Patent GB-829142-A (GB)
Title: Fungicidal compounds
IPC: C07C381/04
Filed: 1957-06-07
Abstract: The invention comprises fungicidal trichloromethyl-thio-derivatives of aromatic sulphinic acids, comprising the following classes of compounds: (1) compounds of the formula <FORM:0829142/IV (b)/1> wherein R1 is an aliphatic hydrocarbon radical (preferably of 1-6 carbon atoms) substituted by a halogen atom or an amino, alkylamino, dialkylamino, trialkylammonium, carboxyl or esterified carboxyl group, a carboxyl group which has reacted with the group -NH to form an acylamino group, or an ether group; for example, R1 is a FCH2-, ClCH2-, (CH3)3-N+(Cl-).CH2-, HOOC.CH2.CH2-, (C2H5-OOC.CH2-, C2H5OOC.CH2.CH2- or C6H5-O.CH2- group or the group R1CONH is replaced by a succinimido group; (2) compounds of the formula R2O(R2O) m.C6H4.SO2.S.C.Cl3, wherein R2 and R3 are aliphatic hydrocarbon radicals which may be such that R2O.(R3O)m forms a bicyclic system with the benzene ring and m is a whole number from 1-6; for example, R2O(R3O)mis a C2H5O.C2H4O-, C4H9O.C2H4O-, C2H5O.C2H4O.C2H4O- or a -O-CH2-CH2-O- group; (3) compounds of the formula HOOC.R4.C6H4.SO2.S.C-Cl3 and salts and esters thereof, wherein R4 is a saturated or unsaturated aliphatic hydrocarbon group, preferably containing 1-6 carbon atoms; for example, compounds in which R4 is the group -CH=CH-, -CH2.CH2- and -CH2-, and the ethyl ester corresponding to the latter compound; (4) compounds of the formula R5(R6)N.CO.C6H4.SO2S.CCl2, wherein R5 and R6 are hydrogen or hydrocarbon radicals; for example R5R6NCO- is a H2N.CO-, CH3.NH.CO- or (CH3)2N.CO- group; (5) compounds of the formula R10.CO.NH.C6H4.-SO2.S.CCl3 or salts thereof, wherein R10 is an amino or mono- or di-alkylamino group; for example R10 is an amino or dimethylamino group; (6) compounds of the formula R11O.CO.NH.C6H4.SO2.S.CCl3 or salts thereof, wherein R11 may be a methyl, ethyl, isopropyl or butyl group; (7) compounds of the formula R14.CO.N(R15).C6H4.SO2.S.CCl3, in which R14 is hydrogen or a saturated or unsaturated aliphatic hydrocarbon radical and R15 is a saturated or unsaturated aliphatic hydrocarbon radical; for example, R14 and R15 are methyl groups or may be ethyl or butyl groups; (8) compounds of the formula HOOC.R16.O.C6H4-SO2.S.CCl3 or salts or esters thereof, wherein R16 is a saturated or unsaturated aliphatic hydrocarbon radical; for example, R16 may be a methylene radical to give a phenoxyacetic acid derivative or its methyl or ethyl esters or R16 may be an ethylene group; (9) compounds of the formula R17.SO2.NH.C6H4.SO2.S.CCl3, wherein R17 is an aliphatic hydrocarbon group which may contain one or more unsaturated bonds; for example R17 is a methyl, ethyl, propyl, isopropyl or butyl group.  The compounds are made by reacting the corresponding sulphinic acid or an alkali metal or ammonium salt thereof with perchloromethyl mercaptan to replace the -SO2Me group (Me being hydrogen ammonium or an alkali metal) by the group -SO2.S.C.Cl3.  The reaction is suitably carried out either in an organic solvent, which is preferably of low polarity, suitable solvents being aromatic, aliphatic or cycloaliphatic hydrocarbons, ethers such as dimethyl-, diethyl- or methyl-ethyl ether, dioxane, anisole or phenetole or chlorinated hydrocarbons such as carbon tetrachloride, chloroform, methylene dichloride, 1:2-dichloroethane or chlorobenzene, the reaction temperature being between 40 DEG  and 100 DEG  C.; or in water or a mixture of water and an organic solvent at a temperature of 10 DEG to 40 DEG  C., the reaction medium being preferably maintained in a neutral state for example by the addition of sodium carbonate or bicarbonate.  Many examples are given.  Sulphinic acids or salts thereof which are used as starting materials according to the invention are made by reducing the corresponding sulphonyl chlorides, e.g. with sodium sulphite or stannous chloride, or by other methods. Sulphonyl chlorides used for the preparation of the above sulphinic acids, e.g. p-fluoroacetylamino-, p,b -carboxypropionylamino-, p-carboethoxyacetyl - amino -, p - b  - carboethoxypropionyl-amino-, p-succinimido-, p-b -ethoxy-ethoxy-, p - b  - butoxy - ethoxy -, p - b :b 1 - ethoxy - ethoxy - ethoxy -, p - b  - carboxyethyl -, p - carboethoxymethyl -, p - carbamoyl -, p - N - methylcarbamoyl -, p - N:N - dimethylcarbamoyl -, p - N1:N1 - dimethylureido -, p - carbomethoxy - methoxy -, p - carboethoxy - and p-methylsulphonylamino -, benzenesulphonyl chloride are prepared by treating the corresponding substituted benzene with chlorsulphonic acid or by other methods.  Specification 822,237 is referred to.ALSO:Fungicidal compositions comprise a compound chosen from the following classes (see Group IV (b)): (1) compounds of the formula <FORM:0829142/VI/1> wherein R1 is an aliphatic hydrocarbon radical substituted by a halogen atom or an amino, alkylamino, dialkylamino, trialkylammonium, carboxyl or esterified carboxyl group, a carboxyl group which has reacted with the -NH-residue to form an acylamino group, or an ether group; for example R1 is FCH2-, ClCH2-, (CH3)3N+(Cl -)-CH2-, HOOC.CH2CH2-, C2H5OOC.CH2-, C2H5OOCCH2.CH2- or C6H5OCH2-, or the group R1CONH is replaced by a succinimido group; (2) compounds of the formula R2O(R3O)m.C6H4.SO2.S.CCL3, wherein R2 and R3 are aliphatic hydrocarbon groups which may be such that R2O.(R3O)m forms a bicyclic system with the benzene ring, m is a whole number from 1-6, e.g. R2O(R3O)mis a C2H5OC2H4O-, C4H9OC2H4O-, C5H4OC2H4-OC2H4O- or -O-CH2.CH2-O-, group; (3) compounds of the formula HOOC.R4.C6H4.-SO2.S.CCl3 and salts and esters thereof, where R4 is an aliphatic hydrocarbon group of 1-6 carbon atoms, e.g. -CH:CH-, -CH2.CH2-and -CH2-; (4) compounds of the formula R5(R6).N.CO.C6H4.SO2.S.CCl3, where R5 and R6 are hydrogen or hydrocarbon radicals, e.g. R5(R6)N- is NH2-, CH3NH- or (CH3)2N-; (5) compounds of the formula R10CO.NH.C6H4-SO2.S.CCl3 and salts thereof, where R10 is an amino or mono- or di-alkylamino group, e.g. NH2- or (CH3)2N-; (6) compounds of the formula R11O.CO.NH.C6H4.SO2.S.CCl3 and salts thereof wherein R11 is an aliphatic hydrocarbon group, e.g. methyl, ethyl, isopropyl or butyl; (7) compounds of the formula R14.CO.N(R15).-C6H4.SO2.S.CCl3, wherein R14 is hydrogen or an aliphatic hydrocarbon radical and R15 is an aliphatic hydrocarbon radical, e.g. R14 and R15 are methyl, ethyl or butyl; (8) compounds of the formula HOOC.R16.O.C6H4.SO2.S.CCl3, and salts and esters thereof, wherein R16 is an aliphatic hydrocarbon radical, e.g. methylene or ethylene; (9) compounds of the formula R17.SO2.NH.C6H4.SO2.S.CCl3, wherein R17 is an aliphatic hydrocarbon group, e.g. methyl, ethyl, propyl, isopropyl or butyl, in admixture with an inert solid or liquid carrier or diluent.  Preparations include (a) miscible oils containing 15-20% active constituent, 15% non-ionogeneous emulsifier and solvents such as ketones, e.g. cyclohexanone; (b) aerosols containing solvents, e.g. acetone, methyl ethyl ketone and cyclohexanone and as a propellent methyl chloride or "Freon" (Registered Trade Mark); (c) spray powders containing 25-80% active substance, dispersing agents, carriers, e.g. kaolin, chalk, alum earth and attapulgite and admixtures to prevent clod-formation, e.g. colloidal silicic acid; (d) dusts containing 1-20% active substance infusorial earth and dolomite; p  (e) seed-protecting mixtures containing, for example, 50% active substance, kaolin and adhesives, e.g. watchmaker's oil; and (f) coated dusts in which the active substance is applied to an absorbing carrier, e.g. infusorial earth.  Specification 822,237 is referred to.