Cyclohexene oxide, 1-phenyl

Racemic trans-2-phenylcyclohexanol has previously been prepared in a yield comparable to that realized in this procedure via copper-catalyzed phenyl Grignard addition to cyclohexene oxide using the more expensive copper(l) oxide.14... 

Treatment of 2-methoxycyclohexyl phenyl tellurium oxide, prepared from cyclohexene and phenyl tellurium tribromide in methanol followed by hydrolysis of the tellurium dibromide, with 3-chloroperoxybenzoic acid in methanol caused ring contraction with formation of the dimethyl acetal of cyclopentanecarbaldehyde1,2. 

The acid-catalyzed hydrolysis of p-phenyl-substituted cyclohexene oxides 49a-d yields diols resulting from cis and "trans addition of water to the epoxide group (Scheme 14). It was initially reported that the cis/trans diol ratio correlates well with the electronic effect of the / -substituent, and varied from 7.5 93.5 for p-nitro-sub-stituted oxide 49d to 95.3 4.7 for p-methoxy-substituted epoxide 49a.56 58 Later work established that methoxy-substituted diols 50a and 51a underwent isomerization under the conditions of acid-catalyzed epoxide hydrolysis, and that the cis/ trans diol ratios for hydrolysis of 49a-c are quite similar.59... 

The cis and trans diols 55b and 56b are sufficiently reactive in dilute acid solution to undergo equilibration, and the tram diol was determined to be more stable than the cis diol by a factor of 3. In this system, therefore, the major diol from acid-catalyzed hydrolysis is the less stable isomer. This result contrasts with the results from acid-catalyzed hydrolysis of phenyl-substituted cyclohexene oxides, where the major cis diol product is also more stable than the corresponding trans diol. In the hydrolysis of indene oxides 53a, b, therefore, effects that are present in the transition state but absent in the products must play major roles in controlling the cis/trans product ratio. 

Styrene oxide presents further complications and is polymerized most readily by catalysts which are poor for homopolymerization of cyclohexene oxide such as trlfllc acid, but phenyl dlsulfone, which Is an active catalyst for cyclohexene oxide. Is surprisingly slow for styrene oxide (Figure 4). 

Poly(cyclohexene carbonate-6-ethylene oxide-i-cyclohexene carbonate) Poly(cyclohexene oxide-co-carbon dioxide) Poly[A -cyclopropylacrylamide-co-4-(2-phenyl-diazenyl)benzamido-A -(2-aminoethyl)acrylamide]... 

Although in photocurable formulations, difunctional oxirane derivatives are employed for mechanistic studies, monofunctional oxiranes are used including cyclohexene oxide, styrene oxide, or phenyl glycidyl ether. These studies indicate that the cationic polymerizations proceeding as a result of photoinitiation by onium salts have typical characteristics of polymerizations initiated by strong protonic adds. Thus, initiation involves protonation of oxirane ring while propagation proceeds on tertiary oxonium ions as active species, that is, by the ACE mechanism. 

The addition of the anion of a-bromo-a-nitrotoluerie (564) to cyclohexene gave the hexahydro derivative (565) of 3-phenyl-l,2-benzisoxazole (75TL2131). An unusual hexahydro derivative (566) was produced by the bis addition of benzonitrile N-oxide to benzoquinone (67AHC(8)277). 

The epoxidation method developed by Noyori was subsequently applied to the direct formation of dicarboxylic acids from olefins [55], Cyclohexene was oxidized to adipic acid in 93% yield with the tungstate/ammonium bisulfate system and 4 equivalents of hydrogen peroxide. The selectivity problem associated with the Noyori method was circumvented to a certain degree by the improvements introduced by Jacobs and coworkers [56]. Additional amounts of (aminomethyl)phos-phonic acid and Na2W04 were introduced into the standard catalytic mixture, and the pH of the reaction media was adjusted to 4.2-5 with aqueous NaOH. These changes allowed for the formation of epoxides from ot-pinene, 1 -phenyl- 1-cyclohex-ene, and indene, with high levels of conversion and good selectivity (Scheme 6.3). 

The linear co-oxidation dependence was observed for the following pairs of hydrocarbons (333 K, initiator AIBN) tetralin-ethylbenzene, phenylcyclopentane-ethylbenzene, phenyl-cyclohexane-ethylbenzene, tetralin-phenylcyclohexane, cyclohexene-2-butene, 2,3-dimethyl, and cyclohexene-pinane [8]. 

---