Synthesis of fluorinated telomers. Part 4. Telomerization of vinylidene fluoride with commercially available α,ω-diiodoperfluoroalkanes
作者:Abdellatif Manséri、Bruno Améduri、Bernard Boutevin、Richard D. Chambers、Gerardo Caporiccio、Anthony P. Wright
DOI:10.1016/0022-1139(95)03245-9
日期:1995.9
The synthesis of a new fluorinated αω-diiodo telomerI[(TFE)(VDF),]I (A), where TFE and VDF represent tetrafluoroethylene and vinylidene fluoride respectively, has been carried out by telomerization of VDF with αω-diiodoperfluoroalkanes. The thermal telomerization of VDF with 1,2-diiodoperfluoroethane IC2 F4I led to good yields of the monoadduct IC2F4CH2CF2I and of the diadduct which was composed of
通过用αω-二碘全氟代烷烃将VDF端粒化,可以合成新的氟化αω-二碘端粒I [(TFE)(VDF),] I(A),其中TFE和VDF分别代表四氟乙烯和偏二氟乙烯。VDF与1,2-二碘全氟乙烷IC 2 F 4 I的热端聚反应导致单加合物IC 2 F 4 CH 2 CF 2 I和由几乎等摩尔的ICF 2 CH 2 C组成的二加合物的良率2 F 4 CH 2 CF 2 I和IC 2 F 4(CH 2CF 2)2 I,以及少量的IC 2 F 4 CH 2 CF 2 CF 2 CH 2 I和包含I(VDF)C 2 F 4(VDF)2 I和IC 2 F 4(VDF)的三加合物3。该方法已成功应用于αω-二碘正n-全氟丁烷和α,ω-二碘正n-全氟己烷。已经研究了VDF相对于氟化的α,ω-二碘代telogens的反应性,结果表明,telogen末端基团的环境是影响反应性的主要因素。
Unexpected telomerization of hexafluoropropene with dissymetrical halogenated telechelic telogens
The synthesis of new fluorinated α,ω-diiodo telomersI(TFE)x(VDF)y(HFP)zI (A) where TFE, VDF and HFP represent tetrafluoro-ethylene, vinylidene fluoride and hexafluoropropene, respectively, was carried out by thermal telomerization of HFP with VDF oligomers, I(TFE)x(VDF)yI, as transfer agents. Compound A was obtained in 55% yield when x = y = 1, whereas almost no reaction occurred when x = 1 and y
合成新的氟化α,ω-二碘代端粒I(TFE)x(VDF)y(HFP)z I (A),其中TFE,VDF和HFP分别代表四氟乙烯,偏二氟乙烯和六氟丙烯用VDF低聚物I(TFE)x(VDF)y I作为转移剂对HFP进行热端聚。当x = y = 1时,化合物A的产率为55%,而当x = 1和y = 2时,几乎没有反应发生。有趣的是,HFP与IC 2 F 4 CH 2 CF 2 ·选择性反应,而不与ICF反应2 CH 2 CF 2 CF 2 ·,而从IC 4 F 8 CH 2 CF 2 I,可以在两个端基上引入HFP,但是产生的I(TFE)2(VDF)(HFP)I的量更高。将HFP的反应性与VDF的反应性与氟化的α,ω-二碘化的端基发生了反应,并将其表明端基中末端CI键的环境会影响反应的方向。
Synthèse de diènes téléchéliques à partir d' α,ω-diiodo-alcanes fluorés Partie II: Divinyls et diallyls présentant des motifs constitutifs tétrafluoroéthylène, fluorure de vinylidène et hexafluoropropène
Synthesis of new fluorinated non-conjugated dienes containing tetrafluoroethylene, vinylidene fluoride (VDF) and/or hexafluoropropene from alpha,omega-diiodofluorinated cotelomers was carried out by two methods in two steps. Divinyl monomers were obtained by alpha,omega-bis ethylenation of these cotelomers followed by a bis-dehydroiodination in medium yields which were lower when the cotelomers contained the VDF base unit. Diallylic olefins were produced by addition of these alpha,omega-diiodofluoroalkanes to allyl acetate followed by a 'deiodoacetatization' in high yields. Each telechelic diene was carefully characterized by H-1 and F-19 NMR.