The production of tertiary phosphites including new cyclic phosphites

摘要

A tertiary phosphite is obtained by transesterifying tris 2-chloropropyl phosphite with an alcohol having a higher boiling point than propylene chlorhydrin or by transesterifying tris 2-chlorobutyl phosphite with an alcohol having a higher boiling point than 2-chlorobutanol. The alcohol may be monohydric or polyhydric, e.g. an alkanol or cycloalkanol such as n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, isoctyl alcohol, octanol-2, 2-methyl-heptanol-2, n-decyl, isodecyl-, lauryl-, myristyl-, cetyl- or stearyl alcohol, cyclohexanol, or methyl cyclohexanol, or a glycol e.g. ethylene-, propylene-, trimethylene-, 1, 2-butylene-, 2, 3-butylene-, 1, 4-butylene-, 1, 3-butylene- or neopentyl-glycol, 1, 6-hexanediol, pinacol, 1, 2-pentanediol, 2-methyl-2, 4-pentanediol, 2-ethyl, 1, 3-hexanediol, 2, 4-pentanediol, 2, 4-heptanediol, 2, 2-diethyl-1, 3-propanediol and 2-ethyl-2-n-butyl 1, 3-propanediol. The transesterification of the tris-2-chloropropyl phosphite can be carried out at from room temperature to the boiling point of propylene chlorhydrin and at atmospheric or sub-atmospheric pressure, preferably the latter, e.g. a pressure of 50 mm or less. Mixed phosphites, e.g. diceryl (or distearyl) 2-chloropropyl phosphite, may be obtained by using less than 3 moles of the monohydric alcohol per mole of tris 2-chloropropyl phosphite. When using a , b or a , g glycols in an amount of one equivalent (or more) of the polyhydric alcohol per equivalent of tris 2-chloropropyl phosphite, e.g. 3 moles of glycol with 2-moles of tris 2-chloropropyl phosphite cyclic phosphites of the general formula: are obtained wherein R1, R2, R3, R4, R5 and R6 are hydrogen or C1-C4 alkyl radicals and n is 0 or 1. If less than one equivalent of the diol is used products are formed which still contain a 2-chloropropyl group, thus when reacting one mole of tris 2-chloropropyl phosphite with one mole (or less) of the above diols there are formed products of the general formula: wherein R1, R2, R3, R4, R5 and R6 are hydrogen or C1-C4 alkyl and n is 0 or 1. The invention includes per se compounds of the first general formula given above and compounds of the second general formula given above in which n is 1. The products are useful as insecticides and as stabilizers or plasticizers for plastics, e.g. vinyl chloride resins (see Division C3).ALSO:Tertiary phosphite esters obtainable by reacting tris (2-chloropropyl) phosphite with a mono- or polyhydric alcohol having a higher boiling point than 2-chloropropanol or by reacting tris (2-chlorobutyl) phosphite with a mono- or polyhydric alcohol having a higher boilding point than 2-chloro-butanol (see Division C2) are useful as stabilizers and plasticizers for vinyl chloride resins. The tertiary phosphite esters include cyclic phosphites having the general formulae: and wherein R1, R2, R3, R4, R5 and R6 are hydrogen or C1-C4 alkyl groups and n is 0 or 1.