Patent GB-494423-A (GB)
Title: The manufacture of new coupling components and azo-dyestuffs therefrom
IPC: C09B29/18
Filed: 1937-04-28
Abstract: Amides of 3-hydroxyfluorene-2-carboxylic acids, which have a free 4-position, but which may contain substituents, e.g. alkyl, alkoxy, nitro, halogen, trifluoromethyl, phenylamino, alkyl-, aralkyl- or arylsulphone, alkyl-CO- or aryl-CO-, in that benzene nucleus of the fluorene which does not contain the hydroxy and carboxylic groups, or which may have condensed thereto a further non-hydrogenated or hydrogenated nucleus, are manufactured by reacting the halides or esters of the said acids with aromatic or heterocyclic mono- or diamines or by reacting the free acids with aromatic or heterocyclic isocyanic acid esters.  In an example, 3-hydroxyfluorene-2-carboxylic acid is heated with o-anisidine in toluene with the addition of phosphorus trichloride.  Arylamides may be similarly obtained from 1-amino-2 : 5-dimethoxybenzene, aniline, o-, m- and p-toluidine, 2-amino-1-ethylbenzene, m- and p-anisidine, o-phenetidine, m- and p-chloraniline, m-fluoroaniline, m-nitraniline, m-aminobenzotrifluoride, 1-amino-2 : 3-, 2 : 4-, 2 : 5-, 3 : 4- and 3 : 5-dimethylbenzene, 1-amino-2-methyl-4- and 5-methoxybenzene, 1-amino-3-methyl-4- and 6-methoxybenzene, 1-amino-4-methyl-3-methoxybenzene, 1-amino-2-methyl-4- and 5-chlorobenzene, 1-amino-2 : 4-dimethoxybenzene, 1-amino-2-methoxy-4- and 5-chlorobenzene, 1 - amino - 4 - methoxy - 3-chlorobenzene, 1 - amino - 2 : 4 - dimethoxy-5 - chlorobenzene, 1 - amino - 2 : 5 - dimethoxy-4 - chlorobenzene, 1 - amino - 2 - methoxy - 5 methyl - 4 - chlorobenzene, b  - naphthylamine, 2 - amino - 5 : 6 : 7 : 8 - tetrahydronaphthalene, and dianisidine (with two molecular proportions of acid).  Amides are also obtainable in the same way from substituted 3-hydroxyfluorene-2-carboxylic acids, e.g. from 6-methyl-3-hydroxyfluorene - 2 - carboxylic acid with o-anisidine, o-toluidine, 1-amino-2 : 5-dimethoxybenzene and 1 - amino - 2 : 5 - dimethoxy - 4-chlorobenzene, and from 6 : 7-benzo-3-hydroxyfluorene-2-carboxylic acid with o-anisidine and 1-amino-2 : 5-dimethoxybenzene.  A sample (15) has been furnished under Sect. 2 (5) of the amide prepared from 3-hydroxyfluorene - 2 - carboxylic acid and 2-amino-3-methoxydiphenylene oxide.  3 - Hydroxyfluorene - 2 - carboxylic acids are obtainable by causing carbon dioxide to react at an elevated temperature on 3-hydroxyfluorenes having a free 2- and 4-position, in the presence of alkali metal hydroxides or carbonates, or on the alkali metal salts of the 3-hydroxyfluorenes, e.g. on an alkaline solution of 3-hydroxyfluorene (obtainable by the action of caustic soda on 3-bromofluorene).  Specification 330,305, [Class 2 (iii)], is referred to.  Azo dyes; azo dyes forming upon the material.-Water-insoluble azo dyestuffs are manufactured by coupling the amides described above in substance or on the fibre with diazotized primary aromatic or heterocyclic amines, the components being free from groups inducing solubility in water.  In an example, cotton yarn is impregnated with 1 1-(3-hydroxyfluorene - 2 - carboylamino) p  - 21 - methoxybenzene, and a greenish khaki shade is developed by means of diazotized 1-amino-2-methoxybenzene-5-sulphodiethylamide.  A table gives the shades of further dyestuffs obtained from the amides specifically described above, with the addition of 11 - (3 - hydroxyfluorene - 2-carboylamino) - 51 : 61 : 71 : 81 - tetrahydronaphthalene but with the omission of the arylamides from 3-hydroxyfluorene-2-carboxylic acid with b -naphthylamine and 2-amino-5 : 6 : 7 : 8 - tetrahydronaphthalene, and from 6 : 7 - benzo - 3 - hydroxyfluorene - 2 - carboxylic acid with 1-amino-2 : 5-dimethoxybenzene, the list including primary disazo dyestuffs from 41 : 411-di-(3-hydroxyfluorene-2 - carboylamino) - 31 : 311 - dimethoxydiphenyl.  The following additional diazo components are specified: 1-amino-2-methyl-3-, 4- and 5-chlorobenzene, 2-amino-4-chlorodiphenyl ether, 1 - amino - 4 - benzoylamino-2 - chloro - 5 - methoxybenzene, 1 - amino-2 - chloro - 5 - trifluoromethylbenzene, 1-amino - 2 : 5 - dichlorobenzene, 1 - amino-2 - methoxybenzene - 5 - benzylsulphone, 1 - amino - 2 - methoxy - 5 - chlorobenzene, 4 - amino - 21 : 3 - dimethyl - 1 : 11 - azobenzene, 2- and 3-chloraniline, 1-amino-2-methyl-4- and 5-nitrobenzene, 2-amino-4 : 41-dichlorodiphenyl ether, 4 - amino - 21 : 41 - dimethyl-2 - nitro - 5 - methoxy - 1 : 11 - azobenzene, 1 - amino - 2 - methoxy - 4- and 5 - nitrobenzene, 1 - amino - 2 - trifluoromethyl - 4-chlorobenzene, 1 - amino - 3 : 5 - di - (trifluoromethyl) - benzene, 2 : 5 - dichloraniline, o-and m-aminoazotoluene, 1-amino-2-nitro-4-methoxybenzene, 1 - amino - 2 - nitro - 3- and 5 - chlorobenzene, 1 - amino - 2 - methoxybenzene - 5 - ethylsulphone, 2 - aminodiphenyl-sulphone, 2-, 3- and 4-nitroaniline and 1-aminoanthraquinone.  Samples have been furnished under Sect. 2 (5) of cotton yarn dyed by the formation thereon of the following dyestuffs: (1) 3-aminodiphenylene oxide --> 11-(3-hydroxyfluorene - 2 - carboylamino) - 21 - ethoxybenzene (yellow-brown); (2) 3 - aminodiphenylene oxide --> 11 - (3 - hydroxyfluorene - 2 - carboylamino) - 31 : 51 - dimethylbenzene (yellow brown); (3) 2 - aminocarbazole --> 11-(3-hydroxyfluorene - 2 - carboylamino) - 31 : 51-dimethylbenzene (yellowish brown); (4) 2-aminocarbazole --> 11-(3-hydroxyfluorene-2-carboylamino) - 31 - methylbenzene (yellow brown); (5) 3 - amino - 9 - ethylcarbazole --> 11 - (3 - hydroxyfluorene - 2 - carboylamino) - 31 - methylbenzene (reddish brown); (6) 3 - amino - 9 - ethylcarbazole --> 11-(3 - hydroxyfluorene - 2 - carboylamino) - 31-chloro - 41 - methoxybenzene (reddish brown); (7) 2 : 7 - diaminodiphenylenesulphone \sQ 11 - (3 - hydroxyfluorene - 2 - carboylamino)-31 - nitrobenzene (reddish brown); (8) 2 : 7-diaminodiphenylenesulphone \sQ 11 - (3-hydroxyfluorene - 2 - carboylamino) - 31 - fluorobenzene (reddish brown); (9) 3 : 6-diaminodiphenylene oxide \sQ 11 - (3 - hydroxyfluorene-2 - carboylamino) - 31 - methylbenzene (yellow-brown); (10) 3 : 6 - diaminodiphenylene oxide \sQ 11 - (3 - hydroxyfluorene - 2 - carboylamino) - 31 - chloro - 41 - methoxybenzene (yellow-brown); (11) 1 - aminocarbazole --> 11 - (3 - hydroxyfluorene - 2 - carboylamino) - 31 : 51 - dimethylbenzene (reddish brown); (12) 3 - aminodiphenylene sulphide --> 11 - (3 - hydroxyfluorene - 2 - carboylamino) -31 : 51 - dimethylbenzene (yellow-brown); (13) 2 - amino - 3 - methoxydiphenylene oxide --> 11 - (3 - hydroxyfluorene - 2 - carboylamino) -31 : 51 - dimethylbenzene (yellowish dark brown); (14) 4-chloro-2-aminodiphenyl ether --> 21 - (3 - hydroxyfluorene - 21 - carboylamino) - 31 - methoxydiphenylene oxide (yellow-brown); (16) 2 : 5 - dichloraniline --> 11 - (3 - hydroxyfluorene - 2 - carboylamino)-31 : 51 - di - (trifluoromethyl) - benzene (olive green); (17) 1 - amino - 2 - methyl - 5 - nitrobenzene --> the same coupling component (olive green); (18) m-nitraniline --> the same coupling component (greenish yellow olive); (19) 1 - amino - 2 - trifluoromethyl - 4 - chlorobenzene --> the same coupling component (yellow olive); (20) 1-amino-2-chloro-5-trifluoromethylbenzene --> the same coupling component (greenish khaki); (21) 1-amino-3 : 5 - di - (trifluoromethyl) - benzene --> the same coupling component (yellow olive); (22) 1 - amino - 2 - methoxy - 5 - nitrobenzene --> the same coupling component (olive).