THE CONDENSATION REACTION OF BIS(PERFLUOROALKANESULFONYL)METHANES WITH AROMATIC ALDEHYDES

The ccndensation reactions occurred when heating bis(perfluoroalkane- sulfonyl)methanes with aromatic aldehydes in acetic acid anhydride and gave high yields of 1-aryl-2,2-di(perfluoroalkanesulfonyl)ethylenes The perfluoroalkanesulfonyl groups R_FSO_2 are known as the strongest electron-attracting substituents^(1-2).This property is often used in the activation of C-C multiple and 2,2'-C-H bonds.The synthesis and reactions of perfluoroalkanesulfonyl substituted alkenes and alkynes are of great interest in synthetic organic chemistry^(3-6). Recently,Hanack^7 reported the preparation of 2-aryl-l-(perfluoroalkane- sulfonyl)acrylonitrile R_FSO_2C(CN)=CHAr.However,he failed to obtain the 1,1-di(perfluoroalkanesulfonyl)alkenes by the Knoevenagel reaction of bis(perfluoroalkanesulfonyl)methane with aldehydes.

PERFLUOROALKANESULFONYL IODIDE GENERATED FROM THE REACTION OF PERFLUOROALKANESULFINATE SALT WITH IC1

The reaction between perfluoroalkanesulfinate salts(1)[R_fSO_2M R_f=a,Cl(CF_2)_4;b,Cl(CF_2)_6;c,Cl(CF_2)8;d,n-C_6F_(13);e,n-C_8F_(17);M-Na;K; Hg(I)]and iodine monochloride in dichloromethane at low temperature(e.g. -30--50℃)resulted in the formation of the corresponding perfluoroalkane- sulfonyl iodides(2),which were identified by their 19_F NMR spectra.The perfluoroalkanesulfonyl iodides generated in situ reacted smoothly with olefins to forum 1:1 adducts with good yields.Thus,these reactions provide another method for the synthesis of the very unstable perfluoroalkanesulfonyl iodide.

Reaction of perfluoroalkanesulfonyl halide——3. The reactions of perfluoroalkanesulfonyl bromide with α,β-un-saturated esters and chemical conversions of the products

The reactions of perfluoroalkanesulfonyl bromide with a,β-unsaturated esters were studied in detail. The reaction products were further converted to a series of perfluoroalkyl-substituted a, β-unsaturated acids or esters, a-amino acids and γ-lactones. A peculiar peak (M+15)was found to appear in the mass spectra of some perfluoroalkyl-substituted methyl esters. It was interpreted to be the result of a CH_3 group transfer to the molecular ion. Magnetic nonequivalence was observed in the ^(19)F NMR spectra of CF_2 group linked to CH_2 in compounds 2t, g and 3t', g which showed a typical AB pattern, and was attributed to the effect of steric hindrance.

The reaction of perfluoroalkanesulfonyl halides Ⅷ. A mild method for introducing BrCF_2 group to organic molecules

BrCF_2SO_2Br, prepared from sulfinatodehalogenation of CF_2Br_2 followed by bromination of the intermediate BrCF_2SO_2Na, was shown to be a mild and efficient bromodifluoromethylating agent.

The reaction of perfluoroalkanesulfonyl halides Ⅶ. Preparation and reactions of trifluoromethanesulfonyl bromide

The reaction between sodium trifluoromethanesulfinate, which was prepared from trifluorome- thyl bromide, with bromine in aqueous solution resulted in the formation of trifluoromethanesulfonyl bromide (CF_3SO_2Br). CF_3SO_2Br reacted with alkenes and alkyne to give the corresponding adducts with the loss of SO_2 in good yields, and with compounds containing active hydrogen to give brominated derivatives. A radical reaction mechanism was proposed and confirmed by EPR study.

含氟活泼亚甲基类化合物的研究

本研究工作包括下列三个方面的内容 :(1)双 - (全氟烷砜基 )甲烷 ,双 - (三氟乙酰基 )甲烷的合成及其反应 .(2 ) 2 氟烷基取代的醛和酮的合成和反应 .(3)氟烷基取代的 1,3 二羰基化合物的化学转化及其在合成含氟杂环化合物中的应用 .

全氟烷基磺酰卤化学

本文介绍了全氟烷基磺酰卤化学的现状和进展,并对全氟烷基磺酰氟、磺酰氯、磺酰溴、磺酰碘的制备,特性,反应性及应用作了比较与论述,得到了一定的规律性。