Patent GB-554101-A (GB)
Title: New colouring matters
IPC: C09B23/16
Filed: 1941-12-17
Abstract: 554,101. 2:2<SP>1</SP>:4:4<SP>1</SP> - Tetraaryl - aza - dipyrromethines. ROGERS, M. A. T., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. Dec. 17, 1941, Nos. 16276/41 and 9668/42. [Class 2 (iii)] 2 : 2<SP>1</SP> : 4 : 4<SP>1</SP> - Tetraaryl - aza - dipyrromethines are prepared by (a) reacting one molecular proportion of a 5-nitroso-2:4-diarylpyrrole with one molecular proportion of a 2:4-diarylpyrrole, e.g. by heating the reactants together in a mutual solvent, and preferably in presence of an acid condensing agent such as acetic acid or acetic anhydride ; (b) heating a 5-nitroso- 2:4-diarylpyrrole or its hydrochloride to about 190‹C., with the former preferably in presence of a small proportion of acid ; or (c) treating 5 - amino - 2:4 - diarylpyrrole with an oxidizing agent, e.g. atmospheric oxygen. 2:4 - diarylpyrroles specified are compounds of formula wherein R<SP>1</SP> and R<SP>11</SP> represents an aryl radical e.g. of the benzene or naphthalene series, substituted or not and the same or different (such as phenyl, p-methoxyphenyl, p-dimethylaminophenyl, m - nitrophenyl, o - chlorophenyl, m - hydroxyphenyl, p - acetaminophenyl, or naphthyl), R<SP>111</SP> represents hydrogen or a non-reactive substituent, e.g. an aryl, alkyl, alkylamino, benzylideneamino, or acylamino radical, and X represents hydrogen or a nitroso or amino radical. 2:4 - diarylpyrroles specified are 2:4 - diphenylpyrrole, 2 - phenyl - 4 - (p - methoxyphenyl) - pyrrole, 2 - (p - methoxy - phenyl) - 4 - phenylpyrrole, 2 - (m - hydroxyphenyl) - 4 - phenylpyrrole, 2 - (o - chlorophenyl) - 4 - phenylpyrrole, 2 - (p - acetamino - phenyl) - 4 - phenylpyrrole, 2 - a - naphthyl - 4 - phenylpyrrole, 2 - phenyl - 4 - # - naphthyl - pyrrole, 2:3:4 - triphenylpyrrole, 3 - benzoyl - amino - 2 : 4 - diphenylpyrrole, 3 - acetamino - 2:4 - diphenylpyrrole, 3 - benzoylamino - 2:4 - di - p - tolylpyrrole, and 3 - acetoacetamino - 2:4 - diphenylpyrrole. The sulphonic acids (and salts) and 5-nitroso- or 5-amino-derivatives may also be used. 2:21:4:41- Tetraaryl-aza-dipyrromethines may also be prepared by heating 1-nitromethyl- or 1-cyano-1:3-diaryl-3-propanones (which may contain a non-reactive 2- substituent) or simple functional derivatives thereof with ammonia or an ammonia-yielding agent, an oxidizing agent being present when the 1-cyanopropanones are used. The reagents may be heated together to 120-200‹C. or may be heated in a mutual solvent. A current of air may be used as oxidizing means. Where water is evolved, the heating is carried out under such conditions that the water is removed. The aryl radicals may be phenyl, p-methoxyphenyl, p-dimethylaminophenyl, m-nitrophenyl, o-chlorophenyl, m-hydroxyphenyl, p-acetaminophenyl, or naphthyl, and the non-reactive 2-substituent an aryl, alkyl, alkylamino, benzylideneamino, or acylamino radical. Suitable 1-nitromethyl- 1:3-diaryl-3-propanones (named as butanones) are 1-nitro-2:4-diphenyl-butanone-4, 1-nitro- 2:4-di-(p-methoxyphenyl)-butanone-4, 1-nitro- 2-(p-methoxyphenyl)-4-phenylbutanone-4, 1- nitro-2-phenyl-4- (p-methoxyphenyl) - butanone- 4, 1-nitro-2-(m-nitrophenyl)-4-phenyl-butanone- 4, 1-nitro-2-(m-hydroxyphenyl)-4-phenylbutanone-4, 1-nitro-2-(p-dimethylaminophenyl)-4- phenylbutanone-4, and 1-nitro-2-(3:4-methylenedioxyphenyl)-4-phenylbutanone-4, and their oximes. Suitable 1-cyano-1:3-diaryl-3-propanones (named as 1-aryl-2-aroyl-propionitriles) are 1-phenyl-2-benzoylpropionitrile, 1-(p-methoxyphenyl)-2-benzoylpropionitrile, 1-phenyl-2-(p methoxybenzoyl)-propionitrile, 1-(m-hydroxyphenyl) - 2 - benzoylpropionitrile, 1- (o - chlorophenyl)-2-benzoylpropionitrile, 1-(p-acetamino)- 2-benzoylpropionitrile, 1-α-naphthyl-2-benzoylpropionitrile, 1-phenyl-2-#-naphthoylpropionitrile, and 1-(p-dimethylaminophenyl)-2-benzoylpropionitrile, and their oximes. Suitable ammonia-yielding reagents are formamide, urea, thiourea, ammonium formate, ammonium phosphate, and ammonium carbamate. In Example 1, 1-nitro-2:4-diphenylbutanone-4 and formamide are heated together to 190‹C., and the cooled mixture is treated with methyl alcohol and the suspension filtered to give 2:2<SP>1</SP>:4:4<SP>1</SP>-tetraphenyl-aza-dipyrromethine. In Example 2, 2:2<SP>1</SP>:4:4<SP>1</SP>-tetra-(p-methoxyphenyl)- aza-dipyrromethine is prepared by heating together 1-nitro-2:4-di- (p-methoxyphenyl) -butanone-4 and ammonium formate to 180‹C. The following compounds are similarly prepared (using ammonium formate):-2:2-diphenyl - 4:4<SP>1</SP> - di-(p-methoxyphenyl-aza-dipyrromethine (from 1-nitro-2-(p-methoxyphenyl)-4- phenylbutanone-4) ; 2:2<SP>1</SP>-di-(p-methoxyphenyl)- 4:4<SP>1</SP>-diphenyl-aza-dipyrromethine (from 1-nitro- 2-phenyl-4-(p-methoxyphenyl)-butanone-4) ; 2:- 2<SP>1</SP> - diphenyl-4:4<SP>1</SP>- di - (m-nitrophenyl)-aza-dipyrromethine (from 1-nitro - 2 - (m - nitrophenyl) - 4- phenylbutanone-4); 2:2<SP>1</SP>-diphenyl-4:4<SP>1</SP>-di-(mhydroxyphenyl) - aza - dipyrromethine (from 1 - nitro-2-(mhydroxyphenyl) - 4 - phenylbutanone- 4) ; 2:21 - diphenyl - 4:4<SP>1</SP> - di - (p - dimethylamino - phenyl)-aza-dipyrromethine (from 1-nitro-2-(pdimethylaminophenyl) - 4 - phenylbutanone-4) ; 2:2<SP>1</SP>-diphenyl-4:4<SP>1</SP>-di-(3:4-methylenedioxyphenyl)- aza-dipyrromethine (from 1-nitro-2-(3:4-methylenedioxyphenyl)-4-phenylbutanone-4); 2:2<SP>1</SP>:4:- 41-tetra-(p - methoxyphenyl) - aza - dipyrromethine (from 1-nitro-2:4-di-(p - methoxyphenyl) - buta - none-4) ; 2:2<SP>1</SP>:4:4<SP>1</SP>-tetraphenyl-aza-dipyrromethine (from 1-phenyl-2-benzoylpropionitrile); 2:2<SP>1</SP>- diphenyl-4:4<SP>1</SP>-di-(p-methoxyphenyl) - aza-dipyrromethine (from 1-p-methoxyphenyl-2-benzoylpropionitrile ; 2:2<SP>1</SP>-di-(p-methoxyphenyl)-4:4<SP>1</SP>- diphenyl-aza-dipyrromethine (from 1-phenyl-2- (p-methoxybenzoyl)-propionitrile) ; 2:2<SP>1</SP>:4:4<SP>1</SP>- tetraphenyl-aza-dipyrromethine (from 1-nitro- 2:4-diphenylbutanone-4-oxime) ; 2:2<SP>1</SP>:4:4 <SP>1</SP>-tetraphenyl-aza-dipyrromethine (from 1-phenyl-2- benzoylpropionitrile oxime) ; and 2:2<SP>1</SP>:diphenyl- 4:4<SP>1</SP>-di-(p - dimethylaminophenyl) - aza - dipyrro - methine (from 1-nitro-2-(p-dimethylaminophenyl)-4-phenylbutanone-4-oxime). 2:2<SP>1</SP>:4:4<SP>1</SP>-Tetraphenyl-aza-dipyrromethine is also prepared by refluxing together 5-nitroso- 2:4-diphenylpyrrole and 2:4-diphenylpyrrole. 2:2<SP>1</SP>:4-triphenyl-4<SP>1</SP>-p-methoxyphenyl-aza-dipyrromethine is similarly prepared (using 2-phenyl- 4-p-methoxyphenylpyrrole). 2:2<SP>1</SP>:4:4<SP>1</SP>-Tetraphenyl-aza-dipyrromethine may also be prepared by heating 1-nitro-2:4-diphenylbutanone-4 with aqueous ammonia in a closed vessel at 180‹C. 2:2<SP>1</SP>:4:4<SP>1</SP> - Tetraphenyl - aza - dipyrromethine monosulphonic acid is prepared by heating together sodium 2:4-diphenylpyrrole monosulphonate, 5-nitroso-2:4-diphenylpyrrole hydrochloride, acetic acid, and acetic anhydride. 2:2<SP>1</SP>:4:4<SP>1</SP>-Tetraphenyl-aza-dipyrromethine disulphonic acid is similarly prepared using 2:4- diphenylpyrrole disulphonic acid. 2<SP>1</SP>:4:4<SP>1</SP>-. Triphenyl-2 - (p - - methoxyphenyl) - aza - dipyrro - methine disulphonic acid is similarly prepared using 5-nitroso-2-(p-methoxyphenyl)-4-phenylpyrrole. Another 2:2<SP>1</SP>:4:4<SP>1</SP>-Tetraphenyl-aza-dipyrromethine disulphonic acid is prepared by heating together 5-nitroso-2:4-diphenylpyrrolemonosulphonic acid, sodium 2:4-diphenylpyrrole monosulphonate, acetic acid, and acetic anhydride. 2:2<SP>1</SP>-Diphenyl-4:4<SP>1</SP>-di-(p-dimethylaminophenyl)- aza-dipyrromethine dimethiodide is prepared by mixing 2:2<SP>1</SP>-diphenyl-4:4<SP>1</SP>-di-(p-dimethylaminophenyl)-aza-dipyrromethine with methyl iodide dissolved in nitrobenzene. 2:2<SP>1</SP>:4:4<SP>1</SP>- Tetraphenyl-3-benzoylamino-aza - di - pyrromethine is prepared by refluxing together 5-nitroso-2:4-diphenylpyrrole hydrochloride and 3-benzoylamino-2:4-diphenylpyrrole dissolved in acetic anhydride and stirring into cold water. 2:2<SP>1</SP>:4:4<SP>1</SP> - Tetraphenyl - aza - dipyrromethine is also prepared by passing a stream of air through a boiling ethyl alcohol solution of 5- amino-2:4-diphenylpyrrole. 2:2<SP>1</SP> - Diphenyl - 4:4<SP>1</SP> - di - α - naphthyl - aza - dipyrromethine is prepared by heating together (in the presence of air) 1-α-naphthyl-2-benzoylpropionitrile and ammonium formate. 4:4<SP>1</SP>-diphenyl - 2:2' - di - # - naphthyl - aza - dipyrromethine is similarly prepared from 1-phenyl-2-#- naphthoylpropionitrile, and 2:2<SP>1</SP> - di - # - naphthyl - 4:4<SP>1</SP> - di - α - naphthyl - aza - dipyrromethine is similarly prepared from 1-α-naphthyl- 2-#-naphthoylpropionitrile. 2:2<SP>1</SP>:4 - Triphenyl - 4<SP>1</SP> - α - naphthyl - aza - dipyrromethine is prepared by refluxing together 2 - phenyl - 4 - α - naphthylpyrrole, 5 - nitrosodiphenylpyrrole, acetic acid, and acetic anhydride. The 2:2<SP>1</SP>:4:4<SP>1</SP>-tetraaryl-aza-dipyrromethines may be used as pigments, in dyeing textiles (e.g. wool), and in the production of coating compositions. Water-soluble derivatives may be produced by (a) forming salts, e.g. with sulphonic acid, (b) forming quaternary ammonium salts, e.g. with methyl iodide, and (c) sulphonation. 1 - nitro - 2:4 - di - (p - methoxyphenyl) - butanone-4 is prepared by condensing p:p<SP>1</SP>-dimethoxychalkone with nitromethane. 1-nitro-2- (p - methoxyphenyl) - 4 - phenyl - butanone - 4, 1 - nitro - 2 - phenyl 4 - (p - methoxyphenyl) - butanone - 4, 1 - nitro - 2 - (m - nitrophenyl) - 4 - phenyl - butanone - 4, 1 - nitro - 2 - (m - hydroxyphenyl) - 4 - phenyl - butanone - 4, 1 - nitro - 2 - (p - dimethylaminophenyl) - 4 - phenyl - butanone- 4, and 1 - nitro - 2 - (3:4 - methylenedioxyphenyl) - 4-phenylbutanone-4 are similarly prepared. 1-phenyl-2-benzoylpropionitrite is prepared from hydrogen cyanide and benzalacetophenone. 1 - α - naphthyl - 2 -