Patent GB-949371-A (GB)
Title: Alpha substituted benzaldoximes
Inventor: HACKMANN JOHANNES THOMAS
IPC: C07C275/56
Filed: 1960-01-01
Abstract: The invention comprises compounds of the formula: <FORM:0949371/C2/1> and salts thereof, wherein X is halogen, W is halogen or alkyl, n is 1-4, and Y is halogen, hydroxy, hydrocarbyloxy, cyano, thiocyano, nitro, or -NR1R2 where R1 and R2 are hydrogen or hydrocarbyl, \sB halogen and/or hydroxy, or together with the nitrogen form a heterocyclic ring; or R1 is hydrogen or hydrocarbyl and R2 is hydroxy or -NR3R4 where R3 and R4 are hydrogen or hydrocarbyl; or Y is -NR5.CO.NR6R7 or -NR5.CS.NR6R7 or a tautomer thereof, R5, R6 and R7 being hydrogen or hydrocarbyl; or Y is -SR8 or-SO2R8, R8 being hydrocarbyl \sB halogen; and Z is hydrogen, aliphatic carboxylic acyl, or alkoxycarbonyl; and various processes for making such compounds, involving (i) chlorinating or nitrating a substituted benzaldoxime to give a compound with Y=Cl or NO2; (ii) reacting a compound with Y=Cl with a cyanate, thiocyanate, mercaptide, sulphinate or alkoxide to give Y=CN, SCN, S-, SO2- and O-; (iii) reacting a benzyl cyanide with nitrous acid to give Y=CN; (iv) reacting a compound with Y=Cl with HNR1R2; (v) reacting a benzonitrile oxide with HNR1R2; (vi) reacting a benzonitrile with hydroxylamine to give Y=NH2; (vii) reacting an a -aminobenzaldoxime with a cyanate or thiocyanate salt or an isocyanic or isothiocyanic ester to give Y=ureido or thioureido; (viii) acylating a compound with Z=H to give Z=acyl; (ix) reacting a compound with Z=H with an alkylchloroformate to give Z=alkoxycarbonyl; and (x) reacting an a -aminobenzaldoxime with chloral to give Y=-NH.CHOH.CCl3. Examples and suitable Y groups are listed.   The compounds of the invention are pesticides (see Division A5).  In examples, 2, 6-dichlorobenzal dichloride, 2, 6-dichlorobenzonitrile N-oxide and 2-chloro-6-methylbenzamide were obtained as by-products. Specification 949,372 is referred to.ALSO:The invention comprises (a) a method of protecting crop plants from undesirable competition with weeds or from attack by seed-or soil-borne fungus diseases or snails, comprising treating the soil in which the crop is to be grown, or the weed plants or their seeds, or the crop seeds with an a -substituted benzaldoxime as defined below having herbicidal snail-controlling or fungicidal properties, or a composition thereof; (b) a method of disinfecting and protecting seeds from seed- and soil-borne fungus attack by treating said seed with an a -cyanobenzaldoxime falling within the definition below, or with a composition thereof; and (c) a composition comprising an a -substituted benzaldoxime as defined below with a carrier (solid, liquid or gaseous) and/or surface-active agent.  The active materials are a -substituted benzaldoximes of the formula <FORM:0949371/A5-A6/1> or salts thereof of hydrohalides, sulphates, nitrates or alkali or alkaline earth metal, ammonium, triethylammonium or triethanolammonium salts, wherein X is halogen, W is halogen or alkyl, n is 1-4, and Y is halogen, hydroxy, hydrocarbyloxy, cyano, thiocyano, nitro or -NR1R2, where R1 and R2 are hydrogen or hydrocarbyl \sB halogen and/or hydroxy, or together with the nitrogen form a heterocyclic ring; or R1 is hydrogen or hydrocarbyl and R2 is hydroxy or -NR3R4, where R3 and R4 are hydrogen or hydrocarbyl; or Y is -NR5.CO.NR6R7 or -NR5.CS.NR6R7, or a tautomer thereof, where R5, R6 and R7 are hydrogen or hydrocarbyl; or Y is -SR8 or -SO2R8, R8 being hydrocarbyl + halogen; and Z is hydrogen, aliphatic carboxylic acyl, or alkoxycarbonyl (see Division C2). Specified carriers for the active materials are: gypsum, tripolite, diatomite, mica, vermiculite, talc, pyrophyllite, clays of montincrillonite, kaolinite and attapulgite groups, calcium and magnesium limes, calcite, dolomite, synthetic hydrated silicon dioxides, synthetic calcium silicates, sulphur, carbon, coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, poly-(chlorophenol), bitumens, asphaltites, waxes; water, fertilizers, and dispersing agents such as gelatin, glue, casein, gums, polyvinyl alcohol, sodium or calcium salts of high molecular weight sulphonic acids, e.g. lignin sulphonic acids, and condensed aryl sulphonic acids, non-ionic emulsifiers such as alkylene oxide condensation products with C12 and higher fatty acids, abietic acid and naphthenic acids, and partial esters thereof with polyhydric alcohols; and wetting agents such as alkali metal salts of C10 and higher sulphuric acid esters and sulphonic acids, and polyalkylene oxides and their condensation products with aromatic compounds such as octyl cresol; organic liquids such as petroleum oils, alcohols, ketones, ethers, hydrocarbons, dimethylformamide, and polyalkylene glycol ethers and esters; long-chain alkyl ammonium salts, alkyl sulphosuccinates, sodium polyphosphates, cellulose ethers, and other herbicides, pesticides or stickers.  If the carrier tends to decompose the active material a stabilizer such as urea or hexamethylene tetramine may be added.  Specified forms are dusts, pellets, granules, aqueous dispersions and aqueous emulsions. Specification 949,372 is referred to.ALSO:The invention relates to a method of protecting crop plants from undesirable competition with weeds or from attack by seed- or soil-borne fungus diseases, which comprises treating the weed or the crop seeds with an a  -substituted benzaldoxime having the general formula: <FORM:0949371/A1-A3/1> or a salt thereof or a composition containing it and a carrier; in the formula X is halogen, W is halogen or alkyl, n is 1-4 and Y is halogen, hydroxy, hydrocarbyloxy, cyano, thiocyano, nitro or -NR1R2 where R1 and R2 are hydrogen or hydrocarbyl \sB halogen and/or hydroxy, or together with the nitrogen form a heterocyclic ring; or R1 is hydrogen or hydrocarbyl and R2 is hydroxy or -NR3R4, where R3 and R4 are hydrogen or hydrocarbyl; or Y is -NR5.CO.NR6R7 or -NR5.CS.NR6R7 or a tautomer thereof, R5, R6 and R7 being hydrogen or hydrocarbyl; or Y is -SR8 or -SO2R8,R8, being hydrocarbyl \sB halogen; and Z is hydrogen, aliphatic carboxylic acyl or alkoxy carbonyl (see Divisions A5 and C2).  Examples relate to the treatment of imbibed seeds of oats and mustard, and the treatment of pea and bean seeds is referred to.  Specified carriers are:- gypsum, tripolite, diatomite, mica, vermiculite, talc, pyrophyllite, clays of montmorillonite, kaolinite and attapulgite groups, calcium and magnesium limes, calcite, dolomite, synthetic hydrated silicon dioxides, synthetic calcium silicates, sulphur, carbon, coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, poly(chlorophenol), bitumens, asphaltites, waxes; water, fertilizers, and dispersing agents such as gelatin, glue, casein, gums, polyvinyl alcohol, sodium or calcium salts of high molecular weight, sulphonic acids, e.g. lignin sulphonic acids, and condensed aryl sulphonic acids, non-ionic emulsifiers such as alkylene oxide condensation products with C12 and higher fatty acids, abietic acid and naphthenic acids, and partial esters thereof with polyhydric alcohols; and wetting agents such as alkali metal salts of C10 and higher sulphuric acid esters and sulphonic acids, and polyalkylene oxides and their condensation products with aromatic compounds such as octyl cresol; organic liquids such as petroleum oils, alcohols, ketones, ethers, hydrocarbons, dimethylformamide, and polyalkylene glycol ethers and esters; long-chain alkyl ammonium salts, alkyl sulpho-succinates, sodium polyphosphates, cellulose ethers, and other herbicides, pesticides or stickers.  If the carrier tends to decompose the active material a stabilizer such as urea or hexamethylene tetramine may be added.  Specified forms are dusts, pellets, granules, aqueous dispersions and aqueous emulsions. Specification 949,372 is referred to.