氟代芳基碘化物和高价碘化合物的简便合成：可通过简单液/液双相后处理回收的ArI(L)n试剂及其在对苯二酚氧化反应中的应用
Convenient syntheses of fluorous aryl iodides and hypervalent iodine compounds: ArI(L)n reagents that are recoverable by simple liquid/liquid biphase workups, and applications in oxidations of hydroquinones.
作者信息
Rocaboy Christian, Gladysz John A
机构信息
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestrasse 42, 91054 Erlangen, Germany.
出版信息
Chemistry. 2003 Jan 3;9(1):88-95. doi: 10.1002/chem.200390034.
Iodinations of the ortho, meta, and para fluorous arenes (R(f8)CH(2)CH(2)CH(2))(2)C(6)H(4) (R(f8)=(CF(2))(7)CF(3)) with I(2)/H(5)IO(6) in AcOH/H(2)SO(4)/H(2)O give 3,4-(R(f8)CH(2)CH(2)CH(2))(2)C(6)H(3)I (5) and the analogous 2,4- (6) and 2,5- (7) isomers, respectively. Spectroscopic yields are >90 %, but 5 and 7 must be separated by chromatography from by-products (yields isolated: 70 %, 97 %, 61 %). Reaction of 1,3,5-(R(f8)CH(2)CH(2)CH(2))(3)C(6)H(3) with PhI(OAc)(2)/I(2) gives 2,4,6-(R(f8)CH(2)CH(2)CH(2))(3)C(6)H(2)I (8) on multigram scales in 97 % yield. The CF(3)C(6)F(11)/toluene partition coefficients of 5-8 (24 degrees C: 69.5:30.5 (5), 74.7:25.3 (6), 73.9:26.1 (7), 98.0:2.0 (8)) are lower than those of the precursors, but CF(3)C(6)F(11)/MeOH gives higher values (97.0:3.0 (5), 98.6:1.4 (6), 98.0:2.0 (7), >99.3:<0.3 (8)). Reactions of 5-8 with excess NaBO(3) in AcOH yield the corresponding ArI(OAc)(2) species 9-12 (9, 85 % as a 90:10 9/5 mixture; 10, 97 %; 11, 95 %; 12, 93 % as a 95:5 12/8 mixture). These rapidly oxidize 1,4-hydroquinones in MeOH. Subsequent additions of CF(3)C(6)F(11) give liquid biphase systems. Solvent removal from the CF(3)C(6)F(11) phases gives 5-8 in >99-98 % yields, and solvent removal from the MeOH phases gives the quinone products, normally in >99-95 % yields. The recovered compounds 5-8 are easily reoxidized to 9-12 and used again.
在醋酸/硫酸/水体系中，用碘/高碘酸（I₂/H₅IO₆）对邻、间、对氟代芳烃（R(f8)CH₂CH₂CH₂）₂C₆H₄（R(f8)=(CF₂)₇CF₃）进行碘化反应，分别得到3,4-(R(f8)CH₂CH₂CH₂)₂C₆H₃I（5）以及类似的2,4-（6）和2,5-（7）异构体。光谱产率大于90%，但5和7必须通过色谱法从副产物中分离出来（分离产率：70%、97%、61%）。1,3,5-(R(f8)CH₂CH₂CH₂)₃C₆H₃与醋酸碘苯（PhI(OAc)₂）/碘反应，能以97%的产率在多克规模上得到2,4,6-(R(f8)CH₂CH₂CH₂)₃C₆H₂I（8）。5 - 8在CF₃C₆F₁₁/甲苯中的分配系数（24℃：69.5:30.5（5），74.7:25.3（6），73.9:26.1（7），98.0:2.0（8））低于前体，但在CF₃C₆F₁₁/甲醇中则给出更高的值（97.0:3.0（5），98.6:1.4（6），98.0:2.0（7），>99.3:<0.3（8））。5 - 8与过量的硼酸钠（NaBO₃）在醋酸中反应，生成相应的ArI(OAc)₂物种9 - 12（9，85%，为90:10的9/5混合物；10，97%；11，95%；12，93%，为95:5的12/8混合物）。这些物质能在甲醇中快速氧化1,4 - 对苯二酚。随后加入CF₃C₆F₁₁得到液 -液相体系。从CF₃C₆F₁₁相中除去溶剂，以>99 - 98%的产率得到5 - 8，从甲醇相中除去溶剂，通常以>99 - 95%的产率得到醌类产物。回收的化合物5 - 8很容易再氧化为9 - 12并可再次使用。
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