Patent GB-511193-A (GB)
Title: The manufacture of nitro dyestuffs of the azine series
IPC: C09B17/02
Filed: 1938-01-14
Abstract: 511,193. Dyes. CARPMAEL, A. (I.G, Farbenindustrie Akt.-Ges.). Jan. 14, 1938. No. 1335. [Class 2 (iii)] Nitro dyestuffs of the azine series for the dyeing of wool and silk and which are fast to pulling, ironing, sea-water, light and perspiration are prepared by. condensing diphenylamine derivatives of the general formula:- (wherein one Z stands for an amino group and the other for a sulphonic acid group, X stands for hydrogen, alkyl or aralkyl and Y stands for acyl, and X and Y together contain at least five carbon atoms, and the benzene nucleus containing the -N##<SP>X> group may contain further substituents) with such substitution derivatives of 1.3.5:-trinitrobenzene as contain in the 2-position a halogen atom or an alkoxy group, by heating in an aqueous solution in the presence of an acid binding agent. In examples, (1) 1-(N-benzoyl-ethylamino)-4-aminobenzene is condensed with 1-chloro-2.4-dinitrobenzene-6- sulphonic acid and the resulting 2<1>.4<1>-dinitro-4- (N-benzoyl-ethylamino)-diphenylamine - 6<1> - sulphonic acid is reduced with acetic acid and iron filings; the sodium salt of the 2<1>.4<1>-diamino-4- (N-benzoyl-ethylamino)-diphenylamine-6<1>-sulphonic acid thus obtained is condensed with 2.4.6.-trinitroanisole by heating with calcium carbonate and then sodium carbonate, to form the azine ; similar dyestuffs are obtained by replacing 1-chloro-2.4-dinitrobenzene-6-sulphonic acid by 1-chloro-2.6-dinitrobenzene-4- sulphonic acid, and by-replacing 1-(N-benzoylethylamino)-4-aminobenzene by 1-(N-cyclohexylpropionyl-ethylamino)-4-aminobenzene,(2) the amino compound obtainedby condensing 1-(N-benzoyl-n-butylamino) - 4 - amino -benzene with 1-chloro-2.6-dinitrobenzene-4-sulphonic acid and reducing the product, is condensed with 2.4.6.-trinitro-1-chloro-benzene; similardyestuffs are obtained by employing 1 -(N- benzoyl-isopropylamino) - 4 - or 1 - (N - hexahydrobenzoyl-ethylamino)-4-aminobenzene, (3) the amino compound obtained by the condensation and subsequent reduction of 4- or 5- (N-benzoyl-ethyl-amino)-2 -amino- 1 -methylbenzene - I - chloro - 2.6 - dinitrobenzene - 4 - sulphonic acid, is condensed with 2.4.6.-trinitro-1- chlorobenzene, (4) 1-(N-4<1>-methylphenylsulphonyl-ethylamino)-4-, 1-(N-#-chloropiopionylisopropylamino) -4 1-(N-acetyl-benzyl-amino)- 4-, 1-(N-benzoyl-benzylamino)-4-, or 1- cyclohexylpropionylamino-4-aminobenzene are condensed with 1-chloro-2.4-dinitrobenzene-6- sulphonic acid or with 1-chlor-2.6 dinitrobenzene-4-sulphonic acid and the corresponding amino compound, obtained by. reduction, is condensed with 2.4.6-trinitroanisole ; similar dyestuffs are obtained by employing 1-capionylamino-, 1-caprylyl-amino, or 1-caprinyl-amino- 4-aminobenzene, or by employing 1-acylamino-4-aminobenzenes in which the acyl radicle is derived from a mixture of fatty acids, e.g., is of the general formula C4-6 H9-13, .CO-. 1 - (N - cyclohexylpropionyl - ethylamino) - 4 - aminobenzene is prepared by hydrogenating cinnamic acid, converting the cyclo-hexylpropionic acid thus obtained into its chloride which is then condensed with ethylamino-4- nitrobenzene and reducing the condensation product; 1-cyclohexylpropionylamino-4-aminobenzene is obtained from cyclohexylpropionic acid chloride similarly. 1-(N - #-chloropropionyl isopropylamino-4-aminobenzene is prepared by reducing the condensation product from 1- isopropylamino-4-nitrobenzene and #-chloropropionic acid chloride. Specification 348,902 is referred to.