Patent GB-795396-A (GB)
Title: Organic compounds containing phosphorus and sulphur and compositions containing the same
IPC: C07F9/40
Filed: 1955-11-23
Abstract: The invention comprises tetra-esters of (dithiodimethylene) diphosphonic acid having the general formula: <FORM:0795396/IV (b)/1> in which each X is an oxygen or sulphur atom and R, R1, R2 and R3 are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl or alkaryl groups having up to 18 carbon atoms and which may contain a halogen, nitro or alkoxy substituent or substituents.  The compounds may be obtained by reacting a di(halomethyl) disulphide having the formula Hal.CH2S.SCH2-Hal in which Hal is a halogen atom, e.g. chlorine, bromine or iodine, with one mol. of an ester of phosphorous acid having the formula RXP (X.R1)(X.A) in which X, R and R1 are as defined above and A is an alkali metal or an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl or alkaryl group having up to 18 carbon atoms and which may contain a halogen, nitro, or alkoxy substituent or substituents and with one mol. of an ester of phosphorous acid of the formula R3.X.P(XR2((XA) in which X, R2, R3 and A are as defined above.  The symmetrical esters may be obtained by treating two mols. of a compound of the formula RXP(X.R1)(X.A) with one mol. of a bis-(halomethyl) sulphide of the formula Hal.CH2SSCH2Hal in which R,R1A and Hal are as defined above.  A large number of triesters of phosphorous acid which may be used as starting materials are specified, including trialkyl and mixed trialkyl phosphites, tricycloalkyl and mixed cycloalkyl aryl phosphites, triaryl and mixed alkyl aryl phosphites, tris-(alkaryl) and mixed alkaryl phosphites, tris-(aralkyl) and mixed aralkyl phosphites, tris-(alkenyl) and mixed alkenyl phosphites, and tris-(alkynyl) and mixed alkynyl phosphites such as tripropargyl and diethyl propargyl phosphite.  Especially valuable phosphites are those derived from OXO alcohols, e.g. from the tridecanol obtained from triisobutylene or tetrapropylene, carbon monoxide, and hydrogen, and phosphites derived from branched chain alcohols such as 2-n-propylheptanol; 2,6,8-trimethyl nonanol-4, and 5-ethyl-nonanol-2.  Suitable alkali metal diesters which may be used are compounds of the formula M.O.P(OY)2 in which Y is a hydrocarbon group of 1 to 18 carbon atoms and M is an alkali metal such as sodium, potassium, or lithium, e.g. sodium di-n-butyl phosphite, sodium di-dodecyl phosphite, sodium diethyl phosphite, potassium dibenzyl phosphite, sodium di-4-tolyl phosphite, lithium di-2-naphthyl phosphite, potassium amyl tridecyl phosphite, potassium bis-(2-phenylethyl) phosphite, sodium diallyl phosphite and potassium dipropargyl phosphite.  Specified starting materials containing substituent groups or atoms are tris-(2-chloroethyl) phosphite, potassium bis-(2,4-dichlorophenyl) phosphite, sodium bis-(4-nitrodiphenylyl) phosphite, potassium bis-(4-nitrocyclohexyl) phosphite, tris-(3-methoxypropyl) phosphite, potassium bis-(2-methoxyphenylyl) phosphite and sodium bis-(4-methoxydiphenyl) phosphite.  Instead of the phosphites there may be employed esters of phosphorothious acid, e.g. the triethyl ester or the O,O-diamyl S-ethyl ester or the sodium O,O-dimethyl ester, esters of phosphorodithious acid, e.g. the tridodecyl ester or the O-phenyl, S,S-dimethyl ester, or the sodium S,S-di-n-butyl ester, and esters of phosphorotrithious acid or the alkali metal diesters thereof, e.g. the sodium dimethyl ester, the potassium di-p-tolyl ester and the sodium diallyl ester.  Mixed sulphur-containing phosphonates are obtainable by condensing one mol. of the bis-(halomethyl) disulphide with one mol. of a thiophosphorous ester and then condensing the resulting monophosphono compound with another phosphorous ester.  Thus a bis-(halomethyl) disulphide may be reacted with O-sodium dimethyl phosphorodithioate to form a monophosphonodithiolate of the structure Hal-CH2SSCH2-P(O)(SCH3)2 which may then be condensed with a different phosphorous ester, e.g. with triethyl phosphite to form a tetra ester of the structure <FORM:0795396/IV (b)/2> In preparing the ester products the reaction may be carried out at ordinary, decreased, or moderately elevated temperatures, e.g. 40 DEG  to 140 DEG  C., and reduced pressure may be employed.  If an alkali metal diester is used the reaction may be carried out in the presence of an inert diluent, e.g. benzene, hexane, or ethyl ether.  Examples are given for the production of tetraethyl(dithiodimethylene) diphosphonate, and tetramethyl-, tetra-isopropyl-, tetra-butyl-, tetrakis (2-ethyl hexyl)-, tetrakis (2-chloroethyl)-, dibutyl diethyl-, diethyl di-isopropyl-, diethyl dimethyl-, bis-(2-chloroethyl) diethyl- and bis-(2-chloroethyl) dimethyl-(dithiodimethylene) diphosphonates. A large number of other dithiodimethylene diphosphonates obtainable by the process of the invention is also given and this includes tetrabenzyl-, tetrakis-(4-chlorophenyl)-, tetrakis - (3 - chloro - 4 - nitrophenyl) -, tetrakis-(3 - ethoxypropyl) -, tetracyclohexyl -, tetrapropargyl -, diallyl diphenyl -, tetrakis - (2-methoxy - 1 - naphthyl) -, tetraphenyl -, tetrakis - (4 - iodophenyl) -, tetra - (4 - diphenylyl)-, tetrakis - (3,4 - dichlorobenzyl) -, bis - (2-bromoethyl) di - n - butyl -, amyl butyl ethyl methyl -, tetraterpinyl -, bis - (3 - nitrobenzyl) bis - (4 - chlorobenzyl) -, tetrakis - (4 - tert.-butyl - 2 - chlorophenyl) -, tetracarvacryl -, and tetrakis - (2 - bromoallyl) - dithiodimethylene diphosphonates, tetramethyl - (dithiodimethylene) bis - (phosphonodithiolate), tetrakis - (2-chloroethyl) - and tetrakis - (2 - nitrophenyl)-(dithiomethylene) diphosphonothiolates, tetra n - hexyl - (dithio dimethylene) diphosphonothiolothionate, tetrakis - (2 - isopropoxyethyl) (dithiodimethylene) bis - (phosphonotrithioate), bis - (4 - chlorobenzyl) dicyclohexyl (dithiodimethylene) bis - (phosphonodithiolate), tetraallyl - and tetra - propargyl - (dithiodimethylene) di - (phosphonodiothiolates) and tetradecyl triethyl - (dithiodimethylene) - diphosphonothionate.  The products are stated to be valuable as pesticides (see Group VI).ALSO:An insecticidal composition comprises a tetraester of (dithiodimethylene) diphosphonic acid having the general formula: <FORM:0795396/VI/1> in which each X is an oxygen or sulphur atom and R, R1, R2 and R3 are alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl or alkaryl groups having up to 18 carbon atoms and which may contain a halogen, nitro or alkoxy substituent or substituents (see Group IV (b)) together with a finely divided solid or liquid carrier. The composition may be in the form of a spray or aerosol.  The spray may be prepared by dissolving the tetraester in an organic solvent such as acetone, hexane, benzene, or carbon tetrachloride or by first preparing a solution and then dispersing in water to form an emulsion in which the tetraester is present in a concentration of for example 0.001 to 1.0 per cent by weight of the total emulsion.  The emulsifying agent may be a long chain polyalkylene glycol or sulphosuccinate.  The tetraesters may also be dissolved in liquefied gases such as the fluorochloroethanes or methyl chloride and applied as aerosols. Solid carriers specified are talc, clay, bentonite, pumice and fuller's earth.  Examples are given to show the insecticidal activity of compositions comprising tetraethyl-, tetra-methyl-, diethyl dibutyl, diethyl diisopropyl and tetrakis (2-chloro-ethyl)- (dithiodimethylene) diphosphonates respectively.  A large number of other tetraesters are also specified including tetrabenzyl-, tetrakis (4-chlorophenyl) -, tetrakis (3 - chloro - 4 - nitrophenyl-, tetracyclohexyl -, diallyl diphenyl -, tetraphenyl -, tetrakis (4 - iodophenyl) -, tetrakis-(3,4 - dichlorobenzyl) -, bis (2 - bromoethyl) din-butyl-, tetradodec-1-enyl, tetraterpinyl-, bis (3 - nitrobenzyl) - bis (4 - chlorobenzyl) -, tetrakis (4 - tert. butyl - 2 - chlorophenyl)-, tetracarvacryl -, tetrakis (2 - bromoallyl)-, tetra isopropyl-, tetrabutyl-, diethyl dimethyl-, tetrakis (2-ethylhexyl)-, bis (2-chloroethyl) diethyl- and bis (2-chloroethyl) dimethyl dithiodimethylene diphosphonates. Several tetraesters in which one or more of the X atoms in the above formula are sulphur are also specified including tetramethyl (dithiodimethylene) bis (phosphonodithiolate), tetrakis (2-chloroethyl)-and tetrakis (2-nitrophenyl)-(dithiodimethylene) diphosphonothiolates, and tetrakis (4-tert.-amylphenyl) (dithiodimethylene) di (phosphonotrithisate).