Vinylcyclohexene selective

The process which was developed hy DOW involves cyclodimerization of hutadiene over a proprietary copper-loaded zeolite catalyst at moderate temperature and pressure (100°C and 250 psig). To increase the yield, the cyclodimerization step takes place in a liquid phase process over the catalyst. Selectivity for vinylcyclohexene (VCH) was over 99%. In the second step VCH is oxidized with oxygen over a proprietary oxide catalyst in presence of steam. Conversion over 90% and selectivity to styrene of 92% could he achieved. ... 

Overman, Hehre and coworkers reported anti rr-fadal selectivity in Diels-Alder reactions of vinylcyclopenten 73, 74 and 4,5-dihydro-3-etliynylthiophen S-oxide 75 [38] (Scheme 31). These results are not in agreement with the Cieplak effect, at least in Diels-Alder reactions of the dienes having unsymmetrical rr-plane. Yadav and coworkers reported that the reactions between the vinylcyclohexene 76 and dienophiles favor the reactions syn to oxygen, while 77 and 78 favor the reaction anti to oxygen substituents [39], They discuss the Cieplak effect but the reactions are not suitable. 

P-1 nickel can also be used for the selective hydrogenation of dienes. For instance, 4-vinylcyclohexene was hydrogenated with high selectivity (98%) to 4-ethylcyclohexene (equation 18), whilst 2-methyl-1-hexene was obtained with 93% selectivity from 2-methyl-1,5-hexadiene over it (equation 19)66. 

Figure 25. Evolution with time of the chemical reaction in liquid butadiene at 0.6 GPa and 300 K. Upper panel Purely pressure-induced reaction, the formation of vinylcyclohexene is revealed by the growth of the bands of the dimer in the 650- to 750-cm frequency range. Lower panel In this case the reaction is assisted by the irradiation with few milliwatts of the 488-nm line of an Ar+ laser. The fast increase of the characteristic polymer band at 980 cm indicates the selective formation of polybutadiene.

Figure 26. Dimerization of butadiene in the crystalline phase. Lower panel Logarithmic plots of the room-temperature evolution of the integrated absorption of characteristic vinylcyclohexene absorption bands at different pressures. The linear evolution unambiguously demonstrates the first-order kinetics of the reaction. Upper panel Evolution of the natural logarithm of the dimerization rate constant as a function of pressure (full squares, left axis the dotted line is intended as a guide for the eye) and evolution of the intensity ratio between selected polymer and dimer (vinylcyclohexene) bands (empty dots, right axis).

In acetylenes containing double bonds the triple bond was selectively reduced by controlled treatment with hydrogen over special catalysts such as palladium deactivated with quinoline [565] or lead acetate [56], or with triethylam-monium formate in the presence of palladium [72]. 1-Ethynylcyclohexene was hydrogenated to 1-vinylcyclohexene over a special nickel catalyst (Nic) in 84% isolated yield [49]. 

The abovementioned rate acceleration and selectivity enhancement brought about by catalysts are particularly marked when unactivated dienes and dienophiles are involved. Two molecules of 1,3-butadiene can react in a Diels-Alder reaction, one acting as diene and the other as a dienophile to produce 4-vinylcyclohexene (in 0.1% yield at 250°C in the absence of a catalyst). Cs+, Cu,+ and trivalent transition-metal exchanged montmorillonites534 as well as large-pore sodium zeolites (Na ZSM-20, NaY) and carbon molecular sieves,535 result in 20-35% yields with 95% selectivity. Large rate enhancement was observed when 1,3-cyclohexadiene underwent a similar cycloaddition536 in the presence of K10 montmorillonite doped with Fe3+ ... 

The Cu+/zeolite-catalyzed cyclodimerization of 1,3-butadiene at 100°C and 7 atm was found to give 4-vinylcyclohexene [Eq. (13.12)] with high (>99%) selectivity. Subsequent oxidative dehydrogenation over an oxide catalyst in the presence of steam gives styrene. The overall process developed by Dow Chemical113 offers an alternative to usual styrene processes based on ethylation of benzene (see Section 5.5.2). 

Industrial processes were developed for the selective partial hydrogenation of 4-vinylcyclohexene with Ni catalysts exhibiting minimized isomerization activity in the presence of additives298,299. For example, supported nickel arsenides prepared by reducing nickel arsenate with NaBFLt display high selectivity in the formation of 4-ethylcyclohexene (96% selectivity at 96% conversion on Ni-As-Al2C>3, 398 K, 25 atm H2, acetone additive). 

Cyclization of butadiene catalysed by Ni(0) catalysts proceeds via 7r-allylnickel complexes. At first, the metallacyclic bis-7i-allylnickel complex 6, in which Ni is bivalent, is formed by oxidative cyclization. The bis-7r-allyl complex 6 may also be represented by cr-allyl structures 7, 8 and 9. Reductive elimination of 7, 8 and 9 produces the cyclic dimers 1, 2 and 3 by [2+2], [2+4] and [4+4] cycloadditions. Selectivity for 1, 2 and 3 is controlled by phosphine ligands. The catalyst made of a 1 1 ratio of Ni and a phosphine ligand affords the cyclic dimers 1, 2 and 3. In particular, 1 and 3 are obtained selectively by using the bulky phosphite 11. 1,2-Divinylcyclobutane (1) can be isolated only at a low temperature, because it undergoes facile Cope rearrangement to form 1,5-COD on warming. Use of tricyclohexylpho-sphine produces 4-vinylcyclohexene (2) with high selectivity. 

Highly selective cyclorearrangement of 1,6-enynes is catalysed by a Ru carbonyl complex under CO atmosphere. Smooth cyclization of the 1,7-enyne 378 using [RuCl2(CO)3]2 under CO atmosphere gives the 1-vinylcyclohexene 379 [150]. The 1,6-enyne ester 380 is converted to the expected 1-vinylcyclopentene 382 under similar conditions. In addition, the products 383 and 384, unexpected from the intermediate 381, are also obtained. 

It should be noted that a selective amidation can be achieved with 4-vinylcyclohexene, where only the terminal olefin reacts, and that in the case of cyclooctadiene a reaction across the ring also takes place (P). 

The first work in this area appeared in the form of two patents assigned to Union Carbide in 1969/1970 (172,173). These patents described methods of preparation of monovalent copper-containing zeolites which were claimed to be active and selective catalysts for the cyclodimerization of butadiene to 4-vinylcyclohexene (VCH), i.e.,... 

Vinylcyclohexene is converted to give the corresponding unsaturatcd alkyl iodide selectively (Eq. 107)119). 

Vinylcyclohexene (29) has been selectively hydrogenated to 4-ethylcyclohexene (30) in high yields of 97 and 98% over P-2 Ni19 and Nic,20 respectively, in ethanol at 25°C and 1 atm H2. Both the nickel catalysts are known to be of low isomerization activity and sensitive to the structure of substrates. The same selective hydrogenation was also achieved over a nickel catalyst in the presence of ammonia, which minimized the isomerization to a more highly substituted double bond.72 Similarly, over P-2 Ni,... 

Clear-cut examples of effects of zeolite pore architecture on the selectivity of Diels Alder reactions are not easily found. For instance, 4-vinylcyclohexene is formed with high selectivity from butadiene over a Cu -Y zeolite however, the selectivity is intrinsically due to the properties of Cu1, which can be stabilized by the zeolite, and not to the framework as such (30-31). A simple NaY has been used in the cycloaddition of cyclopentadiene and non-activated dienophiles such as stilbene. With such large primary reactants, formation of secondary products can be impeded by transition state shape selectivity. An exemplary reaction is the condensation of cyclopentadiene and cis-cyclooctene (32) ... 

Similar types of cyclodimerizations were also pointed out with vinyl pyridines and vinyl quinoleines [213]. Lastly, selective cyclodimerization reactions of 1,3-diolefins catalyzed by electrogenerated Fe(NO)2 —from athodic reduction of FeCl3 in the presence of NO—allowed the conversion of butadienes into vinylcyclohexenes in good yields [214] (Scheme 40). 

The dimerization of butadiene catalyzed by Ni(COD)2 and quinidine-DPP (43) as a chiral ligand gave rise to (R)-( + )-vinylcyclohexene with an ee of approximately 30%, accompanied by a selectivity for vinylcyclohexene versus cydooctadiene of approximately 1 (Scheme 4.26) [63, 64],... 

---