Patent GB-987253-A (GB)
Title: Thiobenzamides and derivatives thereof
Inventor: YATES JOHN
IPC: A01N37/18
Filed: 1961-01-05
Abstract: The invention relates to compounds of the general formula <FORM:0987253/C2/1> and salts thereof, wherein X represents a halogen atom; Z represents a halogen atom, or a nitro, hydrocarbyl or hydrocarbylthio group; x=1, 2, 3 or 4; m=0 or 1, n=1 or 2 and n+m=2, the sulphur atom being linked by a double bond to the carbon atom when m=0, and the nitrogen atom being linked by a double bond to the carbon atom when n=1; R represents a hydrogen atom, a hydrocarbyl group or a halogen-substituted hydrocarbyl group or an aliphatic acyl group, or when n=2, R may represent a group completing with the nitrogen atom a saturated or unsaturated heterocyclic ring; and R1 represents a hydrogen atom, a hydrocarbyl group or a substituted hydrocarbyl group.  Compounds claimed per se are 2,6-di-chlorothiobenzamide and its pyridine, triethylamine salts, 2-chloro-6-fluorothiobenzamide, 2-chloro - 6 - iodothiobenzamide, 2,4 - dichlorothiobenzamide, 2 - chloro - 6 - nitrothiobenzamide, S - ethyl - 2,6 - dichlorothiobenzimidate and its hydrochloride and hydrobromide, S-2-bromoethyl - 2,6 - dichlorothiobenzimidate, N -acetyl 2,6-dichlorothiobenzimidate, N-methyl-2,6 - dichlorothiobenzamide, N,N - dimethyl-2,6 - dichlorothiobenzamide, N - phenyl - 2,6 -dichlorothiobenzamide, N - (2,6 - dichlorothiobenzoyl)morpholine, S,S1 - (1,4 - but - 2 - enylene) - bis - 2,6 - dichlorothiobenzimidate, S,S1 - (1,4 - butylene) - bis - 2,6 - dichlorothiobenzimidate. The compounds may be prepared by treating the corresponding halobenzonitriles with hydrogen sulphide or with a compound of the formula <FORM:0987253/C2/2> wherein R1 and R2 each represent an alkyl, aryl or aralkyl group linked directly to the phosphorus atom or through an oxygen atom, in presence of a hydrogen halide or with phosphorus pentasulphide.  They may also be prepared by reacting the corresponding halothionobenzoic acid or ester or halodithiobenzoic acid or ester, or halothiobenzoyl halide with ammonia or a primary or secondary amine, or treating the corresponding halothiobenzamide with a halide R1A or with a sulphate (R1O)2SO2 wherein R1 has the meaning already specified and A represents a halogen atom and, if desired converting the resulting salt to a free base or reacting the corresponding halothiobenzamide with an acylating agent.  In an example 2,6-dichlorothiobenzamide is prepared by reacting 2,6-dichlorobenzonitrile with hydrogen sulphide. In another example N-methyl-2,6-dichlorothiobenzamide is prepared by reacting N - methyl - 2,6 - dichlorobenzamide with phosphorus pentasulphide.  In another example 2-chloro-6-nitrothiobenzamide is prepared by reacting 2 - chloro - 6 - nitrobenzonitrile and O,O - dimethyldithiophosphoric acid.  In another example S,S1-(1,4-but-2-enylene)-bis-2,6-dichlorothiobenzimidate of the general formula <FORM:0987253/C2/3> is prepared by reacting 2,6-dichlorothiobenzamide with 1,4-dibromobut-2-ene.  Many other examples are given.ALSO:A herbicidal composition comprises a carrier and/or surface active agent and as active ingredient a compound of the general formula <FORM:0987253/A5-A6/1> and salts thereof, wherein X represents a halogen atom; Z represents a halogen atom, or a nitro, hydrocarbyl or hydrocarbylthio group; x = 1, 2, 3 or 4; m = 0 or 1, n = 1 or 2 and n + m = 2, the sulphur atom being linked by a double bond to the carbon atom when m = 0, and the nitrogen atom being linked by a double bond to the carbon atom when n = 1; R represents a hydrogen atom, a hydrocarbyl group or a halogen-substituted hydrocarbyl group or an aliphatic acyl group, or when n = 2, R may represent a group completing with the nitrogen atom a saturated or unsaturated heterocyclic ring; and R1 represents a hydrogen atom, a hydrocarbyl group or a substituted hydrocarbyl group. Specified active ingredients are 2,6-dichlorothiobenzamide, 2 - chloro - 6 -fluorothiobenzamide, 2 - chloro - 6 - iodothiobenzamide, 2,4-dichlorothiobenzamide, N-acetyl-2, 6 - dichlorothiobenzimidate, S - ethyl 2,6 - dichlorothiobenzimidate HBr, S - 2 - bromoethyl 2,6 - dichlorothiobenzimidate, S - ethyl 2,6 - dichlorobenzimidate. The carrier may be solid, e.g. china clay, synthetic calcium silicate, sulphur, carbon, natural or synthetic resins, bitumen, waxes or liquid, e.g. petroleum fractions, ketones, aromatic hydrocarbons. Dispersing agents, wetting agents, emulsifying agents (lists given in the Specification) may also be incorporated.  Water conditioning agents for example, sodium polyphosphates, cellulose ethers, or ethylene diamine tetra-acetic acid, other herbicides, pesticides or stickers, for example a non-volatile oil, may also be incorporated.