JPH11199536A - Production of benzaldehyde compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a benzaldehyde compound, capable of improving a hydrolysis rate, when a (non)substituted benzal halide compound and water are mixed and heated, by using a specific catalyst without using a metal salt catalyst. SOLUTION: This method for producing a benzaldehyde compound comprises hydrolyzing a (non)substituted benzal halide compound. Therein, the hydrolysis reaction is carried out in the presence of a catalyst (preferably toluenesulfonic acid) having affinity with water and/or the benzal halide compound. Preferably, a benzal halide compound of formula I [X is a halogen; Y is a halogen, nitro or the like; (n) is 0-5] such as benzal chloride is hydrolyzed to obtain a benzaldehdye of formula II. The catalyst is preferably added in an amount of 0.1-30 mol.% per mole of the benzal halide compound, and the water is allowed to coexist in an amount of 150-300 g on the hydrolysis reaction. The reaction is preferably performed in an atmosphere of nitrogen, because the product is easily oxidized. The reaction temperature is preferably 80-160 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to pharmaceuticals, agricultural chemicals, dyes,
The present invention relates to a method for producing benzaldehydes useful as perfumes and other organic synthesis raw materials.

[0002]

2. Description of the Prior Art Simply mixing and heating benzal halides with water results in a slow rate of hydrolysis to benzaldehydes. Therefore, various metal salt catalysts have conventionally been used to hydrolyze benzal halides. In addition, a method for producing benzaldehydes is known. For example, (1) A method of producing benzaldehyde by making cuprous chloride or cupric chloride exist and hydrolyzing benzal chloride (see Japanese Patent Publication No. 46-7927). (2) A method in which an aqueous solution of an iron salt is added to benzal chlorides and hydrolyzed to produce benzaldehydes (see JP-B-48-693). (3) A method of producing benzaldehydes by hydrolyzing benzal chlorides in the presence of anhydrous zinc chloride (see Japanese Patent Publication No. 38-766).

[0003]

However, these conventional methods have the following disadvantages and are not industrially suitable. That is, in the method (1) using cuprous chloride or cupric chloride, when the amount of the catalyst used is increased or the reaction temperature is increased, a decomposition product is by-produced. The method of (2) using an iron salt as a catalyst has a possibility that the iron salt catalyst acts as a Friedel-Crafts catalyst as a side reaction to cause resinification. The method of (3) using anhydrous zinc chloride as a catalyst is not industrially easy to handle because anhydrous zinc chloride used as a catalyst has such a high hygroscopicity that it is used as a dehydrating agent for organic compounds. In addition, since any of the above methods (1), (2) and (3) involves the generation of hydrogen halide gas as a by-product, when the melting points of benzal halides and benzaldehydes are high, the method is performed in an exhaust gas line. It may crystallize and block. In terms of equipment, equipment for absorbing by-product hydrogen halide gas is required.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for improving the rate of hydrolysis when mixing and heating benzal halides and water without using a metal salt catalyst. It is to provide.

[0005]

Means for Solving the Problems The present inventors have studied an industrial synthesis method of benzaldehydes in order to solve the above problems. As a result, organic sulfonic acid compounds and salts thereof, polyoxyalkylene glycols and derivatives thereof,
It has been found that the hydrolysis rate can be increased by the presence of a catalyst having an affinity for water and / or benzal halides, such as alkoxy alcohols and quaternary ammonium salts. Further, they have found that industrially simple synthesis can be achieved by absorbing part or all of the by-produced hydrogen halide in coexisting water, and have completed the present invention.

That is, the present invention relates to a process for producing a corresponding benzaldehyde by hydrolyzing a substituted or unsubstituted benzal halide, wherein a catalyst having an affinity for water and / or benzal halide is provided. A method for producing benzaldehydes, wherein a hydrolysis reaction is performed under the following conditions.

Hereinafter, the present invention will be described in detail.

The benzal halide used in the method of the present invention is not particularly limited, but may be represented by the following general formula (1):

[0009]

Embedded image

The benzal halides represented by the following formulas are exemplified as preferred ones. In the formula, X represents a halogen atom such as fluorine, chlorine, bromine, iodine, etc., Y represents a substituent such as a halogen atom, an alkyl group, a nitro group, a phenoxy group and the like, and n represents an integer of 0 to 5.

The benzal halides represented by the general formula (1) include, specifically, benzal chloride, benzal bromide, o-, m- or p-chlorobenzal chloride, o-, m- or p-bromobenzal chloride, o-, m- or p-fluorobenzal chloride, o-, m- or p-chlorobenzal bromide, o-, m- or p-bromobenzal bromide, o
-, M- or p-fluorobenzal bromide, 2,4
-Dibromobenzal bromide, 2,6-dibromobenzal bromide, 2,4,6-trichlorobenzal chloride, α, α, α, α-tetrabromo-o-xylene, α, α, α, α-tetrabromo- m-xylene,
α, α, α, α-tetrabromo-p-xylene, o-,
m- or p-nitrobenzal chloride, o-, m- or p-nitrobenzal bromide, o-, m- or p-
Phenoxybenzal chloride, o-, m- or p-phenoxybenzal bromide, o-, m- or p-methoxybenzal chloride, o-, m- or p-methoxybenzal bromide, o-, m- or p-cyanobenzal chloride, o-, m- or p-cyanobenzal bromide, o-, m- or p-methylbenzal chloride, o-, m- or p-methylbenzalbromide, o
-, M- or p-butyl benzal chloride, o-, m
-Or p-butyl benzal bromide and the like.

The catalyst used in the present invention is not particularly limited as long as it has an affinity for water and / or benzal halides. Examples thereof include organic sulfonic acid compounds and salts thereof, and polyoxyalkylenes. Glycols and derivatives thereof, alkoxy alcohols, quaternary ammonium salts and the like can be mentioned.

Specific examples of the organic sulfonic acid compound and salts thereof include toluenesulfonic acid, polystyrenesulfonic acid, sodium toluenesulfonic acid, sodium polystyrenesulfonic acid, sodium dodecyl sulfate and the like. Specific examples of polyoxyalkylene glycols and derivatives thereof include polyethylene glycol,
Examples thereof include polypropylene glycol. Specific examples of the alkoxy alcohols include methyl cellosolve and ethyl cellosolve. 4th
Specific examples of the class ammonium salts include tetrabutylammonium bromide, cetyltrimethylammonium bromide, and the like. Of these, toluene sulfonic acid is particularly preferred.

These catalysts having an affinity for water and / or benzal halides may be used alone or as a mixture of two or more kinds. The amount of the catalyst added increases the hydrolysis rate. Therefore, it is preferable to increase the amount, but preferably 0.1 to 0.1 mol per mol of benzal halides as a raw material.
The ratio is 50.0 mol%, more preferably 0.1 to 30.0 mol%.

[0015] The hydrolysis reaction may be carried out under either pressure or normal pressure, and is preferably carried out at a reaction temperature of 60 ° C to 160 ° C. More preferably 80 ° C to 1
The temperature range is 60 ° C.

The process of the present invention can be carried out in the presence or absence of an inert solvent in which benzal halides are dissolved. Examples of such an inert solvent include toluene, xylene, chlorobenzene, bromobenzene, dichlorobenzene, ethylbenzene, nitrobenzene and the like. Of these, the use of chlorobenzene is preferred.

The amount of water coexisting during the hydrolysis reaction is preferably an amount of water capable of absorbing all by-produced hydrogen halide.
More preferably, the ratio is 150 g to 300 g per 1 mol of the benzal halides as the raw material. In the case where a facility for absorbing the by-product hydrogen halide gas is provided, it is not necessary to absorb all of the by-product hydrogen halide gas in the coexisting water.

The raw materials used in the present invention include not only pure benzal halides but also benzyl halides or benzotrihalides which are by-produced when bronzing toluene to produce benzal halides. Benzal halides containing the following can also be used.

This reaction proceeds under a nitrogen atmosphere or under a condition without nitrogen substitution, but it is generally preferable to carry out the reaction in a nitrogen atmosphere because the generated benzaldehyde is easily oxidized.

[0020]

According to the method of the present invention, the production of benzaldehydes can be easily carried out without clogging the vent condenser and without a facility for absorbing by-product hydrogen halide gas. Useful as a manufacturing method.

[0021]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The analysis of reaction products in the following Examples and Comparative Examples was performed by gas chromatography.

Example 1 8.6 g of p-toluenesulfonic acid monohydrate and 140.5 g of water were added to 146.9 g of O-bromobenzal bromide.
g was added and the mixture was reacted at the boiling point for 23 hours under stirring conditions. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of O-bromobenzaldehyde was 77.3 g.
(Yield 93.5%). No blockage of the vent condenser was observed during this reaction.

Example 2 148.2 g of O-bromobenzal bromide, 11.8 g of polyethylene glycol and 100.2 g of water were added, and the mixture was reacted at a boiling point under a stirring condition for 23 hours. After the reaction, the organic layer was separated and washed with water, and analyzed. As a result, the yield of O-bromobenzaldehyde was 76.3 g (yield 91.
5%). No blockage of the vent condenser was observed during this reaction.

Example 3 145.7 g of O-bromobenzal bromide, 14.6 g of methyl cellosolve and 100.3 g of water were added, and the mixture was reacted at the boiling point under stirring for 23 hours. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of O-bromobenzaldehyde was 72.8 g (88.8% yield).
Met. No blockage of the vent condenser was observed during this reaction.

Example 4 147.3 g of O-bromobenzalbromide, 9.3 g of sodium polystyrenesulfonate, 100 g of water.
1 g was added, and the mixture was reacted at the boiling point for 23 hours under stirring conditions. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of O-bromobenzaldehyde was 74.4 g.
(89.8% yield). No blockage of the vent condenser was observed during this reaction.

Example 5 81.1 g of p-bromobenzal bromide, 4.8 g of p-toluenesulfonic acid monohydrate, 50.0 g of chlorobenzene and 56.3 g of water were added, and the mixture was stirred at a boiling point of 21. Allowed to react for hours. After the reaction, the organic layer was separated and washed with water, and analyzed. As a result, the yield of p-bromobenzaldehyde was 40.9 g (89.7%). No blockage of the vent condenser was observed during this reaction.

Example 6 132.7 g of p-nitrobenzalbromide, 17.1 g of p-toluenesulfonic acid monohydrate, 80.times. Of water
2 g was added, and the mixture was reacted at the boiling point for 23 hours under stirring conditions. After the reaction, the organic layer was separated and washed with water, and analyzed. As a result, the yield of p-nitrobenzaldehyde was 61.5 g.
(90.5% yield). No blockage of the vent condenser was observed during this reaction.

Example 7 153.9 g of m-phenoxybenzal bromide, 9.2 g of tetrabutylammonium bromide, water 8
9.0 g was added, and the mixture was reacted at the boiling point for 23 hours under stirring conditions. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of m-phenoxybenzaldehyde was 79.
9 g (89.6% yield). No blockage of the vent condenser was observed during this reaction.

Example 8 137.5 g of pt-butylbenzalbromide, p
-Toluenesulfonic acid monohydrate 8.5 g, water 8
1.2 g was added, and the mixture was reacted at the boiling point under stirring conditions for 23 hours. After the reaction, the organic layer was separated and washed with water, and analyzed. The yield of pt-butylbenzaldehyde was 67.
1 g (92.1% yield). No blockage of the vent condenser was observed during this reaction.

Example 9 88.2 g of O-chlorobenzal chloride was added to 8.7 g of p-toluenesulfonic acid monohydrate and 80.9 g of water.
Was added, and the mixture was reacted at the boiling point for 23 hours under stirring conditions.
After the reaction, the organic layer was separated and washed with water and analyzed.
The yield of -chlorobenzaldehyde was 58.3 g (yield 9
2.0%). No blockage of the vent condenser was observed during this reaction.

Example 10 In order to compare the hydrolysis rates, the amount of p-toluenesulfonic acid monohydrate was changed as shown in Table 1 and the reaction time was changed to 9 hours. The reaction was performed similarly. Table 1 shows the results.

[0032]

[Table 1]

Example 11 To compare the hydrolysis rates, the reaction was carried out in the same manner as in Example 2 except that the amount of polyethylene glycol added was changed as shown in Table 2 and the reaction time was changed to 9 hours. Table 2 shows the results.

[0034]

[Table 2]

COMPARATIVE EXAMPLE 1 147.5 g of O-bromobenzal bromide was added to water 8
1.8 g was added, and the mixture was reacted at the boiling point under stirring conditions for 9 hours. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of O-bromobenzaldehyde was 17.4 g.
(21.0% yield). No blockage of the vent condenser was observed during this reaction.

Comparative Example 2 A 4 wt% aqueous solution of iron chloride was added to 147.3 g of O-bromobenzal bromide at a reaction temperature of 120 to 130 ° C.
1 g was added dropwise over 2 hours to cause a hydrolysis reaction. After the reaction, the organic layer was separated and washed with water, and was analyzed. The yield of O-bromobenzaldehyde was 77.0 g (yield 92.9).
%)Met. One hour after the start of the dropwise addition of the 4 wt% iron chloride aqueous solution, crystals adhered to the vent condenser, and were almost clogged at the end of the reaction.

Comparative Example 3 A 4 wt% aqueous solution of iron chloride was added to 147.5 g of p-bromobenzal bromide at a reaction temperature of 120 to 130 ° C.
3 g was added dropwise over 2 hours to cause a hydrolysis reaction. After the reaction, the organic layer was separated and washed with water and analyzed. As a result, the yield of p-bromobenzaldehyde was 74.6 g (yield: 89.9).
%)Met. Crystals adhered to the vent condenser immediately after the start of the dropwise addition of the 4 wt% iron chloride aqueous solution, and were almost clogged at the end of the reaction.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 45/80 C07C 45/80 47/542 47/542 47/55 47/55 47/575 47/575 201/12 201/12 205/44 205/44 // C07B 61/00 300 C07B 61/00 300

Claims (6)

[Claims] 1. A method for producing a corresponding benzaldehyde by hydrolyzing a substituted or unsubstituted benzal halide, comprising the step of hydrolyzing the product in the presence of water and / or a catalyst having an affinity for the benzal halide. A method for producing benzaldehydes, comprising performing a decomposition reaction. 2. The following general formula (1): (Wherein, X represents a halogen atom, Y is a halogen atom,
It represents an alkyl group, a nitro group or a phenoxy group. And n
Represents 0 to 5), and hydrolyzes a benzal halide represented by the following general formula (2). The method for producing a benzaldehyde according to claim 1, wherein the benzaldehyde represented by the formula (where Y and n have the same meanings as described above) is produced. 3. A catalyst having an affinity for water and / or a benzal halide, comprising: an organic sulfonic acid compound and a salt thereof; a polyoxyalkylene glycol and a derivative thereof;
The method for producing benzaldehydes according to claim 1 or 2, wherein the method is one or more selected from the group consisting of alkoxy alcohols and quaternary ammonium salts. 4. The process for producing benzaldehydes according to claim 1, wherein the hydrolysis reaction is carried out at a reaction temperature of 60 to 160 ° C. under pressure or normal pressure. 5. The benzaldehyde according to claim 1, wherein the hydrolysis reaction is carried out in the presence or absence of an inert solvent that dissolves the benzal halide. Production method. 6. The method for producing a benzaldehyde according to claim 1, wherein a part or all of the hydrogen halide produced as a by-product in the hydrolysis reaction is absorbed in coexisting water. Method.