4-Vinyl-l-cyclohexene

T. Watabe, T. Sawahata, Metabolism of the Carcinogenic Bifunctional Olefin Oxide, 4-Vinyl-l-cyclohexene, by Hepatic Microsomes , Biochem. Pharmacol. 1976, 25, 601 -602. 

The resulting complex remained dissolved in the biphasic catalytic system. The 4-vinyl-l-cyclohexene product, obtained with 100% selectivity in [BMIM]PF6, was continuously separated from the reaction mixture by decantation, allowing the reuse of the remaining catalyst solution. The 1,3-butadiene conversion in the biphasic system was higher than that observed in homogeneous systems. Because the unconjugated product has a lower solubility in the ionic liquids than the conjugated butadiene feed, continuous separation of product contributes to the increased reaction rate in the ionic liquid. 

SYNS BUTADIENE DIMER 4-ETHENYL-l-CYCLOHEXENE NCI-C54999 1,2,3,4-TETRA-HYDROSTYRENE l-VINYLCYCLOHEXENE-3 1-VINYLCYCLOHEX-3-ENE 4-VINYLCYCLOHEXENE 4-VINYLCYCLOHEXENE-l 4-VINYL-l-CYCLOHEXENE... 

SYNS CHISSONOX206 O EP-206 1.2-EPOXY-4-(EPOXYETHYL)CYCLOHEXANE 1-EPOXYETHYL-3,4-EPOXYCYCLOHEXANE 3-(EPOXYETHYL)-7-OXABI-CYCLO(4.1.0)HEPTANE 3-(l,2-EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE 4-(EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE 4-(l,2-EPOXYETHYL)-7-OXABICYCLO(4.1.0)HEPTANE ERLA-2270 ERLA-2271 l-ETHYLENEOXY-3,4-EPOXYCYCLOHEXANE NCI-C60139 O 3-OXIRANYL-7-OXABICYCLO(4.1.0)HEPT-ENE UCET TEXTILE FINISH 11-74 (OBS.) UNOX EPOXIDE 206 VINYL CYCLOHEXENE DIEPOXIDE 4-VINYLCYCLOHEXENE DIEPOXIDE 4-VINYL-l-CYCLOHEXENE DIEPOXIDE 4-VINYL-1,2-CYCLO-HEXENE DIEPOXIDE 1-VINYL-3-CYCLOHEXENE DIOXIDE 4-VINYLCYCLOHEXENE DIOXIDE 4-VINYL-l-CYCLOHEXENE DIOXIDE (MAK)... 

Certain A-acetyl-a-amino acids may also be prepared from diolefins, including dicyclopentadiene, 4-vinyl-l-cyclohexene, 1,3-butadiene and 1,7-octadiene (Table 1). Monoamido acids are the predominant products obtained from unsym-metrical dienes, such as dicylopentadiene and 4-vinyl-l-cyclohexene diamido acids are formed from symmetrical dienes. A number of these polyamido acids have potential as chelating agents. 

Co-polymerization of ethylene with cyclic dienes such as 1,3-cyclopentadiene, dicyclopentadiene, and 4-vinyl-l-cyclohexene using rac-C2H4(Ind)2ZrCl2 showed that dicyclopentadiene was the most reactive co-monomer. 1,3-Cyclopentadiene rapidly dimerizes to dicyclopentadiene, and thus ethylene/l,3-cyclopentadiene co-polymerization actually resulted in ethylene/l,3-cyclopentadiene terpolymers with dicyclopentadiene. Co-polymers with more than 9mol% of the co-monomer did not show a melt transition.1058... 

Using nitrosyliron catalysts such as [Fe(NO)2(CO)2l or [ FeCl(NO)2l2]/reductant, butadiene is cyclodimerized with high conversions and extraordinary specificity (up to 99.5%) to 4-vinyl-l-cyclohexene. With Fe(0) catalysts of the type [FeCl2(dad)]/RMgX (dad = R N=CR —CR NR ) butadiene can be converted almost quantitatively to cyclodimers. The formation of vch and cod depends markedly on the nature of the group R and can be directed to 98% cod or 80% vch -. With chiral dad-ligands the cyclodimerization of butadiene to 4-vinyl-l-cyclohexene occurs with an enantiomeric excess up to 62%. ... 

VINYL CYCLOHEXENE or 4-VINYL-l-CYCLOHEXENE (100-40-3) Forms explosive mixture with air (flash point 61°F/16°C). Hydrolyzes in water. Violent reaction with strong oxidizers. Incompatible with alcohols, amines, strong acids, strong alkalis. 

Several additional products formed by the Diels-Alder condensations of butadiene and styrene were also characterised by mass spectrometry (MS) and by matching the pyrogram retention times of the samples with retention times obtained for samples spiked with the same dimers. Vapour phase dimerisation of butadiene is known to be a clear-cut bimolecular reaction. Formation of the dimers can take place in the pyrocell as well as in the gas chromatograph (GC) transfer line. Equation 2.4 shows the dimerisation of two molecules of butadiene to form a molecule of 4-vinyl-l-cyclohexene ... 

A soln. of l-methoxy-4-methyl-4-vinyl-l-cyclohexene in benzene added during 40 min. to a stirred mixture of BFg-etherate and dry benzene, then refluxed 20hrs. 5-methoxy-2-methylbicyclo[3.2.1]oct-2-ene. Y 79%. F. e. s. K. Morita, M. Nishimura, and H. Hirose, J. Org. Chem. 30, 3011 (1965). 

In the tetrabromide of 4-vinyl-l-cyclohexene, the higher alkylated double bond could be selectively deprotected by cpe [177]. 

Despite the ability of unsaturated mercaptans to give tars readily they were prepared as early as 1934 by Von Braun, who did not recognize the ability of these compounds to cyclize. Likewise photolysis of hydrogen sulfide in the presence of allyloxyethanol, " or decomposition of the adducts of thiolacetic acid with 4-vinyl-l-cyclohexene or d-limonene, gave only polymers, and no cyclized products, probably because high-dilution conditions were not used. 

Dow Chemical has developed a two-step zeolite-based process to produce styrene from butadiene contained in crude C4 streams. As shown in the following scheme, 1,3-butadiene (in the mixed C4 stream) undergoes a liquid-phase cyclodimerization (Diels-Alder reaction) over a proprietary copper-loaded zeolite catalyst at moderate temperature and pressure, to give 4-vinyl-l-cyclohexene (4-VCH) with 99% selectivity. In the second step, the 4-VCH is catalytically oxidized (in the presence of steam) to styrene over one of Dow s proprietary oxide catalysts. The overall yield of styrene is greater than 90%. This process was originally tested in a 40-lb-per-hour pilot plant, and is now in commercialization. 

Parts a and b of Figure 5.5 show the C-NMR spectra of the compounds corresponding to n = 1 and 2, respectively. The former was prepared by ozonolysis of 4-vinyl-l-cyclohexene, and the latter obtained by GPC fractionation of the ozonolysis product of polybutadiene. It is clear that all the hydroxyl groups have been esterfied with TFAA. 

Figure 6.5 C-NMR spectra of trifluoroacetates corresponding to the 1,4-1,2-1,4 sequence from the ozonolysis product of 4-vinyl-l-cyclohexene (a) and the GPC fraction corresponding to the 1,4-(1,2) -1,4 sequence (h). Reprinted with permission from Y. Tanaka, S. Kawahara, T. Ikeda and H. Tamai, Macromolecules, 1993, 26, 19, 5253. 1993, ACS, USA [43])...

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