Patent GB-760487-A (GB)
Title: Fungicidal compositions
Filed: 1953-09-24
Abstract: Metallic salt complexes of p-nitrosoarylamines of the general formula ON.Ar.NRR1 wherein Ar represents a benzene ring and R and R1 each represent a hydrogen atom or hydrocarbon radical of not more than 16 carbon atoms are prepared by reacting the p-nitrosoarylamines in an organic solvent with a solution of the metal salt.  An emulsifier, preferably a non-ionic emulsifier, may be added to the reaction mixture before precipitation of the complex.  p-Nitrosoarylamines mentioned include p-nitroso-derivatives of N-methyl-, N,N-dimethyl-, N-n-octyl-, N-ethyl-, N-cyclohexylN-ethyl-, N-phenyl, N,N-diphenyl- and N-n-octyl - N - phenyl - anilines.  Complex - forming metal salts mentioned include cuprous, cupric, ferrous, ferric, nickel, mercuric, cadmium, cobalt, manganese, stannous, antimony and calcium chlorides, ferric, nickel and mercuric nitrates, ferrous and ferric sulphates and nickel perchlorate.  Hydrochlorides of the p-nitrosoarylamines are prepared by dissolving the corresponding arylamines in hydrochloric acid, cooling with ice and adding sodium nitrite. Orthophosphates are prepared by reacting the p-nitrosoarylamines in a polar organic solvent, preferably acetone, with orthophosphoric acid. In an example, mono-(p-nitroso-N,N-dimethylaniline) orthophosphate is prepared.ALSO:A fungicidal composition comprises at least one p-introsoarylamine of the general formula ON - Ar - NRR1 wherein Ar represents a benzene ring and R and R1 each represent a hydrogen atom or a hydrocarbon radical of not more than 16 carbon atoms, or an inorganic acid salt thereof or a stable metallic salt complex thereof, and a carrier therefor which is a powder, a mixture of a powder and a dispersing agent, or a mixture of a liquid diluent or solvent and an emulsifying agent. Preferred p nitrosoarylamines are those in which R and R1 are hydrogen atoms, alkyl radicals having not more than ten carbon atoms and phenyl groups.  Specific nitrosoarlyamines mentioned include p-nitroso - N - methyl, N, N-dimethyl, -N-n-octyl-N - ethyl -, - N - cyclohexyl - N - ethyl-, -N - phenyl - and - N, N - diphenyl - anilines.  Salts of the p - nitrosoarylamines with strong inorganic acids, e.g. hydrochloric and orthophosphonic acids, are mentioned.  Metal salts forming complexes with the nitrosoarylamines include cuprous and cupric chlorides, ferrous and ferric chlorides and sulphates, ferric nitrate, nickel chloride, nitrate and perchlorate, mecuric chloride and nitrate, cadmium, cobalt, manganese, stannous, antimony and calcium chlorides. Specific complexes mentioned are those represented by the formul  B. Fe Cl3, B. Fe SO4, (B)3 Fe Cl3, (B)3 Fe(SO)3, (B)3 Fe(NO3)3, (B)2 Cu Cl2, (B)2 Cu(NO3)2, B. Cu SO4, (B)3 Zn HPO4, (B)3. Al Cl3, B.NC Cl2, (B)2 Ni (NO3)2, (B)2 Ni(Cl O4)2, B. MnCl2, (B)2 Hg Cl2, (B)2 Hg(NO3)2, B. Sn Cl2, (B)3 Sb Cl3, B. Cd Cl2, (B1)2. Cu Cl2, B1 (Cu SO4), (B1)2 Zu Cl2, (B1)3. Fe Cl3 and (B2)2, Cu Cl2 wherein B denotes p-nitroso-N, N - dimethylaniline and B1 denotes p-nitroso - N - phenylaniline.  The compositions may be dusting powders containing solid vehicles e.g. talc, chalk or aqueous suspensions, optionally containing some solid vehicle, containing a dispersing agent or wettable powders containing dispersing agents.  The nitrosoarylamines may be dissolved in aromatic hydrocarbons or polar organic solvents together with an emulsifier.  The metal complexes may be prepared by precipitation in the presence of an emulsifier preferably a non-ionic emulsifier.  Non-ionic emulsifiers mentioned include alkyl phenol ethers of polyethylene glycols, sorbitan monocarboxylic acid esters and their polyalkylenoxy derivatives.  Examples relate to aqueous solutions of the orthophosphonic acid salt of p - nitroso- N, N-dimethyl - aniline containing Triton X - 100 p  (Registered Trade Mark) (I) and (II); an aqueous solution of the complex represented by the formula (B)2 Cu Cl2 containing Triton X-100, an aqueous suspension of a wettable powder containing the complex represented by the formula (B1)2 CuCl2, a mixture of clay minerals and a mixture of sodium salts of sec-alkyl esters of sulphuric acid and of similar wettable powders containing complexes represented by the formul  B. Cu Cl2, (B)2 Cu (NO3)2, (B)2 Zn Cl2 and (B)3 Al Cl3, to emulsions containing the complex represented by the formula (B1)3 Fe Cl3, hydrocarbon oil and Triton X 155, and to similar emulsions containing complexes represented by the formul  (B)2 Ni (Cl O4)4 (B)2 Hg(NO3)2, B. Cd Cl2, (B1)2 Zn Cl2 and B1 Mn Cl2 (III).