RU2522553C1 - Method of obtaining 1,1-dichloro-2,2-bis(3-nitro-4-n, n-dimethylaminophenyl)ethylene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a one-stage method of obtaining 1,1-dichloro-2,2-bis(3-nitro-4-N,N,-dimethylaminophenyl)ethylene, which can be applied as an intermediate product in synthesis of soluble aromatic polyimides. The method consists in processing 1,1,1-trichloro-2,2-bis(3-nitro-4-chlorophenyl)ethane in N,N-dimethylformamide or N,N-dimethylacetamide with hydroxides of alkali metals at a temperature of 40-100°C. A molar ratio 1,1,1-trichloro-2,2-bis(3-nitro-4-chlorophenyl)ethane: NaOH (KOH):DMFA (DMAA) constitutes 1:4÷10:20÷30.

EFFECT: method makes it possible to obtain 1 said compound in one stage with the high output.

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Description

The invention relates to a method for producing a new binuclear nitroaromatic compound - 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene. This compound is an intermediate in the synthesis of 1,1-dichloro-2,2-bis (3-amino-4-N, N-dimethylaminophenyl) ethylene. The binuclear aromatic diamine of the 1,1-dichloro-2,2-diphenylethylene series, containing tertiary amino groups as substituents, can be used to obtain new soluble polyimides (A.L. Rusanov, E.G. Bulycheva, G.V. Kazakova, V .V. Kopeikin, VV Kazin, SG Sibrikov, ML Keshtov, AK Mikitaev // High-molecular compounds. Series B, 1997. T. 39, No. 2. P.327-330 )

The purpose of the invention is the creation of a highly efficient method for the synthesis of 1,1-dichloro-2,2-bis (3-nitro-4-K, M-dimethylaminophenyl) ethylene, which minimizes the operational time of the process, to obtain the target product in one step with high yield and high degree of purity.

This goal is achieved in that 1,1,1-trichloro-2,2-bis (3-nitro-4-chlorophenyl) ethane is used as a substrate, the interaction of which with alkali metal hydroxides in amide solvents (DMF, DMAA) allows in one step, the dehydrochlorination reaction and nucleophilic substitution of chlorine atoms bonded to the carbons of benzene rings are carried out by the N, N-dimethylamino groups. The reaction is carried out at a temperature of 40-100 ° C and a molar ratio of 1,1,1-trichloro-2,2-bis (3-nitro-4-chlorophenyl) ethane: NaOH (KOH): DMF (DMAA) = 1: 4 ÷ 10: 20 ÷ 30. Implementation of the proposed synthesis scheme allows for 1 ÷ 2.5 hours to obtain 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene with a yield of 96-98%.

The structure and purity of the target product were analyzed by ¹ H NMR and IR spectroscopy, by determining the melting temperature and elemental composition.

The invention is illustrated by the following examples.

Example 1

To a solution of 4.4 g (0.01 mol) of 1,1,1-trichloro-2,2-bis (3-nitro-4-chlorophenyl) ethane in 15 ml of DMF at 100 ° C, 1.78 g (0.045 mol) of sodium hydroxide was added with stirring . After 1 h, the reaction mass was cooled, poured into water with stirring. The precipitate was separated by filtration, dried. Yield of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene 4.12 g (98%), T _mp = 159-160 ° C, R _f 0.58 (benzene-acetic acid 8: 1).

Found,%: C 50.58; H 2.23; C1 16.29; N 13.10. C ₁₈ H ₁₈ C1 ₂ N ₄ O ₄ .

Calculated,%: C 50.80; H 2.35; C1 16.71; N 13.17. M 425.0

IR spectrum, ν (cm - ^-1 ): 1270, 1300 [ν (CN tert)]; 1340 [ν _S (NO ₂ )], 1530 [V _as (NO ₂ )]; 1616 [ν (C = C)].

¹ H NMR (CDC1 _3), δ, ppm .: 6.97 (d) (2H, H ^{1,1 '),} 7.32 (dd.) (2H, H ^2,2'), 7.70 (d) ( 2H. H, ^{3.3 ′} ), 2.94 (s) [N (CH ₃ ) ₂ ].

Example 2

The process is carried out analogously to example 1, with the difference that instead of DMF use 15 ml of DMAA. The yield of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene is 97%.

Example 3

The process is carried out analogously to example 1, with the difference that 22 ml of DMF is used. The yield of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene is 98%.

Example 4

The process is carried out analogously to example 1, with the difference that 4.0 g (0.1 mol) of sodium hydroxide are added. The yield of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene was 97.4%.

Example 5

The process is carried out analogously to example 1, with the difference that the reaction temperature is 40 ° C, the time is 2.5 hours. The yield of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene is 96%. .

Claims (1)

A one-step process for the preparation of 1,1-dichloro-2,2-bis (3-nitro-4-N, N-dimethylaminophenyl) ethylene, comprising treating 1,1,1-trichloro-2,2-bis (3-nitro-4 -chlorophenyl) ethane in N, N-dimethylformamide or N, N-dimethylacetamide with alkali metal hydroxides at a temperature of 40-100 ° C and a molar ratio of 1,1,1-trichloro-2,2-bis (3-nitro-4-chlorophenyl ) ethane: NaOH (KOH): DMF (DMAA) = 1: 4 ÷ 10: 20 ÷ 30.