Patent GB-877671-A (GB)
Title: Improvements in or relating to phosphoryl and thiophosphoryl isocyanates and isothiocyanates
IPC: C07F9/564
Filed: 1959-07-28
Abstract: Phosphoryl or thiophosphoryl isocyanates or isothiocyanates of the formula:  <FORM:0877671/IV (a)/1> wherein X1 and X2 are the same or different and represent an oxygen or sulphur atom and R1 and R2 are the same or different and each represents a hydrogen atom or an alkyl radical containing less than 5 carbon atoms (see Group IV(b)) are polymerizable to yield plastics.ALSO:The invention comprises compounds of the formula <FORM:0877671/IV (b)/1> in which X1 and X2 are the same or different and each is an oxygen or sulphur atom, and R1 and R2 are the same or different and each is a hydrogen atom or an alkyl radical containing less than 5 carbon atoms.  They may be obtained either by (a) subjecting to pyrolysis in an inert solvent a bis-(ethyleneimido) or appropriate bis-(alkylethyleneimido) phosphoryl or thiophosphoryl carbamate or (b) by treating at least two moles of ethyleneimine or an appropriate alkyl ethyleneimine with one mole of POCl3 or PSCl3 in the presence of a hydrogen chloride acceptor, e.g. triethylamine, and an inert solvent, e.g. dimethoxy ethane, to obtain the corresponding bis(ethyleneimido)- or bis-(alkylethyleneimido) phosphoryl or thiophosphoryl chloride and then treating the latter with potassium cyanate or thiocyanate.  The products may be reacted with an alcohol, mercaptan, or with an amine, to yield the corresponding carbamyl, thiocarbamyl, dithiocarbamyl, ureido or thioureido derivatives.  In Examples: (1) dichlorophosphoryl isocyanate is prepared from PC15 and ethyl carbamate and is then reacted with an alcohol or mercaptan to obtain the corresponding dichlorophosphoryl carbamate or thiocarbamate.  The carbamate or thiocarbamate can be condensed with ethyleneimine or alkyl-substituted ethyleneimine to form the corresponding bis-(ethylenimido) phosphoryl carbamate or thiocarbamate which may then be pyrolysed in an inert solvent to form the corresponding isocyanate, the corresponding thio compounds are also obtained by using ethyl thiocarbamate instead of ethyl carbamate; (2) dichlorophosphoryl isocyanate is reacted with ethanol in toluene and the product solution is then concentrated and reacted with ethyleneimine to form bis(ethylenimido)-phosphoryl urethane which is then boiled in dry toluene to form the corresponding isocyanate; (3) methyl bis(ethylenimido) phosphoryl carbamate and the corresponding isocyanate are obtained as in (2) using methanol instead of ethanol. Examples are also given for the production of benzyl-, cyclohexyl-, and 5-glucosyl-[bis-(ethyleneimido)-phosphoryl] carbamates; N,N - diethyl-[bis-(ethylenimido)-phosphoryl] urea; N-cyclohexyl-N1-bis-(ethylenimido)-phosphoryl urea; bis-(2-methylethyleneimido) phosphoryl urethane and the corresponding isocyanate; 5-uracil [bis-(ethyleneimido)-phosphoryl] thiocarbamate; N-(5-uracil)-N1-bis-(ethylenimido) phosphoryl urea; methyl [bis-(ethylenimido)-thiophosphoryl]-thionocarbamate (using method (b) followed by reaction with methanol); bis-(ethylenimido) - thiophosphoryl urethane; 5 - ribosyl [bis-(ethylenimido)-thiophosphoryl] carbamate and benzyl [bis-(ethylenimido)-phosphoryl] thiocarbamate.  The compounds may be polymerized to yield plastics and are useful in the manufacture of textiles.