SU979338A1 - Process for producing 2-amino3,4,4-tricyano-1,5-substituted-2-pyrrolines - Google Patents

Description

This invention relates to a method for producing new 2-pyrroline derivatives having biological activity and which can be used in agriculture.

A known method for producing N-alkyl-3-amino-4-cyano-3-pyrrolines by cyclating M-alkyl-M-cyanoalkylamines in the presence of strong bases of tert. Butylate kggl, sodium hydroxide 1 J.

However, this method does not make it possible to obtain derivatives of 2-pyrrolines.

The aim of the invention is to develop a method for producing compounds not described in the literature.

The goal is achieved according to the method for producing 2-amine-3, 4,4-tricyano-1,5-substituted 2-garrolines by formula

-Si

NC.

 si

U and -n

kR HpN

R

where a) R SI, S ,,, R SI ,, CH (SI,),; b) to Cfl., R CfcHj;

c) R, Hc, R CjHj-; r) R -M CHCH2-SNGK 2,

R CH CHCCHjk

5 D) CHC6H CfcH, 3; e) R-M CHCH3, R CHj; 3) R-M CH-2-furyl, R 2-fipyl, which implies that 1,1,2,2-tetrachiscian ethane undergoes Q interaction with the corresponding azomethine bases in organic solvent at 10-75 ° C in an inert gas atmosphere.

The compounds thus obtained have a high biological

15 activity and represent a valuable supplement to the already existing drugs, using agricultural products.

Example 1. 2-amino-Z.4,4 20 -triciano-5-isobutyl-N-benzyl-2-pyrrole n.

A mixture of 13 g (0.1 mol of 1,1,2,2-tetracyanoethane, 17.5 g (0.1 mol) of N-isopentylidenebenzylamine is dissolved

25 in 200 ml of dioxane and heated for 1.5 hours under nitrogen at 75 ° C. Thereafter, 100 ml of dioxane is distilled off from the reaction mixture under reduced pressure, the remaining solution is diluted

30 200 MP of an alcohol-water mixture (40 1lp160 ml), the precipitate filtered off, washed with an aqueous-alcoholic mixture {2: 3,) with two 16 ml portions, recrystallized from spin-water (1: 1) and get 18.3 g (60%) of the desired product with mp 1668. Found,%: C, 70.80; H 6.25; N 23.0. C.eH.gN, Calculated,%: C 70, 79; H 6.28; N 22.94 M (mass spectral) 305 M 305.38653. Example 2. 2-amino-3, 4,4-tr cyano-5-phenyl-1-N-benzylideneamino 2-pyrroline. A mixture of 6.5 g (0.05 mol) of 1,1,2,2-tetracyanoethane and 10.4 g (0.05 mol of benzalazine is dissolved in 80 ml of dioxane, heated for 7-8 minutes at 75 ° C in nitrogen, and then the reaction mass is diluted with 150 ml of hot (70 ° C) water and cooled to. The precipitate is filtered off, npoMtJBiojoT is aqueous dioxane (1: 3) recrystallized from isopropyl alcohol in two portions of 10 ml and 12 g are obtained (72%) of the product with m.p., 177-178 ° C. Found,%: C 71.12; F 4.22; N 24/60. C2OHI4NfcCalculated,%:, 98; H 4.18; N 24, 84h; M (mass spectral) 338 M 338.40 Example 3. 2-amino-3, 4,4-tricyano-5-ethyl-1- (N-propylidenes but) -2-p Irrodin. To a suspension of 6.5 g (0.05 mol) of 1,1,2,2-tetracyanoethane in 60 ml of 50% aqueous ethanol under nitrogen atmosphere, with stirring, 5.6 g (0.05 mol) of propanalazine in 20 ml of 50% ethanol for 10 minutes at 10–15 ° C. After 0.5 h after the start of the process, 40 ml of cold (+ 10 ° C) water was added to the reaction mass, the precipitated precipitate was filtered, dried, recrystallized from ethylene chloride. hexane (1: 1) and get 7.5 g (62%) of the product with so pl. 148149 C. Found,%: C 60.05; H 5.65; N 35.00. Cl2 l4NfcCalculated,%: C 59.48; H 5.82; N 34.69; (mass spectral) 242 M 242.28. Example 4. 2-amino-3, 4,4-tr cyano-5-isobutyl-1- (N-isopentylidene amino) -2-pyrroline. To a suspension of 6.5 g (0.05 mol) of 1.1, 2, 2-tetracyanethane in 60 ml of 50% ethanol under a nitrogen atmosphere with stirring, 8.4 g (0.05 mol) of azine isovalerian aldehyde are added dropwise at such a rate that the temperature of the reaction mass is not understood, above 35 ° C. Thereafter, the reaction mass is cooled, diluted with 40 MP with cold (+ 10 ° C) water, and the precipitate is filtered off. After drying in air and recrystallization, 9 g (60%) of the product are obtained from ethyl acetate-hexane, m.p. 115-116 ° C. Found,%: C 63.89; H 7.68; N 28.03. C.gH.N. Calculated,%: C 64.40; H 7.43; N 28.16; M (mass spectral) 298; M 298, .39. Example 5. 2-amino-3, 4,4-tricyano-5-hexyl-1- (L-heptylideneamino) -2-pyrroline. To a solution of 11.2 g (0.05 mol) of enanthalazine in 60 ml of dioxane 5 ml of water are poured and nitrogen (gas) is passed into the resulting solution for 5 minutes. After that, 6.5 g (0.05 mol) of 1,1,2,2-tetracyanethane is added to the solution, heated to 35 ° C and kept at this temperature for 0.5 h. Then the solution is cooled to + 15 ° C and 150 ml of cold (+ 10 ° C) water is poured into it. When this occurs, the gradually crystallizing oil is precipitated, which is filtered off. After drying and recrystallization from ethyl acetate-hexane, 11.3 g (64%) of the product are obtained with a mp. 102103 ° C. Found,%: C 67.70; H 8.32; N 24.01. Calculated,%: C 67.76; H 8.53; N 23.70; M (mass spectral) 354; M 354.50. Example 6. 2-amino-3, 4,6-tricyano-5-methyl-1- (N-ethylideneamino) -2-pyrroline. Nitrogen (gas) is passed into a solution of 4.2 g (0.05 mol) of acetalazine in 40 ml of tetrahydrofuran for 5 minutes, then 6.5 g (0.05 mol) of 1,1,2,2-tetracyanoethane is added and The reaction mixture is mixed at + 10 ° С for two weeks. After that, the solvent is distilled off under reduced pressure and temperature not higher than +. The precipitate was filtered off. After drying and recrystallization from tetrahydrofuran-hexane (3: 2), 6.2 g (58%) of the product are obtained with a mp. 151-152 ° C. Found,%: C 56.02; H 4.83; N 38.92. B Calculated,%: C 56.06; H 4.70; N 39.23; M (mass spectral) 214; M 214.23. Example 7. 2-amino-3, 4,4-tricyano-5- (2-furyl) -1- (N-furfurylideneamino) -2-pyrroline. The reaction mass, consisting of 6.5 g (0.05 mol) 1,1,2,2-tetracyanoethane, 9.4 g (.0.05 mol) of furfural-ein and 100 ml of 70% aqueous echanol, is stirred at 30 ° С for 2 h under nitrogen. After cooling to + 10 ° C, the precipitated precipitate is filtered off, washed with 20% aqueous solution of ethanol, and dried. For repeated purification, the ethyl acetate solution of the product is stirred with activated carbon (30 ml per 0.4 g) - the carbon is filtered off, the filtrate is diluted with hexane. The precipitated crystals are filtered off and dried, and 10.3 g (65%) of product is obtained with a mp. .

Found,%: C 60.05; H 3.25; N 26.07.

 N OZCalculated,% C 60.37j H 3.16; N 26.40; M (mass spectral) 318; M 318.32.

Claims (1)

Invention Formula The method of obtaining 2-amino-3,4,4-tricyano-1, 5-substituted 2-pyrrolino general formula lit / I-g LA .. R NrI E where a R-CH., R-CHPCH (CH),; (B) R-CHjCbHs, -SeJ5; c.) R is -N CHC2H5, R-CjHj-, d) R is -N CHCH2-CH (CH3) 2,  CH5CH (CH3) 2; d) R - -N CHC6n, 3, e) R is —N CHCF1, R is CH 3; 3) R - -N CH-2ipyryl, R-2-pyryl, different from the fact that 1,1,2,2-tetracyanoethane is reacted with the corresponding azomethine bases in organic solvent at 10-75 ° C in an inert gas atmosphere . Sources of information taken into account in the examination 1. J.Chem. Soc. (C), 1967, 693.