide, antimony pentoxide, and antimonic acid.

Bismuth compounds include bismuth oxide, bismuth acid, bismuth salts and esters, bismuth halides, bismuthides, bismuth salts, and bismuth complex compounds, and these compounds include bismuth dioxide, bismuth pentoxide, bismuth acid, and bismuthite. acids, sodium bismuthate, bismuth trifluoride, bismuth pentoxide, bismuth trichloride, trimethyl bismuthine, triethyl bismuthine, triphenyl bismuthine, bismuth carbonate, bismuth phosphate, bismuth arsenite, bismuth arsenate, etc. , bismuth pentoxide, bismuth acid, bismuthous acid, and bismuth trioxide are particularly preferred.

The amount of the second component used is generally 1.0 x 1 per mole of the raw material olefinic carbon-carbon double bond-containing compound.
The amount is 0-s to 5 mol, preferably 1.0 x 10-1 to 1.0 mol.

Magnesium sulfate used in the present invention has the general formula Mg5O,
It is a compound represented by nHlo (in the formula, n l'! an integer from 0 to 6). The amount used varies depending on the amount of water in the reaction system including the water produced in the reaction and the amount of crystallized water of magnesium sulfate, but for the hydrogen peroxide used, generally α01 when n = 0. More than twice the mole, preferably 1
cL01 to 2.0 times the molar range. If the amount of magnesium sulfate is less than 1 mole of CLO per hydrogen peroxide to be added, the yield of the epoxide compound will be extremely reduced, and if it exceeds 2.0 times the mole of CLO, it may not give favorable results and may become economically disadvantageous. I don't like it either.

The production ratio of aldehyde and epoxide can also be controlled by the amount of magnesium sulfate added.

Solvents Preferably used in the method of the present invention include carboxylic acids, phosphoric acids, sulfonic acids, phosphonic acids, phosphinic acids and their esters, acid amides and alcohols, such as ethyl acetate, butyl acetate, amyl acetate, etc. , hexyl acetate,
These include octyl acetate, ethylglobionate, butylglopionate, tributyl phosphate, trioctyl phosphate, methanophosphonic acid dimethyl ester, dimethylacetamide, dimethylacetamide, and the like.

Hydrogen Peroxide Although the process of the present invention can be carried out in the presence of water, a non-aqueous system is more preferred. That is, anhydrous hydrogen peroxide is preferable, but when it is obtained as an aqueous solution, it is preferable to reduce or remove water by extraction with an organic solvent. The amount of hydrogen peroxide used is generally a1 per mole of the raw material compound having an olefinic carbon-carbon double bond.
~10 mol, preferably t! It is in the range of 12 to 2 moles.

Compounds having an olefinic carbon-carbon double bond Compounds having an olefinic carbon-carbon double bond suitable for use in the present invention have the general formula: hydrogen, phenyl group, or halogen, 0. -C8 alkyl group, C8-C1 alkoxy group, phenyl group having a substituent such as nitrile group, or C1-018 linear or branched alkyl group, or halogen, hydroxyl group, alkoxy group, carboalco A chrysanthemum group, a nitrile group, a cycloalkyl group, or a linear or branched alkyl group substituted with an aromatic residue. Further, it is a compound represented by R', R"t! (which can be combined with each other to form a cyclic compound such as a cycloolefin).

Straight-chain or branched alkyl groups include methyl,
ethyl, propyl, n-butyl, inbutyl, tert
-butyl, pentyl, hexyl, hegetyl, octyl,
Nonyl, decyl, undecyl, dotecyl, bentadecyl, hexadecyl, octadecyl, and isomers thereof.

Among these, C8 to C6 alkyl groups are particularly often used.

Examples of substituted straight-chain or branched alkyl groups include chloromethyl, β-chloroethyl, 2-(β-ethyl)
-hexyl, 2,4-cyinoprobil, hydroxymethyl, β-hydroxyethyl, ω-hydroxyhexyl,
2-hydroxymethylhexyl, β-methoxyethyl,
3-Globoxyglopyl, n-hequinocycmethylhexyl, 2,4,6-dorimethoxyhexyl, 2-(methoxymethyl)-propyl, carbomethoxymethyl, 3-(
Carbopropoxy)-propyl, 3-Ccarbomethoxy)-hexyl, β-cyanoethyl, 2-(β-cyanoethyl)-propyl, ω-quanohegtyl and ω-cyanooctyl, phenylmethyl, phenylethyl, phenylpropyl, phenyl-tertr 7' Chill, ω-
Al such as phenylhexyl.

Examples of phenyl groups having substituents include ha, 4-chlorophenyl, 2.4-dichlorophenyl, 4-methquinphenyl, 4-chloro-2-methoxyphenyl, 4-70 poquinphenyl, 4-tert, -butoxyphenyl, 4
-n-hexoxylphenyl, 4-cyanophenyl, 4
Examples include -cyano-5-dimethylphenyl.

Examples of olefins and olefinic compounds having the above substituents are as follows: ethylene, globylene, 1-butylene, 2-7' ethylene, isobutylene, 1-pentene, 2-pentene, 1-hexene. ,
2-hexene, 3-hexene, 1-hegetene, 2-hegetene, 3-hegetene, 1-octene, nonene, 1-decene, 2-decene, 1-undecene, 4-undecene, 5
-decene, 2,5-dimethyl-3-hexene, 2,2-
5,5-tetramethyl-3-hexene and 8-hexadecene, 1,4-difluoro-2-butylene, 1,2-
Ditrifluoromethylethylene, 3-chloro0-1-nia'robilene, 4-chloro-1-butylene, 3-chloro-
2-butylene, 1,4-dichloro-o-2-butene, 1,1
-4,4-tetrachloro-2-butene, 6-chloro-1
-hexene, 1,6-dichloro-3-hexene, 7-chloro-1-heptene, 7,6-dichloro-2-hegetene, 1,7-chloro-3-hegetene, 3,5,7-tric(10 -1-octene, 1,8-dichloro-4-octene, 1,2-dicyclobutylethylene, 1,2-synchrohexylethylene, 1,2-dicyclobentylethylene, 1,2-dicyclodobufur Ethylene, 3-hydroxy-1-chloroben, 1,6-hydroxy-3-hexene, 3-methoxy-1-chloroben, 1,4-dimethoxy-1-butene, 1,6-dimethoxy-3-hexene, 1
・6-siglobokyu-3-hexene, 1,10-dimethoxy-5-decene, 1,10-dicarbohexoxy 5
-decene, 1,4-dicarbomethoxy-2-butene, 1
・8-Dicarbomethoxy-4-octene, 1,8-dicarboethoxy-4-octene, 1 fist 8-dicarbomethoxy-2,7-zinchlorohexyl-4-octene, 1,4
-dicyano-2-butene, 1,6-tscuano-3-hexene, 1-7ano-3-pentene, 2-cyano-3-pentene, phenylethylene, 1,2-diphenylethylene, 1,4-diphenyl-2 -Butene, 1,2-G(
p-chlorophenyl)-ethylene, 1-2-diCp-
ytquinphenyl)-ethylene, 1,2-di(p-
fluorophenyl)-ethylene, 1,2-c(2,4
-dimethylphenyl)-ethylene, 1,2-c(p-
7chlorohexylphenyl)-ethylene, 1,2-cy(2-po).

-4-tert, -butylphenyl)-ethylene, 1.
2-di(1-tart,-butylphenyl)-ethylene, 1,4-divinylpentene, 2,4-divinylpentene, p-chlorophenylethylene! and p-fluorophenylethylene, i-7ene2A/-2-7'f, 1-phenyl-3-7'f, cyclopentene,
6-Chloroto-2-cyclopentene, 3,5-dichloro-1,2-7 clobentene, 4-hydrochloro-1,2-
Cyclopentene, 3,5-dimethyl-1,2-7 clobentene, 3,5-diethyl-1,2-7 clobentene,
4-isopropyl-1・2-7 clobentene, 4-t
art.

-Phthyroot 2-7 clobentene, 3,5-diphenyl-1,2-7 clobentene, 3,S-di(4-70 lophenyl)-1,2-cyclopentene, 4-phenyl-
1-2-cyclopentene, 3-methoxy-1-2-7 clobentene, 4-globocycline-1,2-7 clobentene, 6,5-dihydroxy-1,2-cyclopentene, 4
-tert, -butoxy-1,2-cyclopentene, 4
-n-hexoxy-1,2-cyclopentene, 3-carbomethoxy-1,2-7 clobenfy, 4-calfocropoquine-1,2-cyclopentene, 3,5-di[(β-
Carbomethycin)-ethyl]-1,2-7 clobentene, 3-cyanocyclopentene, 4-7 anocyclobentene, 4-(β-cyanoethyl)-1,2-cyclopentene, 3-fluoro2-cyclopentene, 3
-trifluoromethyl-1,2-7 clobentene, cyclohexene, 3-fluoro-1,2-cyclohexene,
3-trifluoromethyl-1.2-7 chlorohexene, 3
-Chloro-1,.2-cyclohexene, 4-chloro-2-7-chlorohexene, 5-chloro-2-7-chlorohexene, 4.5-dichloro-1.2-cyclohexene, 3-
Hydroxy-1,2-cyclohexene, 3a5-dihydroxy-1,2-7chlorohexene, 3-methyl-1,2
-Cyclohexene, 4-methyl-1,2-cyclohexene, ethyl-1,2-cyclohexene, 3,5-diisopropyl-1,2-7chlorohexene, 4,5-di-
n-hexyl-1, 2-7 chlorhexene, 4-phenyl-2-7 chlorohexene, 4, 5-diphenyl-1, 2
-7 Chlorhexene, 4-(p-chlorophenyl)-1.
2-cyclohexene, 3-methoxylate 2-cyclohexene, 4-ethoxy-1,2-7chlorohexene, 5-ingropoquin-1,2-7chlorohexene, 4-hexoxyk-1,2-cyclohexene, a-(β-77noethyl )-1, 2-7 chlorohexene, cyclohegetene, 3-methyl-1, 2-7 chlorohegatene, 3, 7-cyphthyl-1
・2-cyclohegetene, 4,5,6-drimethyl-1・
2-cycloheptene, 5-'1770 biruto 2-cyclohe1tene, 5-tert, -butyroto2-7chloroheptene, 3-chloro-cyclohe1tene, 4-(β-chloroethyl)-1,2-cyclohegetene, 4.6-shipp
.

Roth 2-Schiff a to 1 ten, 5-hydroxy-1,2-
cyclohegetene-4,5-dihydroxy-1,2-cyclohe1ten, 5-phenyl-1,2-cyclohe1ten,
5-phenyroot 2-7 cloheptene, 4,5-di[
(p-tert,-butyl)-phenyl]-1,2-
Cycloheptene, 3-methoxy-1,2-cycloheptene, 5-methoxy-1,2-cyclohegetene, 3-globogisheet 2-cycloheptene, 5-tart, -
ptoxito 2-cyclohegetene, 3-carbomethoxy-1,2-cycloheptene, 4-carbomethoxycoute 2
-cyclohe1ten, 3,1-dicarbomethoxyk-1,2
-7 clohegutene and 5-(β-carbomethoxy)-
Ethyl-1,2-cyclohegte ν and the like.

Reaction conditions The method of the present invention is carried out at -40°C to 80°C, particularly preferably at 0°C.
Perform at a temperature range of ~60°C. Although the pressure is determined by other conditions (temperature, solvent, etc.), it does not have a significant effect on the reaction. Although the reaction time varies depending on the raw materials, reaction temperature, amount of catalyst, etc., it is generally short and can be carried out either batchwise or continuously. Further, aldehyde and epoxide in the reaction mixture after completion of the reaction can be separated by a known method such as distillation.

Effects of the Invention In the method for producing aldehyde and epoxide compounds according to the present invention, the reaction rate can be improved under milder conditions than before, and the by-product of diols, which are high-boiling substances, can be suppressed.

Furthermore, the coordination ratio of the polyatoms of the heteropolyacid catalyst and/or
Furthermore, the production ratio of aldehyde and epoxide can be arbitrarily controlled by adjusting the amount of magnesium sulfate added.

Furthermore, the method for creating aldehyde and epoxide compounds according to the present invention allows efficient production under mild conditions using inexpensive reagents such as hydrogen peroxide and magnesium sulfate.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

It should be noted that the weights in the examples are based on weight unless otherwise specified.

In addition, in the actual examples, all products were analyzed using diatomaceous earth carriers with
The analysis was carried out by nine gas chromatographic analysis using a 3 m column supporting ethanol and using butyl acetate as an internal standard.

Example 1 Preparation of catalyst Na1HPO, * 2 If, O (manufactured by Kokan Chemical Co., Ltd.) &
2fi200- dissolved in water, and further Na, WO4-2
H, 0 (manufactured by Kokan Chemicals) 4! LIF and Ma1MO
O4a2H,O (manufactured by Kokan Chemical) 350? was added and dissolved. After maintaining the temperature at 80° C. for 2 to 3 hours while stirring, the solution was concentrated to 80 m using a rotary evaporator.

When 100 μl of a 24% F1 aqueous solution was added dropwise at 80° C., the liquid did not turn yellow. The solution was then cooled to room temperature, and the precipitate formed was extracted with ether without filtration.
, W, O, catalyst 9512.

In a 200ml glass reactor equipped with a stirrer and a reflux condenser, cyclopentene 14.4F and the H prepared above were added.
, PMo, W6111. n, O55f and phosphoric acid CL14F and anhydrous magnesium sulfate 4.02 (
Of this amount, 1.61 is the amount required to dehydrate the trace amount of water in the tributyl phosphate solution containing hydrogen peroxide.
(Similarly below) After t-addition, the temperature was raised to 45°C, and tributyl phosphate solution 4r1.3f containing 11.8% hydrogen peroxide was added dropwise over 20 minutes while stirring.9. After further stirring at 45° C. for 6 hours, the reaction solution was analyzed by gas chromatography.

As a result, the liquid contained 74% glutaraldehyde and 5% glutaraldehyde.
．． 7% cyclopentene oxide and 2.2 parts 1
．． 2-cyclobentanediol was present. The produced glutaraldehyde and cyclopentene oxide correspond to 1a3 mole and 1&7 mole, respectively, based on the raw material cyclopentene.

Example 2 Catalyst preparation and oxidation reaction of cyclohexene were carried out in the same manner as in Example 1 except that cyclohexene 17.22 was used instead of cyclohentene.

As a result, the reaction solution contained 64% 1,6-hexane dial, 4.7% 7 chlorohexene oxide, and 1.
There was 5% 1.2-7 chlorohexanediol. 1 &
This corresponds to 7 molar units and 147 molar units.

Example 3 A catalyst was prepared and a styrene oxidation reaction was carried out in the same manner as in Example 1 except that styrene 2t5fk was used instead of cyclohentene.

As a result, ij 4.4% of benzaldehyde and 2.4 liters of styrene oxide were present in the reaction solution.

The produced benzaldehyde and styrene oxide each have a mole ratio of 12.2 moles and a
This corresponds to well over 0 moles.

Comparative Example 1 Catalyst preparation and cyclopentene oxidation reaction were carried out in the same manner as in Example 1 except that anhydrous magnesium sulfate was not added.

As a result, the reaction solution contained 6% ia of glutaraldehyde and Q, 4% of cyclopentene oxide, and 4.6% of ia.
of 1,2-7 clopentanediol was present. The amount of glutaraldehyde and cyclobentene oxide produced was 2t7mol)v%, respectively, based on the raw material cyclohentene.
and corresponds to 1.3 molar ratio.

The catalyst preparation and the oxidation reaction of 7 clobentene were carried out in the same manner as in Example 1 except that the addition t' of anhydrous magnesium sulfate was changed.

The results are shown in Table 1.

Examples 6 to 11 1ialWo, 2H1O, which is a raw material in catalyst preparation
Various phosphomolybdotungstic acid catalysts with different ratios of MO and W were prepared in the same manner as in Example 1, except for changing the amounts of MoO, .2H and O added. Using the prepared catalyst, the oxidation reaction of cyclopentene was carried out in the same manner as in Example 1 except that the amount used was 10 times the mole of Example 1 in Examples 9 and 14.

The results are shown in Table 2.

Comparative Examples 2 to 8 Instead of anhydrous magnesium sulfate, various dehydrating agents t-4,
Catalyst preparation and oxidation reaction of cyclopentene were carried out in the same manner as in Example 1, except that Of was used. Zeolite 3:3 and neutral activated alumina manufactured by Nishio Kogyo Co., Ltd. were used. Silica gel was prepared by placing 409 grams of methyl silicate and 90 grams of water in an Erlenmeyer flask and raising the temperature to 80°C.
The two were mixed and stirred to form a gel, then dried under reduced pressure and baked in an electric furnace at SSa°C for 4 hours. The super absorbent resin used was Sanwet (trade name) manufactured by Sanyo Kasei Co., Ltd.

The results are shown in Table 3.

Comparative Example 9 An oxidation reaction of cyclopentene was carried out in the same manner as in Example 1 except that the phosphomolybdotungstic acid catalyst was not added.

As a result, the reaction solution contained i[17% glutaraldehyde, α3% 7 clopentene oxide, and α7-related 1
, 2-7 clobentanediol were present. The resulting glutaraldehyde and hiscyclobentene oxide correspond to 2.0 and 0.5 moles, respectively, based on the raw material cyclohentene.

Examples 12 to 14 The oxidation reaction of cyclopentene was carried out in the same manner as in Example 1 except that various heteropolyacid or heteropolyacid salt catalysts were used instead of phosphomolybdotungstic acid.

The results are shown in Table 4.

Example 15 Catalyst preparation and cyclopentene oxidation reaction were carried out in the same manner as in Example 1, except that phosphoric acid was not added and a phosphomolybdotungstic acid catalyst was added @fcL53'l.

As a result, 4.4% glutaraldehyde, 56% 7-chloropentene oxide, and 1.5% 1.2-7 triwhite bentanediol were present in the reaction solution. The produced glutaraldehyde and cyclopentene oxide correspond to 11.2 and 117 moles, respectively, based on the raw material cyclopentene.

Example row 16 Instead of phosphoric acid, arsenic dioxide (As, O,) 0.42
Catalyst preparation and oxidation reaction of cyclopentene were carried out in the same manner as in Example 1 except that 1:t was used.

As a result, the reaction solution contained 4.0% glutaraldehyde, 53% 7-chloropentene oxide, and 0.1% glutaraldehyde. a%
1.2-7 clobentanediol is present. The produced glutaraldehyde and cyclopentene oxide correspond to 1α2 mol and 9.9 mol, respectively, based on the raw material fuclobentene.

Comparative Example 10 Phosphormolybdotungstic acid (B3 PMO@W@Oa
, )&2
B1) 1saa, at) 1f! : An aqueous solution containing an equivalent amount, that is, 50 f.

Added to 20 Decl. After stirring for an additional hour at room temperature, the cetylpyridinium salt of phosphomolybdotungstic acid was prepared by suction filtration, washing with warm water several times, and vacuum drying.

In a reactor similar to Example 1, cetylpyridinium salt α15f1 of phosphomolybdotungstic acid 9.
Add 7F, 8α7t of chloroform, and 3t of anhydrous magnesium sulfate, and add 31% hydrogen peroxide solution dropwise over 20 minutes while stirring at 45°C. After further stirring at 45° C. for 6 hours, the reaction solution was analyzed by gas chromatography, and no products such as aldehyde, oxide, diol, etc. were detected.

Claims (1)

[Claims] (1) Aldehyde and epoxide compounds characterized in that a compound having an olefinic carbon-carbon double bond is oxidized with hydrogen peroxide in the presence of at least one type of heteropolyacid or heteropolyacid salt and magnesium sulfate. Production method.