溴化苄对二乙基胺甲基膦酸锆的季铵化及三相催化反应

QUATERNIZATION OF ZIRCONIUM DIETHYLAMINOMETHYLPHOSPHONATE WITH BENZYLBROMIDE AND THEIR PTC REACTIONS

首次制得二乙基胺甲基膦酸锆－亚磷酸锆Ｚｒ（ＨＰＯ＿３）＿（２－ｘ）·（Ｏ＿３ＰＣＨ＿２ＮＥｔ＿２）＿ｘ·Ｈ＿２Ｏ（ＺＤＥＡＭＰ－ＺＰ，ｘ＝０．７５，０．６０，０．５０）．将ＺＤＥＡＭＰ－ＺＰ用溴化苄季铵化，得到部分季铵化的产物：溴化苄基二乙基铵甲基膦酸锆－二乙基胺甲基膦酸锆－业磷酸锆Ｚｒ（ＨＰＯ＿３）＿（２－ｘ）·（Ｏ＿３ＰＣＨ＿２ＮＥｔ＿２）＿（ｘ－ｙ）·（Ｏ＿３ＰＣＨ＿２Ｎ￣＋Ｅｔ＿２·ＣＨ＿２Ｐｈ·Ｂｒ￣－）＿ｙ·Ｈ＿２Ｏ（Ｙ＜Ｘ，ＺＢＤＥＡＭＰＢ－ＺＤＥＡＭＰ－ＺＰ）．ＺＢＤＥＡＭＰＢ－ＺＤＥＡＭＰ－ＺＰ用于进行液／固／液或固固／液三相催化的亲核取代成醚、卤代烃和羧酸盐合成酯及二氯卡宾加成反应，均得到良好的结果。催化剂易于分离和回收，通常回收７０％～１００％，催化剂重复使用１０次以上无明显失活。

Zirconium(diethylaminomethylphosphonate-phosphite),Zt(HPO_3)_(2一x)(O_3PCH_2NEt_2)_x·H_2O(ZDEAMP-ZP,x=0.75,0.6,0.5)was prepoed for the first time,Quaternization of ZDEAMP-ZP with benaylbromide, partly quaternized,ZDEAMP-ZP:Zirconium(benzyldiethylammoniome thylphophonate bromide-diethylaminomethylphcaphonate-phosphite) Zr(HPO_3)_(2一x)(O_3PCH_2NEt_2)_(x-y)·(O_3PCH_2N￣+Et_2 ·CH_2Ph·Br￣一)_y · H_2O(y<X,ZBDEAMPB-ZDEAMP-ZP) was obtained, ZBDEAMPB-ZDEAMP-ZP catalyzed PTC reactions such as nucleophilic substitution, ether formation ester from halides and carboxylates,and addition of dichloreearbene in L/s/L orS/S/L phase,were carried out to give fairly good results,The catalyst can be easily separated and usually re-covered 7o%～100%,The catalyst can be reused more than 10 times without lose of catalytic activi-ty.