The Key Laboratory for Special Functional Materials, Ministry of Education, Henan University, Kaifeng, Henan, 475-004, China.
Dalton Trans. 2010 Nov 7;39(41):9823-9. doi: 10.1039/c0dt00539h. Epub 2010 Sep 22.
Alcohols 8 bearing two identical perfluoroalkyl groups were prepared by the reaction of the corresponding perfluoroalkyl phenyl ketones 7 with 0.5 equivalents of t-BuOK via Cannizzaro-type disproportionation. Utilizing the new bulky bidentate ligand with two n-C(3)F(7) groups generated from 8c, anti-apicophilic phosphorane 5a and its stable isomer 6a were synthesized. The crystal structures of 5a and 6a were slightly affected by the steric repulsion of heptafluoropropyl groups. Kinetic studies on the isomerization of 5a to 6a showed that the new ligand was effective for decreasing the isomerization rate compared with its C(2)F(5) analog 3a to about half.
通过相应的全氟烷基苯乙酮 7 与 0.5 当量的叔丁醇钾在 Cannizzaro 型歧化反应，制备了带有两个相同全氟烷基的醇 8。利用从 8c 生成的具有两个 n-C(3)F(7)基团的新型大位双齿配体，合成了反-apicophilic 膦 5a 和其稳定的异构体 6a。5a 和 6a 的晶体结构受到七氟丙基基团的空间位阻的轻微影响。对 5a 到 6a 的异构化动力学研究表明，与 C(2)F(5)类似物 3a 相比，新型配体对于降低异构化速率是有效的，大约降低了一半。
