PROCEDIMIENTO PARA LA OBTENCION DE DERIVADOS PIRAZOLINICOS.

摘要

1412003 Diphenylpyrazoline optical brightening agents SANDOZ Ltd 5 Oct 1972 [8 Oct 1971 20 June 1972 21 June 1972] 45957/72 Heading C2C Novel optical brightening agents are of the formula in which A 1 and A 2 are C 1-6 optionally substituted alkylene radicals, X is O or NR 10 where R 10 is H or C 1-8 optionally substituted alkyl, R 1 is H or C 1-8 optionally substituted alkyl, R 2 is C 1-8 optionally substituted alkyl or optionally substituted C 5-7 cycloalkyl or aryl, or, when X is NR 10 , R 2 and R 10 may together form a C 1-3 hydrocarbon bridge, R 3 is C 1-8 optionally substituted alkyl or R 2 and R 3 with the N form a saturated heterocyclic ring, R 4 and R 5 are H, halogen or C 1-8 optionally substituted alkyl or alkoxy, R 6 is H, C 1-8 optionally substituted alkyl or optionally substituted phenyl, R 7 , R 8 and R 9 are H, halogen, C 1-8 optionally substituted alkyl, alkylthio or alkoxy, cyano, or an optionally substituted aryl, alkylsulphonyl, carboxylic acid amide, carboxylic acid ester, sulphonic acid amide, or sulphonic acid ester group ("alkyl" being C 1-8 ) or acylamino, n is 1 or 2 and the anion is non-chromophoric; and are prepared by reacting with Hal-A 1 -COX-A 2 NR 2 R 3 or with CH 2 = C(R 11 )COX-A 2 NR 2 R 3 (where R 11 is H or C 1-8 alkyl); or by reacting or a functional derivative thereof with or by reacting with E 1 -A 2 NR 2 R 3 where E 1 is a radical convertible into an anion; and in each case, if desired, forming an acid addition of quaternary ammonium salt. The sodium salt of 1 - (41- sulphinophenyl)- 3 - p - chlorophenyl - A2 - pyrazoline is prepared from the 41-chlorosulphonyl compound and Na 2 S solution. Reaction of chloroacetyl chloride with the appropriate amine or alcohol gives ClCH 2 CONHCH 2 CH 2 NEt 2 .HCl, and the HC1 salt of 1-chloroacetyl-4-methylpiperazine. The HC1 salt of 1 -acrylyl-4-methylpiperazine is prepared from N-methyl piperazine and acrylyl chloride. is prepared from 4-#-carboxyethylsulphonylphenylhydrazinophenyl hydrochloride at pH 2-3; other compounds substituted in one or both of the phenyl rings by Cl, Ph, OCH 3 , SCH 3 , or SO 2 CH 3 are prepared similarly. The compound is prepared by reacting 1-(41-chlorosulphonyl-31- chlorophenyl - 3 - p - chlorophenyl - A2 - pyrazoline (from the sodium sulphonate and SOCl 2 ) with Na 2 S and then with methyl acrylate; the free acid is obtained by hydrolysis.