SYNTHESIS OF NOVEL FLUORINATED COMPOUNDS BY THE USE OF ACTIVE FLUORINATING REAGENTS

1) C-F键活化生成二氟乙烯单元的研究进展了对体系上的三氟甲基选择性脱氟生成二氟乙烯和脱氟三甲基硅基甲基化合物的研究进展。特别是二氟烯基硅醚、二氟胺和4′-三氟甲基1,1 -二氟乙酶-三甲基硅烷已被有效制备。2摩尔金属镁和4摩尔TMS-C1在0℃下反应30 min，反应非常顺利。实现了工业上可行的生产二氟乙烯基单体用于二氟乙烯和八氟[2.2]对环己烷用于氟化苝聚合物。在3,3,3 -三氟乙醇中钯催化还原了3,3,3 -三氟-2-亚氨基丙酸酯的亚胺基，对不对称加氢反应起着重要作用。全氟烷基化α-二亚胺、2,2,3,3，-四氟- 1,4 -二酮和蒎醇的合成。以钯为催化剂，用相应的酰卤化物偶联反应制备了新型的三氟烷基和全氟烷基-α-二亚胺。二亚胺是一种很有前途的烯烃聚合催化剂，值得进一步研究。同样，二氟烯基硅醚和三氟甲基酮分别通过Cu （II）氧化和Zn还原偶联。

1) C-F bond activation for the creation of difluoromethylene units Selective defluorination from trifluoromethyl group attached to p-system leading to the formation of difluoromethylene and defluorotrimethylsilylmethyl compounds has been developed. In particular, difluoroenolsilyl ethers, difluoroenamines, and 4'-trfluoromethy1, 1-difluorobenzy1 trimethylsilane nave been effectively prepared. The reductive reaction proceeded very smoothy1 by the action of two mole equivalents of metallic magnesium and four mole equivalents of TMS-C1 at 0℃ for 30 min. The industrially feasible production of difluorovinyl monomer for difluorovinyron and octafluoro [2.2 paracyclophane for flurorinated perarylene polymer would be realized.2) Synthesis of optically active fluorinated amino acids Asymmetric reduction of imino group of 3, 3, 3-trifluoro-2-iminopropanoates was achieved by palladium catalyzed reduction in 3, 3, 3-trifluoroethanol which played an essentially important role for the asymmetric hydrogenation.Syntheses of perfluoroalkylated α-diimines, 2, 2, 3, 3,-tetrafluoro-1, 4-diketones and pinacols.Novel trifluoro- and perfluoroalkyl-α-diimines have been efficiently prepared by the palladium catalyzed coupling reaction of the corresponding imidoyl halides. The diimines could be a promising catalyst for polymerization of alkenes which would be studied in future. Likewise, difluoroenolsilyl ethers and trifluoromethyl ketones have been coupled by Cu (II) oxidation and Zn reduction, respectively.