Butyraldehyde, hydration

The reactions of 3- and 4-picolylamine with perfluorinated butyraldehyde give the expected results when considering that the reactivity of R groups in compound 14 is H > benzyl, i.e. aldimine 14b in Table 3 is more reactive than ketimine 14m. Aldimine 24 derived from perfluorinated butyraldehyde hydrate with 3-picolylamine isomcrizes completely to Shiff base 25 in triethylamine at room temperature in only a few minutes, a dramatic increase in rate over /V-benzylimine 14b, which requires 90 hours under similar conditions (sec Table 3). 

The results with 4-picolylamine are even more spectacular. The condensation of perfluorinated butyraldehyde hydrate with 4-picolylamine affords the isomerized 4-pyridyl analog of 25 directly.15... 

Ethyl alcohol has been made by the hydration of ethylene (9) since 1930. Like isopropyl alcohol, part of the output is used as a solvent, but most is converted to other oxygenated chemicals. Its most important raw material use is conversion to acetaldehyde by catalytic air oxidation. Acetaldehyde, in turn, is the raw material source of acetic acid, acetic anhydride, pentaerythritol, synthetic n-butyl alcohol (via aldol condensation), butyraldehyde, and other products. Butyraldehyde is the source of butyric acid, polyvinyl butyral resin, and 2-ethylhexanol (octyl alcohol). The last-named eight-carbon alcohol is based on the aldol condensation of butyraldehyde and is used to make the important plasticizer di-2-ethylhexyl phthalate. A few examples of the important reactions of acetaldehyde are as follows ... 

Hydration of the double bond of 288 gave 289, on which a Reformatski reaction was performed to yield harringtonine (107) together with epiharring-tonine (because of the two modes of hydration of the double bond in 288) (Scheme 59). The required ester (283) was prepared by first condensing iso-butyraldehyde with malonic acid to form 290, followed by isomerizing with... 

Higher aldehydes, for example acetaldehyde or n-butyraldehyde, have much less tendency to polymerize compared to formaldehyde [5, 6]. Reasons have been given in thermodynamic terms by referring to the lower enthalpy of polymerization (about —7 kcal mole" ) as compared to formaldehydes (—12 kcal mole" ), which results in ceiling temperatures of —40°C. In terms of reactivity, aliphatic aldehydes undergo hydration and hemiacetal formation to an extent of about 50%. 

Most acetone is manufactured today in the United States by thermochemical cumene oxidation. It is a co-product with phenol. Acetone is also manufactured by dehydrogenation of 2-propanol, which is made by hydration of propylene. Most 1-butanol is manufactured today by hydrogenation of n-butyraldehyde, which is obtained by the hydroformylation of propylene (0x0 reaction). It is also manufactured by hydrogenation of crotonaldehyde, which is obtained by the... 

Uses Intermediate in mfg. of n-butanol, crotonic acid, sorbic acids mfg. of resin and rubber antioxidants solvent in min. oil purification warning agent in fuel gas for locating breaks and leaks in pipes alcohol denaturant mfg. of butyraldehyde, quinaldine minor amts, in mfg. of maleic acid, crotyl alcohol, butyl chloral hydrate, rubber accelerators in org. synthesis insecticides chemical warfare... 

Erlenmeyer found that the butyl alcohol present in fusel oil yields iso-butyric acid (see below) on oxidation, and is therefore isobutyl alcohol, and he also showed that from isobutyl iodide the same valeric acid is obtained as from the amyl alcohol of fusel oil, which is therefore isoamyl alcohol, derived from dimethylethylmethane. Secondary butyl alcohol was first obtained as hydrate de butylene from erythritol by de Luynes. A. Lieben obtained it from zinc ethyl and dichloroethyl ether, and since he found that on oxidation it gives a ketone he recognised it as secondary butyl alcohol. Lieben and A. Rossi obtained normal butyl alcohol from butyric acid, which was converted into butyraldehyde by distilling calcium butyrate and calcium formate, and a solution of this reduced with a large amount of sodium amalgam. They give structural formulae for the four butyl alcohols, with the boiling-points. 

TrichIor- butyraldehyd CH3 CHCI CCI2 CHO liq 175,44 1,4219 bei 18,8 °C sehr hygroskopisch mit W— Butylchloral-hydrat CHaCHClCCU-CHCOH )2... 

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