Patent GB-789122-A (GB)
Title: New organic compounds containing phosphorus, processes for their manufacture and preparations containing them
IPC: C07F9/58
Filed: 1954-04-20
Abstract: The invention comprises phosphorus-containing organic compounds having the general formula <FORM:0789122/IV (b)/1> in which R and R1 represent an alkyl, cycloalkyl, aralkyl, aryl, or heterocyclic residue, which may contain substituents, or R and R1 taken together may form part of a ring system, R2 and R3 are hydrogen or an alkyl residue, X and Y represent -O-, -S-, -NH-, or -N-R1 (R1 having the meaning given above, Z and Z1 represent oxygen or sulphur, R4 is a residue which represents a cycloaliphatic or heterocyclic ring, either of which may be substituted by an aliphatic hydrocarbon group, m represents 0 or 1 and n represents a whole number from 2 to 4, the residue R4 being bound to the sulphur atom S by a carbon atom of the said aliphatic hydrocarbon group of the cycloaliphatic or heterocyclic ring or by a ring carbon atom of the cycloaliphatic or heterocyclic ring, provided that when m is 0 and the residue R4 is a heterocyclic ring or a heterocyclic ring attached to the exocyclic sulphur atom by a carbon atom of the said aliphatic hydrocarbon group, the latter ring contains at most one atom of oxygen or sulphur and provided that when m is 0 and the residue R4 is a heterocyclic ring the latter ring is not connected to the exocyclic sulphur atom by a ring carbon atom which is bound to a double bond, and further provided that when the residue R4 is a heterocyclic ring substituted by an aliphatic hydrocarbon group and is bound to the exocyclic sulphur atom by a carbon atom of the said aliphatic hydrocarbon group said ring is not bound to the said aliphatic hydrocarbon group through its hetero atom.  The compounds may be prepared by one of the following methods: (a) by reacting a compound of the formula <FORM:0789122/IV (b)/2> with a compound of the formula <FORM:0789122/IV (b)/3> (b) by reacting a compound of the formula <FORM:0789122/IV (b)/4> with a compound of the formula Me-S-R4; (c) be reacting a compound of the formula <FORM:0789122/IV (b)/5> with a compound of the formula <FORM:0789122/IV (b)/6> (d) by reacting a compound of the formula <FORM:0789122/IV (b)/7> with a compound of the formula Hal-R4; or (e) by reacting a compound of the formula <FORM:0789122/IV (b)/8> with a compound of the formula <FORM:0789122/IV (b)/9> In each case the symbols "Hal" and Me represent a halogen atom and a metal, especially an alkali metal, respectively.  The above methods are generally carried out at room temperature or at moderately raised temperature and in the presence of an inert diluent.  They may also be carried out in the presence of metallic copper as catalyst.  In examples: (1) the compound <FORM:0789122/IV (b)/100> is obtained by reacting cyclohexyl-b -oxyethyl sulphide dissolved in benzene with diethyl chlorothiophosphate in the presence of anhydrous potassium carbonate and copper powder; (2) cyclopentenyl-b -oxyethyl-sulphide (obtained by reacting sodium cyclopentene mercaptan with ethylene chlorhydrin) is converted to its sodium salt which is then reacted with diethyl chlorothiophosphate in the presence of toluene to form a colourless oil; (3) the addition product of camphene and monothioethylene glycol is reacted with diethylchlorothiophosphate in the presence of benzene, calcined potassium carbonate, and copper powder to form a water-insoluble oil; (4) furfuryl-b -oxyethyl-sulphide of the formula <FORM:0789122/IV (b)/111> is obtained by condensing furfuryl mercaptan with ethylene chlorhydrin and is then reacted with diethyl chlorothiophosphate in the presence of pyridine to form a clear water-insoluble oil; (5) the compound <FORM:0789122/IV (b)/122> is obtained by reacting the sodium salt of (b -mercaptoethyl)-cyclohexyl sulphide with diethyl chlorophosphate in the presence of toluene; (6) diethylchlorothiophosphate is reacted with the addition product of thioglycol and vinyl pyridine in the presence of benzene, potassium carbonate and copper powder to form a yellowish oil of the formula <FORM:0789122/IV (b)/133> (7) sodium cyclopentene mercaptide is reacted with diethyl chlorophosphate in the presence of benzene to form a yellowish oil; (8) b -hydroxyethyl)-thiophene sulphide is converted to its sodium salt which is then reacted with diethyl chlorothiophosphate in the presence of benzene to form a yellow oil; (9) sodium cyclohexyl mercaptide is formed by adding cyclohexyl mercaptan to a suspension of sodium in toluene at 30-40 DEG  C. and diethyl chlorophosphate is then added when reaction occurs to form a yellowish oil which on distillation under reduced pressure yields a colourless liquid; (10) the sodium salt of b -mercapto-ethyl-cyclohexyl sulphide is reacted with tetramethyl-diamido-chlorophosphate in the presence of toluene to give a yellowish oil; (11) b -mercaptoethyl cyclohexyl sulphide is converted to its sodium salt by reaction with sodium in toluene and the sodium salt is then reacted with 1 : 2-propylene chlorothiophosphate of the formula <FORM:0789122/IV (b)/14> in the presence of toluene to form a yellowish oily product.  When R and R1 in the formula of the products are alkyl groups they may be straight chain or branched and may contain substituents, specified radicals being methyl, ethyl, isopropyl, butyl, hexyl, 2-ethyl butyl, octyl, 2-butyloctyl, lauryl, octadecyl, 2-chloroethyl, and radicals containing thiocyano, cyano, or ester groups.  Other specified radicals which R and R1 may represent are phenyl, 2- or 4-chlorophenyl, 2 : 4-dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl, naphthyl, 4-diphenyl, benzyl, cyclohexyl, and tetrahydrofurfuryl. The product are stated to be valuable as pesticides (see Group VI). Specification 714,509 is referred to.ALSO:A pesticidal preparation comprises a liquid or solid diluent and a compound of the general formula <FORM:0789122/VI/1> (see Group IV (b)) in which R and R1 represent an alkyl, cycloalkyl, aralkyl, aryl, or heterocyclic residue, which may contain substituents, or R and R1 taken together form part of a ring system, R2 and R3 represent hydrogen or an alkyl residue, X and Y represent -O-, -S-, -NH-, -NR1- (R1 being as defined above), Z and Z1 represent oxygen or sulphur, R4 is a residue which represents a cycloaliphatic or heterocyclic ring either of which may be substituted by an aliphatic hydrocarbon group, m is 0 or 1 and n is a whole number from 2 to 4, the residue R4 being bound to the sulphur atom S by a carbon atom of the said aliphatic hydrocarbon group of the cycloaliphatic or heterocyclic ring or by a ring carbon atom of the cycloaliphatic or heterocyclic ring provided that when m is O and the residue R4 is a heterocyclic ring or a heterocyclic ring attached to the exocyclic sulphur atom by a carbon atom of the said aliphatic hydrocarbon group the latter ring contains at most one atom of oxygen or sulphur and provided that when m is 0 and the residue R4 is a heterocyclic ring the latter ring is not connected to the exocyclic sulphur atom by a ring carbon atom which is bound to a double bond, and further provided that when the residue R4 is a heterocyclic ring substituted by an aliphatic hydrocarbon group and is bound to the exocyclic sulphur atom by a carbon atom of the said aliphatic hydrocarbon group said ring is not bound to the said aliphatic hydrocarbon group through its hereto atom.  The pesticidal preparation may be in the form of a dusting powder or spraying liquid which latter may be a solution or suspension prepared with water or an organic solvent, e.g. alcohol, petroleum, or a tar distillate. The spraying liquids or dusting powders may contain the usual inert fillers, e.g. kaolin, gypsum or bentonite or other materials such as sulphite cellulose waste liquor or cellulose derivatives.  Wetting agents or adherent agents may also be present as may other insecticides and/or fungicides.  An example is given of the application as a systemic pesticide of a mixture of a product having the formula <FORM:0789122/VI/2> with diethylene glycol and a condensation product obtained from 1 mol. of tertiary octyl phenol and 8 mols. of ethylene oxide.  The preferred products are those having the above formula wherein X and Y are both oxygen atoms, R2 and R3 each represent hydrogen and R and R1 represent alkyl residues or represent alkylene residues which form part of a ring system and other products of this type are specified.  A product in which RX and R1Y are each N(CH3)2, Z is oxygen, Z1 is sulphur, R2 and R3 are each hydrogen, R4 is cyclohexyl, m is 1 and n is 2 is also specified. Specification 714,509, [Group IV (b), is referred to.