CYCLOHEXANOL, 4-tert-BUTYL

Acetic acid, (4-tert-butylcyclohexyl) ester A13-36523 4-t-Butylcyclohexyl acetate 4-tert-Butyl cyclohexyl acetate 4-tert-Butylcyclohexanol acetate 4-tert-Butylhexahydrophenyl acetate Cyclohexanol, 4-(1,1-dimethylethyl)-, acetate Cyclohexanol, 4-tert-butyl-, acetate Cyclohexanol, 4-tert-butyl-, acetate (SCI) EINECS 250-964-9 NSC 163103 p-tert-Butyl cyciohexyl acetate p-tert-Butylcyclohexyl acetate Vertenex,... 

Write the mechanism of the acid-catalyzed cleavage of tert-butyl cyclohexyl ether to yield cyclohexanol and 2-methylpropene. 

An interesting example of etherification of close boiling cis and trans 2-tert-butyl-cyclohexanol with .v amylene may be cited. At 353 K, and Indian 130 as cataly.st at 10 % loading, about 94% selectivity for the cis isomer was realized with a feed consisting of about 68.5 % cis and 31.5% trcms isomer (Matkar and Sharma, 1995). 

The submitters used N-chlorosuccinimidc, 4-tert-butyl-cyclohexanol, methyl sulfide, and triethylamine, available from Aldrich Chemical Company, Inc., without further purification. 

Heptanol, 2-methyl-3-hexanol, 2,4-dimethyl-3-pentanol, cyclo-pentanol, cyclohexanol, cyclo-heptanol, cyclooctanol, cis-and trans-2-methylcyclohexanol, cis- and trans-4-tert-butyl-cyclohexanol ai2o3 180-210 94... 

For industrial-scale syntheses of simple epoxides, however, these reactions all suffer from the drawback that they produce a coproduct (tert-butyl alcohol, styrene, cyclohexanol, etc.). The ultimate goal of industrial research on epoxi-... 

By the same method ethyl a-cyclohexylacetoacetate (b.p. 146-148°/20 mm.) has been prepared in 34% yield from cyclohexanol and acetoacetic ester, and ethyl a-fer/.-butylaceto-acetate (b.p. 101-102°/20 mm.) in 10-14% yield from tert.-butyl alcohol and acetoacetic ester. 

Some interesting solvent effects observed in the TBHP-SOi-initiated polymerization of MMA have been mentioned before. It has been further observed that when polymerization of MMA and AN is carried out in the presence of alcohols, the rate of polymerization is in the order methanol > ethanol > isopropyl alcohol > tert-butyl alcohol, cyclohexanol. This suggests that the over-all polymerization mechanism (or the initiation mechanism itself) depends on the polar contribution of the alcohol. A similar observation was made by Imoto et al. with a benzoic anhydride— dimethylaniline N-oxide system as the initiator (20). 

The oxidized dimer, [Fe2(TPA)20(0Ac)]3+, 41, was shown to be an efficient catalyst for cyclohexane oxidation using tert-BuOOH as a source of oxygen (69). This catalyst reacts in CH3CN to yield cyclohexanol (9 equiv), cyclohexanone (11 equiv), and (tert-butylperoxy)cyclohexane (16 equiv) in 0.25 h at ambient temperatures and pressures under an inert atmosphere. The catalyst is not degraded during the catalytic reaction as determined by spectroscopic measurements and the fact that it can maintain its turnover efficiency with subsequent additions of oxidant. Solvent effects on product distribution were significant benzo-nitrile favored the hydroxylated products at the expense of (tert-butyl-peroxy)cyclohexane, whereas pyridine had the opposite effect. Addition of the two-electron oxidant trap, dimethyl sulfide, to the catalytic system completely suppressed the formation of cyclohexanol and cyclohexanone, but had no effect on the production of (tert-butylper-oxy)cyclohexane. These and other studies suggested that cyclohexanol and cyclohexanone must arise from an oxidant different from that responsible for the formation of (tert-butylperoxy)cyclohexane. Thus, two modes of tert-BuOOH decomposition were postulated a heterolytic... 

To investigate the mechanism of the reaction, a decomposition experiment was carried out in the presence of cyclohexanol to see if cyclohexanone, which is the intermolecular oxidation product of cyclohexanol and cyclohexene hydroperoxide, was formed (Table 2). To compare the oxidizability of cyclohexanol and 2-cyclohexen-l-ol, oxidation of both substrates were carried out with CrAPO-5 as catalyst and tert-butyl hydroperoxide (TBHP) as oxidant (Table 2). 

A) Solubility. To 4 ml of distilled water add, drop by drop, 10-15 drops of l-butanol until no more dissolves. Save the tube. Repeat, using ethanol, tert-butyl alcohol, cyclohexanol, and phenol. The last is solid, therefore use 0.5 g. Likewise determine the solubility of a nitrophenol if available. Treat solutions as directed in section (B). 

Finally, both methyllithium and methylmagnesium iodide added non-stereoselectively and at a considerably slower rate to the tert-butyl-cyclohexanone 27 (Fig. 1.5) at —80 °C, yielded in each case a mixture of both Cl epimers trans-A-ferf-butyl-cyclohexanol 28 and c 5-4-ferf-butyl-cyclohexanol 29. The isomer with the equatorial methyl group 28 (fra 5-product) was the predominant product in both reactions (28 29 = 3.6 1 in the first case and 3 1 in the second case). 

Spiniello, M., White, J. M. (2003). Low-temperature X-ray structural studies of the ester and ether derivatives of cis- and trans-4-tert-butyl cyclohexanol and 2-adamantanol apphcation of the variable oxygen probe to determine the relative a -donor ability of C-H and C-C bonds. Organic, Biomolecular Chemistry, 1, 3094—3101. This paper also provides an excellent historic survey of this problem. 

An example illustrating this possibility is the reaction of sodium diethyl phosphite with methanesulfonate of cis- and tra 3 -tert-butyl-4-cyclohexanols. The products of this interaction are 3-ieri-butylcyclohexene I, (4-feri-butyl) cyclohexyl diethylphosphite II and (4-iert-buty) cyclohexanedialkylphosphonate III [355],... 

It has already been mentioned that the K, in NCW is several orders of magnitude greater than in water at room temperature. Thus, as shown previously, acid and base catalysis can be facilitated without the use of additional acid. Certainly CO2 reacts with water to form carbonic acid and, as a consequence, the concentration of hydronium ion in NCW can be increased by enriching the medium with CO2. From an environmental point of view this procedure wiU not only facilitate specific acid-catalyzed reactions but will not require neutralization of the acid after the reaction is complete. A simple cooling and depressurization will eliminate the CO2 and phase separates the product(s) of reaction. Thus, Aleman et al. have reported that the conversion of mesitoic acid to mesitylene over a period of 120 min at 250°C increased from 50 to 80% in the presence of 10 bar (rt) of CO2. Hunter and Savage reported the dehydration of cyclohexanol in water at 250 and 275°C and the reaction of p-cresol with tert-butanol in water at 275°C in the absence and presence of CO2. Their results indicated that in the presence of CO2 the rate of dehydration of the cyclohexanol increased by more than a factor of 2 and the rate of formation of 2-tert-butyl-4-methylphenol increased 40-120%. Modest increases in rate were reported for the hydration of cyclohexene to cyclohexanol. 

C12H24 0 l-ethyl-3cis-tert-butyl-cyclohexanol 97029-33-9... 

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

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