- Self-Disproportionation of Enantiomers (SDE) via achiral gravity-driven column chromatography of N-fluoroacyl-1-phenylethylamines
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The study of the self-disproportionation of enantiomers (SDE) via gravity-driven achiral column chromatography of a series of N-fluoroacetylated amides derived from 1-phenylethylamine is described. The chromatographic experiments performed with N-fluoroacetylated amides confirmed, that the process of molecular association in solution leading to the SDE manifestation, is sensitive to the fluorine content and type of solvent used. Thus, the two opposite eluting profiles for the same compound were observed in two different eluents. Moreover, the amides bearing perfluoroalkyl groups showed opposite eluting order as compared to the established profile for fluorine-free N-acetyl-1-phenylethylamine.
- Wzorek, Alicja,Kamizela, Angelika,Sato, Azusa,Soloshonok, Vadim A.
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- Synthesis and properties of β-ethoxyvinyl polyfluoroalkyl ketones
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A number of β-ethoxyvinyl polyfluoroalkyl ketones were synthesized by acylation of ethyl vinyl ether with acid chlorides containing polyfluoroalkyl groups of different composition and structure. Some typical nucleophilic reactions of the title compounds with amines were carried out. Two new fluoro-containing pyrimidinoles were synthesized by the reaction of β- ethoxyvinyl polyfluoroalkyl ketones with urea.
- Gorbunova, Marine G.,Gerus, Igor I.,Kukhar, Valery P.
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p. 738 - 742
(2007/10/03)
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- Multiple pathways in cyclodextrin-catalyzed hydrolysis of perfluoroalkylamides
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The hydrolysis of p-nitroanilide of perfluoroalkanoic acids, CF3(CF2)nCO-, with n = 1, 2, 3, 5, 6, and 7, 1a-f, was studied in the presence of β-cyclodextrin (CD). All reactions were catalyzed by CD through the formation of a 1:1 and 1:2 inclusion complexes. The association equilibrium constants for the 1:1 complexes were dependent on the number of carbons of the fluoroalkyl chain, whereas those of the 1:2 complexes were almost independent. These results indicate that, in the former case, the perfluoroalkyl chain is included, while in the latter, the CD unit encloses the aryl ring. For compounds 1a,b both complexes were more reactive than the substrate itself. The ratio of the reaction of complexed to uncomplexed substrate had its highest value for 1a in the case of the 1:1 complex, and for 1b, the 1:2 complex. This is attributed to the geometry of the complexes. Although compounds 1c-e reacted at the same rates in the free or 1:1 complexed form, CD accelerated the reactions because of an increase of the pKa of the substrate, which results in a higher concentration of the neutral reactive substrate at the same pH. Compound 1f formed aggregates even at 10-6 M concentration, and CD-induced deaggregation resulted in catalysis of the reaction.
- Granados, Alejandro,De Rossi, Rita H.
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p. 3690 - 3696
(2007/10/02)
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- Process for omega-halo-perfluoro acid chlorides
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A liquid phase process for preparing ω-haloperfluoroacid chlorides by the photo oxidation of polyfluoroalkyl mono- and di-chloromethanes in the presence of chlorine using light wavelengths greater than 280 nm.
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- REGIOSPECIFIC PREPARATION OF α,α-DIHALOFLUOROMETHYL PERFLUOROALKYL KETONES.
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Acylation of F-phosphoranium salts with F-acyl chlorides gives the corresponding Z-perfluoro betaine in high yield.Subsequent chlorination or bromination regiospecifically yields the α,α-dihalofluoromethyl perfluoroalkyl ketones.
- Jeong, In Howa,Burton, Donald J.,Cox, Daryl G.
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p. 3709 - 3712
(2007/10/02)
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