JP2000072737A - Production of oxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an oxime using a titanosilicate catalyst. SOLUTION: The concentration of ammonia dissolved in a reactional solvent is made to >=15 wt.% in the initial period of a reaction in a method for producing an oxime from a ketone, a quinone or an aldehyde using hydrogen peroxide and ammonia in the presence of a titanosilicate catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for economically and efficiently producing various oxime compounds useful as analytical reagents and the like.

[0002]

2. Description of the Related Art Ammoximation of producing an oxime by liquid phase oxidation using hydrogen peroxide and ammonia in the presence of a ketone or aldehyde having a carbonyl group in the presence of a catalyst is widely known (German Patent 1,245,371). Etc.), in particular, the synthesis of cyclohexinosan oxime, which is an intermediate raw material for 6-nylon, using titanosilicate as a catalyst has been widely studied (Japanese Patent Publication No. 8-16091). This method is an excellent process in which ammonium sulfate produced as a by-product in the conventional oxime production process is not generated, and has many advantages such as easy separation operation because it is a solid catalyst.

However, this titanosilicate catalyst requires an activation treatment using an inorganic acid such as, for example, sulfuric acid-hydrogen peroxide after the catalyst preparation and before use (European Patent No. 2).
08311, 267362, and 314147
The above operation is repeated every time the activation of the catalyst is reduced, which is troublesome and requires extra capital investment for the regeneration of the catalyst. are doing.

[0004]

The object of the present invention is to solve the above-mentioned problems and to provide a method for obtaining oximes in high yield.

[0005]

Means for Solving the Problems The present inventors have intensively studied the reaction conditions of oxime in order to solve the above-mentioned problems, and found that the pressure during the reaction conditions was increased to 2 kg / cm ² (gauge) or more. By adjusting and maintaining until the end of the reaction, the concentration of ammonia dissolved in water is always 5% by weight or more, so that the catalyst activation treatment is omitted and a compound having a carbonyl group having relatively low reactivity is obtained. Even when used, they find that the corresponding oxime compound can be obtained in high yield,
The present invention has been completed.

In a method for producing an oxime from a ketone, a quinone or an aldehyde using hydrogen peroxide and ammonia in the presence of a titanosilicalite catalyst, the concentration of ammonia dissolved in a reaction solvent is increased to 15% by weight or more at the beginning of the reaction. The present invention relates to a method for producing an oxime.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As a catalyst used in the oxime synthesis of the present invention, titanosilicate is preferably used. The titanosilicate is obtained by substituting a part of silicon of crystalline silicalite having a zeolite structure with titanium. The method for synthesizing titanosilicate used in the present invention is not particularly limited, and examples thereof include JP-A-56-97720. The titanosilicate having a Si / Ti ratio of 10 to 1000 is used. In the present invention, the amount of the titanosilicate catalyst used is not particularly limited. In the case of a suspension bed system, it is usually used in a range of 0.1% by weight to 10% by weight in the reaction solution. The catalyst may be in any form such as fine powder or pellets.

[0008] The hydrogen peroxide used in the present invention is usually
Hydrogen peroxide synthesized by the anthraquinone method or the direct oxidation method in which hydrogen and oxygen are brought into contact with a catalyst under high pressure, and are generally commercially available as a 10% to 70% by weight aqueous solution. Hydrogen peroxide is used as a stabilizer of phosphate, polyphosphate (sodium pyrophosphate, sodium tripolyphosphate, etc.), stannate, pyrophosphoric acid, ascorbic acid, ethylenediaminetetraacetic acid, nitrotriphosphate. Acetic acid, aminotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetra (methylenephosphonic acid) diethylenetriaminopenta (methylenephosphonic acid) may be added.

Ammonia used in the present invention is exemplified by a method of supplying a gas before the start of the reaction, an aqueous ammonia solution, water or hydrogen peroxide, ammonium sulfate, ammonium phosphate, ammonium chloride, etc., which are soluble in the reaction solvent and the like. A method of adding an ammonium salt to be used can be used.

The ketone, quinone or aldehyde used in the present invention is a compound having one or more carbonyl groups represented by the general formulas R ₁ and R ₂ —CＯO. Here, R ₁ and R ₂ include hydrogen, an alkyl group containing 1 to 12 carbon atoms, a branched alkyl group or a cycloalkyl group containing 3 to 12 carbon atoms, and 6 to 12 carbon atoms. represents a linear or branched alkylene group containing an aromatic group or a 3 to 12 carbon atoms, these alkyl groups, halogen, NO ₂ group, hydroxy group, may be substituted by an alkoxy group or a carboxylic acid ester.
R ₁ and R ₂ may be the same or different from each other.

Specifically, acetone, methyl ethyl ketone and methyl isobutyl ketone, 2-peptanone,
Peptanone, 4-peptanone, 2,2-dimethyl-3-
Ketones such as peptanone, t-butylphenyl ketone and cyclohexanone, quinones such as P-benzoquinone and O-benzoquinone, and aldehydes such as benzaldehyde are preferably used.

The method for synthesizing an oxime of the present invention is characterized in that a raw material, a solvent, a catalyst and an additive are previously charged into a reactor, and hydrogen peroxide or a reaction solvent of hydrogen peroxide and a ketone are mixed with sufficient stirring while blowing ammonia gas. After supplying the mixed solution and conducting the reaction, and after a certain period of time, complete the reaction,
A batch method for separating the generated oxime or a continuous reaction in which the raw materials, the catalyst, the solvent, and the additive are continuously supplied using a single-stage or multi-stage reactor may be used.

As the material of the reactor, an inert material that prevents decomposition of hydrogen peroxide is suitable. For example, a glass lining or a stainless steel reaction vessel is preferable. In addition, the method of adjusting the pressure at the beginning of the reaction may be such that after adding each raw material, the pressure may be adjusted by ammonia gas supplied as a raw material, or the pressure of ammonia moving from a liquid phase to a gas phase after a predetermined temperature rise. May be used.

The reaction temperature for synthesizing oximes in the present invention is from 50 ° C. to 100 ° C., but an appropriate temperature must be selected depending on the compound having a carbonyl group to be used. Since the reaction pressure needs to maintain the ammonia concentration in water in the liquid phase at 15% by weight or more, the relationship with the temperature which affects the solubility of the gas is important, and is related to the reaction temperature. For example, when the reaction temperature is 80 ° C., the initial pressure is 2 kg.
It is preferably carried out at a pressure of at least / cm ² (gauge). Although the solubility of ammonia is expected to be affected by other reaction solvents and the ketones, aldehydes and quinones used, water is basically the most ammonia-soluble, and its solubility in water is It has the greatest effect on the amount of dissolved ammonia in the air. Therefore, using the solubility in water as an index,
It is important to control the pressure for each reaction temperature.

The preferred range of the molar ratio of hydrogen peroxide to ketone in the present invention is 0.5 to 3, preferably 0.5 to 1.5, per mole of ketone or the like. The molar ratio of ammonia to ketones is 1 or more, preferably 1.5 or more, per mole of ketone or the like.

As a reaction solvent used in the present invention, alcohol is preferably used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, t-butanol, t-amyl alcohol and the like. Among them t
Butanol is most preferably used. Two or more of these alcohols may be used as a mixture.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. The pressure is a gauge pressure. Example 1 In an autoclave with a stirrer made of stainless steel (SUS316), 7.0 g of acetone and 15.0 g of aqueous ammonia were added.
-15.0 g of butanol and 1.5 g of titanosilicate not subjected to the activation treatment were charged, and ammonia was supplied with a gas while stirring to increase the pressure in the reaction vessel to 1.0 kg / cm ² . Thereafter, when the temperature was raised to 80 ° C., the pressure in the reaction vessel rose to 4.4 kg / cm ² (the solubility of ammonia in water was about 27% by weight). After reaching a predetermined temperature, a hydrogen peroxide solution diluted to 15% by weight.
0 g was added over 3 hours.

The yield of acetone oxime was measured by gas chromatography. The final reaction vessel pressure was 1.6 kg / cm ²
Down to. The resulting reaction solution was separated by filtration through five kinds of C filter paper to separate the catalyst, and the oxime yield was measured by gas chromatography (GC-14A, manufactured by Shimadzu Corporation). As a result, the acetone oxime yield based on acetone was determined to be 96.4%. The conversion of hydrogen peroxide was determined to be 99.9% by iodine titration.

Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 without performing a pressurizing operation. As a result, the initial reaction pressure was 1.6 kg / cm ² (the solubility of ammonia in water was about 12% by weight), and the pressure at the end of the reaction was 0.6 kg / cm ² . The acetone oxime yield of acetone in this reaction was 63.9%.

Example 2 11.8 g of cyclohexanone and aqueous ammonia 1 were placed in an autoclave with a stirrer made of stainless steel (SUS316).
5.0 g, 15.0 g of t-butanol and 1.5 g of titanosilicate not activated were charged, and ammonia was supplied with gas while stirring to increase the pressure in the reaction vessel to 1.0 kg / cm ^2. I let it. Thereafter, when the temperature was raised to 80 ° C., the pressure in the reaction vessel rose to 4.6 kg / cm ² (the solubility of ammonia in water was about 27% by weight). After reaching the predetermined temperature, 34.0 g of a hydrogen peroxide solution diluted to 15% by weight was added over 3 hours. After the completion of dropping of hydrogen peroxide, the temperature and pressure are maintained as they are for one more hour.
Reaction was carried out for a time to synthesize cyclohexanone oxime. At this time, the final pressure in the reaction vessel was 1.7 kg / cm ² . After completion of the reaction, the inside of the reaction vessel was replaced with nitrogen to collect ammonia gas, and the pressure was reduced to atmospheric pressure to perform cooling. The catalyst was separated from the obtained reaction solution in the same manner as in Example 1, and the yield of cyclohexanone oxime was measured by gas chromatography. As a result, the cyclohexanone oxime yield based on cyclohexanone was 99.0%.

Comparative Example 2 A reaction was carried out under the same conditions as in Example 3 without performing a pressurizing operation. As a result, the initial reaction pressure was 1.7 kg / cm ² (the solubility of ammonia in water was about 12% by weight), and the pressure at the end of the reaction was 1.2 kg / cm ² . The cyclohexanone oxime yield based on hydrogen peroxide in this reaction was 81.3%.

Example 3 10.6 g of benzaldehyde and 1 part of aqueous ammonia were placed in an autoclave with a stirrer made of stainless steel (SUS316).
5.0 g, 15.0 g of t-butanol and 1.5 g of titanosilicate not activated were charged, and ammonia was supplied with gas while stirring to increase the pressure in the reaction vessel to 1.0 kg / cm ^2. I let it. Thereafter, when the temperature was raised to 80 ° C., the pressure in the reaction vessel rose to 4.4 kg / cm ² (the solubility of ammonia in water was about 27% by weight). After reaching the predetermined temperature, 22.7 g of a hydrogen peroxide solution diluted to 15% by weight was added over 3 hours. Hydrogen peroxide was prepared by the method described in Example 1, and the reaction was carried out in the same manner as in Example 1, and the yield of benzaldoxime was measured by gas chromatography. Also, the final reaction vessel pressure is
It decreased to 1.6 kg / cm ² . As a result, the benzaldoxime yield based on benzaldehyde was 97.5%. The conversion of hydrogen peroxide was determined by iodine titration to be 99.9%.

Comparative Example 3 A reaction was carried out under the same conditions as in Example 4 without performing a pressurizing operation. As a result, the initial reaction pressure was 1.6 kg / cm ² (the solubility of ammonia in water was about 12% by weight), and the pressure at the end of the reaction was 1.0 kg / cm ² . The benzaldoxime yield based on hydrogen peroxide in this reaction was 76.3%.

[0024]

According to the present invention, the target compound can be obtained in high yield even if the catalyst activation treatment is omitted, and the production of an oxime which is economically advantageous can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Naoko Matsuya Hiinahigashi Yokkaichi City, Mie Prefecture F-term (reference) 4G069 AA01 AA08 BA02A BA02B BA04A BA04B BA15A BA15B CB01 DA05 EA01Y EA02Y FB10 FC07 FC08 4H006 AA02 AC59 BA10 BA33 BA71 BB14 BC10 BE35 BD32 4H039 CA72 CD50

Claims (2)

[Claims] 1. A method for producing an oxime from a ketone, a quinone or an aldehyde using hydrogen peroxide and ammonia in the presence of a titanosilicate catalyst, wherein the concentration of ammonia dissolved in the reaction solvent is 15% by weight or more at the beginning of the reaction. A method for producing an oxime, comprising: 2. The method according to claim 1, wherein the reaction temperature is 50 to 100 ° C.