M-Butyl alcohol

M-Hexyl alcohol has been prepared by the reduction of ethyl caproate by means of sodium and absolute alcohoB alone or in anhydrous ammonia solution by the reduction of -caproamide by means of sodium and absolute alcohol by the reduction of -caproaldehyde by means of sodium amalgam in dilute sulfuric acid and by means of living yeast, It has also been produced by the action of nitrous acid upon w-hexylamine by the action of sodium upon a mixture of ethyl alcohol and M-butyl alcohol ... 

Attempts to prepare 2-butoxy-3//-azepines by heating nitro compounds with tris(di-ethylamino)phosphane in /m-butyl alcohol failed, as diethylamine, liberated by alcoholysis of the aminophosphane, reacts in preference with the alcohol (vide supra) to give the Ar,/V-di-ethyl-3//-azepin-2-amine in good yield.176 However, the deoxygenation of nitroarenes with tributylphosphane in the presence of primary and secondary alcohols furnishes 2-alkoxy-3//-azepines 98 in practicable yields.79... 

When M-butyl alcohol is oxidized to butyric acid in the presence of a high concentration of sulfuric acid, esterification takes place at once, even in the cold, as long as an excess of the alcohol is present. 

Because the compound reacts with Na, it must be an alcohol. Furthermore, because the compound does not react with a strong oxidizing agent, it must be a tertiary (3°) alcohol. Therefore, the structure of C4H10O is [Pg.265]

CaHjCI, AICI3, 80 isobutylene, HF /m-butyl alcohol, H2SO4 cyclohexene, HF... 

Problem 20.19 Acidic hydrolysis of /e/7-butyl acetate in water enriched in has been found to yield /m-butyl alcohol enriched in and acetic acid containing ordinary oxygen. Acidic hydrolysis of the acetate of optically active 3,7-dimeihyI-3-octanol has been found to yield alcohol oT much lower optical purity than the starting... 

The passage of ethanol vapors over such an activated copper catalyst at one atmosphere pressure and about 350° C. at such a rate that only 50 per cent is decomposed results in the conversion of about 11 per cent of the reacted alcohol to ester and the rest to aldehyde. However, when a pressure of 270 atmospheres is employed and the ethanol conducted over the catalyst at 350° C. at a rate equal to four volumes of liquid ethanol per volume of catalyst per hour, about 50 per cent of the alcohol is converted per pass, 5 per cent is decomposed to carbon monoxide and methane and 45 per cent passes through unchanged. Of the alcohol converted about half goes to ethyl acetate, a quarter goes to form M-butyl alcohol, and the remainder forms acetic add and acetaldehyde. These products are separated by a process of distillation and the hydrogen recovered as such. 

In a 2-1. round-bottomed flask fitted with a reflux condenser, liquid-sealed mechanical stirrer, dropping funnel (Note r), and thermometer are placed 222 g. (274 cc., 3 moles) of dry M-butyl alcohol, 260 g. (263 cc., 3.3 moles) of pyridine, and 275 cc. of dry benzene (Note 2). The solution is stirred and the flask is cooled in an ice-salt mixture until the temperature has fallen to — 50. With efficient stirring (Note 3), 153 g. (91 cc., 1 mole) of phosphorus oxychloride (b.p. 106-107°) is added dropwise at such a rate that the temperature does not exceed io°. After the addition is completed the reaction mixture is heated slowly to the reflux point and held at that temperature for two hours. The mixture is cooled to room temperature, and 400-500 cc. of water is added to dissolve the pyridine hydrochloride (Note 4). The benzene layer is separated, washed with 100-150 cc. of water (Note 5), and dried over 20 g. of anhydrous sodium sulfate. 

Base-catalysed hydrolysis using alkali metal hydroxides or carbonates in aqueous methanol or THF remains the commonest method for cleaving simple esters limited mainly by the stability of the substrate to the basic conditions. In more complex substrates, lithium hydroxide in a mixture of THF-methanol-H20 (2 2 1) is the base of choice. In a synthesis of Lepicidin A, Evans and Black accomplished the hydrolysis of a methyl ester with lithium hydroxide in aqueous /m-butyl alcohol at 35 [Scheme 6.1]. Destannylation that accompanied hydrolysis with other solvents was not observed nor was harm inflicted on the TIPS and TES ethers. In a synthesis of cycloisodityrosine derivatives, Boger and co-workers attempted to hydrolyse methyl ester 2.1 [Scheme 6.2] with 1-3 equivalents of lithium hydroxide in a mixture of THF-methanol-H20 (3 1 1) at room temperature, but the desired hydrolysis was accompanied by scission of the tripeptide side chain from the ring system. However, when the reaction was conducted in the presence of the more nucleophilic lithium hydroperoxide, the desired hydrolysis was achieved in 97% yield without racemisation. 

The simplest example is /m-butyl alcohol (CH3)3COH. The propyl and butyl alcohols are used as solvents for lacquers and other materials. 

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