Patent GB-797603-A (GB)
Title: New basic esters of thiophosphonic acids and salts thereof
Inventor: GHOSH RANAJIT
IPC: C07F9/40
Filed: 1955-06-29
Abstract: The invention comprises basic esters of the formula O.P(R)(OR1)-S-L-Z, wherein R and R1 are like or unlike alkyl radicals, L is a saturated straight or branched chain aliphatic hydrocarbon radical containing at east 2 carbon atoms and Z is a secondary aliphatic or heterocyclic amino radical attached to L through the amino nitrogen atom, and the salts thereof.  They may be obtained by reacting a compound of the formula O.P(R)(OR1)Y wherein R and R1 are as defined above and Y is a halogen atom with a compound of the formula HSLZ wherein L and Z are as defined above, in the presence of an acid-absorbing agent, or with a metal salt thereof. The reaction may be carried out in an inert diluent or solvent, e.g. benzene or toluene.  Suitable acid-absorbing agents are organic bases, e.g. a tertiary organic base such as triethylamine, and alkali metal carbonates, e.g. sodium carbonate.  Suitable metal salts are the alkali metal salts, e.g. the sodium salt of b -diethylaminoethane thiol.  The basic ester products may be converted into the salts thereof by reacting, conveniently in an inert diluent or solvent such as ether, acetone, or ethyl acetate, with an appropriate acid, e.g. oxalic, toluene-p-sulphonic, hydrochloric, or phosphoric acid. Examples are given for the production of (1) to (3), (13) and (14): O-ethyl S-b -diethylaminoethyl ethylphosphonothiolate and its hydrogen oxalate and toluene -p-sulphonate salts; (4) O-ethyl S-b -diethylaminoethyl n-propylphosphonothiolate and its toluene-p-sulphonate; (5) and (6) O-ethyl S-b -diethylaminoethyl isopropyl- and (n-butyl-) phosphonothiolates respectively and their toluene-p-sulphonates; (7) O-ethyl S-b -diethylaminoethyl n-hexylphosphonothiolate and its toluene p-sulphonate and hydrogen oxalate salts; (8) O-ethyl S-b -N-piperidylethyl ethylphosphonothiolate and its hydrogen oxalate; (9) O-ethyl S - b  - dimethylamino - b  - methylpropyl ethylphosphonothiolate; (10) O-n-butyl S-g -diethylaminopropyl n - butylphosphonothiolate; (11) O - ethyl S - b  - dimethylaminoethyl ethylphosphonothiolate and its hydrogen oxalate; and (12) O - ethyl S - b  - diethylaminoethyl methylphosphonothiolate and its toluene-p-sulphonate and hydrogen oxalate salts.  The products are stated to be valuable as pesticides (see Group VI).  The compounds of the formula O.P(R)(OR1)Cl used as starting materials may be obtained by reacting a compound of the formula O.P(R)(OR1)2 with phosgene at about 30 DEG  to 40 DEG  C. Thus ethyl ethylphosphonochloridate used as starting material in (1) above may be obtained by passing phosgene into diethyl ethylphosphonate at 35 DEG  C. and the analogous starting materials used in the other examples may be obtained in a similar manner.  b  - Dimethylamino - b  - methylpropanethiol which is used as a starting material in (9) above may be obtained by heating a solution of b  - dimethylamino - b  - methylpropyl chloride hydrochloride with thiourea in ethanol under reflux for 40 hours.ALSO:A pesticidal composition contains as the active ingredient at least one basic ester of the formula: <FORM:0797603/VI/1> wherein R and R1 are like or unlike alkyl radicals, L is a saturated straight or branched chain aliphatic hydrocarbon radical containing at least 2 carbon atoms and Z is a secondary aliphatic or heterocyclic amino radical attached to L through the amino nitrogen atom, or a salt thereof, e.g. with oxalic, toluene p-sulphonic, hydrochloric, or phosphoric acid (see Group IV (b)). The composition may contain a carrier and, if desired, an auxiliary agent and/or a plant nutrient.  The carrier may be a liquid, e.g. water or an organic solvent, or a solid such as an inert pulverulent diluent, e.g. talc, kieselguhr, bentonite or other colloidal clay or powdered chalk, or a water-soluble organic or inorganic compound in which case the active ingredient may be incorporated to give a shaped tablet or block or a non-hygroscopic free-flowing granular preparation.  The auxiliary agent may be a dust-binding agent, e.g. spindle oil, glycerol, or wool fat or a wetting, spreading, or dispersing agent such as a condensation product of ethylene oxide with an alkyl phenol, e.g. octyl cresol, or with a long chain alcohol, e.g. cetyl alcohol or stearyl alcohol, an alkali metal dinaphthylmethane sulphonate, an alkali metal salt of a sulphated fatty alcohol, e.g. sodium lauryl sulphate, or a substance adapted to promote adhesion, e.g. glue or resin.  Specified plant nutrients are urea and mangesium sulphate. In examples, pesticidal compositions are made by (1) dissolving a mixture of 1 part O-ethyl S-b -diethylaminoethyl methylphosphonothiolate and 20 parts of a 30 per cent aqueous solution of a condensation product of n-octyl cresol with 9 molecular proportions of ethylene oxide in 1000 parts of water and then diluting one part of the resulting solution with 400 parts of water; (2) dissolving 1 part of O-ethyl S-b -diethyl aminoethyl ethylphosphonothiolate toluene-p-sulphonate in 100,000 parts of water; (3) mixing 1 part of O-ethyl S-b -diethylaminoethyl ethyl n-butylphosphonothiolate with 100 parts diacetone alcohol and then diluting with 1500 parts of water; (4) mixing one part of O-ethyl S-b -diethylaminoethyl ethylphosphonothiolate with 10 parts of a preparation made up from 1 part of a condensation product of cetyl alcohol with 3 molecular proportions of ethylene oxide, 1 part of a condensation product of cetyl alcohol with 17 molecular proportions of ethylene oxide, and 5 parts each of ethanol, diacetone alcohol, and ethyl acetate and then diluting with 500 parts of water; (5) mixing 1 part of O-ethyl S-b -diethylamino ethyl ethylphosphonothiolate hydrogen oxalate and 500 parts of p  urea and either dissolving 1 part of the mixture in 50 parts of water or compressing it into granules or tablets which may subsequently be dissolved in an aqueous medium.