83168-67-6Relevant articles and documents
Transformations of F-Alkyl Iodides and Bromides Induced by Nickel(0) Carbonyl
Krespan, Carl G.,Dixon, David A.
, p. 36 - 43 (2007/10/03)
Adducts of primary F-alkyl iodides with nickel carbonyl are formed readily in donor solvents and pyrolyze at 100-150 °C to give olefinic coupling products in high yield. The mechanism proposed to account for the observed chemistry involves preferential α-elimination of fluorine with formation of a carbenoid species complex coordinated to nickel. Differences in reaction paths among several types of substrate halides are rationalized on the basis of polarization of the Ni-C bond in the adducts. Support for these proposals is provided by state-of-the-art calculations.
Kinetic and Thermodynamic Studies of the Thermal Electrocyclic Interconversions of Perfluorinated Dienes and Cyclobutenes
Dolbier, Jr., William R.,Koroniak, Henryk,Burton, Donald J.,Heinze, Pamela L.,Bailey, A.R.,et al.
, p. 219 - 225 (2007/10/02)
Detailed kinetic and thermodynamic analyses were carried out for the thermal interconversions of (Z,Z)- and (E,E)-perfluoro-2,4-hexadienes with trans-perfluoro-3,4-dimethylcyclobutene, (E,Z)-perfluoro-2,4-hexadiene with perfluoro-cis-3,4-dimethylcyclobutene, (Z,Z)- and (E,E)-perfluoro-3,5-octadienes with trans-perfluoro-3,4-diethylcyclobutene, and (Z)- and (E)-perfluoro-1,3-pentadiene with perfluoro-3-methylcyclobutene.In each case the (Z,Z)- or (Z)-dienes exhibited substantial kinetic advantage over the (E,E)-or (E)-dienes in their cyclization precesses.
REACTION OF 3-CHLORONONAFLUORO-1,5-HEXADIENE WITH SODIUM CYANIDE
Linhart, Igor,Dedek, Vaclav
, p. 1737 - 1744 (2007/10/02)
3-Chlorononafluoro-1,5-hexadiene (I) is isomerized into 6-chlorononafluoro-1,4-hexadiene (II) by action of basic catalysts as sodium cyanide in anhydrous dimethylformamide, lithium chloride in dimethylformamide, and triethylamine in dioxane or dimethylformamide.Sodium cyanide also catalyzes addition of methanol to the chlorodiene I.The reaction course is more complex than in the alkoxide-catalyzed addition of primary alcohols to I. 6-Methoxynonafluoro-1,4-hexadiene (III), methyl perfluoro-3,6-heptadienoate (VII), and 3,6-dimethoxy-1,1,2,3,4,4,5,6,6-nonafluoro-1-hexene (VIII) have been isolated besides the known products 1,6-dimethoxy-1,1,2,3,4,5,6,6-octafluoro-2,4-hexadiene (IV) and 1,6-dimethoxy-1,1,2,3,4,4,5,6,6-nonafluoro-2-hexene (V).The hexene VIII reacts with sodium methoxide in methanol to give the diether V, and with lithium chloride in dimethylformamide it gives 1-chloro-6-methoxy-1,1,2,3,4,4,5,6,6-nonafluoro-2-hexene (IX).Stereospecificity and mechanism of the reaction are discussed.