- Reaction of Perfluoroalkyl Iodides with Electron-Deficient Olefins under UV Irradiation
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The reaction of perfluoroalkyl iodides 1 with acrylates, acrylic acid, acrylamide, and acrylonitrile has been investigated.In the presence of a catalytic amount of palladium(0), the reaction of Rf with ethyl acrylate produces mostly polymer.Under irradiation with 254 nm UV light, perfluoroalkyl iodides react with ethyl acrylate to give high yields of the 1:1 addition products (74-88percent isolated yield, CnF(2n+1)CH2CHICO2Et) and small amounts of 1:2 adducts ( are formed when methyl acrylate reacts with short-chain perfluoroalkyl iodides , whereas the reaction of perfluorohexyl or longer chain perfluoroalkyl iodides /= 6> gives predominantly the 1:1 addition products (>85percent).The formation of the 1:2 adduct can be efficiently suppressed by using excess RfI in the reaction.The reaction of N,N-dimethylacrylamide with perfluoropropyl iodide (1a) produces exclusively the 1:1 adduct.Products from the further elimination, reduction, and decarboxylation of the 1:1 and 1:2 adducts are observed when 1a reacts with methyl methacrylate under similar conditions.The reaction of 1a with acrylonitrile produces the 1:1 and 1:2 adducts in 53percent and 74percent yields, respectively.An addition-reduction product, n-C3H7CH2CH2CO2H (68percent), is obtained in the reaction of acrylic acid with 1a.
- Qiu, Zai-Ming,Burton, Donald J.
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- Synthesis of Amino Acids with Modified Principal Properties 1. Amino Acids with Fluorinated Side Chains
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The synthesis and characterization of chiral fluorinated analogues of norvaline and norleucine from commercially available starting materials are presented.Full experimental details for the synthesis of the following amino acids are given: (S)-4,4-difluoronorvaline, (S)-4,4,5,5,5-pentafluoronorvaline, (S)-5,5-difluoronorleucine, (S)-5,5,6,6,6-pentafluoronorleucine, and (S)-4,4,5,5,6,6,6-heptafluoronorleucine.These compounds were prepared with a view to obtaining new amino acids which possess physical and chemical properties so that their principal properties would be outside the range of variation of hitherto known amino acids.The principal properties are determined as latent variables in principal component analysis of molecular property descriptors.Two of the fluorinated amino acids, (S)-5,5,6,6,6-pentafluoronorleucine and (S)-4,4,5,5,6,6,6-heptafluoronorleucine were found to have principal properties outside the variation of previously characterized natural and synthetic amino acids.The principal properties, z parameters, for the five new fluorinated amino acids are given.
- Larsson, Ulf,Carlson, Rolf,Leroy, Jacques
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p. 380 - 390
(2007/10/02)
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