GB700710A - Process for the production of nitro phenyl amino diol derivatives - Google Patents

Abstract

The invention comprises: (i) the production of compounds of the general formula <FORM:0700710/IV(b)/1> (wherein R represents hydrogen or a carboxylic acid acyl radical, and R1 represents hydrogen, halogen or an alkyl or alkoxy group of 1-4 carbon atoms) by the following steps: (a) reacting a 1-phenyl-2-acylamidopropane-1 : 3-diol of the general formula <FORM:0700710/IV(b)/2> with a thionyl halide (preferably at 20-35 DEG C.) or a carbonyl chloride (preferably below 20 DEG C.) to form the cyclic sulphite or carbonate thereof, (b) nitrating the phenyl ring and any phenyl ring present in the acyl radical, thus producing a compound of the general formula <FORM:0700710/IV(b)/3> (wherein -Y- represents -SO- or -CO-), and (c) hydrolyzing the product of (b); (ii) step (b) as an independent process, advantageously effected below about -10 DEG C. with fuming or 100 per cent. nitric acid or a mixture of concentrated nitric and sulphuric acids; (iii) step (c) as an independent process when effected under mild conditions in a solvent composed of water and a water-miscible organic solvent with an acidic or alkaline hydrolytic agent so as to produce the compound in which R is an acyl radical in preponderant proportions; (iv) the compounds of the third general formula above; (v) the compounds of the first general formula above when prepared according to (i) or (iii). To obtain these last compounds in which R represents hydrogen, the hydrolysis step (c) is carried to completion using a dilute mineral acid, or the compounds in which R represents an acyl radical may be further hydrolyzed. The various products are antibiotics or intermediates therefor. Examples describe the preparation of: (1) to (4) dl- and lq -1-p-nitrophenyl - 2 - dichloracetamido - and - 2 - amino - propane - 1 : 3 - diol from dl - or l - q - 1 - phenyl - 2 - dichloracetamidopropane - 1 : 3 - diol via the cyclic sulphites and via the cyclic carbonates; (5) dlq -1-p-nitrophenyl - 2 - m1 - nitrobenzamidopropane - 1 : 3 - diol from dlq -1-phenyl-2-benzamidopropane-1 : 3-diol via the cyclic sulphites; (6) and (7) dl - q - 1 - p - nitrophenyl - 2 - acetamido - and -2-amino-propane-1 : 3-diol from dl - q 1-phenyl-2-acetamidopropane-1 : 3-diol via the cyclic carbonates and via the cyclic sulphites; (8) dl - q - 1 - (31 - methoxy - 41 - nitrophenyl) - 2-aminopropane-1 : 3-diol from dl - q - 1 - (31 - methoxyphenyl) - 2 - phenylacetamidopropane - 1 : 3-diol via the cyclic sulphites; (9) dlq - 1-(21 - methyl - 41 - nitrophenyl) - 2 - methoxyacetamidopropane-1 : 3-diol from dlq -1-(21-methylphenyl) - 2 - methoxyacetamidopropane-1 : 3-diol via the cyclic sulphites; (10) l-q -1-p-nitrophenyl-2-aminopropane-1 : 3-diol from l-q - 1-phenyl-2-benzamidopropane - 1 : 3-diol via the cyclic carbonates; (11) dl-q -1-(21-chloro-51 - nitrophenyl) - 2 - (a - bromopropionamido) - propane - 1 : 3 - diol from dl - q - 1 - (21 - chlorophenyl) - 2 - (a - bromopropionamido) - propane-1 : 3-diol via the cyclic sulphites.