Patent GB-1199641-A (GB)
Title: New Anthraquinone and Nitro Dyestuffs
Inventor: KALOPISSIS GREGOIRE
IPC: C09B69/00
Filed: 1967-07-25
Abstract: 1,199,641. Nitrobenzene compounds and intermediates therefor. L'OREAL. 25 July, 1967 [25 July, 1966; 6 July, 1967; 7 July, 1967], No. 34190/67. Heading C2C. [Also in Divisions C4 and D1] The invention comprises (1) compounds of the formula wherein each of the Z radicals represents a nitrobenzene radical, at least one of which Z radicals being substituted by an amino group which is unsubstituted or substituted by one or two alkyl, hydroxyalkyl, aminoalkyl,mono- or dialkylaminoalkyl radicals, the alkyl radicals in the said substituents containing 1 to 4 C atoms or by a C 1 -C 4  alkyl or alkoxy radical; E represents H or OH; m is 0, 1, 2, 3 or 4; and each of the R radicals represents H, C 1 -C 4  alkyl or hydroxyalkyl radical or a radical of the formula wherein n is 2, 3, 4, 5 or 6; and each of R 6  and R 7  represents H or a C 1 -C 4  alkyl radical subject to the proviso that at least one of R 6  and R 7  is alkyl or R 6  and R, together with the N atom form a heterocyclic ring; subject to the proviso that when E represents OH, m is not 2, and acid addition salts and quaternary ammonium salts thereof and (2) compounds of the formulµ and acid addition salts and quaternary ammonium salts thereof, and where X represents a halogen atom. These compounds including those in which E represents OH and m is 2 may be obtained by condensing a compound of the formula wherein Y represents a halogen atom, an alkali metal or alkaline earth metal atom, or a primary, secondary or tertiary amine group, Q represents H or a halogen atom, V is the same as R or represents the radical SO 2 -Z<SP>11</SP> wherein Z<SP>11</SP> represents phenyl or tolyl radical; with (i) a compound of the formula if Y represents a halogen atom; (ii) a compound of the formula wherein Q 1  represents a mobile group, such as NO 2  or a halogen atom, which is readily substituted by an amino group if Y represents a primary amino group; (iii) a compound of the formula if Y represents a secondary or tertiary amino group; (iv) a compound of the formula or of the formula if Y represents an alkali metal or alkaline earth metal and n in Formula IV is 0 and hydrolysing the SO 2 -Z<SP>11</SP> group; and optionally reacting the resulting compound so as to replace Q by a radical of the formula where R 5  represents H, C 1 -C 4  alkyl, hydroxy (C 1 -C 4 ) alkyl or (C 1 -C 4 ) alkoxy-(C 1 -C 4 ) alkyl or a radical of the formula where R 8  and R 9  represent H, C 1 -C 4  alkyl or hydroxyalkyl, acetyl or together with the N atom to which they are attached form a heterocyclic ring; in which Z<SP>111</SP> is the same as, or is a radical capable of being converted during the course of the reaction into Z and when Z<SP>111</SP> is not the same as Z converting it thereto, X represents a halogen atom, M represents an alkali metal or alkaline earth metal atom and n is an integer from 2 to 6, except where indicated otherwise, and, optionally, hydrolysing the product. Further embodiments describe the preparation of restricted classes of compounds falling within the scope of the general Formulµ I, II and III above and methods of modifying the compounds obtained by the said processes. Examples are given for the preparation of the compounds. They are useful as hair dyes. The following intermediates are also prepared:-N,N<SP>1</SP> - dibenzenesulphonyl - N - [(3 - nitro - 4 - methylamino) - phenyl] - N<SP>1</SP> - [4<SP>1</SP> - nitrophenyl] ethylenediamine; N,N<SP>1</SP> - dibenzenesulphonyl - N - [(2 - nitro - 4 - acetamino)- phenyl] - N<SP>1</SP> - [4 - nitrophenyl] - ethylenediamine and N - [(2 - nitro - 4 - amino) phenyl]- N<SP>1</SP> - [41 - nitrophenyl] ethylenediamine; N - [(3 - nitro - 4 - methylamino) phenyl - N - methyl - N<SP>1</SP> - benzenesulphonyl - N<SP>1</SP> - [(3<SP>1</SP> - nitro - 4<SP>1</SP> - methylamino) phenylethylenediamine; N - [(2 - nitro - 4 - benzenesulphonylamino) phenyl] - N<SP>1</SP> - [41 - nitrophenyl] ethylenediamine, N - [(2 - nitro - 4 - (benzenesulphonyl, # - diethylaminoethyl) amino) phenyl] - N<SP>1</SP> - [41 - nitrophenyl]- ethylene diamine and N-[(2-nitro-4-#-diethylaminoethylamino) phenyl] - N<SP>1</SP> - [4 - nitrophenyl] ethylenediamine; N - benzenesulphonyl - N - [(3 - nitro - 4 - methylamino) phenyl] - N<SP>1</SP> - [(2<SP>1</SP> - nitro - 41 - methoxy) phenyl] ethylenediamine; 2 - nitro - 4 - N - benzenesulphonyl - N - # - bromoethylamino - chlorobenzene, N,N<SP>1</SP>- dibenzenesulphonyl - N - [(3 - nitro - 4 - chloro)- phenyl] - N<SP>1</SP> - [4<SP>1</SP> - nitrophenyl] ethylenediamine, N,N<SP>1</SP> - dibenzenesulphonyl - N - [(3 - nitro - 4 - # - acetaminoethylamino) phenyl] - N<SP>1</SP> - [4<SP>1</SP> - nitrophenyl] ethylenediamine and N- [(3 - nitro - 4 - # - acetaminoethylamino) phenyl]- N<SP>1</SP> - [4<SP>1</SP> - nitrophenyl] ethylenediamine; 1 - N - benzenesulphonylamino - 3 - dimethylamino - 4 - nitrobenzene, 1 - N - benzenesulphonyl - N - # - bromoethylamino - 3 - dimethylamino - 4 - nitrobenzene, 1 - N - # - bromoethylamino - 3 - dimethylamino - 4 - nitrobenzene and N - [(4 - nitro - 3 - dimethylamino) phenyl] - N<SP>1</SP> - benzenesulphonyl - N<SP>1</SP> - [(31 - nitro - 4<SP>1</SP> - methylamino) - phenyl] ethylenediamine; 1 - benzenesulphonylamino - 2 - nitro - 4 - acetaminobenzene and N,N<SP>1</SP> - dibenzenesulphonyl - N,N<SP>1</SP> - bis [(2 - nitro - 4 - acetamino) phenyl] tetramethylenediamine; 1 - (N - benzenesulphonyl - N - # - bromoethyl) amino - 2 - nitro - 4 - acetaminobenzene and N,N<SP>1</SP> - dibenzenesulphonyl - N,N<SP>1</SP> - bis [(2 - nitro - 4 - acetamino) phenyl] ethylenediamine; N,N<SP>1</SP> - di - benzenesulphonyl - N,N<SP>1</SP> - bis [(3 - nitro - 4 - methylamino) phenyl] tetramethylenediamine; N,N<SP>1</SP> - di - benzenesulphonyl - N,N<SP>1</SP> - bis [(3- nitro - 4 - chloro)- phenyl] tetramethylenediamine and N,N<SP>1</SP>-dibenzenesulphonyl - N,N<SP>1</SP> - bis [(3 - nitro - 4 - # - aminoethylamino) phenyl] tetramethylenediamine; and N,N<SP>1</SP>-di-benzenesulphonyl-N,N<SP>1</SP>-[(3- nitro - 4 - # - hydroxyethylamino) phenyl] tetramethylenediamine.