The reaction of perfluoroalkyliodides,perfluoroalkylbromide,1,1, 1-trifluoro-2,2,2-trichloro-ethane,and carbon tetrachloride with thiourea dioxide in aqueous acetonitrile solution gave the corresponding sulfinate in g...The reaction of perfluoroalkyliodides,perfluoroalkylbromide,1,1, 1-trifluoro-2,2,2-trichloro-ethane,and carbon tetrachloride with thiourea dioxide in aqueous acetonitrile solution gave the corresponding sulfinate in good yield.展开更多
The sulfinatodehalogenation reaction of α,α-difluorobenzyl handes, ArCF_2X (Ar = CAFS, C_6H_5; X = Br, I ), with sodium dithionite took place readily in aqueous acetonitrile under mild conditions. giving the corresp...The sulfinatodehalogenation reaction of α,α-difluorobenzyl handes, ArCF_2X (Ar = CAFS, C_6H_5; X = Br, I ), with sodium dithionite took place readily in aqueous acetonitrile under mild conditions. giving the corresponding sodium sulfinate. The 1: 1 adducts were obtained when alkenes were added to the reaction system in some cases.展开更多
A novel simple bromodifluoromethylation method by the addition of CF_2Br_2 to alkenes initiated by sulfinatodehalogenation reagents under mild conditions is described.
Sodium dithionite-initiated addition of R_FI(1)[R_F.=1a,Cl(CF_2)_4;1b,Cl(CF_2)_6;1c, Cl(CF_2)_6;1d,n-C_6F_(13);1e,n-C_8F_(17)]to the properly protected glucose derivatives 2,9,12 and 15 gave polyfluoroalkylated glucos...Sodium dithionite-initiated addition of R_FI(1)[R_F.=1a,Cl(CF_2)_4;1b,Cl(CF_2)_6;1c, Cl(CF_2)_6;1d,n-C_6F_(13);1e,n-C_8F_(17)]to the properly protected glucose derivatives 2,9,12 and 15 gave polyfluoroalkylated glucose derivatives 7,11,14 and 17 respectively in good yields after reduction and deprotection.These compounds are strongly surface active.展开更多
Treatment of difluorodiiodomethane with N sodium salts of imidazoles at -15 ℃ gave N difluoroiodomethylated imidazoles (3) in good yields. The addition of 3 to alkyne or alkenes initiated by sodium dithiona...Treatment of difluorodiiodomethane with N sodium salts of imidazoles at -15 ℃ gave N difluoroiodomethylated imidazoles (3) in good yields. The addition of 3 to alkyne or alkenes initiated by sodium dithionate at room temperature resulted in the corresponding adducts in high yields.展开更多
The study on the factors influencing sulfinatodehalogenation of perfluorohexyl chloride plus octene-1 by using Na2S2O4/NaHCO3 discovered that among the various solvents tested (e.g. Me2SO, NMP, DMAc, CH3CN, CH3CN/H2O)...The study on the factors influencing sulfinatodehalogenation of perfluorohexyl chloride plus octene-1 by using Na2S2O4/NaHCO3 discovered that among the various solvents tested (e.g. Me2SO, NMP, DMAc, CH3CN, CH3CN/H2O) at different temperatures, Me2SO was found to be the most suitable solvent and the conversion of the chloride was very dependent on the reaction temperature. When Me2SO was used in the reaction of perfluoroalkyl iodides, the reaction temperature could be decreased by 20 ℃ as compared with that carried out in CH3CN/H2O to reach the comparable yields.展开更多
Without oxidant, sodium bisulfite reacted with polyfluoroalkyl iodides and bromides in aqueous DMF solution to give the corresponding sulfinates in good yields.
Polyfluoroalkyl iodides, such as Cl(CF2)nI(n=4, 6, 8, 1b-1d) and F(CF2)nI (n=6, 8,1e-1f) reacted with sodium sulfite in neutral aqueous DMF solution to give the corresponding sulfinates Cl(CF2)nSO2Na (n=4, 6, 8, 2b-2d...Polyfluoroalkyl iodides, such as Cl(CF2)nI(n=4, 6, 8, 1b-1d) and F(CF2)nI (n=6, 8,1e-1f) reacted with sodium sulfite in neutral aqueous DMF solution to give the corresponding sulfinates Cl(CF2)nSO2Na (n=4, 6, 8, 2b-2d) and F(CF2)nSO2Na (n=6, 8, 2e-2f) in moderate yields. I(CF2)2O(CF2)2SO2F ( la ) reacted under the same condition to give 3-oxa-octafluoropentane-1,5-disulfinates (2a).展开更多
The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dia...The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dialkylanilines,2,5-dimethylpyrrole,N-methylpyrrole initiated by Na_2S_2O_4- NaHCO_3 gave the corresponding perfluoroalkylated products in moderate to good yields.展开更多
The reaction of perfluoroalkyl iodide or perfluoroalkyl bromide with sulfite radical anion (SO_3^-)generated from sodium bisulfite/potassium ferricyanide in water/DMF at 70—75°C gave the corresponding perfluoroa...The reaction of perfluoroalkyl iodide or perfluoroalkyl bromide with sulfite radical anion (SO_3^-)generated from sodium bisulfite/potassium ferricyanide in water/DMF at 70—75°C gave the corresponding perfluoroalkanesulfinate ia good yield.Furthermore,it was shown that the reagent system can also initiate the addition of perfluoroalkyl iodide to olefins or alkynes at 50—65℃.展开更多
Polyfluoroalkyl iodides reacted with olefins in aqueous DMF solution of sodium disulfite under mild conditions to give the corresponding 1:1 adducts in good yields,providing a convenient polyfluoroalkylation method.Th...Polyfluoroalkyl iodides reacted with olefins in aqueous DMF solution of sodium disulfite under mild conditions to give the corresponding 1:1 adducts in good yields,providing a convenient polyfluoroalkylation method.This indicated that R_F radicals were formed in the reaction of polyfluoroalkyl iodides and sodium disulfite.A SET mechanism is proposed for the sulfinatodehalogenation reaction of sodium disulfite.展开更多
Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new metho...Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same con- dition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction.展开更多
An efficient, highly selective method for polyfluoroalkylation of 2-aminothiazole derivatives was described. Specifically, a di-polyfluoroalkylated derivative was produced when 2-amino-4-chloromethylthiazole was react...An efficient, highly selective method for polyfluoroalkylation of 2-aminothiazole derivatives was described. Specifically, a di-polyfluoroalkylated derivative was produced when 2-amino-4-chloromethylthiazole was reacted with perfluoroalkyl iodides under very mild conditions.展开更多
文摘The reaction of perfluoroalkyliodides,perfluoroalkylbromide,1,1, 1-trifluoro-2,2,2-trichloro-ethane,and carbon tetrachloride with thiourea dioxide in aqueous acetonitrile solution gave the corresponding sulfinate in good yield.
基金the National Natural Science Foundation of China ! 29772041.29632003
文摘The sulfinatodehalogenation reaction of α,α-difluorobenzyl handes, ArCF_2X (Ar = CAFS, C_6H_5; X = Br, I ), with sodium dithionite took place readily in aqueous acetonitrile under mild conditions. giving the corresponding sodium sulfinate. The 1: 1 adducts were obtained when alkenes were added to the reaction system in some cases.
文摘A novel simple bromodifluoromethylation method by the addition of CF_2Br_2 to alkenes initiated by sulfinatodehalogenation reagents under mild conditions is described.
基金This work was partially supported by the National Natural Science Foundation of China.
文摘Sodium dithionite-initiated addition of R_FI(1)[R_F.=1a,Cl(CF_2)_4;1b,Cl(CF_2)_6;1c, Cl(CF_2)_6;1d,n-C_6F_(13);1e,n-C_8F_(17)]to the properly protected glucose derivatives 2,9,12 and 15 gave polyfluoroalkylated glucose derivatives 7,11,14 and 17 respectively in good yields after reduction and deprotection.These compounds are strongly surface active.
文摘Treatment of difluorodiiodomethane with N sodium salts of imidazoles at -15 ℃ gave N difluoroiodomethylated imidazoles (3) in good yields. The addition of 3 to alkyne or alkenes initiated by sodium dithionate at room temperature resulted in the corresponding adducts in high yields.
文摘The study on the factors influencing sulfinatodehalogenation of perfluorohexyl chloride plus octene-1 by using Na2S2O4/NaHCO3 discovered that among the various solvents tested (e.g. Me2SO, NMP, DMAc, CH3CN, CH3CN/H2O) at different temperatures, Me2SO was found to be the most suitable solvent and the conversion of the chloride was very dependent on the reaction temperature. When Me2SO was used in the reaction of perfluoroalkyl iodides, the reaction temperature could be decreased by 20 ℃ as compared with that carried out in CH3CN/H2O to reach the comparable yields.
文摘Without oxidant, sodium bisulfite reacted with polyfluoroalkyl iodides and bromides in aqueous DMF solution to give the corresponding sulfinates in good yields.
文摘Polyfluoroalkyl iodides, such as Cl(CF2)nI(n=4, 6, 8, 1b-1d) and F(CF2)nI (n=6, 8,1e-1f) reacted with sodium sulfite in neutral aqueous DMF solution to give the corresponding sulfinates Cl(CF2)nSO2Na (n=4, 6, 8, 2b-2d) and F(CF2)nSO2Na (n=6, 8, 2e-2f) in moderate yields. I(CF2)2O(CF2)2SO2F ( la ) reacted under the same condition to give 3-oxa-octafluoropentane-1,5-disulfinates (2a).
基金the National Natural Science Foundation of China.Part ⅩⅩⅢ in this series,see Huang,W.-Y.Zhuang,J.-L.,Chinese J.Chem.,9,270 (1991).
文摘The application ot the sulfinatodehalogenation reaction system for the perfluoroalkylation of electron-rich aromatics is further studied.It was shown that perfluoroalkyl iodides reacted with polyhydric phenols,N,N-dialkylanilines,2,5-dimethylpyrrole,N-methylpyrrole initiated by Na_2S_2O_4- NaHCO_3 gave the corresponding perfluoroalkylated products in moderate to good yields.
基金This work was partially supported by the National Natural Science Foundation of China.
文摘The reaction of perfluoroalkyl iodide or perfluoroalkyl bromide with sulfite radical anion (SO_3^-)generated from sodium bisulfite/potassium ferricyanide in water/DMF at 70—75°C gave the corresponding perfluoroalkanesulfinate ia good yield.Furthermore,it was shown that the reagent system can also initiate the addition of perfluoroalkyl iodide to olefins or alkynes at 50—65℃.
文摘Polyfluoroalkyl iodides reacted with olefins in aqueous DMF solution of sodium disulfite under mild conditions to give the corresponding 1:1 adducts in good yields,providing a convenient polyfluoroalkylation method.This indicated that R_F radicals were formed in the reaction of polyfluoroalkyl iodides and sodium disulfite.A SET mechanism is proposed for the sulfinatodehalogenation reaction of sodium disulfite.
文摘Reaction of perfluoroalkyl iodides with a series of alkynes under sulfinatodehalogenation condition gave a mixture of E/Z adducts very readily in high yield, thus constituted a mild, convenient and effective new method for the addition of perfluoroalkyl iodides to alkynes. Under the same con- dition, in the presence of 1-hexyne perfluoroalkyl bromide and 1,1,1-trichlorotrifluoroethane reacted only to give sulfinates as the major products. A radical mechanism was proposed for the addition reaction.
基金Project supported by special Fund for Agro-scientific Research in the Public Interest （No. 201103007）, the National Key Technologies R＆D Program （No. 2011BAE06B05）, National Basic Research Program of China （No. 2010CB126103）, the Key Program of National Natural Science Foundation of China （No. 21032006） and SIOC startup fund.
文摘An efficient, highly selective method for polyfluoroalkylation of 2-aminothiazole derivatives was described. Specifically, a di-polyfluoroalkylated derivative was produced when 2-amino-4-chloromethylthiazole was reacted with perfluoroalkyl iodides under very mild conditions.
