F-Butyl alcohol

A remarkable feature of the Birch reduction of estradiol 3-methyl ether derivatives, as well as of other metal-ammonia reductions, is the extreme rapidity of reaction. Sodium and -butyl alcohol, a metal-alcohol combination having a comparatively slow rate of reduction, effects the reduction of estradiol 3-methyl ether to the extent of 96% in 5 minutes at —33° lithium also effects complete reduction under the same conditions as is to be expected. Shorter reaction times were not studied. At —70°, reduction with sodium occurs to the extent of 56 % in 5 minutes, although reduction with lithium is virtually complete (96%) in the same time. (The slow rates of reduction of compounds of the 5-methoxytetralin type is exemplified by 5-methoxy-tetralin itself with sodium and f-butyl alcohol reduction occurs to the extent of only 50% in 6 hours vs. 99+% with lithium.) The iron catalyzed reaction of sodium with alcohols must be very fast since it competes so well with the rapid Birch reduction. One cannot compensate for the presence of iron in a Birch reduction mixture containing sodium by adding additional metal to extend the reaction time. The iron catalyzed sodium-alcohol reaction is sufficiently rapid that the aromatic steroid still remains largely unreduced. 

A 20-ketone can be reduced selectively in the presence of an 11-ketone. In an example quoted in the previous paragraph the reduction was done in ethanol for 1 hour at room temperature. In f-butyl alcohol, NaBH4 reduces a 20-ketone within 5 minutes reduction of the... 

Some unusual behaviour was displayed by the benzodisilacyclobutane 84 as described by Ishikawa et al.95 When thermolyzed, it appeared to form the quinodimethane bis-silene species 85 shown in Scheme 13, as confirmed by trapping reactions with f-butyl alcohol, alkynes, or aldehydes, all of which added in a 1,4-manner (see Scheme 13). In the absence of a trapping reagent, 85 decomposed, but not to 86 as claimed earlier.95 ... 

As seen earlier in this section, the energy released upon formation of the benzophenone ketyl radical is about 104 kcal/mole. This value is almost identical to that released upon formation of f-butyl alcohol from the f-butoxy radical,... 

The f-butoxy radicals thus formed then abstract hydrogen from hydrocarbons to generate hydrocarbon radicals and f-butyl alcohol. The hydrocarbon radicals in turn generate more r-butoxy radicals by attacking the t-butyl-hypochlorite ... 

Modifying the reaction medium to involve liquid ammonia with metallic lithium, f-butyl alcohol, and white phosphorus, to which is added the haloalkane, is reported to provide the primary alkylphos-phine derived from the haloalkane.19 Similar results are reported for the reaction of red phosphorus with sodium acetylides20 and by treatment of red phosphorus with sodium metal in an organic medium followed by the addition of two equivalents of f-butyl alcohol and the haloalkane.21 The latter approach is noteworthy in that moderate yields (45%) are obtained for primary phosphines derived from secondary haloalkanes (Figure 2.6). Mixtures of tertiary phosphines bearing one or two acetylenic linkages are produced in low yield ( 15%) by the reaction of lithium acetylides with white phosphorus in liquid ammonia followed by addition of a haloalkane.22... 

Formation of the conjugate base of phosphine under the conditions of aqueous dioxane and KOH with red phosphorus allows also for the formation of C-P bonds by attack of oxiranes.33 Under these conditions, mixtures of phosphines and phosphine oxides are formed. Using red phosphorus in liquid ammonia with sodium metal and f-butyl alcohol, good yields of primary (2-hydroxyalkyl)phos-phines are obtained.34... 

Difficulties that arise using simple primary alcohols (ketal and enol-ether formation) may be avoided by using phenol or f-butyl alcohol.360... 

Chloro compounds, poly, reduction with sodium and f-butyl alcohol, 48, 72... 

It is important that all volatile solvents are removed, particularly f-butyl alcohol, since its presence will interfere with the subsequent chromatography procedure. The checkers obtained approximately 9.0 g. of crude material. 

As the chain length of the primary alcohols increases, thermal decomposition through fracture of C—C bonds becomes more prevalent. In the pyrolysis of n-butanol, following the rupture of the C3Ht—CH2OH bond, the species found are primarily formaldehyde and small hydrocarbons. However, because of the relative weakness of the C—OH bond at a tertiary site, f-butyl alcohol loses its OH group quite readily. In fact, the reaction... 

Butyl alcohol, see 1-Butanol n-Butyl alcohol, see 1-Butanol s-Butyl alcohol, see sec-Butyl alcohol f-Butyl alcohol, see ferf-Butyl alcohol... 

Wallington, T.J., Dagaut, P., Liu, R., and Kurylo, MJ. Gas-phase reactions of hydroxy radicals with the fuel additives methyl f-butyl ether and f-butyl alcohol over the temperature range 240-440 K, Environ. Sci. TechnoL, 22(7) 842-844, 1988c. Wallington, T.J. and Japar, S.M. Atmospheric chemistry of diethyl ether and ethyl ferf-butyl ether. Environ. Sci TechnoL, 25(3) 410-415, 1991. 

A commercial grade of f-butyl alcohol (b.p. 83°) should be distilled from calcium hydride before use. 

Not mentioned in the table is the direct use of methanol as fuel for automobiles. It is added in small amounts to gasoline, sometimes as a blend with other alcohols such as f-butyl alcohol, to increase octane ratings and lower the price of the gasoline. Experimentation is even being done on vehicles that bum pure methanol. This fuel use is usually captive but a good estimate is that it may account for almost 10% of the methanol produced. 

Like those of biacetyl, the photoreactions of pyruvic acid in solution are entirely different from the reaction in the vapor state. Pyruvic acid is an excellent hydrogen abstractor which is photoreduced to dimethyltartaric acid (27) in isopropyl alcohol, methanol, f-butyl alcohol, chloroform, or diethyl ether.87,88 No reaction was observed in benzene, but photoreduction was... 

Simple ketones and esters are inert. On the other hand, nitroalkanes react smoothly in f-butyl alcohol as a solvent with butadiene, and their acidic hydrogens are displaced with the octadienyl group. From nitromethane. three products, 64, 65, and 66, are formed, accompanied by 3-substituted 1,7-octadiene as a minor product. Hydrogenation of 65 affords a fatty amine 67 which has a primary amino function at the center of the long linear chain[46,61]. 

---