Patent GB-815203-A (GB)
Title: Substituted-4-metathiazanones
IPC: C07D417/04
Filed: 1957-07-03
Abstract: The invention comprises compounds of the general formula <FORM:0815203/IV (b)/1> wherein Z is S or SO2; Ar is an aromatic radical, including substituted or unsubstituted phenyl, naphthyl, biphenylyl, furyl, pyridyl and thienyl radicals; R is H or a lower hydrocarbyl radical having an aliphatic carbon atom linked to the ring-nitrogen atom (containing 1-8 carbon atoms); R1, R2 and R3 are each H or a lower alkyl radical (containing 1-3 carbon atoms) and the manufacture thereof by heating an aldehyde of the formula Ar-CAO, a betamercapto propionic acid of the general formula HS.CH(R1)C(R2)(R3)COOH and an aminating agent, i.e. a compound having a high ammonia partial pressure which usually loses ammonia on standing and which readily decomposes when heated to lose ammonia, or a hydrocarbylamine of the general formula R-NH2 and, if desired, oxidizing (for example, by potassium permanganate, hydrogen peroxide or chromium trioxide) the resulting compound where Z is S to the analogue where Z is SO2.  Examples are given of the preparation of 2-(3,4-dichlorophenyl) - 3 - methyl - 4 - metathiazanone by reacting 3,4-dichlorobenzaldehyde, beta-mercaptopropionic acid and methylamine; of 2-(2,4-dichlorophenyl) -, 2 - (4 - isopropylphenyl) -, 2-(4 - chlorophenyl) -, 2 - (4 - methoxyphenyl)-, 2 - phenyl -, 2 - (2 - chlorophenyl) -, 2 - (3-chlorophenyl) -, 2 - (2 - thienyl) -, and 2 - (3-pyridyl) - 3 - methyl - 4 - metathiazanones, 4-(4 - chloro phenyl) - 3 - ethyl -, 2 - (4 - chlorophenyl) - 3 - n - propyl and 2 - phenyl - 3-benzyl - 4 - metathiazanones by a similar method using the appropriately substituted benzaldehyde and amine; of 2-phenyl-, 2-(4-methoxyphenyl) -, 2 - (4 - bromophenyl) -, 2-(3,4 - dichlorophenyl) -, 2 - (2,4 - dichlorophenyl)-, and 2-(4-chlorophenyl)-4-metathiazanones by reacting the corresponding aldehyde with ammonium carbonate, or carbamate, and betamercaptopropionic acid or its ammonium salt alone, whilst similarly may be prepared 2 - (3 - chlorophenyl) - 5 - methyl -, 2-(3,4 - dibromophenyl) - 6 - methyl -, 2 - (3,4 - dichlorophenyl) - 5 - ethyl - 6 - n - propyl -, 2 - (4-iodophenyl) -, 2 - (4 - fluorophenyl) -, 2 - (2,4,6-trichlorophenyl) - 5,6 - dimethyl -, 2 - (4 - isobutoxyphenyl) - 5,5,6 - trimethyl -, 2 - (3,4,5-trimethylphenyl) - 5,5,6 - trimethyl -, 2 - (4-ethylphenyl) - 5,5 - diethyl -, 2 - (3 - ethyl - 4-isopropoxyphenyl) - 5 - isopropoxy -, 2 - (3-ethoxy - 4 - chlorophenyl) -, 2 - (3 - n - hexylphenyl) - 5 - methyl - 2 - (1 - naphthyl) -, and 2 - (2 - biphenylyl) - 4 - metathiazanones.  Further examples are also given of the preparation of 2 - (4 - chlorophenyl) - and 2 - (3,4 - dichlorophenyl) - 3 - methyl - 4 - metathiazanone-1-dioxides by oxidizing the corresponding 4-metathiazanones with potassium permanganate in aqueous acetic acid and, using a similar process and the corresponding 4 - metathiazanones, of 2-(2,4-dichlorophenyl)-, 2-phenyl-, 2 - (4 - methoxyphenyl) -, 2 - (4 - isopropylphenyl) -, 2 - (2 - chlorophenyl) -, 2 - (3 - chlorophenyl) -, 2 - (2 - thienyl) -, and 2 - (3 - pyridyl)-3 - methyl - 4 - metathiazanone - 1 - dioxides, 2-(4 - chlorophenyl) - 3 - n - propyl -, 2 - (4 - chlorophenyl) - 3 - ethyl -, 2 - phenyl - 3 - benzyl -, 2-(3,4 - dichlorophenyl) -, 2 - (4 - chlorophenyl)-, 2 - (4 - bromophenyl) -, and 2 - phenyl - 4-metathiazanone-1-dioxides.ALSO:Tablets, capsules, solutions and suspensions for oral or injectable administration may contain <FORM:0815203/VI/1> wherein Z is S or SO2; Ar is an aromatic radical, including substituted or unsubstituted phenyl, naphthyl, biphenylyl, furyl, pyridyl, and thienyl radicals; R is H, or a lower hydrocarbyl radical having an aliphatic carbon atom linked to a ring-nitrogen atom and containing 1-8 carbon atoms; R1-3 are each H, or a lower alkyl radical containing 1-3 carbon atoms, either alone or in combination with one or other medicinals such as asprin, phenacetin, salicylamide, para-acetylaminophenol, caffeine, and meperidine.  Tablets may contain as adjuvants, calcium carbonate, starch, gelatin talc, magnesium stearate or acacia, and solutions and suspension may be made in water, alcohol/water oil or oil/water emulsions.