JPS6219548A - Synthesis of aldehyde - Google Patents

Abstract

PURPOSE:To obtain the titled compound at a high reaction rate and in high selectivity, by oxidizing a compound having olefinic carbon.carbon double bond with hydrogen peroxide in the presence of a heteropolyacid as a catalyst and further a compound of elements selected from boron, phosphorus, etc. CONSTITUTION:A compound having olefinic carbon.carbon double bond as a raw material is oxidized with hydrogen peroxide in the presence of a catalyst consisting of two components of at least one of heteropolyacid and/or a salt thereof as the first component and at least one of a compound of elements selectd from boron, phosphorus, arsenic, antimony and bismuth as the second component as a catalyst to afford the aimed compound. Anhydrous hydrogen peroxide is preferred, and the amount thereof to be used is preferably 0.2-2mol based on one mol raw material compound. Preferably, the amount of the first component in the above-mentioned catalyst is 1.0X10<-4>-1.0X10<-2>mol based on one mol raw material, and the amount of the second component is 1.0X10<3>-1.0mol based on one mol raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of a heteropolyacid or a heteropolyacid salt and a compound having an olefinic carbon-carbon double bond in the presence of a compound selected from boron, phosphorus, arsenic, antimony, and bismuth, and peroxidation. This invention relates to a method for producing aldehydes by reacting hydrogen.

Conventional technologyAldehydes are important intermediate raw materials for various chemical products.Some aldehydes, such as glutaraldehyde, are also used in applications such as disinfectants, leather tanning agents, and microcapsule hardening agents, and are inexpensive and efficient. Development of a good manufacturing method is desired.

Conventionally known methods for producing aldehydes include a method in which 1,2-diol is synthesized from an olefin and oxidized with an oxidizing agent, or a method in which an oxydiamine compound (for example, cyclopentene oxide) is obtained from an olefin and oxidized. However, studies have also been conducted on processes for producing directly from olefins in consideration of simplifying the reaction route, improving aldehyde yield, safety, etc.

That is, as a method for producing aldehydes using compounds having olefinic carbon-carbon bonds as raw materials, a method using hydrogen peroxide with boron compounds and molybdenum salts as essential components (%
Publication No. 51-28606), a method using hydrogen peroxide containing a boron compound and a tungsten compound as essential components (Japanese Unexamined Patent Publication No. 57-95921), Periodic Table 4. yb, vb, wb, wb in the fifth and sixth periods.

and a method using alkylidene peroxide using one or more compounds of group II elements (Japanese Patent Application Laid-Open No. 57-145
Publication No. 826).

The above method for producing aldehydes using a compound having an olefinic carbon-carbon bond as a raw material requires a large amount of boron compound when a boron compound is used as a cocatalyst, and water in hydrogen peroxide used as an oxidizing agent or There is a problem in that there are many by-products such as 1,2-diol and carboxylic acid whose catalytic activity is significantly reduced due to the water produced by the reaction. 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 and is not necessarily advantageous in industrial production. I can't say it.

SUMMARY OF THE INVENTION The present inventors have discovered that the present inventors have developed an olefinic carbon-carbon double bond, which does not produce potentially explosive reaction intermediates such as ocinide, and which requires the shortest synthesis steps and is considered to be industrially promising. We investigated a one-step synthesis method for aldehydes by hydrogen peroxide oxidation of compounds, and first discovered a catalyst system consisting of at least 1s of heteropolyacids and/or heteropolyacid salts and filed an application (No. 4?m 1986-129958). )
. This time, we have completed the present invention by discovering that the reaction rate and selectivity can be significantly increased by further adding a compound of an element selected from boron, phosphorus, arsenic, antimony, and bismuth to the above catalyst.

That is, the present invention provides olefinic carbon/carbon dioxide in the presence of at least Ial of a heteropolyacid and/or heteropolyacid salt and at least one compound of an element selected from boron, phosphorus, arsenic, antimony, and bismuth. The present invention relates to a method for synthesizing aldehydes, which is characterized by oxidizing a compound having a heavy bond with hydrogen peroxide.

Catalyst The first component of the catalyst used in the present invention comprises at least one known heteropolyacid and/or heteropolyacid salt. Particularly preferred heteropolyacids include heteroatoms of P and A.
s, Si, B or Ge, IJ child is Mo, W,
It is a heteropolyacid of Nb, V, and a Keggin structure or its angular body, which is a mixed coordination thereof. Further, the heteropolyacid salts are those of the above-mentioned heteropolyacids of Group Xia, Group X, and Group II of the periodic table.

Group 1 metal salts, organic base salts such as ammonium and amine salts, and partial salts may also be used. Heteropolyacids and heteropolyacids can be prepared using known methods such as iM! It can be torn. For example, a heteropolyacid having a Keggi (n) structure can be obtained by heating an acidic aqueous solution containing a polyatom oxyacid salt such as sodium molybdate, a heteroatom simple oxyacid, or a salt thereof.

12 Na2Mob4+Na25in3+26 HCI
! 4 H4SiMo1204o+26 Nac/! +
11 H20 heteropolyacid, for example, by neutralizing the free heteropolyacid with a predetermined amount of base! Ill get it.

Examples of the base include alkali metal carbonates, monobicarbonate alcolade, and organic bases such as pyridine and triethylamine. Examples of heteropolyacids and heteropolyacids include the following.

Phosphormolybdic acid, arsenic molybdic acid, silicomolybdic acid, germanomolybdic acid, boromolybdic acid, phosphomolybdotungstic acid, phosphomolybdovanadate, phosphomolybdoniobic acid, phosphomolybdotungstoniobic acid, phosphomolybdotane Guest vanadate, arsenic molybdotungstic acid, arsenic molybdovanadate, arsenic molybdoniobic acid, arsenic molybdotungest niobic acid, arsenic molybdotungest vanadate, silicon molybdo tungstic acid, silicon molybdo tungstoniobate, silicon molybdo tungest Nocunadic acid, germanomolybdotungstic acid, germanomolybdotungstoniobic acid, germanomolybdotungstvanadate, bomolybdotungstic acid, bomolybdotungestonacnadic acid, bomolybdotungstoniobate, Phosphotungstic acid, arsenic tungstic acid, silicotungstic acid, germactungstic acid, borotungstic acid, phosphotungstovanadic acid.

Phosphorous tungstoniobate, arsenic tungstovanadate,
Arsenic tungstonniobic acid, silica stovanadic acid,
Silicotungstonniobic acid, germanotungustvanadic acid, germanotanstvanadic acid, borotungstvanadic acid, phosphorvanadic acid, phosphovanadic acid, arsenic vanadate, civanadic acid, germanovanadic acid,
Bovanadic acid, phosphoniobic acid, arsenic niobic acid, keiniobic acid, germanoniobic acid, boronibic acid and their lithium salts, sodium salts, potassium salts, rubidium salts, and cesium salts.

Beryllium salts, magnesium salts, calcium salts.

Strontium salts, barium salts, copper salts, silver salts.

Metal salts such as zinc salts, cadmium salts, iron salts, cobalt salts, nickel salts, ruthenium salts, rhodium salts, palladium salts, platinum salts, and organic base salts such as ammonium salts, trimethylamine salts, triethylamine salts, pyridine salts, etc. It will be done.

When a heteropolyacid is used as a catalyst, it can be used as a heteropolyacid and a base separately in advance, or the heteropolyacid and a base can be added to the reaction system and used as a heteropolyacid in the reactor. .

Although heteropolyacids and heteropolyacid salts 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 first catalyst of the present invention
The use of components i can vary over a wide range, but in general, j, OX 10-5 to 1. OX 10-1
moles, preferably 1. OX 10 ~1. OX10
It is in the molar range.

Next, the second component of the present invention, a compound of selected elements such as boron, phosphorus, arsenic, antimony, and bismuth, is
It is as follows.

Boron compounds include boron oxide, boric acid, borates, boric esters, boron halide, boron phosphate, and boron complex compounds, boric anhydride, metaboric acid, orthoboric acid, and sodium orthoborate. , sodium metaborate, magnesium orthoborate, magnesium metaborate, calcium orthoborate, zinc orthophosphate, aluminum orthoborate,
Trimethylboric acid, triethylboric acid, triphenylboronic acid, trimethylboroxine, triethylboroxine,
Examples include tributylboroxine, boron trifluoride, and dimethyl etherate, diethyl etherate, phenolate, and acetate thereof, and boric anhydride, metaboric acid, orthoboric acid, and boron trifluoride are particularly preferred.

Phosphorus compounds include phosphorus oxide, phosphorus oxyacids, phosphorus oxyacids and esters, phosphorus halides, phosphides and phosphorus complex compounds, phosphorus pentoxide, phosphorus trioxide, orthophosphoric acid,
Birophosphoric acid, metaphosphoric acid, northophosphorous acid, pyrophosphorous acid,
Polymetaphosphoric acid, polymetaphosphorous acid, monoperphosphoric acid, diperphosphate, sodium orthophosphate, sodium birophosphate, sodium metaphosphate, sodium phosphite, magnesium orthophosphate, magnesium pyrophosphate, magnesium metaphosphate, Magnesium phosphate, 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 trioxide, orthophosphoric acid, and birophosphoric acid are preferred.

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

Antimony compounds include antimony oxide, antimonic acid,
Antimony salts and esters, antimony norogenides, antimonides, antimony salts, and antimony complex compounds, and these compounds include antimony trioxide, antimony tetroxide, antimony pentoxide, antimonite, antimonic acid, antimony suboxide. acid sodium,
Sodium antimonate, magnesium antimonite, magnesium antimonate, calcium antimonite, calcium antimonate, antimony trichloride, antimony pentafluoride, antimony trichloride, antimony pentachloride, antimony arsenite, antimony arsenate, phosphoric acid Particularly preferred are antimony, tetramethylbistivine, tetramethylbistivine, triphenylstipine, tetramethylbistivine, etc., antimony trioxide, 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. acid, sodium bismuthate, bismuth trioxide, bismuth pentafluoride, bismuth trimide, trimethyl bismuthine, triethyl bismuthine, triphenyl bismuthine, bismuth carbonate, bismuth phosphate, bismuth arsenite, bismuth arsenate, etc. Particularly preferred are reed, bismuth pentoxide, bismuth acid, bismuthous acid, and bismuth trioxide.

The amount of the second component to be used is generally 1.0 mol per mol of the raw material olefinic carbon-carbon double bond-containing compound. OX
10 to 5 moles, preferably 1. OX 10-'~1.0
It is a mole.

Solvents preferably used in the method of the invention include carboxylic acids, phosphoric acids, sulfonic acids, 7-osphonic acids, phosphinic acids and their esters, acid amides and alcohols, such as ethyl acetate, butyl acetate, amyl acetate. , hexyl acetate,
These include octyl acetate, ethylglobionate, butylpropionate, tributyl phosphate, trioctyl phosphate, methanophosptaonic acid dimethyl ester, dimethylformamide, 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 preferred. That is, anhydrous hydrogen peroxide is preferred, but
When 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 0.1 to 10% per mole of the raw material compound having an olefinic carbon-carbon double bond.
mol, preferably in the range of 0.2 to 2 mol.

Compounds having an olefinic carbon-carbon double bond suitable for use in the present invention have the following general formulas: hydrogen, phenyl group, hafyl group, C1-C6 alkyl group, C4-C6 alkoxy group, nitrile group, etc. A phenyl group or a C1-C180 chain or branched alkyl group having a substituent, or a straight chain or branched alkyl group substituted with a halogen, hydroxyl group, alkoxy group, carbalkoxy group, nitrile group, cycloalkyl group, or aromatic residue. , is a branched alkyl group. Furthermore, 4CR and R can be combined with each other to form a cyclic compound such as a cycloolefin).

Examples of straight-chain or branched alkyl groups include methyl,
ethyl, propyl, n-butyl, isobutyl, tart
-7” tyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, hexadecyl, octadecyl, and isomers thereof.

Among these, alkyl groups of KC2 to C6 are often used.

Examples of substituted linear or branched alkyl groups include chloromethyl, β-chloroethyl, 2-(β-ethyl)
-hexyl, 2,4-diisopropyl, hydroxymethyl, l-hydroxyethyl, ω-hydroxyhexyl,
2-hydroxymethylhexyl, /-methoxyethyl,
3-propoxypropyl, n-hexoxymethylhexyl, 2, 4, 6-)! J methoxyhexyl, 2-(methoxymethyl)-propyl, carbomethoxymethyl, 5-
(carbopropoxy)-propyl, 3-(carbomethoxy)-hexyl,! -cyanoethyl, 2-(β-cyanoethyl)-propyl, ω-cyanoheptyl and ω-cyanooctyl, phenylmethyl, phenylethyl, phenylpropyl, phenyl-tert, -7'thyl, ω-
f8 such as phenylhexyl.

Examples of phenyl groups having substituents include mineral, 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, 4-chloro-2-methoxyphenyl, 4-7' loboxyphenyl, 4-tart, -butoxyphenyl,
4-n-hexoxylphenyl, 4-cyanophenyl,
Examples include 4-cyano-3,5-dimethylphel.

Examples of olefins and olefinic compounds having the above substituents are as follows: ethylene, propylene, 1-butylene, 2-butylene, imbutylene, 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, 1.1.4.4-tetrachloro-2-butene, 6-chloro-1-hexene, 1.
6-X) ley o -3-hexene, 7-chloro-1-heptene, 7,6-dichloro-2-heptene? y,
1,7-chloro-3-heptene, 3,5,7-dolichloro-1-octene, 1,8-dichloro-4-octene,
1e2-dicyclobutylethylene, 1,2-dicyclohexylethylene, 1,2-dicyclopentylethylene,
1a2-dicyclododecylethylene, 3-hydroxy-
1-propene, 1,6-cyhydroxy-3-hexene,
3-methoxy-1-propene, 1,4-dimethoxy-1
-butene, 1-dimethoxy-3-hexene, 1,6-
Diproboxy-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, 1,2-9-(p-fluorophenyl)-ethylene , 1,2-di(2,4-dimethylphenyl)-ethylene, 1,2->-(p-cyclohexylphenyl)-ethylene, 2-di(2-chloro-
4-tart, -butylphenyl)-ethylene, 1.2
-di(1-tert,-butylphenyl)-ethylene, 1,4-divinylbenzene, 2,4-cyhinylbenzene, p-/lorophenylethylene and p-fluorophenylethylene.

1-phenyl-2-butene, 1-phenyl-3-butene, cyclopentene,! -Chloroto 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-'1710 piroute 2-cyclopentene, 4-tart, -butyrote 2-cyclopentene, 3,5-diphenyl-1,2-cyclopentene, 6,5-di (4-chlorophenyl)-1,2- Cyclopentene, 4-phenylroot 2-cyclopentene,
3-methoxy-1,2-cyclopentene, 4-propoxyto-2-cyclopentene, 3,5-diynepropoxy-1,2-cyclopentene, 4-tart, -butoxy-1,2-cyclopentene, 4-n-hexoxy-1・
2-cyclopentene, 5-carbomethoxy-1,2-cyclopentene, 4-carbobroboxyto-2-cyclopentene, 3,5-di[(β-carbomethoxy)-ethyl]-1,2-cyclopentene, 3-cyanof・2-cyclopentene, 4-cyanocyclopentene, 4-(β-
cyanethyl)-1,2-cyclopentene, 3-fluoro2-cyclopentene, 3-trifluoromethyl-
1,2-cyclopentene, cyclohexene, 3-fluoro-1,2-cyclohexene, 3-trifluoromethyl-1,2-cyclohexene, 3-chloroa-1,2-cyclohexene, 4-chloro-2-cyclohexene, 5-
Chloroto 2-cyclohexene, 4,5-dichloro-1
・2-cyclohexene, 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-2-cyclohexene,
4,5-diphenyl-1,2-cyclohexene, 4-(
p-chlorophenyl)-1,2-cyclohexene, 3-
Methoxylate 2-cyclohexene, 4-ethoxy-1.
2-cyclohexene, 5-isoproboxyto 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-tri)thiruto 2-cycloheptene, 5-isopropyl-1,2-cycloheptene, 5-tart,
-Butyroot 2-cycloheptene, 3-k o o -'
y rio hair'ten, a-(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-cyclohebutene, 5-phenylroot 2-cycloheptene, 4,5-di((p -t
art, -butyl)-phenyl]-1,2-cycloheptene, 3-methoxy-1,2-cycloheptene, 5-methoxy-1,2-cycloheptene, 5-proboxito2-cycloheptene, 5-tart, -butoxyto2
-Cycloheptene, 3-carbomethoxy-1,2-cycloheptene, 4-carbomethoxy-1,2-cycloheptene, 3,1-dicarbomethoxy-1,2-cycloheptene and 5-(β-carbomethoxy)-ethyl- 1・
2-cycloheptene and the like.

Reaction conditions The method of the present invention is carried out at -40C to 80C, preferably OC
Perform at a temperature range of ~60C. Pressure is determined by other conditions (temperature, solvent, etc.) but has no 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. After the reaction, the aldehyde in the reaction mixture can be separated by a known method such as distillation. For example, the aldehyde can be separated by a method such as distillation. Distillation may involve thermal decomposition and reduce the yield of the product, so consideration should be given to conducting it under reduced pressure.

Effects of the invention When producing an aldehyde in one step in the presence of a compound having an olefinic carbon-carbon double bond, hydrogen peroxide, and a siheteroboric acid (in-situ) catalyst, a compound selected from boron, phosphorus, arsenic, antimony, and bismuth at least one compound of the element
The method of the present invention in which the two coexist allows the process to be carried out more efficiently.

The present invention will be explained in more detail below using actual examples, but the present invention is not limited thereto.

In addition, in all the examples, analysis of products was carried out using diatomaceous earth carrier.
Gas chromatographic analysis was performed using a 3 m column supporting 5% (5% nonylphenoxy polyethylene oxy) ethanol and using butyl acetate as an internal standard.

Example-1 In a 200TILt glass crack reactor equipped with a stirrer and a reflux condenser, 14.0.9% of cyclopentene, 0.15 mol% of phosphomolybdic acid (Kokan Kagaku M) and 150% of phosphomolybdic acid (Kokan Kagaku M) were added to hydrogen peroxide. ! After adding 1.0 mol% of i (manufactured by Kokan Kagaku), the temperature was raised to 35G, and while stirring, 10% of hydrogen peroxide was added.
．． A solution of tributyl phosphate containing 4% by weight45.
9 was added dropwise over 20 minutes.

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

As a result, 5.9% by weight of glutaraldehyde, 1.0% by weight of 1,2-cyclobentanediol,
% cyclopentene oxide was present. The produced glutaraldehyde was equivalent to 16.9 mol % based on the raw material cyclopentene.

Example 2 A reaction was carried out in the same manner and under the same conditions as in Example 1, except that 1.0 mol % of niline pentoxide (Kokan Kakishiki) was added to hydrogen peroxide in place of arsenous acid.

As a result, 3.6% by weight of glutaraldehyde and 0.54% by weight of 1,2-cyclobentanediol were present in the liquid. The amount of glutaraldehyde produced was equivalent to 10.5 mol 5 based on the raw material cyclopentene.

Example-3 The reaction was carried out in the same manner and under the same conditions as in Example-1, except that 1.0 mol% of nitimony dioxide (sb203 manufactured by Koso Chemical Co., Ltd.) was added to hydrogen peroxide instead of arsenite. Ta. As a result, the liquid contained 2.6% glutaraldehyde and 0% glutaraldehyde.
There was 25% by weight of 1,2-cyclobentanediol. The produced glutaraldehyde corresponds to 7.5 mol % based on the raw material cyclopentene.

Example-4 The same method and conditions as Example-1 were used except that 0.5 mol% of bismuth oxide (B-Ko 203, I-Toso Kagaku Co., Ltd.) was added to hydrogen peroxide instead of arsenite. The reaction was carried out. As a result, 1.8% by weight of glutaraldehyde and 0% by weight of glutaraldehyde were found in the liquid.
24 weight i% of 1,2-cyclohentanediol was present. The produced glutaraldehyde corresponds to 5.1 mol % based on the raw material cyclopentene.

Example-5 Example-5 except that 1.0 mol% of boric anhydride (B203, manufactured by Kokan Kagaku) was added to hydrogen peroxide instead of arsenous acid.
The reaction was carried out in the same manner and under the same conditions as in Example 1. As a result, 2.4% by weight of glutaraldehyde and 0.18% by weight of 1,2-cyclobentanediol were present in the liquid. The amount of glutaraldehyde produced is 6.9% based on the raw material cyclopentene.
Corresponds to mol%.

Example-6 1 part of boric anhydride from Example-5 per hydrogen peroxide
The amount was increased to 0 mol %, and the reaction was carried out in the same manner and under the same conditions as in Example-1. As a result, 2.2% by weight of glutaraldehyde was present in the liquid! :(106 weight 5 of 1,2-cyclobentanediol was present. The produced glutaraldehyde corresponded to 6.1 mol% based on the raw material cyclopentene.

Example 7 A reaction was carried out in the same manner and under the same conditions as in Example 1, except that phosphoric acid (H3PO4, Okan University of Science and Technology) was added in an amount of 10 mol % based on hydrogen peroxide instead of arsenous acid.

As a result, 3.5% by weight of glutaraldehyde and 0.40% by weight of 1,2-cyclobentanediol were present in the liquid. The produced glutaraldehyde is 9.9% of the raw material cyclopentene.・Equivalent to 7 mol%.

Example-8 Example-8 except that 2.0 mol% of phosphorous acid (83P03, Kokan Kagaku #) was added to hydrogen peroxide instead of arsenous acid.
Reaction 1 was carried out using the same method and conditions as in Example 1. As a result, 2.1% by weight of glutaraldehyde and 0.43% by weight of 1,2-cyclobentanediol were present in the liquid. The generated glutaraldehyde is 6.
It corresponds to 1 mol%.

Example-9 Cyclopentenes 1a and 21 were placed in the same reactor as Example-1.
and phosphomolybdic acid 0.42 mol5 per hydrogen peroxide
After adding 1.0 mol% of niline pentoxide, the temperature was raised to 35C, and 45.9% of a solution of tributyl phosphate containing 10.5% by weight of hydrogen peroxide was added dropwise over 20 minutes while stirring. After further stirring at 55C for 3 hours, the reaction solution was analyzed by gas chromatography. As a result, 7.8 weight percent of glutaraldehyde and 1.6 weight percent of O1,2-cyclobentanediol were present in the liquid.

The produced glutaraldehyde is 2 times the raw material cyclopentene.
This corresponds to 2.5 mol%.

Comparative Example-1 A solution of tributyl phosphate containing 10.6% by weight of hydrogen peroxide and phosphomolybdic acid (Shokankajiten) were mixed with hydrogen peroxide in a 200-glass reactor equipped with a stirrer and a reflux condenser. After adding 0.42 mol% to
Cyclopentene 14.5.19 was added dropwise over 10 minutes while stirring.

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

As a result, the liquid contained 5.5% by weight of glutaramphiitide and 1.47% by weight of 1,2-cyclobentanediol.
O,Oa wt% cyclopentene oxide was present.

The amount of glutaraldehyde produced is 1 for the raw material cyclopentene.
This corresponds to 5.5 mol%.

Comparative Example-2 A reaction was carried out in the same manner and under the same conditions as in Example-1 without adding arsenous acid. As a result, 1.3% by weight of glutaraldehyde and 0.31% by weight of 1.2-cyclobentanediol were present in the liquid. The amount of glutaraldehyde produced was 3.8 mol% based on the raw material cyclopentene.

Comparative Example 2 and Examples 1 to 8 show that the addition of arsenic, phosphorus, antimony, bismuth, and boron compounds also improved the reaction rate and glutaraldehyde selectivity. In this example, the effects of the compounds of arsenic, phosphorus, and antimony are remarkable. Further, Example 9 and Comparative Example 1 show that this tendency remains the same even when the concentration of heteropolyacid is changed.

Dissolve Na2HPO4-2H208,15# in 200cc of water and add Na2WO4-2H2049,87J there.
' and Na2WO4''2H2022,66& were added and dissolved. It was kept at 80C for 3 hours with stirring.The solution was concentrated by about 100 CCK in an evaporator.Then, the concentrated solution was heated to 80 CIC and dissolved by 24% by weight while stirring.
100 cc of salt Mt was added dropwise. After cooling to room temperature 200
cc of ethyl ether was added. The heteropolyacid etherate in the bottom layer separated into three layers was separated using a separating funnel, evaporated to dryness again using an evaporator, and further evacuated at room temperature to form a mixed coordinated phosphorus molybdenum with 9 molybdenum atoms and 5 tungsten atoms. 1 l of tungstic acid was prepared.

14.51 cyclopentene was added to the same reactor as in Example-1.
After adding 0.05 mol% of phosphomolyptanstonic acid and 2.0 mol% of phosphoric acid prepared above to hydrogen peroxide, the temperature was raised to 35 CK, and 10 mol% of hydrogen peroxide was added while stirring.
．． Solution of tributyl phosphate containing 7% by weight 459
was added dropwise over 20 minutes. After further stirring at 35C for 5 hours, the reaction solution was analyzed by gas chromatography. As a result, the solution contained 8.0% by weight of 2.1% by weight of glutaric acid.
% of 1,2-cyclobentanediol was present. The produced glutaraldehyde is 22% of the raw material cyclopentene.
This corresponds to 5 mol%.

14.51 cyclopentene was added to the same reactor as in Example-1.
1 and hydrogen peroxide in Example-10! After adding 0.05 mol% of phosphomolybdotungstic acid and 2.0 mol% of boric anhydride, the temperature was raised to 35C, and while stirring, a solution of tributyl phosphate containing 1α7% of hydrogen peroxide, 9 t. -Dropped in 20 minutes. 55 more
After stirring at C for 5 hours, the reaction solution was analyzed by gas chromatography. As a result, 4.2% by weight of glutaraldehyde and 0.43"M% of 1,2-cyclobentanediol were present in the liquid. The produced glutaraldehyde was 11.9 mol 5 based on the raw material cyclopentene. Equivalent to.

Example-12 Cyclopentene 14.2 was added to the same reactor as Example-1.
After adding 0.15 mol % of phosphomolybdotungstic acid prepared in Example-IQ and 10 mol of boric anhydride to N and hydrogen peroxide, the temperature was raised to 35 C, and 10.5 mol % of hydrogen peroxide was added while stirring. A solution 451 of tributyl phosphate containing heavy weight was added dropwise over a period of 20 minutes. Furthermore, 3 with 35tZ'
After stirring for an hour, the reaction solution was analyzed by gas chromatography. As a result, 8.2% by weight of glutaraldehyde and 2.6% by weight of 1,2-cyclobentanediol were present in the liquid. The produced glutaraldehyde was equivalent to 23.6 mol % based on the raw material cyclopentene.

The reaction was carried out in the same manner and under the same conditions as in Example 12, except that the anhydrous sulfur was used in an amount of 20 mol %. As a result, 7.
1 weight 5 of glutaraldehyde and 1.3 weight of glutaraldehyde 1,2
- cyclobentanediol was present. The generated glutaraldehyde was equivalent to 20.8 mol % based on the raw material cyclopentene.

Comparative Example-3 Cyclopentene 14.2 was added to the same reactor as Example-1.
After adding phosphomolybdotungstic acid O, OS mol% prepared in Example-10 to jl and hydrogen peroxide, 35
The temperature was raised to C.C., and while stirring, a solution 45II of tributyl phosphate containing 10.5 weight grams of hydrogen peroxide was added dropwise over 20 minutes.

After further stirring at 35C for 5 hours, the reaction solution was analyzed by gas chromatography. As a result, 111 (3,8
% by weight of glutaraldehyde and 1.2% by weight of 1,2-
Cyclobentanediol was present. The generated glutaraldehyde was equivalent to 10.9 mol% based on the raw material cyclopentene.

In addition, even in the case of a complex coordination type heteropolyacid, as in Examples 10 to 13, it can be seen that when a cocatalyst is added to the heteropolyacid, the reaction rate and selectivity are improved.

Na2MoO4.2H20 and Na2No4'' so that the atomic ratio of molybdenum and tungsten is 6:6.
Phosphormolybdotungstic acid was used under the same conditions as Example 10, but with a different amount of 2H20! ! Made by lil. Next, this phosphomolybdotungstic acid was dissolved in pure water, and a chemical equivalent of N12CO3 of the phosphomolybdotungstic acid was added. Water was removed and evaporated to dryness using an evaporator. Further, vacuum evacuation was carried out at room temperature for 3 hours to obtain phosphomolybdotungstic acid league (Ha3PM06W604 (1).
and hydrogen peroxide, 0.15 mol% of the above prepared sodium phosphomolybdotungstate and 5.0% of boric anhydride.
After adding 0 mol%, the temperature was raised to 35C, and while stirring, a solution 45II of tributyl phosphate containing 10.5% by weight of hydrogen peroxide was added dropwise over 20 minutes. After further stirring at 35C for 3 hours, the reaction solution was analyzed by gas chromatography. As a result, 8.0 weight units of glutaraldehyde and 1.2 weight units of 1,2-cyclobentanediol were present in the liquid. The produced glutaraldehyde was equivalent to 23.2 mol % based on the raw material cyclopentene.

Comparative Example 4 A reaction was carried out in the same manner and under the same conditions as in Example 14, except that boric anhydride was not added, and the reaction solution was analyzed by gas chromatography. As a result, 6.7% by weight of glutaraldehyde and 2.0% by weight of 1,2-cyclobentanediol were present in the liquid.

The amount of glutaraldehyde produced is 1 for the raw material cyclopentene.
This corresponds to 9.3 mol%.

Reactor similar to Example-1 VC3-hexene 17.5.
After adding 0.42 mol% of phosphomolybdic acid and 1.0 mol% of niline pentoxide to 9 and hydrogen peroxide, the temperature was raised to 35C, and while stirring, tributyl phosphoric acid containing 10.4% by weight of hydrogen peroxide was added. 45.9 was added dropwise over 20 minutes. After further stirring at 35C for 3 hours, the reaction solution was analyzed by gas chromatography. As a result, 2.5 times ■
% propionaldehyde was present. The amount of pyrropionaldehyde produced was 14.6 mol % based on the raw material 3-hexane.

Comparative Example-5 10.4 heavy fr of hydrogen peroxide was added to the same reactor as in Example-1.
After adding 0.42 molsi of tributylphos 7a) 45Ji' trimolybdic acid to hydrogen peroxide, the temperature was raised to 35CK, and without stirring, 17.3% of 3-hexene was added.
p was added dropwise over 10 minutes.

After continuing to stir at 35C for 3 hours, the reaction solution was analyzed by gas chromatography, and it was found that 2.15% by weight was present in the reaction solution.
of propionaldehyde. This accounts for 10.8 mol% of the added 3-hexene.

This result shows that Example 15, in which niline pentoxide was added, had a higher reaction rate even in the case of oxidizing 6-hexene.

Claims (1)

[Claims] At least one of the heteropolyacids and/or heteropolyacids
oxidizing a compound having an olefinic carbon-carbon double bond with hydrogen peroxide in the presence of at least one compound of type and element selected from boron, phosphorus, arsenic, antimony, and bismuth. A method for synthesizing aldehydes.