Tert-Butylalcohol

Note 3. If after 15 min the refractive index has not increased considerably, 2 g of tert.-butylalcohol should be added. This may activate the base. 

Butylation of phenol with tert-butylalcohol (TBA) is reported on medium pore alumino-phosphates AIPO4 -11, -31 and -41. Their activity is compared with their silicon substituted versions SAPO-11, -31 and -41. AIPO4 frameworks without silicon substitution were found to be active. Terminal hydroxyls in AlP04 s are active for butylation of phenol. It was found that a temperature as moderate as HO C is sufficient for considerable butylation of phenol. However, selectivities of the industrially important 4-TBP and 2,4-DTBP are enhanced at higher temperatures. An equimolar feed concentration of phenol and TBA is optimum to yield 4-TBP and 2,4-DTBP selectively and also a lower space velocity of about Ihr favours this reaction. 

Trimethyl-TTF was dissolved in dry THF, and treated with a slight excess of LDA (lithium diisopropylamide) for one hour at -78 C. One equivalent of sulfur was added, and the mixture stired for 2 hours, while the temperature was allowed to rise to -10 C. The mixture was buffered by the addition of one mL of tert-butylalcohol, and a THF-DMF slurry of the potassium salt of 0)-bromohexadecanoic acid was added, and the mixture stirred for 20 hours. Water was added, the mixture was acidified with HCl, and extracted several times with diethyl ether. The product was purified through flash column chromatography (silica/dichloro-methane-acetone gradient) and recrystallization from toluene-hexane. Yields of 5 were typically 30-40%. Compounds 4, 6, 7, and 8 were prepared in a similar manner. 

Potassium/tert-butylalcohol 2-Pyridones from 2-halogenopyridines... 

Two primary alkyl groups are readily introduced in this way, whereas introduction of more-hindered groups, such as isobutyl or cyclopentyl, is more sluggish and requires reflux in THF for an extended period. As the protonolysis of the boron intermediate in these cases is slow, a mixed solvent, tert-butylalcohol-THF (1 4), is used to liberate the desired product (Chart 10.2). 

The synthesis of clavine derivatives substituted in the C-14 position was described by Benes and Beran (1989). A mixture of 1-ferf-butyl-, -0-d -tert-butyl-, 2, 13-di-tert-butyl- and 2, 14-di-fert-butyl-elymoclavine resulted from the reaction of elymoclavine with tert-butylalcohol and trifluoroacetic anhydride. Sauer et al. (1990) prepared 13, 14-dibromo derivatives by bromination of 2-methyl-ergolines by different bromination reagents (bromine, pyridinehydrotribromide, pyrrolidone-hydrotribromide) in trifluoroacetic acid. When only one equivalent of bromine was used, 13-bromo derivative was preferentially formed. 

The mixture was then cooled to 30-40 C and the dissolved acetylene was "sucked over" in a water-pump vacuum (10-20 mmHg) and condensed in a receiver cooled at -78°C. The contents of the receiver were shaken three times with 20-ml portions of ice-water in a small separating funnel or dropping funnel in order to remove small amounts of tert.-butylalcohol. After drying over a very small amount of... 

The photoreduction of nitrobenzene using p5o ex filtered light from a medium pressure mercury arc was studied in petroleum, toluene, ether, 2-propanol, tert-butyl alcohol, diethylamine, triethylamine, aqueous solutions of 2-propanol and diethylamine and also in aqueous t-butylalcohol containing sodium boro-hydiide 3 >. Varying amounts of aniline, azo- and azoxybenzene were obtained. In the presence of a fourty-fold excess of benzophenone, a six-fold increase in the rate of aniline formation in ethereal solution was observed, and aniline formation was completely suppressed by addition of biacetyl or octafluomaphthalene Since unreacted nitrobenzene could be recovered in these experiments, it is demonstrated that the triplet state of nitrobenzene was quenched. 

Sustituted l-azolin-5-ones have been described thus, 2-ethoxy-1-azolin-5-one (24) is a stable compound that has been prepared from succinimide [80OS(59) 132]. 2-Ethoxy-l-azolin-5-one undergoes a photochemical ring contraction giving cyclopropanone derivatives. The photochemical reaction of (24) in /< r/-butylalcohol as solvent yield tert-butyl A-(l-ethoxy-cyclopropyl)cabamate (25). 

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