Patent GB-828636-A (GB)
Title: Thiophosphoric acid esters and their production
IPC: C07F9/165
Filed: 1957-03-12
Abstract: The invention comprises compounds of the formula: R-A-Alk-X-P(Y)(OR1)2 in which RA stands for an organic acid radical, R being an organic radical and A being one of the groups -C(O)S-, -C(S)S-, -S(O)(O)S-, Alk is an alkylene chain having from 2 to 4 carbon atoms, X and Y are oxygen or sulphur at least one being sulphur, and R1 is a C1-C4 alkyl radical.  The organic radical (R) is preferably an alkyl radical which may be substituted or an aryl radical which may be substituted (e.g. by alkyl, halogen or nitro group), or a substituted primary or secondary amino radical.  The radical RA may be the residue of a thioalkanoic acid, thio-chloro(dichloro- or trichloro-)acetic acid, or an aroyl-thio-acid, of a heterocyclic thio-acid, or of a thio- or dithio-carbamic acid.  The compounds or certain of the compounds may be prepared by (a) reacting an acylmercapto alkanol (e.g. CH3COSCH2CH2OH) with an O,O-dialkyl thiophosphoric acid halide (e.g. Cl.P(S)(OCH3)2), (b) by reacting a salt of an O,O-dialkyl thio- or dithio-phosphoric acid (e.g. NH4.S.P(O) (or S) (OCH3)2 with an acyl mercapto alkylene halide (e.g. CH3CO.S.CH2CH2Cl), (c) by reacting an haloalkyl O,O-dialkyl thio- or dithio-phosphoric acid ester (e.g. BrCH2CH2S (or O) P(O) (or S) (OC2H5)2 with a salt of a thio-carboxylic acid (e.g. C6H5COSNa) or (d) by reacting an O,O-dialkyl mercapto alkyl thio- or dithio-phosphoric acid ester (e.g. (C2H5O)2 P(S) (or O) O (or S) CH2CH2SH) with an isocyanate or thioisocyanate, e.g. C6H5S (or O) CN.  Examples are given for the production of: (1) CCl3.CO.S.CH2.CH2.O.P(S) (OC2H5)2 by reacting CCl3.CO.S.CH2CH2OH with (C2H5O)2 P(S)Cl in the presence of pyridine, (2) CHCl2CO. S.CH2CH2OP(S)(OC2H5)2 by reacting CHCl2. CO.S.CH2CH2OH with (C2H5O)2P(S)Cl in the presence of pyridine, (3) (CH3)2NCO.S.CH2 CH2OP(S)(OC2H5)2 by reacting (CH3)2N.CO. S.CH2CH2OH with (C2H5O)2P(S)Cl as in (2), (4) CH3.SO2.S.CH2CH2OP(S) (OC2H5)2 by reacting CH3SO2.S.CH2CH2OH with (C2H5O)2 P(S)Cl as in (2), (5) C6H5NHCO.S.CH2CH2O. P(S)(OC2H5)2 by reacting C6H5NH.CO.S.CH2. CH2OH with (C2H5O)2P(S)Cl as in (2), (6) C6H5.NH.CS.S.CH2CH2OP(S) (OC2H5)2 by reacting C6H5NH.CS.S.CH2CH2OH with (C2H5 O)2P(S)Cl as in (2), (7) C6H5.COSCH2CH2OP(S) (OC2H5)2 by reacting (C2H2O)2P(S)Cl with C6H5COSCH2CH2OH as in (2), (8) CH3COS CH2CH2OP(S)(OC2H5)2 by reacting CH3COS CH2CH2OH with (C2H5O)2P(S)CI as in (2). and (9) CH3CO.S.CH2CH2SP(O) (OC2H5)2 and its thiolthiono analogue by reacting CH3.CO.S. CH2CH2CL with NH4S.P(O)(OC2H5)2\t and its thiothiono analogue respectively.  The products are valuable as insecticides (see Group VI).  The following compounds used as starting materials are prepared as described: (a) C.Cl3.CO.S.CH2CH2OH by reacting hydroxyethyl mercaptan in ether with trichloroacetyl chloride in the presence of triethylamine, (b) CHCL2.CO.S.CH2CH2OH by reacting dichloroacetyl chloride with hydroxyethyl mercaptan as in (a), (c) (CH3)2NCO.S.CH2.CH2OH by reacting hydroxyethyl mercaptan dissolved in methylethyl ketone with dimethylamino carbamie acid chloride in the presence of potassium carbonate, (d) CH2SO2.S.CH2.CH2OH by reacting the sodium salt of methyl thiosulphonic acid with bromohydrin, (e) C6H5NHCS.S.CH2CH2.OH by reacting phenylisothiocyanate with hydroxyethylmercaptan.ALSO:An insectidical composition comprises a thiophosphoric acid ester of the formula R-A-AIK-X-P(Y)(OR1)2 in which RA stands for an organic acid radical, A being one of the groups-C(O)S-,-C(S)S-, -S(O)(O)S-, AIK is a C2-C4 alkylene chain, X and Y are oxygen or sulphur, at least one of them being sulphur and R1 is a C1-C4 alkyl radical, together with a solid or liquid carrier, and if desired a further pesticidal agent.  Specified carriers are chalk, talc, bentonite, water, acetone, alcohols and liquid hydrocarbons.  A suitable composition is obtained by dissolving the ester in acetone, adding an emulsifier, e.g. a benzylhydroxydiphenyl polyglycol ether having 15 ethenoxy residues and then diluting with water.  Specified esters are: (C2H5O)2P(S)(or O) SCH2CH2SCOCH3, CCl3CO SCH2CH2OP(S)(OC2H5)2, CHCl2COSCH2CH2 OP(S)(OC2H5)2, (CH3)2NCOSCH2CH2OP(S)(OC2 H5)2, CH3SO2SCH2CH2OP(S) (OC2H5)2, C6H5 NHC(O)(or S)SCH2CH2OP(S)(OC2H5)2, C6H5 COSCH2CH2OP(S)(OC2H5)2, CH3COSCH2CH2 OP(S)(OC2H5)2 and CH3COSCH2CH2SP(O)(or S)(OC2H5)2.