Patent GB-660169-A (GB)
Title: Improvements in organo-phosphorus compounds and process of making same
IPC: H01G4/224
Filed: 1949-05-20
Abstract: Phosphorus compounds of the formula (RO)2P(O)-CHR1-CH2-COOR2, where R is alkyl, R1 is H or COOR2 and R2 is alkyl or alkenyl, are prepared by reacting R1-CH= CH-COOR2 with a dialkyl phosphite in the presence of a basic catalyst; the latter consists of an alkali or alkaline earth metal (e.g. lithium, sodium, potassium, magnesium, calcium) or an oxide, hydroxide or alcoholate thereof.  Examples show the reaction of diethyl phosphite with diallyl fumarate, di-n-butyl maleate and methyl acrylate.  The Specification as open to inspection under Sect. 91 describes generally the addition of esters of phosphorous acid and of phosphinic acids to compounds containing a C=C or C=N double bond. The catalyst may be of the type specified above or an organic nitrogen base such as pyridine, piperidine or benzyltrimethylammonium hydroxide.  Further examples show the reaction of diethyl phosphite with a -naphthyl isocyanate, phorone, furan, benzylidene-aniline, acrylonitrile, mesityl oxide, benzalacetone, furfurylideneacetone and benzyl acrylate.  In the case of phorone, the product is derived from 2 mols. of the phosphite and 1 mol. of phorone.  The following additional phosphorus esters are specified:-dibutyl phosphite, ethyl ethylphosphinate, diphenyl phosphite, ethyl phenylphosphinate, dimethyl phosphite, diallyl phosphite, di-(cyanoethyl)-phosphite, dinaphthyl phosphite, ethyl butylphosphinate, O : O1-di-(cyanoethyl)-thiophosphite, di-(chlorophenyl)-phosphite, di-(chloroethyl) - phosphite, chloroethyl phenylphosphinate, phenyl phenylphosphinate, nitrophenyl butylphosphinate and butyl phenylphosphinate.  Other specified C=C compounds are nitroethylene, N-methyl-acrylamide, methyl crotonate, maleic anhydride, diethyl itaconate, diethyl methylenemalonate, dicyanoethylene, diethyl allylphosphinate, vinyl chlorobenzoate, allyl acetate, methyl vinyl ketone, methyl isopropenyl ketone, acrylophenone (and its nuclear mono- and di-chloro-derivatives), vinyl ethers of ethanol, butanol, chlorophenol, nitrophenol, naphthol and benzyl alcohol, divinyl ether, vinyl ethyl sulphide, vinyl ethyl sulphone, allyl acrylate, diethyl maleate, butyl acrylate and ethylene glycol diacrylate.  Other specified C=N compounds are acetone phenylimide, ethylidene butylamine, phenyl isothiocyanate, butyl isocyanate, propionaldoxime methyl ether, bis acetone azine, bis chlorobenzaldazine, benzylidene-chloroaniline, benzylidene - nitroaniline, benzylidene - hydroxyaniline, benzylidene-methoxyaniline and ethylidene-aniline.  In general, the phosphorus ester is R1-PH(M)-M-R, where M is O or S, R is a hydrocarbon radical (which may be substituted) and R1 is R or MR. The unsaturated reactant is R1R2C=CR3R4 or YY1C=NY11, where R1 is hydrogen, hydrocarbon (possibly substituted), furyl or thienyl; R2 and R3 are hydrogen, hydrocarbon, carboxylic acid, ester, amide or nitrile or R2 and R3 together form a ring of furan, tetrahydrofuran, thiophene or maleic anhydride; R4 is nitro, carboxyl (or derivative thereof), phosphono, phosphato, acyl, sulphonyl, ether, thioether, or methyl substituted by one of these groups; Y and Y1 are H or hydrocarbon (possibly substituted) or together are O, S, tetramethylene or pentamethylene; Y11 is hydrogen, hydrocarbon (possibly substituted), hydroxyl or functional derivative thereof, or is another group -N= CYY1 or is attached to such a group by a divalent hydrocarbon radical.  Many radicals are specified as suitable to be present in the reactants. A group hydrolysable to a free carboxyl group may be so converted. This subject-matter does not appear in the Specification as accepted.