Patent GB-822237-A (GB)
Title: Trichloromethylthio-derivatives of aromatic amines
Filed: 1956-06-15
Abstract: The invention comprises compounds of the general formula X-R-NH-Acyl wherein "Acyl" denotes a carboxylic acid radical such as a saturated or unsaturated, aliphatic carboxylic, mixed aliphatic aromatic carboxylic, or aromatic carboxylic acid radical derived for example from formic, acetic, propionic, butyric, valeric, stearic, palmitic, crotonic, acrylic, oleic, phenylacetic, phenylpropionic, phenylbutyric, benzoic or a - or b -naphthoic acids, X is one of the groups -SO2.S.CCl3, -COO.S.CCl3 and -S.S.CCl3 and R is a phenyl or naphthyl nucleus or in the case where X is the group -SO2.S.CCl3, may also be an alkoxy or alkyl substituted phenyl nucleus.  The compounds are made by reacting perchloromethyl-mercaptan, Cl3.C.S.Cl, with a compound of the formula Y-R-NH-Acyl, wherein Y is one of the groups -SO2Me, COOMe and -SH, Me being a metal, preferably an alkali metal, atom.  Preferred procedures comprise (1) reacting metal salts of acylaminobenzene (or naphthalene)-sulphinic acids of the formula Acyl.NH.C6H4.SO2Me, Acyl.NH. C10H6.SO2Me or Acyl.NH.C6H3.(O.Alkyl).SO2Me with Cl3C.S.Cl in an aqueous medium at a temperature of 0-30 DEG  C. to give products in which X is the group SO2.S.CCl3; (2) reacting a metal salt of an acylamino-benzoic acid of the formula Acyl.NH.C6H4.COOMe with Cl3C.S.Cl in a nonpolar solvent such as benzene or petroleum ether at 60 DEG  to 100 DEG  C., to give products in which X is COO.S.CCl3, these conditions are also suitable for the reaction between Cl3C.S.Cl and Acyl.NH.C6H4SO2Me; and (3) reacting an acylamino - benzene - thiol Acyl.NH.C6H4.SH with CCl3.C.S.Cl in a non-polar solvent such as benzene or petroleum ether at 50 DEG  to 100 DEG  C.  The products are used as fungicides and bactericides especially for the treatment of plants.  Examples describe the preparation of the trichloromethyl esters of p-acetylamino-, p-formylamino-, p-crotonylamino-, p-isobutyroylamino-, p-propionylamino-, p-caprylylamino-, p-valeroylamino-, m-acetylamino- and o-acetylamino-, benzene-thiolsulphonic acid; the trichloromethyl esters of m-acetylamino-p-methoxy-, o - methyl - m - acetylamino -, and o - ethoxy - m - acetylamino -, benzene - thiolsulphonic acid and 4 - acetylamino - naphthalene - 1 - thiolsulphonic acid; S-(p-acetylaminobenzoyloxy)-trichloromethyl-thiol and trichloromethyl p-acetylaminophenyl disulphide.  Comparative examples describe the preparation of trichloromethyl - benzene - thiolsulphonate, trichloromethyl - a  - naphthalene - thiolsulphonate, trichloromethyl - p - methoxybenzene - thiolsulphonate, trichloromethyl-mercapto-benzoate and trichloromethyl-phenyldisulphide.  Acylaminoaryl sulphinic acids used as starting materials such as p-acetamino-, p-formamino-, p - crotonylamino -, p - isobutyroylamino -, p - butyroylamino -, p - propionylamino -, p - caprylylamino -, p - valeroylamino -, m - acetamino - and o-acetamino-, benzene sulphinic acids, 4-acetylamino - naphthalene - 1 - sulphinic acid, 3 - acetamino - 4 - methoxybenzene sulphinic acid and 2 - methyl - 5 - acetylaminobenzene sulphinic acid are made by treating the appropriate acylamino-aryl compound with chlorosulphonic acid to give the corresponding sulphonyl chloride; which is reduced with sodium bisulphite to the sulphinic acid.ALSO:Fungicidal and/or bactericidal preparations comprise compounds of the formula X-R-NH-Acyl wherein "Acyl" denotes a carboxylic acid radical derived for example from formic, acetic, propionic, butyric, valeric, stearic, palmitic, crotonic, acrylic, oleic, phenylacetic, phenylpropionic, phenylbutyric, benzoic or a - or b -naphthoic acids, X is one of the groups -SO2.S.CCl3, -COO.S.CCl3 and S.S.CCl3 and R is a phenyl or naphthyl nucleus or in the case where X is -SO2.S.CCl3 may also be an alkoxy or alkyl substituted phenyl nucleus (see Group IV (b)), mixed with a solid pulverulent inert carrier or dissolved or dispersed in a liquid inert carrier, if desired together with surface-active and/or dispersing agents.  The compounds are suitably formulated as miscible oils containing 15 to 20% of the active compound, 15% of non-ionogeneous emulsifier and a solvent, e.g. cyclohexanone; aerosols containing a solvent such as acetone, methyl ethyl ketone or cyclohexanone and a propellant such as methyl chloride; sprayable powders containing 50 to 80% of active substance, wetting-agents such as fatty alcohol sulphonates, dispersing agents and/or carriers, e.g. kaolin, chalk, clay and additives to prevent lumping, e.g. colloidal silicic acid; sprayable powders containing 5% of active substance in a mixture of infusorial silica and magnesium marlstone; seed-protecting preparations of 50% of the active substance mixed with kaolin and an adhesive such as watchmaker's oil and coated dusts wherein the active substance is applied to an adsorbing carrier such as infusorial silica. Many suitable active compounds are specified including the trichloromethyl esters of ortho-, meta- and para-acylamino-benzene thiolsulphonic acids, 4 - acetylamino - naphthalene - 1 - thiolsulphonic acid and alkyl and alkoxy substituted acylamino-benzene thiolsulphonic acids; S-(p-acetylaminobenzoyloxy) - trichloromethylthiol and trichloromethyl p-acetylaminophenyl disulphide.