Patent GB-761902-A (GB)
Title: Improvements in or relating to cyanamides
IPC: C07C233/00
Filed: 1954-03-29
Abstract: Cyanamides of formula <FORM:0761902/IV(a)/1> wherein R is hydrogen or a hydrocarbon group, R1 and R11 are hydrogen, phenyl or alkyl groups, with the proviso that at least one of the groups R, R1 and R11 is hydrocarbon, and Z is a methylene or polymethylene group which may or may not carry hydrocarbon substituents and the chain of which may or may not be interrupted by oxygen or sulphur atoms, are polymerized in presence of boron fluoride catalysts, (e.g. the boron fluoride ethyl etherate).  Specified monomers are N-methyl-N-vinyloxyethyl-, N - a : a  - dimethyl - b  - vinyloxyethyl-, N - methyl - N - 2 - vinyloxypropyl-, N - 3 : 5 : 5 - trimethylhexyl - N - vinyloxyethyl-, N - 2 - ethylhexyl - N - vinyloxyethyl-, N - cyclohexyl - N - vinyloxyethyl-, N - tert.-butyl - N - vinyloxyethyl-, N - tert. - octyl - N - vinyloxyethyl-N - allyl - N - vinyloxyethyl-, N - a  - ethyl - b  - vinyloxyethyl-, N - 1 : 1 : 5-trimethyl - 7 - vinyloxyheptyl-, 4 - vinyloxy - 2-methyl - 2 - pentyl-, 5 - vinyloxy - 2 - methyl-2 - pentyl-, N - octadecyl - N - vinyloxyethyl-, N-benzyl-N-vinyloxyethyl- and N-phenyl-N-vinyloxyethyl-cyanamides.ALSO:The invention comprises cyanamides of formula <FORM:0761902/IV(b)/1> wherein R is hydrogen or a hydrocarbon group including alkyl, alkenyl, aryl, aralkyl, or cycloalkyl, and R1 and R11 represent hydrogen, phenyl or alkyl groups, provided that at least one of R, R1 and R11 is a hydrocarbon group, and Z is a methylene or polymethylene group with or without hydrocarbon substituents and the chain of which may or may not be interrupted by oxygen or sulphur atoms.  R, R1 and R11 preferably contain no more than 18 carbon atoms and Z is preferably a saturated hydrocarbon group having up to 7 carbon atoms. Preferred classes of compounds are those in which R is a hydrocarbon group of not more than 12 carbon atoms and (1) R1 and R11 are hydrogen while Z is methylene, or (2) R1 and R11 are methyl while Z is a saturated hydrocarbon group having up to 7 carbon atoms.  The compounds are prepared (1) by reacting a compound RNHC(R1)(R11)ZOCH = CH2 with cyanogen chloride or bromide in presence of an acid binding agent, preferably at 0-75 DEG  C., in an inert organic solvent; (2) by reacting a compound <FORM:0761902/IV(b)/2> wherein R0 is a smaller and more reactive hydrocarbon group than R (e.g. aralkyl, C1-C5 alkyl or alkenyl), with cyanogen chloride or bromide at 0-75 DEG  C. or more and decomposing the resulting quaternary compound by heating to 50-125 DEG  C.  A list of starting materials is specified.  The examples describe the preparation of N - methyl - N - vinyloxy -, N - a  : a -dimethyl - b  - vinyloxyethyl -, N - methyl - N - 2 - vinyloxypropyl -, N - 3 : 5 : 5 - trimethylhexyl - N - vinyloxyethyl -, N - 2 - ethylhexyl-N - vinyloxyethyl -, N - cyclohexyl - N - vinyloxyethyl -, N - tert. - butyl - N - vinyloxyethyl-, N - tert. - octyl - N - vinyloxyethyl -, N - allyl-N - vinyloxyethyl -, N - a  - ethyl - b  - vinyloxyethyl -, 1 : 1 : 5 - trimethyl - 7 - vinyloxyheptyl-, 4 - vinyloxy - 2 - methyl - 2 - pentyl -, 5 - vinyloxy - 2 - methyl - 2 - pentyl -, N - octadecyl - N - vinyloxyethyl -, N - benzyl - N - vinyloxyethyl-and N - phenyl - N - vinyloxyethylcyanamides.  Aminoalkyl vinyl ethers of formula <FORM:0761902/IV(b)/3> are prepared by reacting actylene with an amino alcohol <FORM:0761902/IV(b)/4> in presence of an alkaline catalyst (e.g. potassium hydroxide). Preferred conditions are temperatures of 120-150 DEG  C., pressures of 300-500 p.s.i. and a benzene, toluene or high boiling ether solvent.ALSO:Fungicidal and insecticidal compositions contain as the active ingredient cyanamides of formula:-  <FORM:0761902/VI/1> wherein R is hydrogen or a hydrocarbon group (e.g. alkyl, alkenyl, aryl, aralkyl or cycloalkyl) and R1 and R11 represent hydrogen, phenyl or alkyl groups, with the proviso that at least one of the groups R, R1 and R11 is hydrocarbon, and Z is a methylene or polymethylene group which may or may not carry hydrocarbon (e.g. phenyl) substituents and the chain of which may or may not be interrupted by oxygen or sulphur atoms.