Synthesis of 1,4-polyisoprene support of 2-chloroethylphosphonic acid (ethephon), a stimulating compound for the latex production by the Hevea brasiliensis

2-Chloroethylphosphonic acid (ethephon) is a well known stimulating product used to improve the latex production by the rubber tree (Hevea brasiliensis). Its chemical fixation in side position of 1,4-polyisoprene chains by weak chemical bond was considered in order to prepare new derivatives having prolonged stimulating activity. The synthesis was considered by using a chemical modification procedure according to a two-step process. Firstly, an epoxidized 1,4-polyisoprene intermediate was prepared by partial epoxidation of 1,4-polyisoprene. Secondly, the grafting of 2-chloroethylphosphonic acid was achieved by using the reactivity of the P–OH acidic function (or a P–OSiMe3 derived from P–OH) of the reagent toward oxirane rings of epoxidized 1,4-polyisoprene. It was noted that grafting yields are improved when the reaction is carried out in bulk or in a non-polar solvent, and more especially in neutral conditions, that is by replacing ethephon with its trimethylsilylated derivatives [monotrimethylsilyl 2-chloroethylphosphonic acid or, more especially, di(trimethysilyl) 2-chloroethylphosphonate]. With this latter, the addition occurs by the intermediate of the P–OSiMe3 bond, and the formation of 2-oxo-l,3,2-dioxaphospholane structures is highly favored.