JPS6023661B2 - Manufacturing method of cinnamic acid esters - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Chiferic acid esters are compounds useful as agricultural chemicals or raw materials for photosensitive resins.

-There are methods for producing the cinnamic acid esters, such as a method in which penzaldehyde and acetate are reacted in the presence of sodium metal, and a method in which benzaldehyde and acetic anhydride are reacted in the presence of alkali acetate. This method is not satisfactory for industrial scale implementation because it uses relatively expensive benzaldehyde and metallic sodium, which requires careful handling.

In order to solve this problem, the present inventors have conducted intensive research on a method for industrially advantageous production of cinnamic acid esters using inexpensive raw materials. Styrenes, carbon monoxide, alcohol and oxygen in the presence of a main catalyst consisting of a mixture with lead or iron salts,
Cinnamic acid ester is produced in good yield by carrying out the reaction while maintaining the partial pressure of carbon monoxide in the system at 18 kg/g or less at the time of supplying oxygen and/or carbon monoxide at the start of the reaction or during the reaction. He discovered a method and applied for a patent.

0 However, in the above application, it was thought that the yield of cinnamic acid ester was not very high when the partial pressure of carbon monoxide was 18k9/gauge or more, but when the present inventors continued their research, they found that Even if the partial pressure of carbon monoxide in the system is 18k9/■・G or more when oxygen and/or carbon monoxide is supplied at the start of the reaction or in the middle of the reaction, monoxide will not exceed the partial pressure of oxygen in the system. Carbon partial pressure ratio (hereinafter simply Pco/Po
The present inventors have discovered the novel fact that cinnamic acid esters can be obtained in good yield when the reaction is carried out while maintaining the amount of cinnamic acid esters (shown as 2) at 4 or less, and have completed the present invention.

In addition, phenylsuccinic acid gester is produced by reacting styrene, carbon monoxide, alcohol, and oxygen in the presence of a palladium chloride/cupric chloride catalyst at a partial pressure of carbon monoxide of 20k9/g. The fact that a small amount of cinnamic acid ester was created at that time was reported in Tokukan Sho 53-407.
Although it is described in the No. 0y publication, Pco/Po2 is 4 or more, which is different from the scope of the present invention.

In the present invention, as mentioned above, only when the reaction is carried out under specific conditions where Pco/Po2 is 4 or less, the main product is unexpectedly reversed and cinnamic acid esters are obtained in high yield; This is completely unexpected from the above literature. In carrying out the process of the present invention, it is necessary to use as the main catalyst a mixture consisting of a metal of the metal group or a compound thereof and a steel salt or an iron salt. Therefore, in order to improve the yield, '3' tertiary amine is further used in combination as appropriate. '1} Components include palladium, platinum, rhodium, ruthenium, iridium, osmium, and hydrochlorides, nitrates, sulfates, phosphates, acetates, oxides, etc. of these metals, among which palladium and palladium chloride are Particularly effective.

Further, these components can be used by being supported on a carrier such as activated carbon, silica gel, alumina, silica alumina, silica, magnesia, pumice, or molecular sieve. {2) Components include hydrochlorides, nitrates, sulfates, phosphates, and acetates of copper or iron, with cupric chloride and ferric chloride being particularly effective.

Next, {when a tertiary amine is used in the 3' component, trimethylamine, triethylamine, tripropylamine, tributylamine, tri-sec-propylamine, diethylmethylamine, dimethylpropylamine, allyldiethylamine, dimethylbutylamine, diethyl amine.

C3-C20 lipophilic tertiary amines such as lopylamine, penzyldimethylamine, dicyclohexylethylamine, and dimethylcyclohexylamine are useful.
The mixing ratio of {1}, '2) and {3- is the atomic ratio of platinum group metal or its compound '1} and copper or iron 1:0.01
~200, preferably in the range of 1:1 to 100, and the molar ratio of copper salt or iron salt
It is appropriate to use it in a range of 1:0.1 to 50. As raw materials, styrene, carbon monoxide,
Alcohol and oxygen are used, and styrenes include not only styrene but also Q-, 8-methylstyrene, Q-, 8-ethylstyrene, o1, m1, p-methylstyrene, o1, m
Styrene derivatives such as p-, p-ethylstyrene, and p- and rt-butylstyrene are used.

Alcohols include methanol, ethanol, propanol, butanol, oct/ol, nonanol, decanol, ethylene glycol, propylene glycol, cyclobenol, cyclohexanol, cycloheptanol, phenol, benzyl alcohol, etc. Various types can be used depending on the situation.

When carrying out the reaction using such raw materials in the presence of the above catalyst, the partial pressure of carbon monoxide in the system at the start of the reaction or at the time when carbon monoxide and/or oxygen is supplied during the reaction is 18k9. The Pco/Po2 of the reaction system must be set to 4 or less, preferably 3 or less.

When Pco/Po2 is 4 or more, many by-products are produced and the yield of cinnamic acid esters is reduced. Carbon monoxide and oxygen are introduced into the system by any method. Normally, carbon monoxide is charged all at once or in parts, and oxygen is charged in parts to avoid explosive limits, but in short, in the present invention, the carbon monoxide partial pressure at the start of the reaction or when additional raw material gas is charged is 18k9/ Earth/
Cinnamate esters can be obtained in good yield if the Pco/Po2 of the reaction system is maintained at 4 or less in the above reaction. Other conditions will be determined from the following ranges as necessary.

That is, the reaction temperature is room temperature to 250q0, preferably 50 to
17,000, the reaction pressure is normal pressure to 200 kg/G, preferably 5 to 150 k9/G, and the reaction time is 0.1 to 1
A range of 5 hours is appropriate. Further, as mentioned above, oxygen is preferably introduced in several portions so that the gas composition of the gas mixture in the reactor is outside the explosive range, and in view of safety.

Here, the oxygen may be oxygen, air, or an oxygen-containing gas obtained by arbitrarily diluting oxygen with an inert gas such as nitrogen, argon, or carbon dioxide. Furthermore, the reaction of the present invention may be carried out without a solvent or in a solvent that does not inhibit the reaction.

Examples of such soluble soot include methyl ethyl ether, diethyl ether, dipropyl ether, dimethyl ether,
Ethers such as dichloroethyl ether, ethyl phenyl ether, diethylene glycol, diethyl able, triethylene glycol diethyl ether, esters such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, or adipine acids, esters of organic acids such as succinic acid, phenylsuccinic acid, maleic acid, fumaric acid, propionic acid, acetoacetic acid, benzoic acid, aromatic hydrocarbons such as benzene, nitrobenzene, chlorobenzene, toluene, or cyclohexane, methyl Examples include alicyclic hydrocarbons such as cyclohexane. Furthermore, the combined use of a dehydrating agent such as molecular sieve, silica gel, orthoformic acid ester has the effect of improving the yield, making its use advantageous. After the reaction is complete, after cooling, remaining carbon monoxide, oxygen, and other gases are purged.
Separate the precipitate.

The target product is obtained by distilling the furnace liquid. Next, the method of the present invention will be explained in more detail by giving examples.

Example: In a 1300' autoclave, 0.3 mmoles (1.7 mmol) of palladium chloride and 2.0 mmoles (1 mmol) of palladium chloride were added.
4.9 mmol), triethylamine 3.0 mmol (29.
7 mmol), 31.3 mmol (300.3 mmol) of styrene, and 69.2 mmol (1500.0 mmol) of ethanol, and after replacing with carbon monoxide, heated to 120 qo.

Carbon monoxide partial pressure 30k9/G, oxygen partial pressure 10kg'
The reaction was started under the conditions of .G. During the reaction, oxygen was replenished twice at a rate of 3 kg'. 28k9/earth/G),
1 while keeping the Pco/Po2 of the system at about 2.3 to 1.8.
The reaction was carried out for 30 minutes. After the reaction was completed, the precipitate was filtered and the composition of the reactor liquid was analyzed using gas chromatography. It contained 113.1 mmol of styrene and 48.5 mmol of ethyl cinnamate, the conversion rate of styrene was 62.3%, and the yield of ethyl cinnamate based on the consumed styrene was 26%. Example 2 In Example 1, nitrogen gas was supplied at 20 k9/kg at the start of the reaction.
The same experiment as in the same example was conducted except that G was press-fitted.

Yield of ethyl cinnamate based on consumed styrene is 40.5%
Met. Example: 0.1 mol (0.6 mmol) of palladium chloride, 1 mol cupric chloride in a 3100' autoclave.
．． 0 mol (7.4 mmol), triethylamine 1.0 mol (9.9 mmol) and styrene 10.4 mol (100 mmol).
0 mmol), 11.0 mmol of ethanol (239.5 mmol), and 11 mmol of ethyl acetate were supplied.

Heated to 120q C to reduce carbon monoxide partial pressure to 30k9/earth.
The reaction was started under the conditions of G and oxygen partial pressure of 10 k9/unfavorable G.

Add carbon monoxide and oxygen in the same proportion as Example 1,
The reaction was continued for 1 hour and 3 minutes. Styrene 6 is used in the reactor liquid.
The yield of cinnamate ester based on the consumed styrene was 43.9%.

Example 4 The same method as Example 3 was carried out except that tributylamine was replaced with tributylamine.

Yield of ethyl cinnamate based on consumed styrene is 40.6%
Met. Example 5 The same method as Example 3 was carried out except that 22.0 g of n-butanol was used instead of ethanol, and the yield of n-butyl cinnamate based on the consumed styrene was 38.1%.

Example 6 The same method as Example 1 was carried out except that Molecular Sieve (Hiro 1'16) 10 minutes was used in combination.

The yield of cinnamic acid ester based on consumed styrene is 40.0
It was %. Example 7 The same method as Example 3 was carried out except that triethylamine was omitted.

The yield of cinnamic acid ester based on consumed styrene is 22.3
%Met. Example 8 In Example 1, the partial pressure of carbon monoxide at the start of the reaction was set to 27k9.
When the same method as in the same example was carried out except that Pco/Po2 of the reaction system was changed to 2.1 to 1.5, almost the same results were obtained.

Control Example In Example 1, the partial pressure of carbon monoxide at the start of the reaction was 50 kg.
', G, oxygen partial pressure to 10k9/G, and supply of carbon monoxide and oxygen during the reaction to 5k9'G, respectively.
, lk9/G, and the reaction was carried out while maintaining the Pco/Po2 of the reaction system at 5, hardly any formation of cinnamic acid ester was observed.

Claims (1)

[Claims] 1. Cinnamate esters are produced by reacting styrenes, carbon monoxide, alcohol, and oxygen using a mixture of (1) a platinum group metal or its compound, and (2) a copper salt or iron salt as a main catalyst. When producing, the partial pressure of carbon monoxide in the system at the time of starting the reaction or at the time of supplementing oxygen and/or carbon monoxide during the reaction is set to 18 kg/cm^2・G or more, and A method for producing cinnamic acid esters, characterized in that the reaction is carried out while maintaining the ratio of carbon monoxide partial pressure to oxygen partial pressure at 4 or less. 2. The manufacturing method according to claim 1, characterized in that a tertiary amine is used as a promoter.