Synthesis, properties, and reactivity of (1H,1H-perfluoroalkyl)-and (1H-perfluoro-1-alkenyl)aryliodonium triflates and their analogs.
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(1<I>H</I>,1<I>H</I>-Perfluoroalkyl)phenyl- and -(<I>p</I>-fluorophenyl)iodoniurn triflates, fluorosulfate, sulfate (<B>3</B>)–(<B>7</B>) were synthesized in good yields by the oxidation of 1-iodo-1<I>H</I>,1<I>H</I>-perfluoroalkanes (RfCH<SUB>2</SUB>I) with trifluoroperacetic acid followed by treatment with triflic acid and benzene or fluorobenzene. (1<I>H</I>,1<I>H</I>,5<I>H</I>,5<I>H</I>-Perfluoropentane-1,5-diyl)bisphenylbisiodonium triflate was synthesized similarly. (<I>trans</I>-1<I>H</I>-Perfluoro-1-alkenyl)phenyliodonium triflates (<B>11</B>) were synthesized by dehydrofluorination of <B>3</B> with a base in good yields. Thermolysis of <B>3</B> produced 1<I>H</I>,1<I>H</I>-perfluoroalkyl triflate and iodobenzene, while <B>11</B> gave (<I>Z</I>)-1-iodo-1<I>H</I>-perfluoro-1-alkene and phenyl triflate. The thermolysis experiment, including (perfluoroalkyl)phenyliodonium triflate (<B>17</B>), demonstrated that the C–I bond strength of the trivalent iodine compounds increased in the order of RfCH<SUB>2</SUB>–I, Rf–I<Ph–I<RfCF=CH–I. The ionic mechanism containing RfCH<SUB>2</SUB><SUP>+</SUP>, Ph<SUP>+</SUP>, and Rf<SUP>+</SUP> for the thermal decomposition of <B>3</B>, <B>11</B>, and <B>17</B>, respectively, was proposed. The reactivities of <B>3</B> and <B>11</B> to such nucleophiles as phenoxide, alkoxide, and alkanethiolate anions were studied and compared with that of <B>17</B>. Remarkable changes in the reactivity were found depending on the nature of the fluoro-alkyl and -alkenyl groups. The reaction of <B>11</B> with the oxide anions yielded (2-phenoxy- and -alkoxy-1<I>H</I>-perfluoro-1-alkenyl)phenyliodonium triflates.
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関連論文
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