Cyclooctene propene

Treatment of 19 with ethy(aluminum sesquichloride or aluminum bromide results in the formation of a new catalyst, which is active for the dimerization of olefins such as ethylene or propene but inactive for the dimerization of cyclooctene. 

Using a relative rate method, rate constants for the gas-phase reactions of O3 with 1- and 3-methylcyclopentene, 1-, 3- and 4-methylcyclohexene, 1-methylcycloheptene, cw-cyclooctene, 1- and 3-methylcyclooctene, cycloocta-1,3- and 1,5-diene, and cyclo-octa-l,3,5,7-tetraene have been measured at 296 2 K and atmospheric pressure. The rate constants obtained (in units of 10-18 cm3 molecule-1 s-1) are as follows 1-methylcyclopentene, 832 24 3-methylcyclopentene, 334 12 1-methylcyclohex-ene, 146 10 3-methylcyclohexene, 55.3 2.6 4-methylcyclohexene, 73.1 3.6 1-methylcycloheptene, 930 24 d.s-cyclooclcnc, 386 23 1-methylcyclooctene, 1420 100 3-methylcyclooctene, 139 9 d.v.d.v-cycloocta-1,3-diene, 20.0 1.4 cycloocta- 1,5-diene, 152 10 and cycloocta-l,3,5,7-tetraene, 2.60 0.19 the indicated errors are two least-squares standard deviations and do not include the uncertainties in the rate constants for the reference alkenes (propene, but-l-ene, d.s-but-2-ene, trans-but-2-ene, 2-methylbut-2-ene, and terpinolene). These rate data were compared with the few available literature data, and the effects of methyl substitution have been discussed.50... 

The photochemical route provided access not only to olefin metal carbonyls with coordinated ethene, propene, cyclooctene or styrene but also to those with... 

Metathesis is a versatile reaction that forms the basis for several important industrial processes, such as the Phillips triolefin process, which produces propene by cross-metathesis of 2-butene with ethene, and the Shell higher olefins process (SHOP), which involves a combination process that converts ethene to detergent-range olefins. Several interesting polymeric materials are commercially produced via the ROMP of different types of unsaturated cyclic monomers, including nor-bornene, cyclooctene, and dicyclopentadiene [1]. 

Equation (10) then requires the ratio r for the triads that form in metatheses of unsubstituted cyclic olefins with terminal olefins to be also about 100. Reported ratios, r, in experiments using various tungsten catalysts are for cyclooctene plus propene, 10 (52) for cyclooctene plus 1-pentene, 20 (52) for cyclopentene plus 1-pentene, <38 (69) and for cyclooctene plus 1-hexene, about 4 (75). Since in none of these experiments were extrapolations made to zero time, and since with time the measured ratios r will decrease as thermodynamic equilibrium is approached, these figures are in reasonable agreement with expectation. 

The direct alkenylation of aromatics tolerates a variety of alkenes. Besides the alkenes mentioned above, lower alkenes (e.g. 1-butene, propene) [6], alkenes containing polar groups (e.g. acrylonitrile) [4b] and cychc alkenes such as cyclooctene [7] all participate in the palladium(II)-promoted substitution of arenes. In most cases, however, the yields of these reactions were prohibitively low (less than 20%). 

The proof that the C=C bond was itself being broken in these reactions was provided by isotopic labelling studies, first by Calderon in 1967 for the exchange reaction of but-2-ene [7,8], eq. (2), then by Boelhouwer (1968) for the reaction of propene [9], eq.(3), and later by DallAsta in 1971 for the ring-opening copolymerization of [1- C]cyclopentene with unlabelled cyclooctene [10]. 

Reactions with propene and allyl alcohol occur in a similar way. Analogous complexes containing cycloheptene, cyclooctene, 1,5-COD, norbornene, and norbornadiene are also formed from rhodium trichloride in aqueous ethyl alcohol however, the reaction stoichiometry for these olefins was not established. It is possible that the oxidation of alcohol occurs. For the preparation of rhodium and iridium complexes with cycloolefins of the formula [M2Cl2(olefin)4], the best results are obtained if aqueous ethyl or isopropyl alcohol is used as the solvent ... 

CuCl(COT)] , [Cu2Cl2(cyclooctene)3], [Ag(alkene)2]X, [Ag(alkene)3]Bp4, [Ag(diene)]X (alkene = ethylene, propene, cyclohexene, etc. diene = cyclopentadiene. 

After Kaminsky, Brintzinger, and Ewen discovered homogeneous metallocene/ methylaluminoxane (MAO) catalysts for stereospecific a-olefin polymerizatiOTi (for reviews on olefin polymerization, see [13-21]), the first report [22, 23] rai addition cycloolefin polymerization without ROMP appeared. This stimulated a great interest in these polymers and in catalysts for cycloolefin polymerization (Fig. 1). Cycloolefins such as cyclopentene, cyclooctene, and norbomene can be polymerized via addition (Fig. 2). Polycycloolefins by metallocenes are difficult to process due to their high melting points and their low solubility in common organic solvents. However, metallocenes allow the synthesis of cyclic olefin copolymers (COC), especially of cyclopentene and norbomene with ethene or propene, which represent a new class of thermoplastic amorphous materials (Scheme 1) [24, 25]. 

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