Patent GB-934576-A (GB)
Title: Improvements in or relating to halo-alkyl phenyl carbamates
IPC: C07D295/205
Filed: 1961-08-28
Abstract: The invention comprises haloalkylphenyl carbamates of the general formula (A) <FORM:0934576/IV(a)/1> wherein Z is a monoalkylamino, monoalkenylamino, dialkylamino or dialkenylamino group or a saturated heterocyclic radical -NZ1 of 5-9 nuclear atoms, Z1 representing a bivalent alkylene, oxaalkylene or thioalkylene radical and the radical Z containing not more than 10 carbon atoms, X is halogen, R is an alkyl group of 1-4 carbon atoms, R1 is hydrogen or an alkyl group of 1-4 carbon atoms and Y is halogen or an alkyl group of 1-4 carbon atoms.  Many such products are specified, representative examples being 2,4-dichloro-3-methyl-5-ethyl-phenyl methyl carbamate, 2-chloro-3,4,5-tributyl-phenyl ethyl carbamate, 2-bromo-, 2-iodo-and 2-fluoro-4,5-dimethylphenyl methyl carbamate, 2-chloro-4,5-dimethyl phenyl allyl (and diallyl) carbamate, 2-chloro-4,5-dimethyl-phenyl-3-oxapenta methylene carbamate, 2-chloro-4,5-dimethylphenyl 3-thiapentamethylene carbamate and 2-chloro-4,5-dimethyl-phenyl 1-isopropyl tetramethylene carbamate. The products may be prepared by (1) condensing an appropriate 2-halo- or 2,4-dihalo-alkyl-phenol with an appropriate isocyanate, (2) reacting an appropriate 2-halo-or 2,4-dihalo-alkylphenol with phosgene to produce an haloalkylphenyl chloroformate and treating this with an appropriate amine, or (3) reacting an appropriate 2-halo- or 2,4-dihalo-alkylphenol with an appropriate carbamyl halide.  Reaction (1) may be effected in a solvent at 15-100 DEG C. The chloroformate used as an intermediate in reaction (2) may be prepared by mixing an aqueous solution of the phenol containing a base gradually with a solution of phosgene in an inert solvent, suitably at -30 to +30 DEG C.  The chloroformate may then be reacted with the amine at 10-50 DEG C. in the presence of an acidacceptor, which may be an excess of the amine.ALSO:Insecticidal compositions comprise a dispersible carrier and a haloalkylphenyl carbamate of the general formula (A) <FORM:0934576/VI/1> wherein Z is a monoalkylamino, monoalkenylamino, dialkylamino or dialkenylamino group or a saturated heterocyclic radical -NZ1 of 5-9 nuclear atoms, Z1 representing a bivalent alkylene, oxa-alkylene or thia-alkylene radical and the radical Z containing not more than 10 carbon atoms, X is halogen, R is an alkyl group of 1-4 carbon atoms, R1 is hydrogen or an alkyl group of 1-4 carbon atoms and Y is halogen or an alkyl group of 1-4 carbon atoms.  Many such carbamates are specified, representative examples being 2,4-dichloro-3-methyl-5-ethylphenyl methyl carbamate, 2-chloro-3,4,5-tributylphenyl ethyl carbamate, 2-bromo-, 2-iodo- and 2-fluoro-4,5-dimethylphenyl methyl carbamate, 2-chloro-4,5-dimethylphenyl allyl (and diallyl) carbamate, 2-chloro-4,5-dimethylphenyl 3-oxapentamethylene carbamate, 2-chloro-4,5-dimethylphenyl 3-thiapentamethylene carbamate and 2-chloro-4,5-dimethylphenyl 1-isopropyl tetramethylene carbamate. The compositions may be prepared in the form of dusting powders or converted into wettable powders or concentrates suitable for emulsification in an aqueous vehicle. A number of conventional ingredients of such compositions are specified, and specific examples are given.  The products may also be put up in aerosol form.  A synergistic effect is observed when the products are used in association with piperonyl butoxide, sesamex (Sesoxane), dipropyl maleato-isosafrole condensate, the sulphoxide of formula (B) <FORM:0934576/VI/2> sesame oil extracts or bis-2,3,3,3-tetrachlorodipropyl ether.