Patent GB-814264-A (GB)
Title: New pesticidal basic esters of phosphorus-containing acids
Inventor: CALDERBANK ALAN
IPC: C07F9/09
Filed: 1956-09-17
Abstract: The invention comprises phosphorus compounds of formula A=P(OR)(OR1)-B-L-NR2R3 wherein A and B, which may be the same or different, represent oxygen or sulphur, R and R1 stand for like or unlike alkyl radicals, L represents a straight or branched chain aliphatic hydrocarbon radical which may be interrupted by an oxygen atom and R2 and R3, which may be the same or different, stand for alkyl, aryl or aralkyl radicals provided that R2 and R3 are not both alkyl or both aryl radicals.  The aryl and aralkyl radicals may be substituted, e.g. by halogen, alkyl or alkoxy radicals.  They may be prepared by reacting a compound A= P(OR)(OR1)-Y, where Y stands for halogen, either with a compound HBLNR2R3 in the presence of an acid-binding agent or with a compound MBLNR2R3, where M is a metal atom, such as an alkali or alkaline earth metal atom, preferably in an inert diluent such as benzene.  Copper powder may be used as a catalyst.  Suitable acid-binding agents include sodium carbonate or organic bases such as HBLNR2R3.  When A and B are different, reaction below about 50 DEG  C. gives the thionate isomer, whereas reaction at elevated temperatures, such as above about 110 DEG  C., gives the thiolate isomer.  This is also formed by heating the thionate form, e.g. above about 110 DEG  C.  Another method of preparation comprises reacting a compound A=P(OR)(OR1)-B-M1, where M1 is a metal atom, e.g. an alkali or alkaline earth metal atom or ammonium, with a compound YLNR2R3, preferably in an inert diluent such as benzene or ethanol. This method always gives the thiolate isomer, where A and B are different irrespective of the temperature.  A further method of preparing compounds of formula O=P(OR)(OR1)-S-L-NR2R3 comprises reacting a compound M-O-P(OR)(OR1) with a compound NCS-L-NR2R3, preferably in an inert solvent.  The products are pesticides (see Group VI).  In examples: (1) sodium diethyl phosphite is prepared by the action of sodium on diethyl phosphite in benzene and reacted with N - ethyl - N - b  - thiocyanoethyl - p - toluidine to give O,O1 - diethyl S - 2 - (N - ethyl - N - p - tolylamino) - ethyl phosphorothiolate; (2) N-b  - bromoethyl - N - methyl - p - chloroaniline; (4) N,N - dibenzyl - b  - chloroethylamine; (17) b  - (N - benzyl - N - ethylamino) - ethyl bromide; and (23) b  - (N - benzyl - N - phenylamino) - ethyl chloride are heated with sodium O,O1-diethyl phosphorothioate in ethanol or benzene to give O,O1-diethyl S - 2 - (N - methyl - N - p -chlorphenylamino) - ethyl phosphorothiolate, O,O1 - diethyl S-2-(N,N1-dibenzylamino) ethyl phosphorothiolate, O,O1-diethyl S-b -(N-benzylN-ethylamino) ethyl phosphorothiolate and O,O1 - diethyl S - b  - (N - benzyl - N - phenylamino) ethyl phosphorothiolate respectively; (3) O,O1-diethyl S-1-(N-ethyl-N-phenylamino)-3-methoxyprop-2 -yl phosphorothiolothionate ; (5) O,O1-diethyl S-2-(N,N-dibenzylamino) ethyl phosphorothiolothionate; (10) O,O1-diethyl S-2-(N - benzyl - N - phenylamino) ethyl phosphorothiolate; (12) O,O1-diethyl S-2-(N-ethyl-N-phenylamino) ethyl phosphorothiolothionate; and (18) O,O1 - diethyl S - b  - (N - benzyl - N - ethylamino) ethyl phosphorothiolothionate are prepared by adding O,O1-diethyl hydrogen phosphorothiolothionate to an ethanolic solution of sodium ethoxide and then refluxing with a  - (N - ethyl - N - phenyl) amino - b  - chloro - g  - methoxypropane, N,N - dibenzyl - b  - chloroethylamino hydrochloride, b  - (N - benzyl - N - phenylamino) ethyl chloride hydrochloride, N-ethyl - N - b  - chloroethylaniline and b -(N-benzyl-N-ethylamino)-ethyl chloride hydrochloride respectively; (6) O,O1 - diethyl - O11 - b  - (N - methyl - N - phenylamino) ethyl phosphate; (8) O,O1 - diethyl O11 - b  - (N - benzyl - N - phenylamino) ethyl phosphate; (19) O,O1 - diethyl O11 - b  - (N - p - chlorobenzyl - N - ethylamino) ethyl phosphate; and (22) O,O1-diethyl S - b  - (N - benzyl - N - phenylamino) ethyl phosphorothiolate are prepared by refluxing diethyl phosphorochloridate with the sodium salts (prepared by reaction of sodium metal with the compound) in benzene or toluene solution in a nitrogen atmosphere of b -(N-methyl-N-phenylamino) ethanol, b -(N-benzyl-N-phenylamino) ethanol, b  - (N - p - chlorobenzyl - N - ethylamino) ethanol and b -(N-benzyl-N-phenylamino) ethyl mercaptan respectively; (7) O,O1 - diethyl S - b  - (N - ethyl - N - phenylamino) ethyl phosphorothiolate; (9) O,O1-diethyl S - b  - (N - benzyl - N - phenylamino) ethyl phosphorothiolate; (13) O,O1-diethyl S-2-(N - benzyl - N - p - methoxyphenylamino) ethyl phosphorothiolate; (16) O,O1-diethyl S - b  - (N - phenyl - N - b 1 - phenylethylamino) ethyl phosphorothiolate; (20) O,O1-diethyl S - 1 - (N - methyl - N - phenylamino) - prop - 2 - yl phosphorothiolate; and (21) O,O1-diethyl S - b  - (N - methyl - N - p - methoxyphenylamino) ethyl phosphorothiolate are prepared similarly from O,O1-diethyl phosphorochloridothionate and b  - (N - ethyl - N - phenylamino) ethanol, b  - (N - benzyl - N - phenylamino)-ethanol, b  - (N - benzyl - N - p - methoxyphenylamino) ethanol, b  - (N - phenyl - N - b 1 - phenylethylamino) ethanol, b  - (N - methyl - N - phenylamino) isopropanol and N-methyl-N-b -hydroxyethyl-p-anisidine respectively; (15) O-ethyl - O1 - n - propyl phosphorochloridothionate is similarly reacted with b -(N-benzyl-N-p-tolylamino) ethanol to give O-ethyl-O1-n-propyl S - b  - (N - benzyl - N - p - tolylamino) ethyl phosphorothiolate; (14) diethyl phosphorochloridothionate is reacted similarly but at 20-25 DEG  C. with b -(N-benzyl-N-phenylamino)-ethanol sodium salt to give O,O1-diethyl-O11-b -(N-benzyl-N-phenylamino) ethyl phosphorothionate. Starting materials prepared are: N-ethyl-N-b -thiocyanoethyl-p-toluidine by interacting potassium thiocyanate and N-ethyl-N-b -bromoethyl-p-toluidine in acetone at about 20-25 DEG C.; N - b  - bromoethyl - N - methyl - p - chloroaniline by interacting ethylene dibromide and N-methyl - p - chloroaniline; a  - (N - ethyl - N - phenylamino) - b  - chloro - g  - methoxypropane by interacting thionyl chloride and the corresponding alcohol which may be obtained from N-ethylaniline and 1-chloro-3-methoxy-propan-2-ol; b - (N - benzyl - N - p - tolylamino) ethanol from N - benzyl - p - toluidine and ethylene chlorhydrin; b  - (N - phenyl - N - b 1 - phenylethylamino) ethanol from b -hydroxyethylaniline and b -phenylethyl bromide; b -(N-benzyl-N-ethylamino) ethyl bromide from PBr3 and the corresponding alcohol; b  - (N - benzyl - N - ethylamino) ethyl chloride hydrochloride from thionyl chloride and the corresponding alcohol; b -(N-p-chlorobenzyl-N-ethylamino)-ethanol from N-ethyl-p-chlorobenzylamine and ethylene chlorhydrin; b  - (N - benzyl - N - phenylamino) ethyl mercaptan by reacting the corresponding chloride with thiourea and decomposing the resulting thiouronium salt with alkali.ALSO:Pesticidal compositions comprise phosphorus esters of formula A=P(OR)(OR1)-B-L-NR2R3 wherein A and B, which may be the same or different, stand for oxygen or sulphur, R and R1 stand for like or unlike alkyl radicals, L stands for a straight or branched chain aliphatic hydrocarbon radical which may be interrupted by an oxygen atom, and R2 and R3, which may be the same or different, stand for alkyl, aryl or aralkyl radicals provided that R2 and R3 are not both alkyl or both aryl radicals.  The aryl and aralkyl radicals may be substituted, e.g. by halogen, alkyl or alkoxy radicals (for preparation see Group IV (b)).  They may be used with carriers such as water, organic solvents, talc, chalk, kieselguhr or bentonite.  Suspending or dispersing agents such as sodium dinaphthylmethane disulphonate or sodium lauryl sulphate, binders such as spindle oil, glycerol, wool fat, glue or resin, and plant nutrients such as urea and magnesium sulphate may also be present. In Example 11, a composition is prepared comprising O,O1-diethyl S-b -(N-benzyl-N-phenylamine) ethyl phosphorothiolate, diacetone alcohol, water and a condensation product of an alkyl cresol with ethylene oxide.