Lert.-Butyl alcohol

Calcium hydride, for drying of lert-butyl alcohol, 41, 7 CARBODIIMIDE, DrPHENYL-, 43, 31 Carbodiumdes, from isocyanates, 43, 31... 

N,N-Dimethylamlme, condensation with oxyalyl chloride, 41, 1 in reaction of cyanoacctyl chloride and lert-butyl alcohol, 41, 6 N-(2,4-Dimethylbenzyl)-acetamide, 42, 18... 

Prepare anhydrous lert.-butyl alcohol by refluxing the commercial product with sodium (ca. 4 g. per 100 ml.) until the metal is about two-thirds dissolved and then distilling. Free metal should be present during the distillation. 

The commercial constant boiling point alcohol, b.p. 80°/760 mm., containing 88 per cent, of lert.-butyl alcohol, may be used 28 5 g. are required. 

The oxidation is conducted in a two-phase system with lert-butyl alcohol as the organic phase. The advantage of this procedure is that osmium tetroxidc (37) is the only oxidizing agent that enters the organic phase. 

Alcohols other than lert.-butyl alcohol, such as methyl, ethyl, butyl, or isobutyl alcohol, may be used, but with a decrease in yield. If methyl or ethyl alcohol is substituted for terL-butyl alcohol, the potassium should be added in smaller portions and the more vigorous reaction must be controlled by external cooling. Furthermore, if methyl alcohol is used the amount of potassium should be decreased from 0.75 gram atom to 0.5 gram atom. 

At this point the product consisted mostly of the isocyanate, since the reaction with lert-butyl alcohol is relatively slow at 35-40°. If the photolysis is carried out in an aprotic solvent such as tetrahydrofman, the isocyanate may be isolated. However, care must be exercised to avoid losses of this rather volatile and moisture-sensitive compound. 

The aldehyde intermediate can be isolated if a less powerful reducing agent such as lithium tri-tert-butoxyaluminum hydride is used in place of LiAlH4. This reagent, which is obtained by reaction of LiAlH4 with 3 equivalents of lert-butyl alcohol, is particularly effective for carrying out the partial reduction of acid chlorides to aldehydes (Section 19.2). 

Rush Ames, Horst and Mackay, 1956. Dioxane ( Cl+HgOp ) + lert.Butyl alcohol ... 

N-containing substituent Phenol 1 Ethyl alcohol 2 lert-Butyl alcohol 3 Phenyl- acetylene 4 Octylamine 5... 

The rearrangement with ring contraction probably is the most important synthetic application of the Favorskii reaction it is for example used in the synthesis of steroids. Yields can vary from good to moderate. As solvents diethyl ether or alcohols are often used. With acyclic a-halo ketones bearing voluminous substituents in a -position, yields can be low a lert-butyl substituent will prevent the rearrangement. 

The Sharpless epoxidation of allylic alcohols with lert-butyl hydroperoxide/titanium tetraiso-propoxide/diisopropyl tartrate (DIPT) is a highly enantioface-selective reaction and follows the topicity shown51. 

BIS(lert-BUTYL)CHROMATE (1189-85-1) A strong oxidizer. Violent reaction with reducing agents, alcohols, combustible materials, ethers, fluorine, hydrazine, powdered metals including aluminum, magnesium, zirconium, potassium iodide, sodium tetraborate, sodium tetraborate decahydrate, sodium borohydride. Incompatible with water, steam. 

Poly(lert-butyl vinyl ketone). vec-Butyl alcohol 0.097 25 715... 

The steric bulk of the rm-butyl group significantly diminishes the rate of silyla-tion with lert-butyldimethylsilyl chloride (TBSC1, mp 86-89 QC, bp 125 °C) so convenient rates are best achieved by the addition of basic activators such as imidazole or DMAP98 and by using dipolar aprotic solvents such as DMF. Primary alcohols react much faster than secondary alcohols [Scheme 4.60]" but tertiary alcohols are inert. 

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