1-Dodecene, cyclohexene

Ru(ti -C6H,)(CH3CN),](BF4)2 1-octene, 1-decene, styrene, 1-dodecene, cyclohexene, norbomene.dimethy 1 mateate, cyclohex-1 -ene-2-one, benzylideneacetone H20/benzene 90-110 C, 40 bar Hi Slow hydrogenation of ketones and aldehydes, too. [71]... 

Poly(ethylene glycol)-supported manganese porphyrins were tested in the epoxidation of cyclooctene, 1-dodecene, cyclohexene, styrene, and indene with PhIO or H2O2 in the presence of N-alkylimidazoles as axial ligands [51]. The polymers were soluble in the reaction mixtures and could be precipitated and reused. Epoxide yields from 80 to 100%, except for 1-dodecene (38% yield), were obtained using PhIO as oxidant. 

Not only benzene and its alkyl derivatives can be used as the aromatic component but also naphthalene [341], phenol [340,341] and thiophene [341,342]. Low-molecular weight alkenes, Cj to C5, cyclohexene and dodecene have served as alkylating agents. 

Fig. 45. Catalytic activities of solid acids for reaction of liquids Alkylation of 1,3,5-tri-methylbenzene with cyclohexene (373 K) alkylation of phenol with 1-dodecene rearrangement of benzopinacol. (From Ref. 249.)...

The nature of the product varies with the olefin (1) cyclopentene gave the olefinic product only (2) cyclohexene and cycloheptene gave the saturated products only and (3) 1-heptene and 1-dodecene gave a mixture of the disproportionation products. 

Recently, the hydroformylation of 1-dodecene and cyclohexene by the dinuclear doubly bridged pyrazolate complexes [(PR3)(CO)Rh(/i-pz )]2, 46-49, was reported (75). Thus, at 120°C and at a CO and H2 pressure of 28 atm, these two olefins were transformed into the corresponding aldehydes with greater than 95% yield. All four complexes catalyze the transformation of 1-dodecene to 1-undecane-carboxaldheyde in preference to the iso compound, although this regioselectivity is rather poor (75). 

A series of polymer-anchored epoxidation catalysts was obtained by modifying Merrifield resin with imidazole [61], diphosphines [62], or piperazine [63] followed by treatment with UV-activated Mo(CO)6. High activities in the epoxidation of cyclic (cyclooctene, cyclohexene, indene, and a-pinene) as well as linear alkenes (styrene, a-methylstyrene, 1-heptene, 1-dodecene, cis- and frans-stilbene) were observed using TBHP as oxidant. The catalysts were recovered and reused up to 10 times in the epoxidation of cyclooctene without loss of activity. 

Rhodium complexes generated from the water-insoluble carboxylated surfactant phosphine 17 (n = 3, 5, 7, 9, 11) were used as catalysts in the micellar hydrogenation of a- and cyclic olefins, such as 1-octene, 1-dodecene, and cyclohexene, in the presence of conventional cationic or anionic tensides such as cetyltrimethylammo-nium bromide (CTAB) or SDS and co-solvents, e.g., dimethyl sulfoxide [15], After the reaction the catalyst was separated from the organic products by decantation and recycled without loss in activity. There is a critical relationship between the length of the hydrocarbon chain of the ligand 17 and the length and nature of the added conventional surfactant, for obtaining maximum reactivity. For example,... 

TS-1 exhibits a slightly higher conversion, under the same reaction conditions, for the oxidation of 1 -hexene, but its activity is lower for the oxidation of 1 -dodecene than Ti-Beta zeolite. Nevertheless, the activity per Ti is still higher on TS-1 zeolite. However, in the case of cyclic olefins, for which TS-1 presents higher steric restrictions, this zeolite shows a very low activity, while the large pore Ti-Beta zeolite is still active to oxidize these bulkier molecules. No difference in turnover is found for 1-hexene and cyclohexene for Ti-Beta, while this value decreases by a... 

Figure 4. a) Radiolysis/EPR result after reaction of 1,5-dimethylcyclopentene on HZSM5 for 16 h at 318 K, b) Radiolysis/EPR result after reaction of cyclohexene on H-Mordenite for 16 h at 295 K. The spectrum is assigned to the bicyclo[5.5.0] dodecene radical cation. 

Dinuclear Mn(IV) catalysts were successfully applied for the epoxidation of 4-benzoic acid and styrene in aqueous systems [18], for the epoxidation of styrene and dodecene in two-phase systems [19g] as weU as in methanol and acetone [17d, 19b,g,h], and for the epoxidation of olefins in acetonitrile [19i], aqueous acetonitrile [17f, 19c], acetone [17d, 19b,h], methanol [19i], and acetone-methanol-water mixtures [19j]. Enantioselective epoxidations of olefins have been reported for chiral triazacyclononane derivatives boimd to Mn(OAc2) 4 (H2O) in methanol [19k], Heterogenization of the Mn catalysts on silica for the epoxidation of styrene and cyclohexene, on zeolites for olefin epoxidation, and on a solid MnS04 H2O also for olefin epoxidation [20] has also been described. A polymeric structure bearing a dense arrangement of 1,4,7-triazacyclononane moieties can be synthesized by... 

The selectivity of a macromolecular catalyst depends on the size of the substrate as well as on hydrophobic effectis. It becomes increasingly difficult for proper contact between catalytically effective groups and the substrate with increasing substrate size for otherwise identical reaction conditions. Thus, the polymer rhodium catalyst (I) hydrogenates cyclo-dodecene five times more slowly than it does cyclohexene. This substrate size effect is not observed with the analogous isolated low-molecular-weight compound (II) ... 

Dror and Manassen hydrogenated a- and cyclic olefins such as 1-octene, 1 -dodecene and cyclohexene in micellar systems using rhodium catalysts modified with water-insoluble carboxylated tenside phosphines 45 (Table 3 n=3,5,7,9,l 1) in the presence of conventional tensides such as sodium dodecylsulfate (SDS) or cetyltrimethylammonium bromide (CTAB) and cosolvents e.g. dimethyl sulfoxide. Linear olefins were more reactive than cyclic olefins. Maximum efficiency was observed in the presence of the anionic surfactant SDS when 45 contained a chain of 5-7 carbon atoms. In contrast, using the cationic tenside CTAB the ligand 45 with 5 C atoms was almost inactive but became active again with dodecyl trimethylammonium bromide. 

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