Terf-Butyl alcohol

Similarly, sodium methoxide (NaOCHj) is a suitable base and is used in methyl alcohol. Potassium hydroxide in ethyl alcohol is another base-solvent combination often employed in the dehydrohalogenation of alkyl halides. Potassium ferf-butoxide [K0C(CH3)3] is the prefened base when the alkyl halide is primary it is used in either terf-butyl alcohol or dimethyl sulfoxide as solvent. 

The synthesis of the trisubstituted cyclohexane sector 160 commences with the preparation of optically active (/ )-2-cyclohexen-l-ol (199) (see Scheme 49). To accomplish this objective, the decision was made to utilize the powerful catalytic asymmetric reduction process developed by Corey and his colleagues at Harvard.83 Treatment of 2-bromocyclohexenone (196) with BH3 SMe2 in the presence of 5 mol % of oxazaborolidine 197 provides enantiomeri-cally enriched allylic alcohol 198 (99% yield, 96% ee). Reductive cleavage of the C-Br bond in 198 with lithium metal in terf-butyl alcohol and THF then provides optically active (/ )-2-cyclo-hexen-l-ol (199). When the latter substance is treated with wCPBA, a hydroxyl-directed Henbest epoxidation84 takes place to give an epoxy alcohol which can subsequently be protected in the form of a benzyl ether (see 175) under standard conditions. 

Tetrahydrofuran or glyme work equally well in place of terf-butyl alcohol as a cosolvent, but they should be distilled under dry nitrogen... 

Owing to the reactions of the initial primary radiolysis products among themselves, as in Eqs. (11-58)—(11-62), it is usually necessary to add another reagent to remove the unwanted ones. For example, to study reactions of e alone, one must work in neutral or basic solution to avoid its destruction by HsO+ (see Problem 11-12). Also, hydroxyl radicals and hydrogen atoms are removed from the system by prior addition of terf-butyl alcohol to give noninterfering products,... 

Ring transposition reactions have also been described in diazoles. 1,4-Dimethylimidazole is converted on irradiation in terf-butyl alcohol to the... 

The intramolecular photochemistry of the vinylogous amide 173 in terf-butyl alcohol yielded a retro-Mannich type reaction product 174 (equation 114)170. 

Chemical/Physical. The gas-phase reaction of ozone with pyridine in synthetic air at 23 °C yielded a nitrated salt having the formula [CeHsNHJ NOs (Atkinson et al., 1987). Ozonation of pyridine in aqueous solutions at 25 °C was studied with and without the addition of ferf-butyl alcohol (20 mM) as a radical scavenger. With tert-hniyX alcohol, ozonation of pyridine yielded mainly pyridine W-oxide (80% yield), which was very stable towards ozone. Without terf-butyl alcohol, the heterocyclic ring is rapidly cleaved forming ammonia, nitrate, and the amidic compound W-formyl oxamic acid (Andreozzi et al., 1991). 

Vinyl ethers were reductively cleaved by lithium, sodium or potassium in liquid ammonia especially in the absence of alcohols (except terf-butyl alcohol) A mixture of l-methoxy-1,3- and l-methoxy-l,4-cyclohexadiene gave in this way first methoxycyclohexene and, on further reduction, cyclohexene Reductive cleavage of a-alkoxytetrahydrofurans and pyrans will be discussed in the chapter on acetals (p. 104). 

Ring closure was observed by Johnson and Berchtold, who irradiated cyclic ) -ketosulfide 111 and terf-butyl alcohol with 253.7-nm light. A 2-thietanone derivatives was formed following intramolecular electron transfer from the sulfur atom to the excited carbonyl. An unstable dipolar... 

M xanthenol, 0.22M potassium ferf-butoxide in pyridine (80% )—terf-butyl alcohol (20% ) solution at 27° 3°C. b Moles of oxygen/mole of substrate per minute. 

Interrupted oxidations of 9,10-dihydroanthracene or 9,10-dihydro-phenanthrene in DMSO (80% )-terf-butyl alcohol (20%) containing potassium ferf-butoxide produced the 9,10-semiquinone radical anions, apparently as a product of oxidation of the monoanion. 

The product of the absorption of 3 mmoles of oxygen by a solution of 3 mmoles of diphenylmethane and 15 mmoles of potassium tert-butoxide in 20 ml. of DMSO (80% )-terf-butyl alcohol (20%) was poured into water. Upon standing, colorless crystals of benzhydrol (m.p. 64°C.) formed which could be recovered in 75% yield by filtration. Complete oxidation of the diphenylmethane gave an oxidate which after... 

Anthrone did not react with DMSO under the reaction conditions. However, 9,10-anthraquinone (2 mmoles) in 25 ml. of DMSO (80%)-terf-butyl alcohol (20% ) containing potassium tert-butoxide (4 mmoles) gave a deep red solution at 25°C., from which 60% of the adduct could be isolated after 1 hour and 88% after 3 hours. This adduct was isolated from the oxidate of 9,10-dihydroanthracene (after hydrolysis, acidification, and filtrations of anthracene) by extraction of the aqueous filtrate by chloroform. Xanthone and thioxanthone failed to form isoluble adducts with DMSO in basic solution. 

The solvent effect was also shown in the reaction of propylene, tert-butyl hydroperoxide, and molybdenum hexacarbonyl in a mixed solvent of benzene and tert-butyl alcohol (Figure 1). The epoxide yield increases rapidly as the benzene-to-terf-butyl alcohol ratio increases up to 1 4, thereafter the hydroperoxide conversion increases more rapidly with an increase in this ratio. 

Reduction of 1-decene had to be carried out at a lower concentration (0.073M) since decene was not completely soluble at the concentrations used in the case of tetralin (0.22M). Electrolysis was interrupted after 0.0062 Faradays were passed through the solution, corresponding to 42.2% conversion of 1-decene to decane at 100% current efficiency. In these runs, a carbon cathode was used. Current efficiency for reducing 1-decene was 27.3%. In the presence of an equimolar amount of terf-butyl alcohol (0.073M), the current efficiency for 1-decene was 38.6%, corresponding to a 41% increase. 

FIGURE 4.12 Potential energy diagram for the reaction of terf-butyl alcohol and hydrogen chloride according to the SN1 mechanism. 

Terminally unsaturated fluonnated alkenoic acids can be obtained from poly-fluorocycloalkenes by reaction with potassium hydroxide in terf-butyl alcohol [24] (equation 26) The use of a tertiary alcohol is critical because primary and secondary alcohols lead to ethers of the cycloalkenes The use of a polar aprotic solvent such as diglyme generates enols of diketones [26] (equation 27) The compound where... 

Note that the size of the terf-butyl alcohol molecule (5.4 X 6.8 X 6.8 A) distinctly exceeds the aperture of ZSM-5 channel, so that a serious mutual perturbation of the geometry of the ferf-butyl alcohol molecule by the zeolite, and vice versa, operates during diffusion. (The translational movement of the tert-butyl alcohol molecule inside HZSM-5 channel must resemble that of a rabbit inside a snake.) For most of the time, adsorbed alcohol molecules reside... 

Isobutyl alcohol 2-Methylpropene terf-Butyl alcohol... 

Phenyl(propynyl)iodonium tetrafluoroborate reacts with potassium 2-phenyl-1,3-indandionate in tetrahydrofuran to give the alkynyl and spiroannulated indandiones shown in equation 265. With sodium 2-ethyl-1,3-indandionate in terf-butyl alcohol, a vinyl ether is produced (equation 266). These observations are relevant to the general comments in section II.D.7 concerning the fate of 26 and related alkylidenecarbenes in reactions of [5 + OJenolates with alkyliodonium ions containing short (< three carbons) alkyl chains. 

In the reaction flask is placed 600 cc. of commercial terf.-butyl alcohol (Note 1), and the air in the flask is displaced by dry nitrogen gas. Then 29 g. (0.75 gram atom) of metallic potassium is added, in portions, to the alcohol. The mixture is heated on a water bath until all the potassium has dissolved, and then 68 g. (0.5 mole) of o-formotoluide (Note 2) is added and brought into solution. The condenser is set for distillation with a filter flask as the receiver this flask is protected from the air by connecting it to the trap used in the initial operation. The reaction flask is... 

---