Propyl acetate, from oxidation

A common method of improving the yields of oxetanes from the intramolecular Williamson reaction of 1,3-haJohydrins is to use the acetate esters of the 1,3-haLohydrin rather than the halohydiin directly. Thus trimethylene oxide is obtained in 40-45% yield by treating 3-cbloro-1-propyl acetate with concentrated potastium hydroxide at 140-150° whereas only a 20-25% yield is obtained under the same conditiona from d-cMoro-l-propanol. Likewise, 2 pbenyiDxeiane... 

Esterification is one of the most important reactions of fatty acids (25). Several types of esters are produced including those resulting from reaction with monohydric alcohols, polyhydric alcohols, ethylene or propylene oxide, and acetjiene or vinyl acetate. The principal monohydric alcohols used are methyl, ethyl, propyl, isopropyl, butyl, and isobutyl alcohols (26) (see Esterification Esters, organic). 

Nitrostilbene Oxide, high-melting form, crysts (from ale or propyl alc),mp 125—26° readily sol in chlf, eth, acet glac acet ac slsol in ale and low-melting form, crysts (from ale), mp 74—76° more sol than tbe h-melting form. Both forms prepd by treating benzaldehyde with 4-nitrobenzylchloride in ale KOH. (Refs 1 2)... 

Mixed ethers result when alcohols and phenols are used with thoria at 390°—420° and esterification takes place when alcohol and acid interact at 350°-400°. Esterification10 is more complete in the presence of titanic oxide at 280°—300°. One molecule of acid is used with twelve molecules of alcohol, and in this way methyl, ethyl, propyl, butyl, and benzyl esters have been prepared from acetic, propionic and butyric acids. 

An improved synthesis7 of aldosterone acetate lb was based on the readily available dienone 30. Conversion to the nitrite and photolysis affords the oxime 31 with no attack on C19. On warming in iso-propyl alcohol this oxime 31, cyclized smoothly to the nitrone 32 with the loss of water. This nitrone is at the right oxidation level to rearrange to the 21-acetoxyimine. The overall yield of nitrone from 30 was 55%. 

Oxidation of the ethylene acetals of 3-aryl-3-oxo-2-propyl phenyl telluriums, which were prepared from the acetals of 3-aryl-3-oxo-2-bromopropane and arenetellurolates, with 3-chloroperoxybenzoic acid in methanol at 20° produced hydroxyethyl 2-arylpropanoates2. Tellurones were postulated as intermediates that experienced a 1,2-aryl shift and the elimination of an aryltelluro moiety. 

Cavallito (66) reports that neither it nor 3-benzoxypyridine was hydrogenated in the presence of Willstatter s palladium sponge catalyst (67). Under low pressure conditions in ether or dioxane Raney nickel and platinum oxide were ineffective. However, other examples show that reduction takes place readily under a variety of conditions. Biel used Raney nickel at 125° and 50 atm (68), excellent yield of 6-propyl-3-hydroxypiperidine resulted from reduction of the pyridine in acetic acid with platinum oxide (69). Ruthenium in the conversion of 3-hydroxypyridine in aqueous solution gave very high yield of the corre-... 

Propionic acid—CHs,CH2—COOH—is formed by the action of caustic potassa upon sugar, starch, gum, and ethyl cyanid during fermentation, vinous or acetic in the distillation of wood during the putrefaction of peas, beans, etc. by the oxidation of normal propylic alcohol, etc. It is best prepared by heating ethyl cyanid with potash until the odor of the ether has disappeared the acid is then liberated from its potassium compound by HjS04 and purified. 

Tri - n - propyl - n - butylphosphonium hydroxide, (C4H9)P0H.—The corresponding iodide separates from ethyl acetate as needles, M.pt. 239° to 240° C., and jdelds a picrate, consisting of small prisms from dilute acetic acid, M.pt. 67° C. Decomposition of the hydroxide yields phosphine oxides and an 85 per cent, yield of hydrocarbons calculated on the iodide used. 

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