JP2001270855A - Method for producing organic amide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an efficient method for producing an organic amide by reacting an organic carboxylic acid with ammonia or an amine. SOLUTION: This method for producing a high-quality organic amide in high yield is characterized by decreasing reaction time compared with the conventional method by using granular titanium dioxide as the catalyst to suppress formation of nitriles as impurities.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a high-quality and high-quality organic amide.

[0002]

BACKGROUND OF THE INVENTION Generally, organic amides are produced industrially by the reaction of an organic carboxylic acid or a derivative thereof with ammonia or a mono- or di-alkyl monoamine.

In general, the reaction from an organic carboxylic acid uses a dehydration catalyst such as silica gel, alumina, phosphoric acid, etc.
React at around ° C. In this reaction, impurities are inevitably generated easily, and the reaction time becomes longer. Other catalysts include alkyltin compounds (U.S. Pat. No. 4,277,410), titanium hydroxide (Dutch Patent 8,302,367), alkoxytitanium, alkoxyzinc (German Patent No. 2,11).
0,060), boron trifluoride (JP-B-52-288)
2) and the like are known, but all have limitations such as difficulty in removing the catalyst and limited reaction conditions, and are not industrially common. In addition, the production method using a fixed bed using a catalyst such as silica gel (Japanese Patent Publication No. 57-37854) has a short catalyst life and is not practical.

[0004]

Means for Solving the Problems The present inventors have found that particulate titanium dioxide has a high activity as a catalyst, and have completed the present invention. That is, the present invention is a method for producing an organic amide in which an organic carboxylic acid is reacted with ammonia or a mono- or dialkyl monoamine in the presence of particulate titanium dioxide.

[0005]

Embodiments of the present invention will be described below. The organic carboxylic acid of the present invention refers to an aliphatic carboxylic acid and / or an aromatic carboxylic acid having one or more carboxy groups in a molecular skeleton. These organic carboxylic acids can be used alone or in combination of two or more.

Specific examples of these organic carboxylic acids are preferably aliphatic carboxylic acids and / or aromatic carboxylic acids having 6 to 30 carbon atoms. Examples of the linear or branched aliphatic saturated carboxylic acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, arachiic acid, behenic acid, dimethyloctanoic acid, and butylheptylnonanoic acid. Examples of linear or branched aliphatic unsaturated carboxylic acids include hexenoic acid, octenoic acid, decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosenoic acid, docosenoic acid, zomaric acid, oleic acid, linoleic acid, Linoleic acid, gadrenic acid, erucic acid, seraconic acid, and the like. Examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, hexadecamethylenedicarboxylic acid, and octadecamethylenedicarboxylic acid. As aromatic monocarboxylic acids, benzoic acid, toluic acid, dimethylbenzoic acid, trimethylbenzoic acid, salicylic acid, anisic acid, gallic acid, syringic acid, phenylacetic acid, hydrocinnamic acid, γ-phenylbutyric acid, δ-phenylvaleric acid, ε-phenylcaproic acid, cinnamic acid, phenylpropiolic acid and the like. And the like. As aromatic carboxylic acids having two or more carboxy groups in the molecule, phthalic acid, isophthalic acid,
Terephthalic acid, hemicellitic acid, trimellitic acid, trimesic acid, prenitic acid, melophanic acid, pyromellitic acid,
Melitic acid and the like can be mentioned. Specific examples of mono- or dialkyl monoamines preferably have one or two alkyl groups having 1 to 30 carbon atoms, and monoalkyl monoamines include methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine,
Laurylamine, myristinamine, stearinamine, arakinamine, behenamine, aniline and the like. Examples of the dialkyl monoamine include dimethylamine, diethylamine, methylethylamine, dipropylamine, diphenylamine and the like.

The particulate titanium dioxide used in the present invention has a larger specific surface area and a finer particle, the shorter the reaction time, the lower the reaction temperature, or the less the amount of catalyst used, and the generation of fatty acid nitrile as an impurity is suppressed. Can be
The specific surface area can be measured by the BET method, and is not particularly limited, but is 1 m2 / g or more, preferably 10 m2 / g or more, and more preferably 40 m2 / g or more.

The particulate titanium dioxide used in the present invention may be one produced by a sulfuric acid method or one produced by a hydrochloric acid method. Further, a rutile type may be used, but an anatase type is preferable. In addition, generally commercially available products may be used, but preferably those produced mainly by the sulfuric acid method and having sulfate groups remaining in the pores of the particles.

The particulate titanium dioxide used in the present invention may be, for example, a mixture of titanium dioxide and silicon dioxide, or a composite oxide such as silica titania. The composite oxide may be a titanium-containing zeolite.

[0010] In the method of the present invention, the reaction temperature is not particularly limited, but is preferably in the range of 150 to 200 ° C. The pressure during the reaction is preferably in a pressurized state, but may be normal pressure. The amount of the particulate titanium dioxide to be used is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 3% by weight, based on the organic carboxylic acid.

The method of the present invention uses a particulate titanium dioxide as a catalyst, thereby reducing the reaction time, suppressing the production of nitrile as an impurity, and producing an organic amide of excellent quality as compared with the conventional method. It can be produced in high yield and is industrially very significant.

[0012]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 A four-necked flask equipped with a stirrer, a gas inlet tube, a thermometer and a dehydrator was charged with a particulate anatase-type titanium dioxide catalyst having a specific surface area of 300 m2 / g (MC-Ishihara Sangyo Co., Ltd.).
150) 4.5 g of erucic acid and 150 g of erucic acid are mixed, and the mixture is allowed to react under atmospheric pressure at 175 ° C. by introducing 200 normal ml / min of ammonia, thereby neutralizing the reaction product obtained by separating the catalyst. The reaction was continued until the value was 1 or less. Table 1 shows the results. In the reaction, the neutralization value became 1 or less in 7 hours, and the reaction product was subjected to gas chromatography [gas chromatography: Shimadzu GC-17A, column: J & W, DB-1]
(Inner diameter × length: 0.25 mm × 30 m)], the resulting nitric acid erucate was 1.3%.

[0013]

[Table 1]

Example 2 A particulate anatase-type titanium dioxide catalyst (Ishihara Sangyo Co., Ltd.)
The reaction was carried out under the same conditions as in Example 1 using a product having a specific surface area of 70 m 2 / g manufactured by MC-50). The reaction product was analyzed as in Example 1. Table 1 shows the results.

Example 3 A reaction was carried out under the same conditions as in Example 1 using a particulate rutile type titanium dioxide catalyst having a specific surface area of 40 m2 / g (PT-101, manufactured by Ishihara Sangyo Co., Ltd.). The reaction product was analyzed as in Example 1. Table 1 shows the results.

Comparative Example 1 For comparison, a reaction was carried out under the same conditions as in Example 1 using titanium hydroxide as a catalyst. The titanium hydroxide used as the catalyst was obtained by reacting titanium chloride (a first-class reagent manufactured by Aldrich) with water. The reaction product was analyzed as in Example 1. Table 1 shows the results.

Comparative Example 2 For comparison, tetrabutoxytitanium (Al
The reaction was carried out under the same conditions as in Example 1 using a primary reagent (manufactured by Drich). The reaction product was analyzed as in Example 1.
Table 1 shows the results.

Examples 4-5 Except that the amount of the particulate anatase type titanium dioxide catalyst having a specific surface area of 300 m 2 / g (MC-150, manufactured by Ishihara Sangyo Co., Ltd.) was changed to the amount shown in Table 1, The reaction was carried out under the same conditions as in Example 1. The reaction product was analyzed as in Example 1. Table 1 shows the results. When the amount of the catalyst used was reduced as compared with Example 1, the reaction time was prolonged, but a result which was industrially feasible was obtained.

Examples 6 and 7 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was changed as shown in Table 1. The reaction product was analyzed as in Example 1. Table 1 shows the results. When the reaction temperature is lowered as in Example 6, the reaction time is prolonged, but the generation of by-product nitrile erucate is also suppressed. When the reaction temperature is increased as in Example 7, the reaction time is shortened, but the formation of by-product nitrile erucate is also promoted. In Examples 6 and 7, results that can be industrially implemented were obtained.

Examples 8 to 10 In an autoclave equipped with a stirrer, a gas inlet tube, a thermometer and a dehydrator, a particulate anatase-type titanium dioxide catalyst having a specific surface area of 300 m 2 / g (MC-Ishihara Sangyo Co., Ltd.
150) and erucic acid 20 shown in Table 2, respectively.
The reaction product obtained by separating the catalyst at a neutralization value of 1 was introduced by introducing 4.5 normal l / min of ammonia at the reaction temperature and reaction pressure shown in Table 2. The reaction was carried out until the following conditions were satisfied, and the reaction time was compared with the% of erucic acid nitrile produced. Increasing the reaction pressure shortens the reaction time, suppresses the production of nitrile as a by-product, and uses a small amount of catalyst, which is industrially extremely advantageous.

[0021]

[Table 2]

[0022]

According to the method of the present invention, the use of particulate titanium dioxide as a catalyst shortens the reaction time, suppresses the production of nitrile as an impurity, and improves the quality of organic compounds. Amides can be produced in high yields,
It is extremely significant industrially.

Claims (3)

[Claims] 1. A process for producing an organic amide, comprising reacting an organic carboxylic acid with ammonia or a mono- or di-alkyl monoamine in the presence of particulate titanium dioxide. 2. The method for producing an organic amide according to claim 1, wherein the particulate titanium dioxide having a specific surface area of 1 m2 / g or more is used. 3. The method for producing an organic amide according to claim 1, wherein the organic carboxylic acid is an aliphatic carboxylic acid having 6 to 30 carbon atoms and / or an aromatic carboxylic acid.