Patent GB-1011572-A (GB)
Title: Phosphorus-containing carboxylic acid amides
Inventor: ZAHIR SHEIK ABDUL-CADER
IPC: D06M13/288
Filed: 1963-05-03
Abstract: Compounds of the general formula (I):  <FORM:1011572/C3/1> where R represents hydrogen, allyl, or an alkyl group of up to six carbon atoms; n is either 1, when X represents hydrogen, methyl or a -CH2CONHCH2OR group, or zero, when X represents a -CH2CONHCH2OR group; and R1 and R2 either each represent the same or different alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxyalkenyl, aryl, alkoxyaryl or alkylene residues, which may be substituted by one or more chlorine and/or bromine atoms, the terminal valencies of such alkylene residues being linked to a group of Formula II: <FORM:1011572/C3/2> the free valency of which, if only one of R1 and R2 is alkylene, is linked to a further monovalent R1 or R2 residue, or R1 and R2 together represent a polymethylene chain containing from two to six carbon atoms, which may be linked to a second polymethylene chain containing two to six carbon atoms, via a spirocarbon, which polymethylene chains may be substituted by one or more chlorine and/or bromine atoms and/or methyl groups, the terminal valencies of the second polymethylene chain, if such be present, being linked to a group of Formula (II), and in which at least one of R, R1 or R2 is allyl may be polymerized using a free radical catalyst.  The polymers may be used in flame-proofing cellulosic materials.  In Example (XVII), N - hydroxymethyl - 3-(diallyloxyphosphinyl) propionamide is polymerized using ammonium persulphate as catalyst. Specifications 693,742 and 695,782 are referred to.ALSO:The invention comprises compounds of the general Formula I <FORM:1011572/C2/1> where R represents hydrogen, allyl, or an alkyl group of up to six carbon atoms; n is either 1, when X represents hydrogen, methyl or a -CH2CONHCH2OR group, or zero, when X represents a -CH2CONHCH2OR group; and R1 and R2 either each represent the same or different alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxyalkenyl, aryl, alkoxyaryl or alkylene residues, which may be substituted by one or more chlorine and/or bromine atoms, the terminal valencies of such alkylene residues being linked to a group of Formula II <FORM:1011572/C2/2> the free valency of which, if, only one of R1 and R2 is alkylene, is linked to a further monovalent R1 or R2 residue, or R1 and R2 together represent a polymethylene chain containing from two to six carbon atoms, which may be linked to a second polymethylene chain containing two to six carbon atoms, via a spiro-carbon, which polymethylene chains may be substituted by one or more chlorine and/or bromine atoms and/or methyl groups, the terminal valencies of the second polymethylene chain, if such be present, being linked to a group of Formula II. Preparative methods include:  (1) reacting corresponding -CHXCONH2 compounds with formaldehyde or a source thereof to give products in which R=H; (2) etherifying compounds in which R=H by reaction with an alcohol in the presence of acid; (3) reacting compounds of type (CH2=)n-CX1=CONHCH2OR, where X1 is as X except that when n=O, X1 is =CHCONHCH2OR, with an appropriate secondary phosphite; (4) introduction of halogen, e.g. by reacting 3-(diallyloxyphosphinyl)-propionamide with a polyhalomethane (e.g. trichloro-bromo-methane) in the presence of a free radical catalyst and then hydroxymethylating.  A number of starting materials of type <FORM:1011572/C2/3> including compounds illustrating the alkylene, polymethylene chain and spiro aspects of R1 and R2, are prepared by reacting (CH2=)2-CX1-CONH2 and (R1O)(R2O)P(O)H or by the action of ammonia on esters of  (R1O)(R2O)P(O)(CH2)nCH(COOH)2. n-Butyl ethyl phosphite and secondary phosphites derived from butane-1,3-diol/cyclic phosphite, cyclohexanol, neopentyl glycol (cyclic phosphite) pentaerythritol (cyclic diphosphite) and ethylene glycol (diphosphite) are prepared by means of PCl3 or transesterification.  Dimethyl - 2 - (diethoxyphosphinylmethyl)-succinate and di-n-propyl - 2 - (diethoxy - phosphinyl) succinate are prepared from diethyl phosphite and dimethyl itaconate and di-n-propyl maleate respectively.  N - (Allyloxymethyl) acrylamide is prepared from acrylamide, paraformaldehyde and allyl alcohol.  Specifications 693,742 and 695,782 are referred to.ALSO:Compounds of the general formula I <FORM:1011572/D1-D2/1> where R represents hydrogen, allyl, or an alkyl group of up to six carbon atoms; n is either 1, when X represents hydrogen, methyl or a <FORM:1011572/D1-D2/2> group, or zero, when X represents a -CH2CONCH2 or group; and R1 and R2 either each represent the same or different alkyl, alkenl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxyalkenyl, aryl, alkoxyaryl or alkylene residues, which may be substituted by one or more chlorine and/or bromine atoms, the terminal valencies of such alkylene residues being linked to a group of formula II: <FORM:1011572/D1-D2/3> the free valency of which, if only one of R1 and R2 is alkylene, is linked to a further monovalent R1 or R2 residue, or R1 and R2 together represent a polymethylene chain containing from two to six carbon atoms, which may be linked to a second polemethylene chain containing two to six carbon atoms, via a spiro-carbon, which polymethylene chains may be substituted by one or more chlorine and/or chromine atoms and/or methyl groups, the terminal valencies of the second polymethylene chain, if such be present, being linked to a group of formula II, or polymer of uch compounds in which at least one of R, R1 and R2 is alkyl are used in flameproofing cellulosic materials.  If only one -CONHCH2OR group is present in the compound, an aminoplast is also necessary, but this is optional if there are two or more -CONHCH2Or groups.  A latent acid catalyst is preferably present.  Suitable aminoplast include urea-formaldehyde, ethyleneurea-formaldehyde, melamine-formaldehyde and etherified melamine-formaldehyde resins.  Cellulosic materials treated in examples are cotton, viscose and paper.  Other substancess present in examples are Na1CO3, MgCl2, NH4H2PO4, mer emulsion, a polyethylene wax emulsion and a wetting agent derived from ethylene oxide.  Specifications 693,742 and 695,782 are referred to.