1146953-83-4Relevant academic research and scientific papers
Synthesis and reactivity of fluorous and nonfluorous aryl and alkyl iodine(III) dichlorides: New chlorinating reagents that are easily recycled using biphasic protocols
Podgorsek, Ajda,Jurisch, Markus,Stavber, Stojan,Zupan, Marko,Iskra, Jernej,Gladysz, John A.
experimental part, p. 3133 - 3140 (2009/08/15)
Fluorous aryl and alkyl iodine(III) dichlorides of the formulas (R fn(CH2)3)2C6H 3ICl2 (Rfn ) CF3(CF 2)n-1; n ) 8 for 3,5-disubstituted and n ) 6, 8, 10 for 2,4-disubstituted) and RfnCH2ICl2 (n ) 8, 10) are prepared in 71-98% yields by reactions of Cl2 and the corresponding fluorous iodides. These are effective reagents for the conversions of cyclooctene to trans-1,2-dichlorocyclooctene, anisole to 4-chloro- and 2-chloroanisole, 4-tert-butylphenol to 2-chloro-4-tert-butylphenol, PhCOCH 2COPh to PhCOCHClCOPh, and PhCOCH3 to PhCOCH2Cl and PhCOCHCl2 (CH3CN, rt to 40°C, 100-64% conversions). The chlorinated products and fluorous iodide coproducts are easily separated by organic/fluorous liquid/liquid biphase workups. The latter are obtained in 97-90% yields and reoxidized with Cl2. Analogous chlorinations are conducted with 3-Cl2IC6H4COOH (16) and 4,4'-Cl2IC6H4C6H 4ICl2. With the former, the products and coproduct 3-IC6H4COOH (91-85% recoveries) are easily separated by organic/aqueous NaHCO3 liquid/ liquid biphase workups. The coproduct from the latter, 4,4'-IC6H4C6H4I, is insoluble in common organic solvents, allowing separation by liquid/solid phase workups (91-89% recoveries). The effect of the structure of the iodine(III) dichloride upon reactivity is analyzed in detail. The fluorous systems with Rf8 substituents are generally superior, but 16 is more reactive and gives higher selectivities.
