JPH0699355B2 - Method for producing aldehyde - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing an aldehyde by reacting a compound having an olefinic carbon-carbon double bond with hydrogen peroxide in the presence of a heteropolyacid or a heteropolyacid salt. It is a thing.

BACKGROUND ART Aldehydes are important intermediate raw materials for various chemical products, and certain aldehydes such as glutaraldehyde are also used in applications such as bactericides, skin tanning agents, and microcapsule coins, and are inexpensive and efficient. Development of a manufacturing method is desired.

A conventionally known method for producing aldehyde is from olefin.
There is a method of synthesizing a 1,2-diol and oxidizing it with an oxidizing agent, or a method of obtaining an oxirane compound (for example, cyclopentene oxide) from olefin and then oxidizing this, but a simplified reaction path, or A process for producing directly from olefin has also been studied in consideration of improvement of aldehyde yield and safety.

That is, as a method for producing an aldehyde using a compound having an olefinic carbon-carbon bond as a raw material, a method using hydrogen peroxide containing a boron compound and a molybdenum salt as essential components (Japanese Patent Publication No. 51-28606), a boron compound and tungsten. A method using hydrogen peroxide with a compound as an essential component (JP-A-57
-95921), I of the 4th, 5th and 6th periods of the periodic table
One of compounds of V b, V b, VI b, VII b, and VIII elements
There is a method using alkylidene peroxide (see Japanese Patent Laid-Open No. 145826/1982) which uses more than one species.

Problems to be Solved by the Invention In the method for producing an aldehyde using a compound having an olefinic carbon / carbon bond as a raw material, when a boron compound is used as a cocatalyst, a large amount of the boron compound is required and used as an oxidizing agent. There are problems that the catalytic activity is remarkably reduced by the water in the hydrogen peroxide or the water generated by the reaction, and there are a large amount of 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-mentioned problems such as water content to some extent, but the oxidizing agent is expensive as compared with hydrogen peroxide,
It is not always advantageous in industrial production.

Means for Solving the Problem SUMMARY OF THE INVENTION The present inventors have not produced a potentially explosive substance such as ozonide as a reaction intermediate pair, have the shortest synthetic steps, and are considered to be industrially promising olefinic carbons.・ As a result of studying a one-step synthesis method of aldehyde by oxidizing hydrogen peroxide of a compound having a carbon double bond, a catalyst system which does not require addition of a boron compound, which was conventionally required as a catalyst for the present synthesis, was found. Heading, completed the present invention.

That is, the present invention relates to a heteropolyacid comprising a heteroatom composed of phosphorus or germanium and one or more kinds of polyatoms selected from molybdenum, tungsten and vanadium, and a periodic group Ia or II of the heteropolyacid.
The present invention relates to a method for producing an aldehyde, which comprises oxidizing a compound having an olefinic carbon / carbon double bond with hydrogen peroxide in the presence of a catalyst consisting of at least one kind selected from a group a metal salt. .

Catalyst The catalyst used in the present invention has a heteroatom of P or Ge.
Is a heteropoly acid of the Keggin structure or its analogs in which the polyatoms are Mo, W and V, and their mixed coordination species.
Further, the heteropolyacid salt is a compound of the periodic table of the above heteropolyacid.
It is a metal salt of Group Ia or Group IIa and may be a partial salt. The heteropolyacid and the heteropolyacid salt can be prepared by known methods. For example, a Keggin-structured heteropolyacid is obtained by heating an acidic aqueous solution containing an oxygen acid salt of a polyatom such as sodium molybdate and a simple enzymatic acid of a heteroatom, or a salt thereof.

12Na ₂ MoO ₄ ＋ Na ₂ SiO ₃ ＋ 26HCl → H ₄ SiMo ₁₂ O ₄₀ ＋ 26NaCl ＋ 11
The H ₂ 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, bicarbonate alcoholates, and organic bases such as pyridine and triethylamine. Examples of the heteropolyacid and the heteropolyacid salt are as follows.

Phosphomolybdic acid, gelanomolybdic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstic acid, germanomolybdotungstovanadic acid, phosphotungstic acid, germanotungsten Acids, phosphotungstovanadic acid, germanotungstovanadic acid, phosphovanadic acid, germanovanadic acid and their lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, beryllium salts, magnesium salts, calcium salts,
Examples include metal salts such as strontium salt and barium salt. When using the heteropolyacid salt as a catalyst, in addition to the one prepared separately from the heteropolyacid and the base in advance,
It is also possible to add a heteropolyacid and a base to the reaction system and use it as a heteropolyacid salt in the reactor.

The heteropolyacid and the heteropolyacid salt may be used while containing the water of crystallization, but it is preferable to use a part or all of the water of crystallization by heating or the like. The amount of the catalyst component used in the present invention can be varied within a wide range, but in general, 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻¹ mol, relative to 1 mol of the compound having an olefinic carbon / carbon double bond as a raw material, Preferably 1.0 × 10 ^-4
The range is up to 1.0 × 10 ^-2 mol.

Solvents preferably used in the method of the present invention include carboxylic acid, phosphoric acid, sulfonic acid, phosphonic acid,
Phosphonic acids and their esters, acid amides and alcohols such as ethyl acetate, butyl acetate, amyl acetate, hexyl acetate, octyl acetate, ethyl propionate, butyl propionate, tributyl phosphonate, trioctyl phosphite. And methanephosphonic acid dimethyl ester, dimethylformamide, dimethylacetamide and the like.

Hydrogen peroxide The method of the present invention can be performed in the presence of water, but a non-aqueous system is more preferable. That is, anhydrous hydrogen peroxide is preferable, but when obtained as an aqueous solution, it is preferable to reduce or remove water by extracting with an organic solvent. The amount of hydrogen peroxide used is generally 0.1 to 10 mol per mol of the compound having an olefinic carbon / carbon double bond as a raw material,
It is preferably in the range of 0.2 to 2 mol.

Compounds having an olefinic carbon-carbon double bond Suitable compounds for use in the present invention have the general formula: (In the formula, R ¹ and R ² are each hydrogen, a phenyl group, or halogen, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ alkoxy group, a phenyl group having a substituent such as a nitrile group, or C ₁ ~ C ₁₈ straight or branched alkyl group, or a straight or branched alkyl group substituted with a halogen, hydroxyl group, alkoxy group, carboalkoxy group, nitrile group, cycloalkyl group or aromatic residue. Furthermore, R ¹ and R ² are bonded to each other to form a cyclic compound such as cycloolefin and are represented by compounds.

Examples of linear or branched alkyl groups include methyl,
Ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, and isomers thereof. Of these, a C _{2 to} C ₆ alkyl group is often used.

Examples of the substituted linear or branched alkyl group are chloromethyl, β-chloroethyl, 2- (β-ethyl)-
Hexyl, 2,4-diisopropyl, hydroxymethyl,
β-hydroxyethyl, ω-hydroxyhexyl, 2-hydroxymethylhexyl, β-methoxyethyl, 3-brofoxypropyl, n-hexoxymethylhexyl, 2.4
6-trimethoxyhexyl, 2- (methoxymethyl) -propyl, carbomethoxymethyl, 3- (carbopropoxy) -propyl, 3- (carbomethoxy) -hexyl, β
-Cyanoethyl, 2- (β-cyanoethyl) -propyl,
ω-cyanohexyl and ω-cyanooctyl, phenylmethyl, phenylethyl, phenylpropyl, phenyl-tert.-butyl, ω-phenylhexyl and the like.

Examples of the phenyl group having a substituent include 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, 4-chloro-2-methoxyphenyl, 4-propoxyphenyl and 4-tert. Examples include -butoxyphenyl, 4-n-hexoxylphenyl, 4-cyanophenyl, 4-cyano-3,5-dimethylphenyl and the like.

Examples of olefins and olefinic compounds having the above substituents are as follows: ethylene, propylene, 1-butylene, 2-butylene, isobutylene, 1-
Pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-
Heptene, 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-chloro-1-propylene, 4
-Chloro-1-butylene, 3-chloro-2-butylene,
1,4-dichloro-2-butene, 1,1.4-tetrachloro-2-butene, 6-chloro-1-hexene, 1
6-dichloro-3-hexene, 7-chloro-1-heptene, 7-6-dichloro-2-heptene, 1.7-chloro-3-heptene, 3.5 / 5-trichloro-1-octene, 1・ 8-Dichloro-4-octene, 1.2-dicyclobutylethylene, 1.2-dicyclohexylethylene, 1.2-dicyclopentylethylene, 1.2-dicyclododelethylene, 3-hydroxy-1-propene ,
1,6-dihydroxy-3-hexene, 3-methoxy-
1-propene, 1.4-dimethoxy-1-butene, 1
-Dimethoxy-3-hexene, 1.6-dipropoxy-
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, 1,8-dicarbomethoxy-2,7-dicyclohexyl-4-octene, 1,4-dicyano-2-butene,
1,6-dicyano-3-hexene, 1-cyano-3-pentene, 2-cyano-3-pentene, phenylethylene, 1.2-diphenylethylene, 1.4-diphenyl-2-butene, 1 2-di- (p-chlorophenyl)-
Ethylene 1.2-di- (p-methoxyphenyl) -ethylene 1.2-di- (p-fluorophenyl) -ethylene 1.2-di- (2.4-dimethylphenyl) -ethylene 1,2-di- (p-cyclohexylphenyl)
-Ethylene, 1.2-di- (2-chloro-4-tert.-,
Butylphenyl) -ethylene, 1.2-di- (1-ter
t.-Butylphenyl) -ethylene, 1,4-divinylbenzene, 2,4-divinylbenzene, p-chlorophenylethylene and p-fluorophenylethylene, 1-
Phenyl-2-butene, 1-phenyl-3-butene, cyclopentene, 3-chloro-1,2-cyclopentene,
3,5-dichloro-1,2-cyclopentene, 4-hydroxy-1,2-cyclopentene, 3,5-dimethyl-
1,2-cyclopentene, 3,5-diethyl-1,2-
Cyclopentene, 4-isopropyl-1,2-cyclopentene, 4-tert.-butyl-1,2-cyclopentene, 3,5-diphenyl-1,2-cyclopentene, 3
-5-di- (4-chlorophenyl) -1.2-cyclopentene, 4-phenyl-1.2-cyclopentene, 3-methoxy-1.2-cyclopentene, 4-propoxy-1
-2-cyclopentene, 3.5-diisopropoxy-1
-2-cyclopentene, 4-tert.-butoxy-1.2
-Cyclopentene, 4-n-hexoxy-1,2-cyclopentene, 3-carbomethoxy-1,2-cyclopentene, 4-carbopropoxy-1,2-cyclopentene, 3,5-di [(β-carbomethoxy)- Ethyl]-
1,2-cyclopentene, 3-cyano-1,2-cyclopentene, 4-cyanocyclopentene, 4- (β-cyanoethyl) -1,2-cyclopentene, 3-fluoro-
1,2-cyclopentene, 3-trifluoromethyl-1
-2-cyclopentene, cyclohexene, 3-fluoro-1,2-cyclohexene, 3-trifluoromethyl-
1,2-cyclohexane, 3-chloro-1,2-cyclohexene, 4-chloro-1,2-cyclohexane, 5-
Chloro-1,2-cyclohexene, 4,5-dichloro-
1,2-cyclohexane, 3-hydroxy-1,2-cyclohexene, 3,5-dihydroxy-1,2-cyclohexene, 3-methyl-1,2-cyclohexene, 4-
Methyl-1,2-cyclohexene, 5-ethyl-1.2
-Cyclohexene, 3,5-diisopropyl-1,2-
Cyclohexene, 4,5-di-n-hexyl-1.2-cyclohexene, 4-phenyl-1,2-cyclohexene, 4,5-diphenyl-1,2-cyclohexene, 4
-(P-chlorophenyl) -1.2-cyclohexene,
3-methoxy-1,2-cyclohexene, 4-ethoxy-1,2-cyclohexene, 5-isopropoxy-1.
2-cyclohexene, 4-hexoxy-1.2-cyclohexene, 4- (β-cyanoethyl) -1.2-cyclohexene, cycloheptene, 3-methyl-1.2-cycloheptene, 3.7-dimethyl-1.2- Cycloheptene, 4,5,6-trimethyl-1,2-cycloheptene, 5-isopropyl-1,2-cycloheptene, 5-
tert.-Butyl-1,2-cycloheptene, 3-chloro-cycloheptene, 4- (β-chloroethyl) -1.2
-Cycloheptene, 4,6-dichloro-1,2-cycloheptene, 5-hydroxy-1,2-cycloheptene-
4,5-dihydroxy-1,2-cycloheptene, 3-
Phenyl-1,2-cycloheptene, 5-phenyl-1
-2-cycloheptene, 4,5-di-[(p-tert.-
Butyl) -phenyl] -1.2-cycloheptene, 3-
Methoxy-1,2-cycloheptene, 5-methoxy-1
-2-cycloheptene, 3-propoxy-1.2-cycloheptene, 5-tert.-butoxy-1.2-cycloheptene, 3-carbomethoxy-1.2-cycloheptene, 4-carbomethoxy-1.2-cycloheptene, Three
-1-dicarbomethoxy-1.2-cycloheptene and 5 (β-carbomethoxy) -ethyl-1.2-cycloheptene.

Reaction Conditions The method of the present invention is -40 ° C to 80 ° C, particularly preferably 0 ° C to 60 ° C.
Perform in the temperature range of ° C. The pressure is determined by other conditions (temperature, solvent, etc.), but it does not significantly affect the reaction. The reaction time varies depending on the raw materials, the reaction temperature, the amount of catalyst, etc., but is generally short and can be carried out by either a batch method or a continuous method. The aldehyde in the reaction mixture after completion of the reaction can be separated by a known method such as distillation. For example, there is a method in which the reaction is carried out in a solvent immiscible with water, the produced aldehyde is extracted with water and then distilled. It should also be considered to carry out the distillation under reduced pressure, since the distillation sometimes reduces the yield of the product accompanied by thermal decomposition.

EFFECTS OF THE INVENTION According to the method of the present invention, an aldehyde can be synthesized with a higher yield than an olefinic carbon / carbon double bond in a single step. In addition, non-aqueous conditions that were essential in the preceding one-step process,
Alternatively, an aldehyde can be efficiently produced at low cost without necessarily adding a boron compound or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In the examples, all the analysis of products was carried out on a diatomaceous earth carrier.
% Nonylphenooxy poly (ethyleneoxy) ethanol was used in a 3 m column, and gas chromatographic analysis was performed using butyl acetate as an internal standard.

Example-1 A 200 ml glass reactor equipped with a stirrer and a reflux condenser was charged with 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and phosphomolybdic acid (manufactured by Komune Chemical Co.) with respect to hydrogen peroxide. After adding 0.42 mol%, 14.3 g of cyclopentene was added dropwise over 10 minutes while heating to 35 ° C. and stirring.

After further stirring at 35 ° C. for 3 hours, the reaction liquid was analyzed by gas chromatography.

As a result, 5.5% by weight of glutaraldehyde and 1.4
There was 7% by weight of 1,2-cyclopentanediol, 0.08% by weight of cyclopentene oxide. The glutaraldehyde produced corresponds to 15.5 mol% based on the starting cyclopentene.

Example-2 After adding 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and phosphotungstic acid (manufactured by Komune Chemical Co., Ltd.) to the same reactor as in Example 1 at 0.42 mol% relative to hydrogen peroxide. Cyclopentene 14.3 g 1
It was dripped in 0 minutes. After further stirring at 35 ° C. for 3 hours, the reaction liquid was analyzed by gas chromatography. As a result, in the liquid
1.35 wt% glutaraldehyde and 3.14 wt% 1,2-
Cyclopentanediol was present.

The glutaraldehyde produced is 4.
It corresponds to 5 mol%.

Example-3 8.15 g of Na ₂ HPO ₄ 2H ₂ O was dissolved in 220 c.c. of water, and Na ₂ Mo was added thereto.
49.87 g of O ₄ .2H ₂ O and 22.66 g of Na ₂ WO ₄ 2H ₂ O were added and dissolved. The mixture was kept at 80 ° C for 3 hours with stirring, the solution was concentrated to about 100 c.c. by an evaporator, and 24% by weight HCl 100c.c.
Was dripped. Then, cool to room temperature, add 200 c.c. of ethyl ether, separate the heteropoly acid etherate with a separating funnel, evaporate to dryness again with an evaporator, and further evacuate at room temperature to remove molybdenum atom 9 and tungsten atom. A compounded coordination phosphomolybdotungstic acid of 3 was prepared.

In a reactor similar to that of Example 1, 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and 0.15 mol% of phosphomolybdotungstic acid prepared above were added to hydrogen peroxide, and the temperature was raised to 35 ° C. Cyclopentene while warm and stirring
14.3 g was added dropwise over 10 minutes.

After further stirring at 35 ° C. for 3 hours, the reaction liquid was analyzed by gas chromatography. As a result, 6.7% by weight of glutaraldehyde and 4.6% by weight of 1,2-cyclopentanediol were present in the liquid. The produced glutaraldehyde corresponds to 19.0 mol% with respect to the raw material cyclopentene.

Example-4 Example 3 was changed by changing the amounts of Na ₂ MoO ₄ .2H ₂ O and Na ₂ WO ₄ .2H ₂ O so that the atomic ratio of molybdenum to tungsten was 6: 6.
Phosphomolybdotungstic acid was prepared under the same conditions as above. Using 0.15 mol% of this catalyst with respect to hydrogen peroxide, the reaction was carried out under the same method and conditions as in Example 1. As a result, 6.6% by weight of glutaraldehyde and 5.4% by weight of 1,
2-Cyclopentanediol was present. The amount of glutaraldehyde produced is 18.7 mol% based on the starting cyclopentene.
Equivalent to.

Was dissolved NaVO ₃ 24.4 g hot water of Example -5 100c.c., while maintaining the 90 ° C. by mixing NaHPO ₄ 7.1 g dissolved both solutions separately to the water 100C.C.,
Concentrated sulfuric acid 5c.c. was added dropwise. In addition to 200 c.c. of hot water, Na ₂ MoO ₄
121.0 g of 2H ₂ O was dissolved and the solution was added to the above mixture with stirring. After maintaining at 90 ° C. for 1 hour, concentrated sulfuric acid 85 c.c. was added dropwise with stirring. About 200 of that liquid with an evaporator
Concentrate to cc, cool to room temperature, add 200 c.c. of ethyl ether, separate the heteropoly acid etherate with a separatory funnel, evaporate to dryness again with an evaporator, and further evacuate at room temperature to remove molybdenum. A mixed coordination phosphomolybdovanadic acid of atom 10 and vanadium atom 2 was prepared.

Using 0.42 mol% of this catalyst with respect to hydrogen peroxide, the reaction was carried out under the same method and conditions as in Example 1. As a result, 27% by weight of glutaraldehyde and 1.5% by weight of 1,2-cyclopentanediol were present in the liquid. The produced glutaraldehyde corresponds to 7.4 mol% based on the starting material cyclopentene.

Example 6 After dissolving 20.1 g of Na ₂ MoO ₄ · 2H ₂ O in 100 c.c. of water, 80
The mixture was heated to 0 ° C., and 16.7 g of MoO _{3 was} added in 4 portions with stirring. Na ₂ CO _{3 3} g was added thereto, GeO ₂ was added 0.87 g, and then Na ₂ CO ₃ 2 g was further added. GeO ₂ 0.87 g was added again, and the solution was heated to 100 ° C. and stirred for 1 hour. Stop heating and concentrated hydrochloric acid 15
cc was dropped. After cooling to room temperature, concentrated hydrochloric acid 5c.c. was added dropwise, ethyl ether 100c.c. Then, germanomolybdic acid was prepared.

Using 0.42 mol% of this catalyst with respect to hydrogen peroxide, the reaction was carried out by the same method and conditions as in Example 1. As a result, 2.6% by weight of glutaraldehyde and 0.6% by weight of 1,
2-Cyclopentanediol was present. The amount of glutaraldehyde produced is 6.9 mol% based on the raw material cyclopentene.
Equivalent to.

Example-7 45 g of a solution of tributyl phosphate containing 11.1% by weight of hydrogen peroxide and 1.0 mol% of phosphomolybdic acid were added to the same reactor as in Example 1 and the temperature was raised to 35 ° C. Then, with stirring, 15.0 g of cyclopentene was added dropwise over 10 minutes. After stirring at 35 ° C for 3 hours, the reaction solution was analyzed by gas chromatography.
Of glutaraldehyde and 5.31% by weight of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 17.4 mol% with respect to the cyclopentene added.

Example-8 After the reaction was carried out in the same manner as in Example 1 except that the temperature at which cyclopentene was added dropwise was 40 ° C and the reaction temperature was 40 ° C, the reaction solution was analyzed by gas chromatography.
The reaction solution contained 6.80% by weight of glutaraldehyde and 3.37% by weight of 1,2-cyclopentanediol. Glutaraldehyde was 18.9 relative to cyclopentene added.
Corresponds to mol%.

Example-9 35 g of a solution of tributyl phosphate containing 10.5% by weight of hydrogen peroxide and 0.42 mol% of phosphomolybdic acid were added to the same reactor as in Example 1 and the temperature was raised to 35 ° C. While stirring, 14.7 g of cyclopentene corresponding to twice the molar amount of hydrogen peroxide was added dropwise over 10 minutes. After continuing stirring at 35 ° C. for 3 hours, the reaction liquid was analyzed by gas chromatography. As a result, the reaction liquid contained 7.51% by weight of glutaraldehyde and 1.21% by weight of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 16.9 mol% with respect to the cyclopentene added.

Example-10 23.66 g of phosphomolybdic acid was dissolved in distilled water of 100 c.c., 0.53 g of anhydrous sodium carbonate corresponding to 1/3 equivalent of molybdic acid was added thereto, and water was removed by evaporation to dryness. The partial sodium salt of phosphomolybdic acid was prepared by evacuation at room temperature for 2 hours.

To the same reactor as in Example 1 was added 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and 0.42 mol% of a partial sodium salt of phosphomolybdic acid, and the temperature was raised to 35 ° C. Cyclopentene with stirring
14.3 g was added dropwise over 10 minutes. After continuously stirring at 35 ° C for 3 hours, the reaction solution was analyzed by gas chromatograph. As a result, 7.01% by weight of glutaraldehyde and 1.15% by weight were found in the reaction solution.
Of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 19.7 mol% with respect to the cyclopentene added.

Example-11 23.66 g of phosphomolybdic acid was dissolved in 100 c.c. of distilled water, and 1.59 g of anhydrous sodium carbonate corresponding to the equivalent of phosphomolybdic acid was added thereto, and water was removed by evaporation to dryness. It was evacuated for 2 hours to prepare sodium phosphomolybdate.

A solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide in an amount of 45 g was added to the same reactor as in Example 1, 0.42 mol% of partial sodium phosphomolybdic acid was added to hydrogen peroxide, and the temperature was raised to 35 ° C. Cyclopentene 14.3 with stirring
g was added dropwise over 10 minutes. After stirring the mixture at 35 ° C for 3 hours, the reaction mixture was analyzed by gas chromatography. As a result, 6.23% by weight of glutaraldehyde and 1.11% by weight were found in the reaction mixture.
Of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 17.4 mol% with respect to the cyclopentene added.

Example -12 phosphorus molybdate de tungstophosphoric acid _{(H 3 PMo 9 W 3 O} 40) and 11.08 g 5
It was dissolved in distilled water of 0c.c., 0.53 g of anhydrous sodium carbonate corresponding to 2/3 equivalent of phosphomolybdotungstic acid was added thereto, water was removed by evaporation to dryness, and further 2
The partial sodium salt of phosphomolybdotungstic acid was prepared by evacuation for a while.

In a reactor similar to that of Example 1, 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and a partial sodium salt of phosphomolybdotungstic acid with respect to hydrogen peroxide were added.
After adding 42 mol%, the temperature was raised to 35 ° C., and 14.3 g of cyclopentene was added dropwise over 10 minutes while stirring. After continuously stirring at 35 ° C. for 3 hours, the reaction solution was analyzed by gas chromatography. As a result, 6.72% by weight of glutaraldehyde was found in the reaction solution.
It contained 74% by weight of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 18.9 mol% with respect to the cyclopentene added.

Example-13 23.66 g of phosphomolybdic acid was dissolved in 100 c.c. of distilled water,
After adding 0.97 g of basic magnesium carbonate corresponding to 2/3 equivalents of phosphomolybdic acid, water was removed by evaporation to dryness, and then vacuum evacuation was performed at room temperature for 2 hours to form a partial magnesium salt of phosphomolybdic acid. Was prepared.

In the same reactor as in Example 1, 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and 0.42 mol% of a partial magnesium salt of phosphomolybdic acid with respect to hydrogen peroxide.
After adding, the temperature was raised to 35 ° C and cyclopentene was added while stirring.
14.3 g was added dropwise over 10 minutes. After continuing stirring at 35 ° C for 3 hours, the reaction solution was analyzed by gas chromatography.
The reaction solution contained 7.10% by weight of glutaraldehyde and 1.33% by weight of 1,2-cyclopentanediol. Glutaraldehyde is 19.9 relative to cyclopentene added.
Corresponds to mol%.

Example-14 In a reactor similar to that of Example 1, 100 g of isoamyl acetate containing 2.44% by weight of hydrogen peroxide and 0.42 mol% of phosphomolybdic acid were added to hydrogen peroxide, and then the temperature was raised to 35 ° C and the mixture was stirred. While, 7.3 g of cyclopentene was added dropwise over 5 minutes. 35 ° C
After continuously stirring for 3 hours, the reaction solution was analyzed by gas chromatography. As a result, the reaction solution contained 1.22% by weight of glutaraldehyde and 0.25% by weight of 1,2-pentanediol. Glutaraldehyde corresponds to 11.9 mol% with respect to the cyclopentene added.

Example-15 In a reactor similar to that in Example 1, 45 g of tributyl phosphate containing 10.8% by weight of hydrogen peroxide and 0.42 mol% relative to hydrogen peroxide of phosphomolybdic acid were added, and then the temperature was raised to 35 ° C. and stirring was performed. While, 17.6 g of cyclohexene was added dropwise over 10 minutes. 3
After continuing stirring at 5 ° C. for 4 hours, the reaction liquid was analyzed by gas chromatography. As a result, the reaction liquid contained 3.67% by weight of adiboraldehyde. This corresponds to 9.3 mol% with respect to the cyclohexene added.

Example-16 In a reactor similar to that of Example 1, 45 g of tributyl phosphate containing 10.4% by weight of hydrogen peroxide and 0.42 mol% of phosphomolybdic acid were added to the hydrogen peroxide, and the temperature was raised to 35 ° C., followed by stirring. Meanwhile, 17.3 g of 3-hexene was added dropwise over 10 minutes. 35
After continuously stirring at ℃ for 3 hours, the reaction solution was analyzed by gas chromatography, and it was found that the reaction solution contained 2.15% by weight of propionaldehyde. This corresponds to 10.8 mol% with respect to the 3-hexene added.

Example-17 In a reactor similar to that of Example 1, 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and 0.42 mol% relative to hydrogen peroxide of phosphomolybdic acid were added, and the temperature was raised to 40 ° C. , While stirring, 27.8 g of 1-phenyl-2-butene 10
Dropped in minutes. After stirring at 40 ℃ for 2 hours, the reaction mixture was analyzed by gas chromatography.
It contained 2.94% by weight of phenylacetaldehyde and 1.36% by weight of acetaldehyde.

Comparative Example 1 50 g of a solution of tributyl phosphate containing 10.8% by weight of hydrogen peroxide and molybdenum acetylacetonate (MoO ₂ (CH ₂ COCH ₂ COCH ₃ ) ₂ ) were added to hydrogen peroxide in the same reactor as in Example 1. After adding 1.0 mol%, the temperature was raised to 35 ° C,
With stirring, 16.3 g of cyclopentene was added dropwise over 10 minutes.

After stirring at 35 ° C for 3 hours, the reaction solution was analyzed by gas chromatography.
Of glutaraldehyde and 0.32% by weight of 1,2-cyclopentanediol. Glutaraldehyde corresponds to 2.4 mol% with respect to the cyclopentene added.

Comparative Example 2 50 g of a solution of tributyl phosphate containing 6.88% by weight of hydrogen peroxide and 1.0 mol% of tungstic acid were added to the same reactor as in Example 1, and the temperature was raised to 35 ° C. and stirred. While dropping 13.8 g of cyclopentene over 10 minutes.

After continuing stirring at 35 ° C. for 2 hours, the reaction solution was analyzed by gas chromatography, and it was found that the reaction solution contained neither glutaraldehyde nor 1,2-cyclopentanediol.

Comparative Example 3 In a reactor similar to that of Example 1, 45 g of a solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and molybdenum acetylacetonate (MoO ₂ (CH ₂ COC
After adding 1.0 mol% of H ₂ COCH ₃ ) ₂ ) and 30 mol% of boric anhydride, the temperature was raised to 35 ° C and cyclopentene 14.3 was added while stirring.
g was added dropwise over 10 minutes. After continuously stirring at 35 ° C for 3 hours, the reaction solution was analyzed by gas chromatography, and 3.73% by weight of glutaraldehyde and 0.
It contained 31% by weight of 1,2-cyclopentanediol and 0.25% by weight of cyclopentene oxide. Glutaraldehyde corresponds to 10.3 mol% with respect to the cyclopentene added.

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Claims (1)

[Claims] 1. A heteropolyacid comprising a heteroatom composed of phosphorus or germanium and at least one polyatom selected from molybdenum, tungsten and vanadium, and a group Ia or a group IIa of the periodic table of the heteropolyacid. A method for producing an aldehyde, which comprises oxidizing a compound having an olefinic carbon / carbon double bond with hydrogen peroxide in the presence of a catalyst comprising at least one selected from the metal salts of