SU572456A1 - Pyrazole derivatives as monomers for synthesis of metal-containing polymers - Google Patents

Description

one

This invention relates to the synthesis of novel chemical compounds, specifically to pyrazole derivatives of the formula I

  JbNH-eH

..N CgHs where X is COOH, -COS1, -CONHNHg or

CO22H5,

which are monomers for synthesizing metal-containing polymers.

These properties suggest the possibility of their use in the chemical industry.

Z-hydroxy-4-azopyrazolone derivatives are known, which are monopomers for the synthesis of polymers.

A disadvantage of the known compounds is the low reactivity of the oxing groups at position 3 of the pyrazole ring, which limits their use as a monomer.

According to the invention, novel pyrazole derivatives of the formula I are proposed, having highly reactive functional groups such as carbonyl chloride, which increases the ability to polycondensate.

Compounds of formula I are obtained by reacting 1-phenyl-3-carbethoxy-4-dimethylaminomethylene-5-pyrazole with o-, m-, p-phenylenediamine in a solvent medium at the boiling point of the reaction mixture, the resulting 1,3-bis (G-phenyl -3-carbethoxy-5-oxo4-methylaminophenazolyl) -benzene is reacted with caustic soda solution, the resulting 1,3-bis- (l-phenyl-3carboxy-5-oxo-4-methylennampopprazolyl) -benzene is treated with thionyl chloride to form acid chloride.

1,3-Bis- (1-phenyl-3-carbhydrazo-5-oxo-4-methylaminopyrazolyl) -benzene is obtained by reacting 1,3-bis- (G-phenyl-3-carbethoxy-5-oxo-4-methylaminopyrazolyl) benzene with hydrazine hydrate at 120 ° C in dimethylacetamide.

Example 1. 1,3-Bis- (G-phenyl-3-carbethoxy-5-oxo-4 - methyleneamine pyrazolnl) - benzene.

A mixture of 9 g of 1-phenyl-3-carbethoxy-4-dimethylaminomethylene-5-pyrazolone and 1.7 g of lg-phenylene pamine is boiled in 50 ml of dioxane under reflux for 3 hours. Solvent

evaporated to dryness and the residue is recrystallized from dimethylacetamide. Yield 10 g (54%), so pl. 257 ° C. Found,%: N 14.08, 14.28. SzgNgvMbOb.

Calculated,%; N 14.20.

Example 2. 1,3-Bis- (G-phenyl-3-carbox115-oxo-4-methylene amine-pyrazolyl) benzene.

5.9 g of 1,3-bis- (1-phenyl-3-carbethoxy-5-oxo-4-methyleneaminopyrazolyl) benzene is heated in a fourfold excess of 1M sodium hydroxide solution in a water bath until completely dissolved. The cooled solution is filtered and acidified with 10% hydrochloric acid to pH 3-4. The precipitate formed is filtered off, dried and non-recrystallized from glacial acetic acid. The output of 4.1 g (75%), so pl. 226--227 ° С (with decomposition).

Found,%: N 15.46, 15.14.

C28H2oNbOb.

Calculated,%: N 15.69.

Example 3. 1,3-Bis- (1-phenyl-3-carbhydrazo-5-oxo-4-methyleneaminopyraznol) - benzene.

To a solution of 2 g of 1,3-bis- (1-phenyl-3-carbethoxy-5-oxo-4-methylene-aminopyrazolyl) benzene in 40 ml of hot dimethylacetamide is added 1 g of hydrazine hydrate and heated at 120 ° C for 1 hour As a result of the reaction, the color of the solution changes from orange to yellow. The mass is diluted with water to 200 ml and acidified with 10% hydrochloric acid to pH 3-4. The precipitate formed is filtered and dried. The output of 1.4 g (78%), so pl. 340 ° C (from dimethylacetamide).

Found% N 24.50, 24.00.

C28H22N8O4.

Calculated,%: N 24.80.

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Example 4. 1,3-Bis- (G-phenyl-3-carbonyl chloride-5-oxo-4- - methylaminopyrazolyl) benzene.

To 1.5 g of 1,3-bis- (G-phenyl-3-carboxy-5-oxo-4-methylaminophenazolyl) benzene was added 10 ml of thionyl chloride, a few drops of dry dimethylformamide and stirred at 50 ° C for 3 hours. The excess thionyl chloride is distilled off in vacuo to dryness, the residue is washed several times with chloroform and dried. Output 0.9 g (56%), so pl. 260 ° C.

Found,%; C1 11.94, 12.36; N 14.80, 14.70;

C28HigCl2N6O4.

Calculated,%: C1 12.39; N 14.65.

Claims (1)

Formula of the Invention Pyrazole derivatives X W, -, ft..Kj, Jx2 where X is COOH, -CO1, -CONHNHg or - СО2С2Н5, as my measures for the synthesis of metal-containing; their polymers.