SU644780A1 - Method of obtaining p-nitrosoanilines - Google Patents

Description

The present invention relates to a new method for producing new, not described in the literature, l-nitrosoanilines, which can be used as intermediates in the synthesis of diazo compounds (including photosensitive, antioxidants, insecticides). The literature describes various methods for producing l-nitrosoanilines, which, however, involve the use of aromatic compounds as starting materials. Thus, in particular, nitrosation of tertiary aromatic amines, rearrangement of N-nitrosoanilines (Fisher-Hepp), oxidation of arylhydroxyl-5 amines, oxidation of aromatic amines are described. products, which significantly limits the possibilities of the known methods. The purpose of this invention is to develop a new method for the production of w-nitrosoanilines, based on the use of 25 readily available aliphatic compounds, resulting in an aromatic system. Another objective of the described invention is the synthesis of new, previously unknown meta-substituted / g-nitroso-anisoses with different substituents on the nitrogen atom of the amino group and the aromatic ring, which would have valuable properties. This goal is achieved by a new method of obtaining new "-nitrosoanilines of the general formula I, where R is methyl, phenyl, p-chlorophenyl, and-methylphenyl or 4-pyridyl; Ri is methyl or phenyl; R2 is hydrogen, ethyl, hydroxyethyl, isopropyl or cyclohexyl; Hz is ethyl, hydroxyethyl or cyclohexyl, or R2 and Rs together with the nitrogen atom form a piperidine or morpholine group, consisting in that the compound of general formula I is C-C-C-R. II and GS

where R and Ri are as defined above, are reacted with acetone and an amine of the general formula III

/

HN

R,

where R2 and Rs have the above values, or correspondingly, by their Schiff base with a molar ratio of initial reagents equal to 1: 5-15: 1.5-2, respectively.

The process is carried out at room temperature for 24-336 hours. The general method of producing p-nitrosoanilines

To 0.01 mol of isonitroso-p-dicarbonyl compound is added a mixture of 0.02 mol of amine and 4 moles of anhydrous acetone. The mixture is kept at room temperature for 24-336 h, after which the reaction mass is transferred to a separatory funnel containing 100 ml of ether and washed with 3% alkali solution, then with water. The ether is evaporated and the product, in most cases oily, is washed with diethyl ether until it turns into a solid. In some cases, the final product is immediately obtained in crystalline form. The compounds described in the table were prepared according to the described procedure.

Example 1. A mixture of 0.02 mol (1.46 g) of diethanolamine and 4 ml of anhydrous acetone is added to 0.01 mol (1.29 g) of onitrosoacetylacetone. The mixture was kept at room temperature for 96 hours, after which the brown precipitate formed was filtered and washed on the filter with diethyl ether. After recrystallization from chloroform: acetone 1: 3, the yield of 3,5-dimethyl-4-nitroso-M, M-di- (R-OXYETHYL) -aniline is 53.5%; m.p. 144 ° C.

Example 2. In the case of using isonitrosobenzoyl acetone, the reaction is carried out as in Example 1. The reaction mixture is aged for 161 hours. The green crystals formed are filtered off and washed with diethyl ether. The yield of 3-methyl-5-phenyl-4-nitroso-L, M-di (p-hydroxyethyl) -aniline is 70%; m.p. 150 ° C.

Example 3. A mixture of 0.02 mol (3.62 g) of dicyclohexylamine and 3 ml of anhydrous acetone was added to 0.01 mol (1.629 g) of isonitrosoacetylacetone. The mixture is kept at room temperature for 120 hours, after which the light green precipitate formed is filtered off.

washed with a 3% alkali solution and

water The yield of 3,5-dimethyl-4-nitroso-M, K-dicyclohexyl aniline is 41.5%,

m.p. 96 ° C.

Example 4. To 0.01 mol (1.29 g) of isonitrosoacetylacetone, a solution of 0.011 mol (1.4 g) of isopropylidenecyclohexylamine in 2 ml of acetone is added. The mixture was incubated at room temperature for 48 h, after which the reaction mass was treated as indicated in the general procedure. The yield of 3,5-dimethyl-M-cyclohexyl-l-nitrosoaniline is 15%; m.p. 136 ° C.

Example 5. To 0.01 mol (2.53 g) of isonitrosodibenzoylmethane is added a solution

0.02 mol (1.7 g) of piperidine and 3 ml of anhydrous acetone. The mixture was kept at room temperature for 40 days, after which the reaction mass was treated as indicated in the general procedure. The yield of 2,6 diphenyl-4- (N-piperidino) - nitrosobenzene is 26%; m.p. 68-69C.

Example 6. To 0.01 mol (2.53 g) of isonitrosodibenzoylmethane was added a solution of 0.02 mol (1.98 g) of cyclohexylamine and 7 ml

anhydrous acetone. The mixture was kept at room temperature for 22 days, after which the reaction mass was treated according to the general procedure. The yield of 3,5-diphenyl-; L-cyclohexyl-4-nitrosoaniline is 62%; m.p. 72-73 ° C.

Example 7. To a solution of 0.02 mol (1.46 g) diethylamine in 3 ml of acetone was added to 0.01 mol (1.92 g) of 1- (4PIridyl) -1,2,3-butantrione-2-oxime. The mixture is maintained at

room temperature for 72 hours, after which the reaction mass is transferred to a separatory funnel containing 100 ml of ether and washed with 3% alkali solution, then with water. The ether is evaporated, and the product is washed with diethyl ether. The yield of H-methyl-5- (4-pyridyl) -Y, H-diethyl-4-nitrosoaniline is 30%; m.p. 115 ° C

Claims (1)

Continuation Claim Formulation of p-nitrosoanilines of general formula I where R is methyl, phenyl, "-chlorophenyl, / g-methylphenyl, or 4-pyridyl; Ri is methyl or phenyl; R2 is hydrogen, ethyl, hydroxyethyl, isopropyl or cyclohexyl; Ra is ethyl, hydroxyethyl or cyclohexyl, or Rg and Ra together with the nitrogen atom form a piperidine or morpholine group, characterized in that the compound of general formula II where Ra and Rs have the indicated values, or the corresponding Schiff base at a molar ratio of initial reagents equal to 1: 5-15: 1.5-2, respectively. Sources of information taken into account in the examination I. Chem. Nitro and nitroso groups. T. I. Ed. Mr. Feuer. M., “Peace, 1972, p. 163-178. Cc-Cc-C II h oo where R and RI are as defined above, are reacted with acetone and an amine of the general formula III