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将PH₃添加到式为H₂C=CH(CH₂)ₓ(CF₂)ᵧCF₃的单取代烯烃中：便捷的多克规模合成具有可调电子性质和氟相亲和力的部分氟化三烷基膦家族。

Additions of PH(3) to Monosubstituted Alkenes of the Formula H(2)C=CH(CH(2))(x)()(CF(2))(y)()CF(3): Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities.

作者信息

Alvey Luke J., Rutherford Drew, Juliette Jerrick J. J., Gladysz J. A.

机构信息

Department of Chemistry, University of Utah, Salt Lake City, Utah 84112.

出版信息

J Org Chem. 1998 Sep 4;63(18):6302-6308. doi: 10.1021/jo980692y.

DOI:10.1021/jo980692y
PMID:11672263
Abstract

Reactions of PH(3) and commercially available H(2)C=CHR(f) (R(f6)(/)(8)(/)(10) = (CF(2))(5)CF(3)/(CF(2))(7)CF(3)/(CF(2))(9)CF(3)) give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80-90 degrees C), the phosphines P(CH(2)CH(2)R(f))(3) (1-3; 63-75%). Analogous reactions with H(2)C=CHCH(2)R(f8) (7) and H(2)C=CHCH(2)CH(2)R(f8) (10) give P(CH(2)CH(2)CH(2)R(f8))(3) (4, 73%) and P(CH(2)CH(2)CH(2)CH(2)R(f8))(3) (5, 66%), in which the phosphorus is increasingly insulated from the electronegative R(f) moiety. The alkenes 7 and 10 are prepared from Bu(3)SnCH(2)CH=CH(2) and IR(f8) (hnu, CH(2)Cl(2), 81%) or ICH(2)R(f8) (VAZO, refluxing CF(3)C(6)H(5), 56%). The reaction of 1 and H(2)O(2) gives O=P(CH(2)CH(2)R(f6))(3) (6, 88%), which can be reduced with HSiCl(3) to 1. Partition coefficients (CF(3)C(6)F(11)/toluene, 27 degrees C) range from 98.8:1.2 (1, 4) through 98.9:1.1 (5) to >99.7:<0.3 (2, 3, 6). Crystals of 4 diffract poorly, but a packing motif that maximizes interactions between R(f) segments is evident.

摘要

在自由基引发剂（偶氮二异丁腈、VAZO；80 - 90℃）存在下分两步进行的反应中，PH(3) 与市售的 H(2)C=CHR(f)（R(f6)(/)(8)(/)(10) = (CF(2))(5)CF(3)/(CF(2))(7)CF(3)/(CF(2))(9)CF(3)）反应生成膦 P(CH(2)CH(2)R(f))(3)（1 - 3；产率 63 - 75%）。与 H(2)C=CHCH(2)R(f8)（7）和 H(2)C=CHCH(2)CH(2)R(f8)（10）的类似反应分别生成 P(CH(2)CH(2)CH(2)R(f8))(3)（4，产率 73%）和 P(CH(2)CH(2)CH(2)CH(2)R(f8))(3)（5，产率 66%），其中磷与电负性的 R(f) 部分的隔离程度逐渐增加。烯烃 7 和 10 由 Bu(3)SnCH(2)CH=CH(2) 与 IR(f8)（光照，二氯甲烷，产率 81%）或 ICH(2)R(f8)（VAZO，三氟甲苯回流，产率 56%）制备。1 与 H(2)O(2) 反应生成 O=P(CH(2)CH(2)R(f6))(3)（6，产率 88%），它可用 HSiCl(3) 还原为 1。分配系数（三氟甲基全氟十一烷/甲苯，27℃）范围从 98.8:1.2（1，4）到 98.9:1.1（5）再到 >99.7:<0.3（2，3，6）。4 的晶体衍射效果不佳，但能明显看出一种使 R(f) 链段间相互作用最大化的堆积模式。

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