Patent GB-778949-A (GB)
Title: Isothiouronium salts and pesticidal compositions containing them
IPC: C07C335/32
Filed: 1954-08-19
Abstract: The invention comprises salts of isothiourea derivatives of the formula <FORM:0778949/IV(b)/1> (wherein R1, R2 and R3 are hydrogen atoms or hydrocarbon radicals and X is an alkyl radical) with an aliphatic or carbocyclic carboxylic acid of at least 6 carbon atoms, or a monoalkylsulphuric acid ester containing at least 6 carbon atoms in the alkyl group, or an aromatic sulphonic acid containing an alkyl group of at least 6 carbon atoms attached to the aromatic nucleus, or Reinecke acid; and their preparation by reacting a thiourea R1R2N.CS.NHR3 with an ester of the appropriate acid and an alcohol XOH.  Suitable acids are higher paraffinic carboxylic acids such as those obtained from wool fat or degras, naphthenic acids, abietic acid, secondary alkyl sulphuric acid mono esters containing from 6-20 carbon atoms obtained by reacting olefins derived from cracking paraffin wax with sulphuric acid, and especially dodecylbenzenesulphonic acid and similar aromatic sulphonic acids. Suitable isothiourea derivatives are N : N : N1-trimethyl-S-n-hexylisothiourea, N : N - dimethyl - S - n - octyliso - thiourea, N : N1 - diphenyl - S - ethylisothiourea, S - n - octylisothiourea and S - "alphanyl"-isothiourea.  Other preparative methods referred to are reaction of the base and the acid in an inert solvent, e.g. alcohol, and double-decomposition of a water-soluble salt, e.g. a hydrochloride, of the isothiourea derivative, dissolved in water, with the sodium salt of the acid.  In examples: (1) S-n-octylisothiourea reineckate is prepared from ammonium reineckate and S-n-octylisothiourea hydrobromide in water at 40 DEG  C.; (2) the octyl ester of sec.-octylbenzene sulphonic acid and thiourea are refluxed in ethanol to give the appropriate salt; and (3) dodecyl benzene sulphonic acid octyl ester and thiourea are similarly reacted.ALSO:A fungicidal composition comprises a salt of an isothiourea derivative of the formula <FORM:0778949/VI/1> (wherein R1, R2 and R3 are hydrogen atoms or hydrocarbon radicals and X is an alkyl radical) with an aliphatic or carbocyclic carboxylic acid or at least 6 carbon atoms, or a monoalkyl sulphuric acid ester containing at least 6 carbon atoms in the alkyl group, or an aromatic sulphonic acid containing an alkyl group of at least 6 carbon atoms attached to the aromatic nucleus, or Reinecke acid H[Cr(SCN)4(NH3)2] together with a liquid or solid carrier or diluent.  Liquids referred to are hydrocarbon oils, vegetable oils, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hydrated naphthalene, alkylated naphthalene and solvent naphtha. Dispersing or emulsifying agents such as mixtures of alkylphenol ethers of polyethylene glycols or sulphonate emulsifiers, e.g. "TEEPOL" (Registered Trade Mark) may be added.  Solid diluents referred to are tricalcium phosphate, precipitated chalk, bentonite, Kaolin, keiselguhr, cork powder and wood powder with wetting agents when required.  Aerosols may be formed by dissolving or dispersing the active ingredient in a solvent boiling below 18 DEG C. at atmospheric pressure.  Concentrated preparations preferably contain up to 50 per cent of the salt in a hydrocarbon oil and these may be diluted with water to form a liquid suitable for spraying until the salt concentration is from 0.1 to 1 per cent.  An additional sticker such as a heavy hydrocarbon oil may also be added to the preparations and the salts may also be combined with biologically active substances such as insecticides, bactericides and phytohormones.  Examples illustrate the use of the Reinecke salts of N;N1-diphenyl-S-ethylisothiourea, S - alphanylisothiourea and S - n - octylisothiourea as aqueous emulsions, the salts of dodecyl benzene sulphonic acids and S-"alphanyl"-isothiurea, N : N : N1 - trimethyl - S - n - hexyl - isothiourea and N : N - dimethyl - S - ethylisothiourea as aqueous emulsions of their solutions in hydrocarbon oil and of the salt of S - decylisothiourea with a mixture of sulphuric acid monoesters of secondary alcohols of 6 to 20 carbon atoms in aqueous emulsion.