JPS5940391B2 - Method for producing benzimidazolone, benzoxazolone or benzthiazolone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing benzimidazolones, benzoxazolones or benzthiazolones.

As is well known, substituted or unsubstituted benzimidazolones, benzoxazolones, and benzthiazolones are useful as intermediates for dyes, pigments, pharmaceuticals, resin raw materials, and the like.

Benzimidazolones have conventionally been produced by reacting 0-phenylenediamine hydrochloride with phosgene in an organic solvent, or by reacting 0-phenylenediamine hydrochloride with phosgene in an organic solvent.
-Produced by a method in which phenylenediamine and urea are reacted in an organic solvent or an aqueous solvent at a temperature of around 150°C. The same applies to benzoxazolones and benzthiazolones, which are produced by a method in which 0-aminophenol and 0-aminothiophenol are reacted with phosgene in an organic solvent, respectively. In this way, the production of benzimidazolones and their oxygen and sulfur analogues requires the use of dangerous reaction reagents such as phosgene, and harsh reaction conditions.
Yields are generally low. The present invention has been made in order to solve the various problems described above, and it is possible to easily produce high-purity benzimidazolones, benzoxazolones, or benzthiazolones in high yield, and if necessary, It is an object of the present invention to provide a method for producing the above-mentioned heterocyclic compound, in which the catalyst can be easily recovered and reused, and post-treatment of the reaction is also simple.

The method for producing benzimidazolones, benzoxazolones, or benzthiazolones according to the present invention uses the general formula.

□”・(However, X represents NH, 0 or S, A represents H when X is NH or O, and H or SAr when Xi)'-S (However, Ar represents an aryl group.

), Y represents an amino group when XA is NH2, 0H or SH, or an amino group or a nitro group when XA is S-SAr, and z represents hydrogen or a substituent. ) is reacted with carbon monoxide in the presence of a base and sulfur in a solvent to obtain a compound represented by the general formula (where X and Z are the same as above) shall be.

In the present invention, the raw material compound 1 is specifically substituted or unsubstituted o-phenylenediamine, o-aminophenol,
o-aminothiophenol, 2,27-diaminodiphenyl disulfide, 2,21 dinitrodiphenyl disulfide, etc., and the substituent Z on the benzene nucleus does not have a harmful effect on hydrogen or the reaction, and , any substituent that participates in the reaction and does not cause undesirable side reactions, such as inert substituents such as aliphatic, alicyclic, aromatic hydrocarbon groups, and heteroaromatic groups. Specific examples include alkoxy groups, allyloxy groups, chlorine, bromine, iodine, etc., nitro groups, amino groups, and the like. As will be readily understood, substituted or unsubstituted 0-J-G nylene diamines give the corresponding benzimidazolones, and substituted or unsubstituted 0-aminophenols and o-aminothiophenols give the corresponding benzimidazolones, respectively. Oxazolones and benzthiazolones are obtained. In addition, as a raw material compound for benzthiazolones, not only aryl-2-aminophenyl disulfide but also aryl-2-
Nitrophenyl disulfides may also be used, the latter being believed in which the nitro group is reduced to an amino group in the reaction of the present invention. Such a disulfide has the general formula (where Y and z are the same as above).

) is preferred, in which case this disulfide is reductively cleaved between sulfur and sulfur in the reaction of the present invention to produce two molecules of benzthiazolones.

The sulfur used in the present invention is preferably powdered sulfur, and general commercial products can be used as they are.

The reaction rate increases as the amount of sulfur used increases, but in consideration of ease of recovery, etc., the amount used is 0.1 to 5 mol, preferably 2 to 3 mol, per 11 mol of the starting material compound.
It is a mole. There is no particular need to use a large amount exceeding 5 mol.

Although the present invention is not limited to any theory, sulfur reacts with carbon monoxide in the presence of a base to form carbonyl sulfide (SCO), and in the presence of water, reacts with water to form hydrogen sulfide. Or produces hydrogen polysulfide. It is thought that this (poly)hydrogen sulfide forms a salt with the base present in the system and is dissolved in the solvent, and the reaction is substantially uniform in the present invention. When the raw material compound is a disulfide having a nitro group as the substituent Y, this nitro group is expected to be reduced by the above (poly) hydrogen sulfide, and therefore, when the raw material compound has a nitro group to be reduced. Water is required in the reaction of the present invention. When the raw material compound is 2,21-diaminodiphenyl disulfide which does not have a nitro group as a substituent, reduction of the nitro group with (poly)hydrogen sulfide is not required, but the disulfide is cleaved at the sulfur-sulfur bond. It appears that (poly)hydrogen sulfide contributes to this. However, it is also possible that the amino group is first carbonylated and then the sulfur-sulfur bond is cleaved without (poly) hydrogen sulfide upon formation of the heterocycle, as explained below. In any case, in the present invention, water is preferably present in the reaction system even when the starting compound is an amino-substituted disulfide. Next, in the reaction of the present invention, carbonyl sulfide performs an insertion reaction between the nitrogen and hydrogen of the amino group to generate -NHCOSH group, and this carbonyl carbon electrophilically binds nitrogen, oxygen, or sulfur at the ortho position. It is thought that the corresponding heterocycle is formed by attack and ring closure.

In the present invention, bases include carbonates, bicarbonates, hydroxides, oxides of alkali metals and alkaline earth metals,
Inorganic bases such as ammonia and organic bases such as amines are used.

Specifically, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, triethylamine, pyridine, dimethylformamide, N-methylpyrrolidine, N-
Examples include methylpyrrolidone, but preferably organic bases are used. The amount of the base to be used is not particularly limited, but is usually 1 to 10 mol, preferably 2 to 5 mol, per 11 mol of the starting compound. The solvent used in the present invention is water, a water-containing organic solvent, or an organic solvent.

Here, organic solvents that do not have a negative effect on the reaction,
In particular, any substance may be used as long as it is not reduced under the reaction conditions, such as ethers, amides, amines, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. Mixtures of more than one species are optionally used. Specifically, tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, dimethylacetamide, triethylamine, pyridine, N-methylpyrrolidine, benzene, hexane, etc. are used, but preferably a polar organic solvent or a mixture of these and water is used. A water-containing organic solvent is used. Incidentally, as is clear from the above, in the present invention, the organic base can also serve as a solvent. When using a water-containing organic solvent, the water content is usually 1 to 100 times the mole of sulfur, preferably 2 to 30 times the mole of sulfur. but,
This water content is not necessarily critical. In the method of the present invention, the raw material compounds are o-phenylenediamine, o-
In the case of aminophenol or o-aminothiophenol, since it does not have a nitro group that can be reduced by hydrogen sulfide or a disulfide group that can be reductively cleaved, the reaction solvent does not need to contain water.

On the other hand, water alone can be used as the reaction solvent regardless of the starting material compound, but in this case, some starting material compounds may not dissolve in water and the reaction may become heterogeneous. Also, since the reaction usually takes a long time, organic solvents or It is desirable to carry out the reaction in an organic solvent containing water. The reaction of the present invention is carried out in a carbon monoxide atmosphere, and the pressure is usually 1 to 5.
0k9/Cd, preferably 3 to 30k9/Cl7i, particularly preferably 5 to 10k9/Cd. If the pressure is too high, side reactions will occur, which is undesirable. Further, the reaction temperature is not particularly limited, but is usually room temperature to 100°C, preferably 50 to 80°C, and the time required for the reaction is usually 1
The reaction time is within 0 hours, and in many cases, the reaction is completed in about 4 to 5 hours. In the method of the present invention, as described above, the reaction system is usually in a substantially solution state, but after the reaction is completed, the solvent is distilled off if necessary, and water is added to the reaction mixture to remove sulfur. The reaction product is extracted by adding a slightly soluble alcohol to water, the sulfur is removed by filtration, the alcohol layer is separated, and the solvent is distilled off. The objective is obtained.

As the above-mentioned alcohol, an aliphatic or alicyclic alcohol having 4 to 9 carbon atoms is preferably used, and specific examples include butanol, pentanol, hexanol, cyclohexanol, and the like. The benzimidazolones, benzoxazolones or benzthiazolones thus obtained are usually of such high purity that recrystallization is not required. When recrystallization is required, for example from water in the case of benzimidazolones and benzoxazolones,
In the case of benzthiazolones, they are recrystallized from alcohols. As described above, the method of the present invention involves reacting the raw material compound 1 with carbon monoxide in a solvent in the presence of a base and sulfur, and has the following advantages. (a) All raw materials required for the reaction, such as raw material compounds, sulfur, carbon monoxide, and base, are easily and inexpensively available.

(b) High purity benzimidazolones, benzoxazolones, or benzthiazolones can be obtained in high yield.

(c) If necessary, sulfur can be easily recovered after the completion of the reaction and can be recycled and reused as is.

(d) The reaction system is substantially homogeneous, and the reaction operation and post-treatment after the reaction is simple.

(a) The reaction conditions are mild and the time required for the reaction is short.

Examples of the present invention are listed below.

Example 1 0-phenylenediamine 0.54y (5.0mm01)
, sulfur powder 0.807 (25 mm 01), triethylamine 3 ml (22 mm 01) and tetrahydrofuran 20 ml were charged into a 100 d capacity autoclave. After replacing the carbon monoxide sufficiently with carbon monoxide, the carbon monoxide pressure was reduced to 5k.
g/Cd.

After heating the inside of the autoclave to 80°C and stirring for 4 hours, the autoclave was cooled to room temperature and carbon monoxide was removed.

Next, after distilling off the solvent, water 1 was added to precipitate sulfur, and then n-butanol was added to extract the reaction product.
After removing the sulfur, the solvent was distilled off from the n-butanol layer to obtain benzimidazolone 1.627 (theoretical yield: 96.6%) in the form of white flakes. The purity of this benzimidazolone was determined by high-performance liquid chromatography, 92.3%.
It was %. Example 2 0-aminophenol 0.60y (5mm01), sulfur powder 0.647 (20mm01), triethyl 2 amine 5ml (22mm01) and tetrahydrofuran 2
After charging 0 ml into a 100 ml autoclave and purging with carbon monoxide, the carbon monoxide pressure was set to 5k9/Cd.

The reaction was carried out at 80° C. for 4 hours in the same manner as in Example 1, and post-treatment was performed to obtain benzoxazolone 0.60V (theoretical yield: 89.1%) in the form of slightly brown flakes. The purity of this benzoxazolone was 9.52% as determined by high performance liquid chromatography. Example 350 -Aminothiophenol 0.637 (5 mm01), sulfur powder 0.67 (20 mm01), potassium carbonate 2.
767 (20mm01) and tetrahydrofuran 20d
into an autoclave, and the carbon monoxide pressure was 5k9/Cd.
The mixture was reacted at 80°C for 6 hours.

Thereafter, the same treatment as in Example 1 was carried out to obtain pale yellow benzthiazolone 0.69y (theoretical yield: 91.4%). The purity was 97.6%. Example 4 2,2'-dinitrodiphenyl disulfide 0,777
(2.5mm01), sulfur powder 0.647 (20mm
01), water 0.6mZ (33mm01), triethylamine 3ml (22mm01) and tetrahydrofuran 2
After charging 0 ml into an autoclave and sufficiently replacing it with carbon monoxide, the carbon monoxide pressure was set to 10 k9/C77 l.

After reacting at a temperature of 80° C. for 1 hour, the same treatment as in Example 1 was carried out to obtain pale yellow benzthiazolone 0.737 (theoretical yield: 97.0%).

The purity was measured in the same manner as in Example 1 and was 92.5%.
Example 52.2! - Diaminodiphenyl disulfide 0.62y (2.5mm01), sulfur powder 0.647
(20 mm01), 0.6 ml (33 mm 01) of water, and 20 ml of pyridine were charged into an autoclave, and the autoclave was sufficiently replaced with carbon monoxide.The carbon monoxide pressure was then set to 10 kg/Cd, and the reaction was carried out at a temperature of 80° C. for 4 hours.

After treatment in the same manner as in Example 1, pale yellow benzthiazolone 0.727 (theoretical yield 96%) was obtained. Purity is 95%
It was hot. lExample 60-
Aminophenol 0.60y (5mm01), sulfur powder 0.647 (20mm01), triethylamine 5m
1 (22 mm01) and 20 ml of water were charged into an autoclave, the carbon monoxide pressure was set to 10 k9/Cd, and the reaction was carried out at 80° C. for 6 hours.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, X represents NH, O or S, A represents H when X is NH or O, and When XA is NH_2, OH or SH, Y represents an amino group, and when XA is S-SAr, represents an amino group or a nitro group, Z represents hydrogen or a substituent) is reacted with carbon monoxide in a solvent in the presence of a base and sulfur to form the general formula ▲Mathematical formula, chemical formula, table, etc.▼II (However, X and Z are the same as above.