66291-47-2

Downstream Products

• 114614-85-6 (E)-dec-1-en-1-ylcyclohexan 
• 4084-07-5 1-butyldecene 

Relevant academic research and scientific papers

Vinylic SN2 Reaction of 1-Decenyliodonium Salt with Halide Ions

Reactions of (E)-1-decenyl(phenyl)iodonium salt with halide ions are examined under various conditions. The products are those of substitution and elimination, usually (Z)-1-halo-1-decene and 1-decyne, as well as iodobenzene, except for the reaction with fluoride which leads exclusively to elimination. The labeling experiments show that the elimination induced by fluoride occurs via an α mode, while that caused by the other halides is a syn β elimination. Kinetic results show that the substitution and β elimination occur mainly from the halo-λ3 -iodane intermediate; the substitution occurs as a bimolecular reaction with the external halide ion while the elimination is a unimolecular (intramolecular) reaction. The imermediacy of the hypervalent λ3-iodane as well as of the iodate are also confirmed by UV spectroscopy. The secondary kinetic isotope effects, leaving group substituent effects, and pressure effects on the rate are compatible with the in-plane vinylic SN2 mechanism for the substitution with inversion. Some retained substitution product, (E)-1-halo-1-decene, is formed in polar protic solvents like trifluoroacetic acid, formic acid, and 1,1,1,3,3,3-hexafluoro-2-propanol. The reaction is very slow in these solvents and no sign of formation of ionic intermediates is found. This slow substitution with retention is considered to occur via ligand coupling within the halo-λ3-iodane intermediate.

In-plane vinylic S(N)2 substitution and intramolecular β elimination of β-alkylvinyl(chloro)-λ3-iodanes

The reactions of four (E)-β-alkylvinyl(phenyl)iodonium salts with chloride ion were examined in acetonitrile and in several other solvents at 25°C. The β-methyl-, β-octyl-, and β-isopropyl-substituted iodonium salts undergo competitive bimolecular nucleophilic substitution to form the corresponding (Z)-1-chloro-1-alkene with inversion of configuration at the vinylic carbon and elimination to form the 1-alkyne. The β-tert-butyl-substituted iodonium salt affords only the products of the elimination reaction. The UV absorption spectra of the reactants show the rapid coversion of chloride and iodonium ions to an equilibrium mixture of the corresponding chloro-λ3-iodane, with an association constant of 5600-7600 mol-1 dm3. A kinetic analysis shows that most of the substitution and elimination products form from reaction of the λ3-iodane. Evidence is presented that the substitution reaction proceeds by a concerted bimolecular S(N)2 mechanism and that the elimination reaction proceeds by a unimolecular reaction mechanism with intramolecular transfer of the β-proton to the leaving group.