Patent GB-911764-A (GB)
Title: Improvements in or relating to phosphoryl and thiophosphoryl carbamates, thiocarbamates, ureides and thioureides
IPC: C07F9/22
Filed: 1959-04-21
Abstract: The invention comprises compounds of the formula <FORM:0911764/IV (b)/1> wherein X1 and X2 are the same or different and each represent an oxygen or sulphur atom, R1 and R2 are the same or different and each represent a hydrogen atom or an alkyl radical containing less than 5 carbon atoms, and W is a heterocyclic amino radical or an -OR3, -SR3, -N(R3) or NHR3 radical wherein R2 is an alkyl or aralkyl radical containing less than 16 carbon atoms, a hydroxyalkyl radical containing less than 7 carbon atoms, an alicyclic radical containing less than 8 carbon atoms, an aromatic radical, or a heterocyclic substituted alkyl radical or R3 in the NHR3 group may additionally be a heterocyclic radical attached to the N atom through a carbon atom of the heterocyclic radical.  The heterocyclic amino radical may be derived from a heterocyclic amine such as piperidine or morpholine, or from the amino derivatives of pyrimidine, pyridine, uracil, thiouracil, thymine, guanamine or cytosine.  They may be obtained by subjecting to pyrolysis a bis(ethylenimido) or bis(alkylethyleneimido)phosphoryl or thiophosphoryl carbamate (obtainable in accordance with the invention by a method as described below) to form the corresponding isocyanate or isothiocyanate and then reacting the latter with an appropriate alcohol, mercaptan or amine.  In an alternative method phosphorus oxychloride or thiochloride (1 mole) is reacted with ethyleneimine or an appropriate alkyl-substituted ethyleneimine (2 moles) in the presence of a hydrogen chloride acceptor (2 moles), e.g. triethylamine, and an inert solvent, e.g. dimethoxy ethane, to obtain the corresponding bis(ethyleneimido) or bis-(alkylethyleneimido)phosphoryl or thiophosphoryl chloride which is then treated with an alkali metal cyanate or thiocyanate to obtain the corresponding bis(ethyleneimido) or bis(alkylethyleneimido) phosphoryl or thiophosphoryl isocyanate or isothiocyanate which is then reacted with an appropriate alcohol, mercaptan or amine to form the corresponding carbamyl, thiocarbamyl, dithiocarbamyl, ureido or thioureido compound. The phosphoryl carbamate products may also be obtained by reacting a dihalophosphoryl isocyanate or isothiocyanate with an appropriate alcohol, mercaptan or amine to obtain the corresponding dihalophosphoryl carbamyl, thio(or dithio)carbamyl, ureido, or thioureido compound and then reacting the latter with ethyleneimine or an appropriate alkylethyleneimine in the presence of a hydrogen chloride acceptor, or with a metal salt of the ethyleneimine compound.  Alternatively, bis-(ethyleneimido) or an appropriate bis(alkylethyleneimido)phosphoryl or thiophosphoryl urethane obtainable by the process of the invention may be reacted directly at elevated temperature with an alcohol containing more than 2 carbon atoms to effect interchange of the alcohol radicals. In a preferred method equivalent amounts of phosphorus pentachloride and an appropriate carbamate or thiocarbamate compound are reacted in an inert solvent, e.g. ethylene chloride, to obtain the corresponding dichlorophosphoryl isocyanate or isothiocyanate which is then reacted with an equivalent amount of an appropriate alcohol, mercaptan or amine to form the corresponding dichlorophosphoryl carbamyl, thiocarbamyl, dithiocarbamyl, ureido or thioureido compound which is reacted with ethyleneimine or appropriate alkylethylenimine, or metal salt thereof, in the presence of a hydrogen chloride acceptor e.g. a tertiary amine such as triethylamine (when the free ethylenimine compound is used) and an inert solvent, e.g. toluene.  Several examples are given and the specified products include 5-glucosyl[bis - (ethyleneimido)-phosphoryl]carbamate, N-diethyl - N1 - bis(ethyleneimido)-phosphoryl urea, N - [bis - (ethyleneimido) - phosphoryl]-N1-phenyl urea, ethyl[bis-(ethyleneimido)-phosphoryl]thiolcarbamate, 5-Uracil[bis(ethyleneimido)-phosphoryl]thiolcarbamate, N(5-uracil)-N1-bis - (ethyleneimido) - phosphoryl urea, 5 - ribosyl[bis - (ethyleneimido)-thiophosphoryl]carbamate and furfuryl[bis-(ethyleneimido)-phosphoryl]carbamate.  The products are readily polymerizable to yield plastics and are also useful as textile chemicals.