Normal butyl alcohol process

Normal butyl alcohol (NBA) was first recovered in the 1920s as a by-product of acetone manufacture via cornstarch fermentation. That route is almost extinct now. A small percent is still made from acetaldehyde. The primary source of NBA, however, is the Oxo process. 

Properties Water-white, high-boiling hquid mild odor. Bp 240-250C, refr index 1.425, fp -30C, wt/ gal approximately 8.24 lb (20C), flash p 220F (104.4C) (CC). Miscible with most alcohols, ketones, esters, oils, hydrocarbons. Combustible. Derivation By the standard esterification process using normal butyl alcohol and oxalic acid. Grade According to ester content 90%, 95%, 99-100%. 

As butyl alcohol had only a restricted use, both for war and industrial purposes, ej eriments were started by Dr. Weizmann in order to develop a process for converting normal butyl alcohol into methyl-ethyl ketone which, in the pure state, is equally suitable as acetone for the manufacture of cordite. The process, which was a catalytic one, was worked out on a laboratory scale, and promised to give good yields it was decided to erect a large-scale plant at Toronto, which, however, only commenced successful operation just before the signing of the Armistice,... 

Historically, isobutyl alcohol was an unwanted by-product of the propylene Oxo reaction. Indeed, isobutyraldehyde the precursor of isobutyl alcohol was occasionally burned for fuel. However, more recentiy isobutyl alcohol has replaced -butyl alcohol in some appHcations where the branched alcohol appears to have preferred properties and stmcture. However, suppHes of isobutyl alcohol have declined relative to overall C-4 alcohols, especially in Europe, with the conversion of many Oxo plants to rhodium based processes which give higher normal to isobutyraldehyde isomer ratios. Further the supply of isobutyl alcohol at any given time can fluctuate greatly, since it is the lowest valued derivative of isobutyraldehyde, after neopentyl glycol, methyl isoamyl ketone and certain condensation products (10). 

Unfortunately, secondary and tertiary butyl alcohols (SBA and TBA) cannot be made by the Oxo process. Instead they are produced either by indirect or direct hydration of the corresponding olefin. Normal butylene gives SBA and isobutylene gives TBA. The processes are similar to the corresponding routes to IPA. 

Certain alcohols, notably tertiary alcohols, are not readily acylated or phos-phorylated in the condensed phase under conditions that normally succeed for primary alcohols. Likewise, tertiary alcohols or thiols are not acylated or phosphorylated in the gas phase. Alkylation is the more general reaction. For example, tert-butyl alcohol under ICR conditions condenses with protonated carbonyl and phosphoryl compounds to produce ions of the type X=0+But, where X = C or P. The process has been described previously as a displacement reaction of the type shown in equation 11 (10, 16). 

The aldehydes and alcohols produced are a mixture of normal and iso-compounds. This is due not only to the orientation of the hydrogen with respect to the C-CO bonds in the initial reaction complex but also to the isomerization of the olefin under the process conditions. It may be significant that nickel carbonyl does not readily shift the olefin double bond under the 0X0 process conditions, and nickel compoimds are very poor catalysts for the process. From isooctene 32% n-nonyl alcohol, and from propylene 50% n-butyl alcohol are obtained, the remainder of the products being isoalcohols. In general, using a-olefins as raw material, one obtains about 60% isoalcohols. The synthesis will not occur unless a labile hydrogen atom is available in the olefin reactant. With diolefins the reaction takes place at only one double bond. 

Distillation with reaction, where the normal process is coupled with a liquid phase reaction, is also interesting and esterifications of certain alcohols with acids are typical industrial applications. These include, among others the homogeneously catalyzed butyl acetate process and the production of the plasticizer di-octyl-phthalate from phthalic anhydride and 2-ethyl-hexanol. However, the subject which involves both product formation and separation aspects has not usually been treated in the literature relating specifically to "mass transfer with reaction". 

The aminolysis of esters of pyrimidine occurs normally to yield amides. The reagent is commonly alcoholic ammonia or alcoholic amine, usually at room temperature for 20-24 hours, but occasionally under refiux aqueous amine or even undiluted amine are used sometimes. The process is exemplified in the conversion of methyl pyrimidine-5-carboxylate (193 R = Me) or its 4-isomer by methanolic ammonia at 25 °C into the amide (196) or pyrimidine-4-carboxamide, respectively (60MI21300), and in the butylaminolysis of butyl ttracil-6-carboxylate (butyl orotate) by ethanolic butylamine to give A-butyluracil-5-carboxamide (187) (60JOC1950). Hydrazides are made similarly from esters with ethanolic hydrazine hydrate. 

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