Patent GB-695782-A (GB)
Title: Production of diesterified phosphono derivatives of polyfunctional organic compounds
IPC: D06M13/288
Filed: 1949-06-03
Abstract: Flame-proofing plasticizers for resins are obtained by reacting, in specified manner (see Group IV (b)), an a  : b -ethylenic unsaturated polyfunctional compound, viz. an ester, amide or nitrile containing 2-4 functional groups selected from esterified carboxyl groups, amide groups and the nitrile group with a phosphite diester having the general formula <FORM:0695782/IV (a)/1> wherein each R represents an alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkoxyalkyl (including the saturated heterocyclic radicals containing oxygen as the only heterocyclic atom in the ring), aryloxyalkyl, cycloalkoxyalkyl or a b -chloro, -bromo or other halo-ethyl radical.  The products include those of the general formula <FORM:0695782/IV (a)/2> wherein X is the phosphono radical (RO)2PO, L represents -COOR1, -CONH2, -CONHR, -CONRR1 or -CN, R being as above defined and R1 represents the same radicals except aryl radicals, and Y is hydrogen, alkyl, aryl or -L or -(CH2)nL, wherein n is an integer from 1-5, at least one Y radical being -L or -(CH2)nL.  Numerous examples are given; the following are stated to plasticize vinyl chloride-acetate copolymers: diethyl 2-(diethyl phosphono) succinate, diethyl 2-(dibutyl phosphono) succinate, dibutyl 2-(diallyl phosphono) succinate, diallyl 2-(dibutyl phosphono) succinate, dimethoxyethyl 2-(dimethoxyethyl phosphono) succinate, di(b -chloroethyl) 2-(dibutyl phosphono) succinate, dibutyl 2-(dibutyl phosphono) methyl succinate, triethyl (dibutyl phosphono) tricarballylate, dibutyl 2-(dicyclohexyl phosphono) succinate, dibutyl 2-(di-tetrahydrofurfuryl phosphono) succinate, di-tetrahydrofurfuryl 2-(dibutyl phosphono) succinate, di-2-ethylhexyl 2-(diethylphosphono) succinate, tributyl (dibutyl phosphono) tricarballyate, di-(2-ethyl hexyl) 2-(dimethoxyethyl phosphono) succinate, diphenoxyethyl 2-(dibutyl phosphono) succinate, dibenzyl 2-(dibutyl phosphono) succinate, N : N : N1 : N1-tetramethyl-2-(dibutyl phosphono) succinamide, diethyl 2-(a -dibutyl phosphono) benzyl malonate, dibutyl 2- di-(2-methylcyclohexane methyl) phosphono succinate, dibutyl 2-(diphenyl phosphono) succinate, ethyl 2-cyano-3-phenyl-3-(dibutyl phosphono) propionate, tetraethyl dibutyl phosphono bimalonate and others.ALSO:Di-esterified-phosphono derivatives of esters, amides, nitriles, ester-amides, ester-nitriles or amide-nitriles of saturated carboxylic acids are prepared by reacting at a temperature between 25 DEG  and 200 DEG  C. in the presence of an alkaline non-peroxide type condensation catalyst incapable of forming free radicals, and if necessary in the presence of a solvent for the reactants, an a  : b -ethylenic unsaturated polyfunctional compound, viz. an ester, amide or nitrile containing from 2 to 4 functional groups selected from esterified carboxyl groups, amide groups and the nitrile group, with a phosphite diester having the general formula <FORM:0695782/IV (b)/1> wherein each R represents an alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkoxyalkyl (which may be the open-chain radical or the saturated heterocyclic radical containing only oxygen as the heterocyclic atom in the ring), aryloxy-alkyl, cycloalkoxyalkyl or a b -chloro, -bromo or other halo-ethyl radical.  The products include those having the general formula <FORM:0695782/IV (b)/2> wherein X represents the diesterified phosphono radical (RO)2PO- in which each R is as defined above, L represents -COOR1, -CONH2, -CONHR, -CONRR1 or -CN, wherein R is as above and R1 represents the same radicals as R except aryl radicals and Y is hydrogen, an alkyl or aryl radical or -L or -(CH2)nL, wherein n is an integer from 1 to 5, and at least one Y radical is -L or -(CH2)nL. The reaction is preferably effected by adding the olefinic compound in successive small increments to an agitated solution of the catalyst in the phosphite diester.  The reactants are generally used in the dry state and volatile inert solvents such as ethers, e.g. diethyl ether, dibutyl ether, dimethoxy methane, the diethers of the glycols and dioxane, and aromatic and aliphatic hydrocarbons such as benzene, xylene and n-heptane, may be present.  The resulting reaction product is neutralized or acidified, filtered or water-washed and then fractionally distilled under reduced pressure to recover the ester, amide or nitrile product. Specified catalysts are the alkalimetals, e.g. metallic sodium, potassium and lithium, their amides, hydrides and alcoholates, e.g. sodamide, sodium and potassium hydrides and sodium methylate or ethylate; sodium naphthalene; amines such as diethylamine and triethylamine; and calcium oxide and aluminium isopropoxide.  The alkali metal hydroxides may be used when dissolved in a solvent for the reactants.  Other catalysts are the alkali metal salts and, less effectively, the alkaline earth metal and magnesium salts, of phosphite diesters of the formula <FORM:0695782/IV (b)/3> where M is the metal and R is as defined above.  Some of the products are plasticizers for resins (see Group IV (a)).  Examples describe the production of the following compounds, the phosphono reactant being dibutyl phosphite unless otherwise stated: (1) and (3) dibutyl 2-(dibutylphosphono) succinate from dibutyl maleate or fumarate; (2) di-2-ethylhexyl 2-(dibutylphosphono) succinate from di-2-ethylhexyl maleate; (4) di-(phenoxyethyl) 2-(dibutylphosphono) succinate from diphenoxy ethyl maleate; (5) di-(b -chloroethyl) 2-(dibutyl phosphono) succinate from di-(b -chloroethyl) maleate; (6) dibutyl 2-(dibutylphosphono) methyl succinate from di-butyl itaconate; (7) di-(tetrahydrofurfuryl) 2-(dibutyl phosphono) succinate from di-(tetrahydrofurfuryl) maleate; (8) tetraethyl dibutyl phosphono - bimalonate from tetra - ethyl ethylene tetracarboxylate; (9) di-allyl 2-(di-butyl phosphono) succinate from diallyl maleate; (10) triethyl (dibutyl phosphono) tricarballylate from triethyl aconitate and the tributyl ester similarly from tributyl aconitate; (11) di-(2-ethylhexyl) 2-(dicyclohexyl phosphono) succinate from di-(2-ethyl hexyl) maleate and dicyclohexyl phosphite; (12) dibutyl 2-(diphenyl phosphono) succinate from dibutyl maleate and diphenyl phosphite; (13) di-(methoxyethyl) 2-(dimethoxyethylphosphono) succinate from di-(methoxyethyl) maleate and di-methoxyethyl phosphite; (14) N,N,N,1,N1-tetramethyl 2-(dibutyl phosphono) succinamide from N,N,N1,N1-tetramethyl maleamide; (15) dibutyl 2-(dibenzyl phosphono) succinate from dibutyl maleate and dibenzyl phosphite; (16) dibenzyl 2-(dibutyl phosphono) succinate from dibenzyl maleate; (17) diethyl 2-(a -dibutyl-phosphono) benzyl malonate from diethyl benzylidene-malonate; (18) ethyl 2-cyano-3-phenyl - 3 - dibutylphosphono propionate from ethyl 3-phenyl-2-cyano acrylate; (19) dibutyl 2 - (di - 2 - methylcyclohexane - methyl phosphono) succinate from dibutyl maleate and di-(2-methyl cyclohexane methyl) phosphite; (20) ethyl 2-cyano-3-(dibutyl phosphono) hydrocinnamate from ethyl 2-cyano-3-phenyl crotonate; (21) 2-cyano-3-dibutyl phosphono-3-phenyl propionamide from a  - cyanocinnamic acid amide; (22) dibutyl phosphonosuccinonitrile from fumaric dinitrile; (23) diethyl 2,3-dicyano-2-dibutyl phosphonosuccinate from di-ethyl dicyanomaleate.  Table 1 compares yields in the reaction between dibutyl phosphite and dibutyl maleate with various catalysts, no yield resulting when H2SO4 is used as catalyst.  Table 2 lists physical properties of numerous of the products of the invention including in addition to some of the above, dibutyl 2-(di-n-octylphosphonosuccinate, dibutyl 2-(di-tetrahydrofurfuryl phosphono) succinate, dimethyl 2-(di-ethyl phosphono) succinate, dibutyl di-isopropylphosphonosuccinate among others.  Many further examples of reactants are given.  The phosphite diester reactants may be prepared by reacting the appropriate alcohol with phosphorus trichloride in specified manner.  The Specification as open to inspection under Sect. 91 is not limited to the above process carried out in the presence of the specified type of catalyst, reference being made to the optional use of condensation catalysts in general and an example is given wherein dibutyl phosphite and dibutyl maleate are reacted in absence of a catalyst with low yield of dibutyl 2-dibutyl phosphono) succinate.  This subject-matter does not appear in the Specification as accepted.