Patent GB-877920-A (GB)
Title: Organic tertiary phosphines
IPC: C07F9/54
Filed: 1959-10-20
Abstract: Linear phosphorus containing polymers may be obtained by the reaction of formaldehyde with a tertiary organic phosphine of formula: (A)n-1 P(B)4-n wherein A is NC-CH2-CH2-, <FORM:0877920/IV (a)/1> or <FORM:0877920/IV (a)/2> where R is H or C1-6 alkyl and R1 is C1-6 alkyl, B represents the same or different substituted or unsubstituted alkyl, alkenyl or alicyclic groups, any substituents being on a carbon atom at least 3 carbon atoms removed from the phosphorus atom, and n is 1, 2 or 3.  Specified substituents on B include cyano, phenyl, dialkylamino, nitro, carbalkoxy, dialkylcarbamoyl, carbamoyl, alkyl or aryl ether or thioether, acetal, keto, fluoro, chloro and hydroxy groups.  Specific reference is made to the formation of a polymer from methyl bis (2-cyano-ethyl) phosphine and formaldehyde to give a water-soluble bis-nitrile formaldehyde polyamide which may be cross-linked with melamine.ALSO:Phosphines of the general formula (A)n-1P(B)4-n wherein A is NC - CH2 - CH2 -, <FORM:0877920/IV (b)/1> or R1 - O - C - CH2 - CH2 -, in which R is H or C1-C6 alkyl and R1 is C1-C6 alkyl, B represents the same or different substituted or unsubstituted, branched or straight chain alkyl or alkenyl groups or substituted or unsubstituted, saturated or unsaturated alicyclic groups, said substituted alkyl, alkenyl or alicyclic groups having their substituents on a carbon atom at least 3 carbon atoms removed from the phosphorus atom, and n is an integer from 1 to 3, are prepared by contacting a compound (A)nP(B)3-n with a compound BX where X is halogen to produce the corresponding quaternary phosphonium halide [(A)nP(B)3-nB]+X-and reacting this with a strong base such as a metal alkoxide, sodium cyanide or sodamide.  Inert solvents may be used, e.g. an organic solvent in the first step and an alcohol or liquid ammonia in the second.  Temperatures of about 0-150 DEG C. are mentioned for the first step and about 5-115 DEG C. for the second. The completely unsymmetrical phosphines may be resolved into optically active forms.  Substituents which may be present in the groups represented by B include nitrile, phenyl, dialkylamino, nitro, carbalkoxy, dialkylcarbamoyl, carbamoyl, alkyl or aryl ether or thioether, acetal, keto, fluoro, chloro and hydroxyl.  The phosphines in which B is methyl and n is 2 or 3 are claimed per se.  Compounds prepared in examples are methyl bis(2-cyanoethyl) phosphine, methyl ethyl 2-cyanoethyl phosphine, alkyl bis (2-cyanoethyl) phosphine, cyclopentyl bis (2-cyanoethyl) phosphine, dodecyl bis (2-carbethoxyethyl) phosphine, 3-methylbutyl bis (2 - diethylcarbamoylethyl) phosphine, methyl ethyl n-propyl phosphine, and methyl 2-cyanoethyl 3- cyanopropyl phosphine.  Intermediate quaternary phosphonium compounds prepared are methyl tris (2-cyanoethyl) phosphonium iodide, methyl ethyl bis (2-cyanoethyl) phosphonium iodide, allyl tris (2-cyanoethyl) phosphonium iodide, cyclopentyl tris (2 - cyanoethyl) phosphonium bromide, dodecyl tris (2 - carbethoxyethyl) phosphonium iodide, 3-methylbutyl tris (2-diethylcarbamoylethyl) phosphonium iodide, methyl ethyl n-propyl 2-cyanoethyl phosphonium iodide, and methyl bis (2-cyanoethyl) 3-cyanopropyl phosphonium bromide.