Patent GB-401643-A (GB)
Title: Manufacture of organic acid halides and of derivatives therefrom
IPC: C07D213/78
Filed: 1932-02-11
Abstract: Organic acid halides are prepared by treating the acid with a carbon oxyhalide in the presence of a quantity of a nitrogen base amounting at most to one equivalent proportion for each acid group.  The carbon oxyhalide may be replaced by such equivalent compounds as perchloroformic acid methyl ester and hexachlorocarbonic acid dimethyl ester.  The nitrogen base not only fixes the hydrogen halide produced, but is stated to act catalytically.  Bases mentioned are ammonia, trimethylamine, diethylamine, tetramethylethylenediamine, piperazine, methylaniline, diethylaniline, benzylaniline, diphenylamine, cyclohexylamine, pyridines, quinolines, piperidine, pyrazolones, quaternary ammonium compounds and guanidines.  Acids which may be treated comprise aliphatic acids, e.g. acetic, valeric, palmitic, stearic, acrylic, crotonic, oleic, brassidic, propiolic and p  tetrolic acids, halogenated fatty acids, aminoacetic and aminopropionic acids, nitro-fatty acids, diazo-fatty acids, glycollic and lactic acids, alkoxy-fatty acids, oxalic and malonic acids, alkylmalonic acids, succinic, adipic and tartaric acids, methane mono- and poly-sulphonic acids, ethylene disulphonic and oxyethyl sulphonic acids; cyanic and cyanuric acids; fatty-aromatic acids, such as arylacetic and aryloxyacetic acids, mandelic, tropic, cinnamic, nitro-and amino-cinnamic acids, glycine, hippuric and arylthioglycol-carboxylic acids; aromatic acids, e.g. benzoic, oxy- and polyoxy-benzoic, anisic, aminobenzoic, nitrobenzoic and halogenated benzoic acids, picric acid, phthalic, chlorophthalic, aminophthalic, nitrophthalic and sulphophthalic acids and their terephthalic and isoterephthalic isomers, carboxylic acids of naphthalene, anthracene, phenanthrene, anthraquinone, benzanthrone, oxynaphthalene, oxyaminonaphthalene and aminoanthraquinone, dinaphthyl carboxylic acids, sulphonic acids of toluene, naphthalene, oxynaphthalene, aminonaphthalene, oxyaminonaphthalene, oxydiazonaphthalene and anthraquinone, also benzene sulpho-carboxylic acids; sulphinic acids; hydroaromatic carboxylic acids such as hexahydrobenzoic and camphoric acids; heterocylic carboxylic acids, e.g. of thiophene, pyrrole, indole, pyrazole, pyrazolone, pyridine, quinoline and acridine, including picolinic, nicotinic and oxynicotinic acids, oxyquinoline and phenylquinoline carboxylic acids.  An organic solvent is advantageously present.  Examples are given of the preparation of the acid chlorides of benzoic, cinnamic, salicylic, m-nitrobenzoic, mandelic, anthranilic, p-aminobenzoic, picric, gallic, 2 : 3-oxynaphthoic, glycollic, aminoacetic, hippuric, formic, oxalic, nicotinic, 2-oxypyridine-3-carboxylic, 2-chloropyridine-5-carboxylic, carbostyril-4-carboxylic, 8-oxy-quinoline-7-carboxylic, 1-diazo-2-naphthol-4-sulphonic and 1-amino-2-naphthol-4-sulphonic acids using phosgene in the presence of triethylamine, pyridine, piperidine, quinoline, ammonia and dimethyl- or diethyl-aniline, and of benzoyl bromide using bromophosgene in the presence of pyridine.  When a hydroxyl group is present, it may become replaced by halogen; e.g. salicylic acid gives chlorobenzoyl chloride, oxynaphthalene carboxylic acids give chloronaphthalene carboxylic acid chlorides, mandelic acid yields a -chloro-b -phenylpropionic acid chloride, lactic acid forms a -chlorpropionyl chloride, oxynicotinic acids give chloronicotinic acid chlorides and oxyquinoline carboxylic acids form chloroquinoline carboxylic acids.