JPS5822023B2 - Housouzokunitrile Rui no Suiwahouhou - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for water utilization of aromatic nitriles.

Obtaining a carboxylic acid amide by a water utilization reaction of a nitrile compound is generally a well-known method, and is an industrially extremely important reaction.

This water utilization reaction has conventionally been carried out in the presence of strong mineral acids, but in this method, a large amount of neutralizing agent is used in the neutralization step after the reaction, resulting in extremely large amounts of by-products (mineral acid is sulfuric acid, produces ammonium sulfate),
Not only was it difficult to handle the by-products, but it was also extremely uneconomical.

From this point of view, there has been a strong desire for a new method that does not use an acid as a catalyst and therefore does not produce by-products.

As a somewhat improved method for this purpose, a method using a copper-based catalyst such as metallic copper is known, but the results are still unsatisfactory in terms of the catalyst manufacturing method and the performance of the obtained catalyst. G).

As a result of intensive research into this copper-based catalyst, which is unique in that it does not use acids, the present inventors found that
We discovered a new method of water utilization and arrived at the present invention.

That is, the present invention relates to a method of hydrating aromatic nitriles in the presence of innitriles and cuprous oxide.

The innitriles used in the present invention are compounds represented by the general formula RNC.

R here means an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

Specific examples include methylisonitrile, ethylisonitrile, n-propylisonitrile, isopropylisonitrile, n-butylisonitrile, 5ec-butylisonitrile, t-butylisonitrile, cyclohexylisonitrile, benzylisonide JIJ, phenylinnitrile, Examples include naphthylisonitrile.

Furthermore, the aromatic nitriles used in the present invention refer to compounds in which a cyanide group is bonded to a heterocyclic aromatic group containing a benzene ring or a pyridine ring, and one ring has two or more cyanogen groups. It may have.

Give specific examples: hahenzonitrile, o-tolnitrile,
m-1 lunitrile, p-tolnitrile, α-naphthonitrile, β-naphthonitrile, 2-cyanopyridine, 3-
Examples include cyanopyridine, 4-cyanopyridine, and phthalonitrile.

In carrying out the present invention, a heating reaction is carried out using a combination of the above-mentioned isonyl-IJ compounds and cuprous oxide as a catalyst, according to conventional means.

The reaction temperature may range from room temperature to 300°C, but preferably from 50 to 200°C.

Although the reaction can be carried out using less than the stoichiometric amount of water for the dil-IJ compound, it is usually 1.5 to 1 stoichiometric of the stoichiometric amount of water.
It is preferable to use 0.00 times more water.

Further, a medium inert to the reaction, such as dimethyl sulfoxide or N,N-dimethylformamide, may be present together with water.

The amount of cuprous oxide to be used in the reaction is preferably at least 0.01 times the mole of the nitrile compound.

Further, the amount of the isonyl-IJ compound may be at least one mole per mole of the cuprous oxide used, but preferably at least five times the mole.

The method of the present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Cyclohexylisonitrile 0.2 yd, cuprous oxide 30~. 3-cyanpyridine 1.0,9. Water 107! The internal volume is 50T11. The mixture was placed in a test tube, placed in a thermostatic shaker, and reacted at 80°C for 2 hours.

Analysis was performed using reaction wave high performance liquid chromatography.

The analysis conditions are as follows.

Column: SCX (manufactured by Du Pont), detector: dual differential spectrometer, eluent: 0.05 MIJ sodium dihydrogen phosphate aqueous solution adjusted to pH 3.0 with phosphoric acid, column pressure: 40! A As a result, it was found that nicotinic acid amide was obtained with a yield of 92%.

The product was isolated and purified after solvent extraction, and the infrared absorption spectrum, mass spectrometry spectrum, and melting point all matched those of the standard product, and it was determined to be yolinicotinic acid amide.

Comparative example Cuprous oxide 30m? , 3-cyanopyridine 1. Og and 101 nl of water were placed in a test tube with an internal volume of 50 m, and reaction and analysis were performed under the same conditions as in Example 1.

As a result, it was confirmed that nicotinic acid amide was not produced.

Example 2 Cyclohexylisonitrile 0.2 m, cupric chloride 30
■, Benzonitrile 1. O,! il' and 10 ml of water were placed in an autoclave having an internal volume of 50-100 ml, and heated at 130° C. for 6 hours with stirring.

After the reaction, the mixture was extracted with methyl ethyl ketone.

The organic layer was concentrated, and the resulting solid was washed with petroleum ether to remove unreacted benzyl 1,1, yielding 1.07 g of pale yellow crystals.

This includes infrared absorption spectrum, mass spectrometry spectrum,
It was determined that the melting points were benzamides by Lukoto, which matched those of the standard products.

The yield was 90 buns.

Example 3 Benzylisonitrile 0.2 ml, cuprous oxide 30~
．． 3-cyanopyridine 1.0〃, water 1077+7! The mixture was charged into an autoclave having an internal volume of 50 cm, and heated at 130°C for 5 hours with stirring.

After the reaction, analysis was performed using high performance liquid chromatography under the same conditions as in Example 1.

As a result, it was found that nicotinic acid amide was obtained with a yield of 90%.

Claims (1)

[Claims] 1. In the presence of innitriles represented by the general formula RNC (wherein R means an alkyl group, cycloalkyl group, aralkyl group, or aryl group) and cuprous oxide,
A method for hydrating aromatic nitriles containing a benzene ring or a pyridine ring.