Patent GB-758625-A (GB)
Title: Improvements in organic esters of sulphurous acid
Filed: 1954-11-29
Abstract: The invention comprises a mixed sulphite diester of an aliphatic alcohol and a monoaromatic ether of a polyalkylene glycol in which the esterifying radical from the polyglycol contains 2 to 5 alkylene oxide groups each having 2 to 4 carbon atoms such as a mixed sulphite diester of the general formula <FORM:0758625/IV(a)/1> where R1 is alkyl, haloalkyl, cyanoalkyl, carboethoxy methyl or alkenyl, R is aryl, alkaryl, cycloalkylaryl, haloalkylaryl, alkoxyaryl, nitroaryl or haloaryl, m is 2 to 5 and n is 2 to 4.  The group R1 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, n-amyl, n-hexyl, octyl, capryl, 2-ethyl hexyl, decyl, dodecyl, cyclohexyl, 2-chlorethyl, 2-bromoethyl, 2-cyanoethyl, 2 : 2 : 2-trichloroethyl, 2-chloropropyl, 3 - chloropropyl, 2 : 3 - dichloropropyl, 4-chlorobutyl, trichloroamyl, allyl or methallyl. The group R may be phenyl, 1-naphthyl, 2-naphthyl, p-tolyl, o-tolyl, chlorophenyl, isopropylphenyl, tert.-butylphenyl, tert.-amyl phenyl, a cyclohexylphenyl, chloromethylphenyl, methoxyphenyl, nitrophenyl, bromophenyl, 2 : 4 - dichlorophenyl, 2 : 4 : 6 - trichlorophenyl, 2 : 4 : 5 - trichlorophenyl or pentachlorophenyl.  The -OCnH2ngroup may be ethyleneoxy, trimethyleneoxy, tetramethyleneoxy, propyleneoxy, or 1 : 2-dimethylethyleneoxy. The sulphite diesters are prepared by reacting an alkyl or substituted alkyl chlorosulphinate with a polyalkylene glycol monoaromatic ether in a solvent such as benzene, xylene or solvent naphtha and in the presence of a proton acceptor such as pyridine, dimethyl aniline or trimethylamine at between 0 DEG C. and 50 DEG  C.  In examples (1) the preparation of 2-chloroethyl-2-p - tert. - butylphenoxy isopropoxyisopropyl sulphite and of the di-isopropoxy, tri-, and tetra-isopropoxy analogues, is described; (2) and (3), many compounds are described containing as group R1, methyl, ethyl, n-propyl, n-butyl, amyl, n-octyl, n-decyl, n-dodecyl, carbethoxymethyl, 2-chloroethyl, 2-bromoethyl, 2 - cyanoethyl, 2 - chloropropyl, 3 - chloropropyl, 2 : 3-dichloropropyl, allyl and methallyl and as group R, phenyl, o-tolyl, p-tolyl, p-tert.-butylphenyl, cyclohexylphenyl, p-chlorophenyl, 2 : 4-dichlorophenyl, 2 : 4 : 5-trichlorophenyl, chloromethylphenyl, methoxyphenyl, and nitrophenyl and as the polyalkyleneoxy group, ethoxyethyl, diethoxyethyl, tetraethoxyethyl, isopropoxyisopropyl, di - isopropoxyisopropyl and tri-isopropoxyisopropyl.  The compounds are used in insecticidal compositions (see Group VI).  Aliphatic chlorosulphinates are prepared by reacting thionyl chloride with an aliphatic alcohol or an alkylene oxide to give the alkyl chlorosulphinate or the chloroalkyl chlorosulphinate respectively. In examples (1) 2-chloroethyl chlorosulphinate is prepared from ethylene chlorhydrin and thionyl chloride; (2) methyl-, n-propyl-, decyl-, carbethoxymethyl-, chloropropyl- and 2 : 3-dichloropropyl-chlorosulphinates are prepared from thionylchloride and, respectively, methanol, propanol, decanol, ethyl glycollate, propylene oxide and 2 : 3-dichloro - 1 - propanol.  Monoaromatic polyalkyleneglycol ethers are prepared by reacting a phenol with 2 or more mols. of an alkylene oxide to give a mixture of monoaromatic polyalkyleneglycol ethers containing varying members of alkyleneoxy units.  In examples (1) mono-p-tert.-butylphenyl polypropyleneglycol ethers where m is 2 to 5 are prepared from p-tert.-butylphenol and propylene oxide and the mixture fractionated to obtain individual ethers; (2) 2-phenoxyethoxy ethanol is prepared from phenol and ethylene oxide, and p-toloxy-, p-chlorotoloxy-, and 2 : 4-dichlorophenoxyiso propoxyisopropanol are prepared from propylene oxide and p-cresol, p-chlorophenol, and 2 : 4-dichlorophenol respectively.ALSO:Insecticidal compositions comprising a mixed sulphite diester of an aliphatic alcohol and a mono-aromatic ether of a polyalkylene glycol in which the esterifying radical of the polyglycol contains 2 to 5 alkylene oxide groups each of 2 to 4 carbon atoms such as a compound of the general formula: <FORM:0758625/VI/1> where R1 may be alkyl, haloalkyl, cyanoalkyl, carboethoxymethyl or alkenyl, and R may be aryl, alkaryl, cycloalkylaryl, haloalkylaryl, alkoxyaryl, nitro-aryl or haloaryl, where m is 2 to 5 and where n is 2 to 4, are described.  Compounds specified include 2 - chloroethyl 2 - p-tert - butylphenoxy - isopropyloxyisopropyl sulphite, 2 - chloroethyl 2 - p - tert - butylphenoxy-diisopropyloxy - , - triisopropyloxy - , and - tetraisopropyloxyisopropyl sulphites, chloropropyl 2 - p - tert-butylphenoxyisopropyloxyisopropyl sulphite, carboethoxymethyl 2 - p - tert - butylphenoxy - isopropyloxyisopropyl sulphite, 2 - chloroethyl p - toluoxy - isopropyloxyiso - propylsulphite, 2 - chloroethyl p - chlorophen - oxyisopropyloxyisopropyl sulphite and 2-chloroethyl 2 : 4 - dichlorophenoxyisopropyloxyisopropyl sulphite. The compounds may be applied to loci, such as plants for protection against insects in undiluted form, as dusts when admixed or adsorbed on powdered solid carriers such as mineral silicates e.g. mica, talc, pyrophyllite or clays, as liquids or sprays when dissolved in suitable solvents or dispersed in a medium such as water or as an aqueous emulsion containing a surface-active dispersing agent, as wettable powders when admixed with a mineral silicate and a dispersing agent, as suspensions formed by shaking the wettable powder with water or as an aerosol.  The compounds may be used mixed with other insecticides, fungicides or bactericides.  An example illustrates the use of compositions each containing 1 gm of one of the compounds specified above with 100 gms. of water and 3 drops of a commercial surface-active dispersing agent comprising the reaction product of castor oil and ethylene oxide, in the control of two-spotted spider mites on potted snap beans.