1- Methylcyclohexene, and

Bis(trimethylsilyl)monoperoxysulfate 6 is also an excellent agent for oxygen transfer to nucleophilic substrates such as alkenes and heteroatoms. Compound 6 could oxidize alkenes such as 1-methylcyclohexene and fraw5-/3-methylstyrene, producing 2-methyl-cyclohexanone and benzyl methyl ketone, respectively, in high yield, most likely via the... 

A surface-mediated (SiC>2 or AI2O3) addition of hydrazoic acid, generated in situ from Me3SiN3 and CF3SO3H, to 1-methylcyclohexene and 1,2-dimethylcyclohexene has been reported69. The reaction obeys the Markovnikov rule and is therefore believed to proceed via the initial protonation of the double bond to generate a carbocation. This mechanism is also supported by the observed non-stereospecificity69. 

Two alkenes may be formed here. The more highly substituted one is 1-methylcyclohexene, and this is predicted to be the major product in accordance with Zaitsev s rule. 

A student adds NBS to a solution of 1-methylcyclohexene and irradiates the mixture with a sunlamp until all the NBS has... 

The reaction worked well when run to ca. 50% conversion, but has yet to be scoped as a general method for the alkenylation of heteroaromatic bases. One further example was examined involving the union of 1-methylcyclohexene and lepidine 31. In that case, elimination of benzoic acid was less favourable and the only product identified was adduct 63, formed in an unspecified yield (Scheme 14). A related metal-catalysed procedure has been described and its effectiveness is also influenced by the nature of the substrates to be coupled <83JCS(P2)531>. 

The reaction of 1-methylcyclohexene and 1-chlorocyclohexene with nitronium tetrafluo-roborate131 in liquid sulfur dioxide gave l-fluoro-2-nitro adducts by predominant . v addition however, satisfactory yield was achieved only from 1-chlorocyclohexene (60%, cis/trans 80 20)131. ot-Nitro ketones were similarly prepared in 37 45% yield from silyl enol ethers112. 

Bicyclo[4.1.0]heptane (58) behaved similarly. When heated with dichloro-(ethylene)platinum in ether at reflux for 1 h an orange complex was formed which underwent decomposition upon treatment with aqueous potassium cyanide to yield methylenecyclohexane, 1-methylcyclohexene and cycloheptene (equation 39). ... 

In 1-methylcyclohexene and 4-propyl-3-heptone, 2J(C-C) is less than 1 Hz in this fragment. (46)... 

An alternative approach to monoalkylboranes via hydroboration is based on thexylborane. The 1 1 reaction of di- and more reactive trisubstituted olefins, e.g., 1-methylcyclopentene at —20° to — 25°C stops at the thexylmonoalkylborane stage . Less reactive trisubstituted olefins, e.g., 1-methylcyclohexene and a-pinene, react slowly, and the corresponding thexylmonoalkylboranes are formed only in 80% and 75 % yields, respectively. At 0°C, dehydroboration of 2,3-dimethyl-2-butene occurs owing to the equilibrium ... 

Bromo-l-methylcyclohexane is not correct. It gives a mixture of 1-methylcyclohexene and methylenecyclohexane on elimination. 

Fig. 6.9 Hydrogenation of olefins (A = 1-hexene, 0 = cyclohexene, = 1 -methylcyclohexene and A = 2,3-dimethyl-2-butene) by lr(0) NPs dispersed in BMI.PFj at 5atm of hydrogen (constant pressure) and 75 °C [103].

Certain alkenes such as 1-methylcyclohexene and styrene react with oxalyl chloride, under ionic conditions without added catalyst, to give alkenoic acid chlorides in variable yields. Alkenes such as octene and stilbene did not react under these conditions. Reactions of aromatic compounds with oxalyl chloride/Lewis acid catalysts have been reviewed. Anthracene is unusual as it undergoes substitution without added catalyst (eq 10). ... 

Starting with 1-methylcyclohexene and using any other needed reagents, outline a synthesis of the following deuterium-labeled compound ... 

The reaction of iodine and silver salts with 1-methylcyclohexene and l-methyl-4-t-butylcyclohexene has been examined. A method for preparation of trans-iodo-hydrin acetates involving reaction of the above substrates with iodine and KIO3 in acetic acid is described. ... 

Figure 14.17 shows the infrared spectra for an alkane (A, 3-methylpentane), an alkene (B, 1-methylcyclohexene), and an alkyne (C, 16-methyl-1-hexadecyne). Note that the CH region is essentially the same in all three spectra, but there is a CsCH absorption in Figure 14.17C. The C=C signal in Figure 14.17B is clearly visible, as is the absorption for the C=C unit in Figure 14.17C. As noted.

Scheme 9.74. A representation of the reaction of methylmagnesium bromide ( CHsMgBr ) with cyclohexanone to produce 1-methylcyclohexanol and the loss of water from the latter to generate a mixtnre of 1-methylcyclohexene and methylenecyclohexene. The former predominates in the alkene product mixture.

The less reactive olefins such as cyclohexene, 1-methylcyclohexene, and 2,3-dimethyl-2-butene exhibit rates that are slower and vary with concentration and the structure of individual olefins. The kinetics establishes these reactions to be first order in olefins and one-half order in the 9-BBN dimer (Eq. 4.2). The calculated three-halves-order rate constants also do not change as the reaction proceeds. The rate constants observed both for the first-order and three-halves-order kinetics are summarized in Table 4.2 [1]. 

Dehydration of alcohols proceeds over aluminum phosphorous oxides. Correlation between 1-butanol dehydration activity and amount of acid sites stronger than Ho - 1.5 has been reported. The dehydration of cis- and phosphorous oxides of different Al/P ratios. While the cis isomer is converted more extensively than the irans with all compositions, the relative amount of the two olefinic products (l-/3-methylcyclohexene) increases markedly on increase in the amount of P. The formation of 3-methylcyclohexene from either alcohol takes place on strong acid sites by the 1 process in which carbenium intermediates are involved. On the other hand, the formation of 1-mediylcydohexene takes place on pairs of acid and base sites by the 2 process. The aluminum atoms and aluminum atoms with hydroxy] groups attached function as Lewis add sites and Bransted acid sites, respectively. 

The first asymmetric epoxidation using a chiral ketone was reported by Curci and co-workers in 1984. Treatment of 1-methylcyclohexene and lra s -2-methylstyrene with chiral ketones 52 and 53 (Figure 35.6) and Oxone in CH2CI2-H2O in the presence of BU4NHSO4 provided the corresponding epoxides in 60-92% yield and 9-12.5% enantomenc excess. 

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