Patent GB-817359-A (GB)
Title: Improvements in and relating to pyrimidine derivatives and fungicidal compositions containing them
IPC: C07D239/38
Filed: 1957-02-14
Abstract: The invention comprises compounds represented by the general formula <FORM:0817359/IV (b)/1> wherein R1 represents an alkyl radical containing 1 or 2 carbon atoms, R2 represents hydrogen, an alkyl radical containing 1 or 2 carbon atoms or, together with R1 represents the tri- or tetramethylene radical or a benzene ring fused on to the pyrimidine ring, X represents O or S and Y represents a trichloromethane sulphenyl group bound by means of an oxygen atom or a second sulphur atom, the hydroxyl group, halogen, hydrogen or an alkyl radical containing 1 or 2 carbon atoms and a process for preparing such compounds which comprises reacting perchloromethyl-mercaptan with a pyrimidine derivative of the general formula <FORM:0817359/IV (b)/2> wherein R1 and R2 have the meanings given above, X1 represents the mercapto group, the -SM or -OM group, where M represents an alkali metal ion and Y1 represents hydrogen, the mercapto group, the hydroxyl group, the -SM or -OM group or an alkyl radical containing 1 or 2 carbon atoms, the group -OM not occurring together with a free mercapto group and if desired replacing any hydroxyl group Y1 present by halogen by treatment with an inorganic acid halide, or, after conversion into the group -OM, reacting it with further perchloromethyl mercaptan, thus converting it into the group -O-S-CCl3.  Suitable starting materials specified include 2-mercapto-4-methyl, 2 - mercapto - 4.6 - dimethyl, 2.6 - di - hydroxy - 4 - methyl, 2 - mercapto - 4 - methyl-6-hydroxy, 2-mercapto-4-methyl-5-ethyl-6-hydroxy, 2 - mercapto - 4 - ethyl - 5 - methyl - 6 - hydroxy, 2 - mercapto - 4.5 - trimethylene - 6 - hydroxy, 2 - mercapto - 4.5 - tetramethylene - 6 - hydroxy, 2 - mercapto - 4.5 - benzo - methyl pyrimidines.  Additional starting materials may be obtained by condensation of thio- or isothiourea ethers and suitable b -dioxo compounds or b -keto-carboxylic acid esters on the other and if necessary hydrolysis of an alkyl mercapto group in the 2-position or replacement of a 6-hydroxyl group by a mercapto group.  In examples: 2-trichloromethane sulphenylmercapto - 4 - methyl - 6 - hydroxy pyrimidine is obtained by reacting perchloromethyl mercaptan with 2-mercapto - 4 - methyl - 6 - hydroxy - pyrimidine in benzene and adding water to the mixture; 2-trichloromethane sulphenyl derivatives of 4-methyl-; 4.6-dimethyl-; 4.5-dimethyl - 6 - hydroxy-; 4 - methyl - 5 - ethyl - 6 - hydroxy; 4.5 - benzo - 6 - hydroxy-; 4.5-benzo-6-trichloromethane sulphenyloxy-; 4.5-tetramethylene - 6 - hydroxy-; 4.5 - trimethylene - 6 - hydroxy-; 4 - ethyl - 5 - methyl - 6 - hydroxy- and 6-trichloromethane sulphenyl-mercapto-4-methyl-pyrimidines are similarly prepared (1); 2-trichloro-methane sulphenyl-mercapto - 4 - methyl - 6 - chloro - pyrimidine is obtained by boiling the corresponding 6-hydroxy compound with phosphorus oxychloride (2); 2-trichloro-methane sulphenylmercapto-4-methyl-6-trichloromethane sulphenyloxy pyrimidine is obtained by reacting 2-mercapto-4-methyl-6-hydroxy pyrimidine with potash and reacting the product with perchlormethyl mercaptan (3) and 2.6-bis-trichloromethane sulphenyloxy-4-methyl pyrimidine is obtained by reacting perchloromethyl mercaptan with the disodium salt of 2.6-dihydroxy-4-methyl pyrimidine (4).  The products are employed in fungicidal compositions (see Group VI).ALSO:Fungicidal compositions comprise as active ingredient a pyrimidine derivative of the general formula <FORM:0817359/VI/1> wherein R1 represents an alkyl radical containing 1 or 2 carbon atoms, R2 represents hydrogen, an alkyl radical containing 1 or 2 carbon atoms or, together with R1 represents the trimethylene or tetramethylene radical or a benzene ring fused on to the pyrimidine ring, X represents O or S and Y represents a trichloromethane sulphenyl group bound by means of an oxygen atom or a second sulphur atom, the hydroxyl group, halogen, hydrogen or an alkyl group containing 1 or 2 carbon atoms (see Group IV (b)) in combination with a suitable carrier and/or distributing agent.  Carriers mentioned include talc, bentonite, kaolin, bole, chalk, ground limestone, powders containing wetting and dispensing agents, aqueous emulsions, organic solvents, e.g. chlorinated hydrocarbons such as trichlorethylene or petroleum fractions, if necessary with auxiliary solvents, e.g. acetone or higher ketones. Examples relate to fungicides containing 2-trichloromethane sulphenylmercapto-4-methyl-6-hydroxy pyrimidine and talc (5); 2-trichloromethane sulphenyl mercapto - 4.5 - benzo - 6 - trichloromethane sulphenyloxy-pyrimidine, kaolin or chalk and sulphite waste liquor or ethylene oxide condensation products of alkyl phenols (6), and 2 - trichloromethane sulphenylmercapto - 4 - methyl-6-chloropyrimidine, xylene and ethylene oxide condensation products.