Patent GB-915457-A (GB)
Title: Process for the production of n-substituted ª--hydroxypropionyl amides and their esters with strong oxygencontaining acids
Inventor: ROHLAND WERNER
IPC: C07F9/09
Filed: 1960-08-08
Abstract: N-substituted b -hydroxy-propionamides and esters thereof of formula R1-O-CH2-CH2-CO-NH-Y (I) wherein R1 is hydrogen or the radical of sulphuric, phosphoric or an arylsulphonic acid and Y is a substituted aromatic radical are prepared by (a) partially saponifying an esterified b -hydroxypropionylamide of formula R11-CO-O-CH2-CH2-CO-NH-Y (II wherein R11 is a C1-C4 aliphatic radical with ammonia, an amine, a hydrazine, hydroxylamine or mixtures thereof preferably in the presence of a solvent and, if desired, esterifying the resultant b -hydroxypropionamide with an appropriate acid; (b) heating a compound of formula II wherein R11 is hydrogen with a C1-C5 aliphatic alcohol and if desired esterifying the resultant b -hydroxypropionamide with an appropriate acid or (c) reacting a compound of formula II with 90 to 100% sulphuric acid at 0 DEG -100 DEG C. to give the esters of formula  HO3S-O-CH2-CH2-CO-NH-Y The compounds may be used in the preparation of azo dyes (see Group IV(c)).  In examples: (1) m- or p-nitroaniline is condensed with diacrylic acid chloride to give diacrylic acid m- or p-nitroanilide which is treated with ammonia in methanol to give b -hydroxypropionyl-m-or-p-nitroanilide which is reduced to b -hydroxypropionyl-m-or-p-aminoanilide and esterified with chlorosulphonic acid to give the sulphuric acid ester of b -hydroxypropionyl - m-or-p - aminoanilide (b -hydroxypropionyl-p-nitroanilide is also converted into its p-toluene-sulphonic acid ester); (2) as in (1) p-chloroaniline is converted successively into diacrylic acid p-chloroanilide and b -hydroxypropionyl-p-chloroanilide; (3) 2-methoxy-4-nitroaniline or 2-amino-5-naphthol-7-sulphonic acid is acylated with b -acetoxypropionylchloride to give the corresponding amide which is treated as in (1) to give b -hydroxypropionyl-(4-nitro-2-methoxyphenyl)amide, which is reduced to b -hydroxypropionyl - (4 - amino - 2 methoxyphenyl)-amide, and 2 - b hydroxypropionylamino-5 - naphthol - 7 - sulphonic acid; (4) m- or p-nitroaniline are acylated with b -formyloxypropionyl chloride to give b -formyl oxypropionyl-m- or p-nitroanilide which is treated as in (1) to yield b -hydroxypropionylm- or p-nitroanilide; (5) b -formyloxypropionylp-nitroanilide or -2-methoxy-4-nitroanilide is refluxed in methanol to give b -hydroxypropionyl-(4-nitro- or 4-nitro-2-methoxy-phenyl) amide; (6) hydrogenation of b -formyloxypropionyl-p-nitroanilide with Raney nickel and hydrogen in methanol solution under pressure gives b -hydroxypropionyl-p-aminoanilide; (7) b -formyloxy- or -acetoxy-propionyl-p-nitroanilide is reduced to b -formyloxy- or -acetoxypropionyl-p-aminoanilide which is reacted with sulphuric acid to give the sulphuric acid ester of b -hydroxypropionyl-p-aminoanilide; (8) as in (7) the b -acetoxypropionyl derivative of 2-amino-5-naphthol-7-sulphonic acid is converted into the sulphuric ester of 2-b -hydroxypropionylamino-5-naphthol-7-sulphonic acid.ALSO:Monoazo dyes containing b -hydroxypropionamide groups and ester derivatives thereof of formula R1-O-CH2-CH2-CO-NH-Y wherein R1 is hydrogen or the radical of phosphoric, an arylsulphonic or, preferably, sulphuric acid and Y is a monoazo dye residue are prepared by (a) partially saponifying an esterified b -hydroxypropionamide of formula R11-CO-O-CH2-CH2-CO-NH-Y (II) wherein R11 is a C1-C4 aliphatic radical with ammonia, an amine, a hydrazine, hydroxylamine or mixtures thereof, preferably in the presence of a solvent and, if desired, esterifying the resultant b -hydroxypropionamide; (b) heating a compound of formula II wherein R11 is hydrogen with a C1-C5 aliphatic alcohol and if desired esterifying the resultant b -hydroxypropionamide or (c) reacting a compound of formula II with 90 to 100% sulphuric acid at 0 DEG -100 DEG C. to give the esters of formula HO3S-O-CH2-CH2-CO-NH-Y. The dyes may also be prepared in the usual way from diazo and/or coupling components containing the groups, prepared by the above methods (see Group IV(b)).  The invention also comprises the dyes of formulae:- <FORM:0915457/IV (b)/1> <FORM:0915457/IV (b)/2> <FORM:0915457/IV (b)/3> <FORM:0915457/IV (b)/4> <FORM:0915457/IV (b)/5> <FORM:0915457/IV (b)/6> <FORM:0915457/IV (b)/7> <FORM:0915457/IV (b)/8> <FORM:0915 dyes are used in the dyeing of nitrogenous materials and particularly polyhydroxylated materials, e.g. cellulose fibres, in the presence of an acid-binding agent.  In examples: (1) the sulphuric acid ester of b -hydroxypropionyl-p-amino-anilide --> 1-phenyl-3-methyl-5-pyrazolone; (2) the aminoazo dye obtained by saponification of the dye 1-amino-4-acetylaminobenzene --> 1-naphthol-4-sulphonic acid is acylated with diacrylic acid chloride, the acyl derivative treated with ammonia to give the b -hydroxypropionylamino-derivative which is esterified with chlorosulphonic or sulphuric acid; (3) the aminoazo dye used in (2) is reacted with b -formyloxypropionyl chloride and the acyl derivative is refluxed with methanol to give the b -hydroxypropionylamino-azo dye which may be esterified with sulphuric acid or heated with sulphuric acid to give the sulphuric acid ester. Further examples are given.