Patent GB-760155-A (GB)
Title: Improvements in and relating to substituted mercaptophenyl aldehydes or ketones
Inventor: GREGORY WALTER ADELMAN
Filed: 1954-05-05
Abstract: Compounds of general formula <FORM:0760155/IV(b)/1> wherein R is a hydrogen atom or a lower alkyl or acylaminomethyl radical, R1 is a hydrogen or halogen atom or a lower alkyl or lower alkoxy radical ("lower" signifies containing not more than five carbon atoms) and R2 is an alkyl, hydroxy- or carboxy-alkyl, or aryl radical, are prepared by reacting a compound of formula <FORM:0760155/IV(b)/2> wherein X is a chloro, bromo, or iodo radical with a compound R2-S-M, wherein M is sodium or potassium, in a liquid medium.  Specified liquid media are ethanol, n-butanol, glycols, dioxane, acetone, methyl ethyl ketone and methyl isobutyl or isopropyl ketone.  The reaction mixture is preferably refluxed or boiled.  Specified halogenated ketones are p-chloro- or -bromo- or -iodo-phenyl methyl, p-chlorophenyl ethyl or n-propyl, 2 - ethyl - 4 - chlorophenyl methyl, 2 - propyl - 4 - iodophenyl methyl, 3-methyl-4-bromophenyl ethyl, 3-chloro-4-iodophenyl methyl, 3-methyl- or -methoxy-4-chlorophenyl methyl, 3-butoxy-4-bromophenyl n-propyl, acetamidomethyl p-chlorophenyl, benzamidomethyl p-bromophenyl, o-carboxybenzamidomethyl p-chlorophenyl, p-chlorophenyl succinimidomethyl, and p-chlorophenyl propionamidomethyl ketone. Specified halogenated aldehydes are p-bromo- or -chloro- or -iodobenzaldehyde, 4-chloro-2-fluoro- or -methyl-or -methoxy-benzaldehyde, and 3 : 4-dichloroor -dibromo-benzaldehyde. Specified mercaptides are potassium methyl- or hydroxyethyl- or butyl- or phenyl- or p-chlorophenyl- or tolylmercaptide and sodium p-nitrophenyl-mercaptide.  The following compounds of the invention are specified in addition to those prepared in the examples: p-methylmercaptophenyl acetamidomethyl or succinimidomethyl ketone, p - ethylmercaptophenyl benzamidomethyl or n-propyl ketone, p-phenylmercaptophenyl propionamidomethyl ketone, methyl p-(p1-nitrophenylmercapto)- or-(p-tolylmercapto)-phenyl ketone, 2 - (p - acetylphenylmercapto) benzoic acid, 3 - methyl - 4 - methylmercaptophenyl methyl ketone, 3-bromo-4-ethylmercaptophenyl methyl ketone, (p - carboxymethylmercapto) acetophenone, 3 - methoxy - 4 - ethylmercaptophenyl methyl ketone, p-methylmercapto-2-fluoro- or -3-chloro-benzaldehyde, p-n-butylmercapto - 2 - methylbenzaldehyde, p - phenylmercaptobenzaldehyde, p-nitrophenylmercaptobenzaldehyde, p-methylmercapto-3-chlorobenzaldehyde, p - (2 - hydroxyethylmercapto) - benzsldehyde, p - ethylmercaptobenzaldehyde, p - carboxymethylmercaptobenzaldehyde.  In examples: (1) methylmercaptan is passed into a solution of potassium hydroxide in ethanol to give a solution of potassium methylmercaptide to which p-bromoacetophenone is added and the solution refluxed in an oxygen-free atmosphere and then poured into ice and water when the methyl p-mercaptophenyl ketone crystallizes; ethyl p - methylmercaptophenyl ketone, p - (2 - hydroxyethylmercapto) phenyl methyl ketone, o - carboxybenzamidomethyl p - methylmercaptophenyl ketone, methyl p-phenylmercaptophenyl ketone and p-methyl mercaptobenzaldehyde are similarly prepared.