Search results for "Carbocation"
showing 10 items of 17 documents
ISomerization of xylene: MINDO/3 study of the cyclization of benzenium cation into bicyclo[3.1.0]hexenyl cation
1989
Abstract A MINDO/3 study of thermal electrocyclic closing of the benzenium cation to form a bicyclo[3.1.0]hexenyl cation is presented. The calculated mechanism discusses the possibility of cyclization of xylenium cations on a silica catalyst or in superacid media. The structure and energy of the transition state, the enthalpies of isomerization and barriers of activation were calculated for the following processes: isomerization of 2,6-dimethylbenzenium cation into 2,6-dimethylbicyclo[3.1.0]hexenyl cation, isomerization of 2,4-dimethylbenzenium cation into 2,4-dimethylbicyclo[3.1.0]-hexenyl cation, and isomerization of benzenium cation into bicyclo[3.1.0]-hexenyl cation. Equilibrium and kin…
ChemInform Abstract: Synthesis of Sesquiterpenes via Silicon-Guided Rearrangement of Epoxydecalins
2009
A survey of the rearrangement of methyldecalins via C-5 carbocation intermediates, with special attention to the silicon-guided rearrangement of epoxydecalins is provided. A TMS group properly posi...
Silicon guided rearrangement of epoxydecalines to spirocyclic compounds. Synthesis of gleenol and axenol from carvone
2005
Abstract The synthesis of the spirocyclic sesquiterpenes (−)-gleenol and (−)-axenol in enantiomerically pure form has been achieved starting from R-(−)-carvone. The key step is the silicon guided acid-promoted rearrangement of a 9-trimethylsilyl-5,6-epoxy-noreudesmane prepared from 3-trimethylsilyldihydrocarvone in several steps involving Robinson annulation, enone deconjugation and epoxidation. Acid treatment of the epoxy-noreudesmane gave a norspiroaxane as the main product, which was used as intermediate for the synthesis of two naturally occurring sesquiterpenes gleenol and axenol.
Methylium Ions with OPV Chains − New NIR Dyes
2001
Carbinols, which contain three OPV chains, were generated in convergent syntheses. The extension of the conjugation leads to a bathochromic effect that shifts the absorption from the UV into the visible region. The carbinol series has a convergence limit of the absorption at λmax = 415 nm. The corresponding carbenium ions exhibit a stronger bathochromic shift with the increasing number of repeating units in each chain. Thus, NIR dyes were obtained which show a convergence limit at λmax = 879 nm. The charge distribution in the ground state of the carbocations is discussed on the basis of 13C NMR spectroscopic data.
Tris[oligo(1,4-phenylenevinylene)]methylium Dyes
2009
The tris[oligo(1,4-phenylenevinylene)]carbinols 2a–f (n =1–4) and the tris(4-styrylphenyl)methanes 7a,b have been prepared by Wittig–Horner (3 + 4a–f 2a–f) and Siegristreactions (5 + 6a,b 7a,b). The Wittig–Horner reactions in these examples are accompanied by an autoxidation, whereas a reduction occurs in the Siegrist reactions. Compound 2a, the lowest member (n = 1) of the series 2a–d with terminal dialkylamino groups, generates first, on treatment with acids, the methylium dye 2′a, which absorbs far into the NIR region (λmax = 1100 nm). The higher members 2b,c (n = 2,3) of the carbinol series yield by acidic treatment only N-protonated methylium dyes 2″′b,c. The different behavior is due …
Supercritical Carbon Dioxide: A Promoter of Carbon-Halogen Bond Heterolysis
2013
as the leaving groupdeparts from the carbon atom prior to the entrance of thenucleophile. Polar protic solvents with high dielectric con-stants promote polar bond heterolysis by providing effectiveH-bonding and electron-pair donation interactions to theleaving group and the incipient carbocation, respectively.Then, the solvent captures the carbocation intermediate togive the corresponding S
ChemInform Abstract: Methylium Ions with OPV Chains - New NIR Dyes.
2010
Carbinols, which contain three OPV chains, were generated in convergent syntheses. The extension of the conjugation leads to a bathochromic effect that shifts the absorption from the UV into the visible region. The carbinol series has a convergence limit of the absorption at λmax = 415 nm. The corresponding carbenium ions exhibit a stronger bathochromic shift with the increasing number of repeating units in each chain. Thus, NIR dyes were obtained which show a convergence limit at λmax = 879 nm. The charge distribution in the ground state of the carbocations is discussed on the basis of 13C NMR spectroscopic data.
Reaktivitäut und reaktionswege von methylsubstituierten bisindolylcarbenium-ionen
1987
Methyl substituted bisindolylcarbenium ions 1 react with some O- and C-nucleophiles regioselectively. The cations 1b, 1c yield with hydroxide ions the tetraindolyldimethyl ether 4 and with methoxide ions the bisin-dolylmethoxymethanes 5. Compounds 1a, 1b, 1c react with several methylindoles to isomeric bis- and trisin-dolylmethanes. An electrophilic reactivity order of cations 1 can be derived supporting on the experimental results.
Reaktionen von elektronenreichen Heterocyclen mit Orthocarbonsäure-Derivaten, 10. Formylierungs- und Alkylierungsreaktionen von Carbazolen mit ambide…
1987
Carbazole werden durch Diethoxycarbenium-tetrafluoroborat mit hoher Regioselektivitat formyliert, wahrend die thermodynamisch stabileren Diethoxymethylcarbenium- und Trimethoxycarbenium-Ionen infolge ausgepragter ambidenter Elektrophilie Carbazole bevorzugt alkylieren. Reactions of Electron-Rich Heterocycles with Orthocarboxylic Acid Derivatives, 10. – Formylation and Alkylation of Carbazoles with Ambident Dialkoxycarbenium Tetrafluoroborates Carbazole and some derivatives were formylated regioselectively with diethoxycarbenium tetrafluoroborate. The thermodynamically more stable diethoxymethylcarbenium and trimethoxycarbenium ions exhibit ambident electrophilic reactivity as predominant al…
MINDO/3 Study of the Rearrangement of 1-Methylcyclohexyl Cation to 1,2-Dimethylcyclopentyl Cation
1986
The rearrangement of the 1-methylcyclohexyl cation to the 1,2-dimethylcyclopentyl cation has been studied by MINDO/3 calculations, as an application of the branching mechanism model for cycloalkanes. Possible intermediates and transition states have been characterized by diagonalization of their Hessian matrixes. Two nonequivalent pathways, α and β scissions, are relatively close in energy. The calculated transition states are almost equivalent in energy to those found for cyclohexyl cation. Hence, the energy barriers are higher for the rearrangement of the 1-methyl than for cyclohexyl cation, because the former is less stable than the latter.