Alcohol - Amine Mixture

Chapter Eight Binary Components ALCOHOL - AMINE MIXTURE... 

The reductive carbonylation has an advantage of low feedstock cost. A wide range of homogenous metal complexes have been tested for both reactions (1-16). The major drawback of the use of metal complex catalysts is the difficulty of catalyst recovery and purification of the reaction products (12). In addition, the gaseous reactants have to be dissolved in the alcohol/amine mixture in order to have an access to the catalyst. The reaction is limited by the solubility of the gaseous CO and 02 reactants in the liquid alcohol reactant (17). 

An interesting example for the type C reaction is the simultaneous reaction of I with alcohol/amine mixtures. In the case of Ic the reaction can be controlled in such a way, that practically exclusively the esteramide of the dithiophosphoric acid is formed (8) ... 

An analogous conclusion was drawn by Ratkovics et al. from a series of studies on the properties of alcohol-amine mixtures. In systematically selected binary model systems, composed of a primary, secondary or tertiary amine and a member of the homologous series of alcohols, these authors examined the compositions and concentrations of the associates formed in solution. They found that numerous physico-chemical characteristics of the mixtures and their components were in such a close correlation with the association phenomena that an understanding of the complicated equilibria might be hoped for on the basis of their joint investigation. 

Ratkovics, F. Liszi, J. Laszlo, M. Properties of some alcohol/amine mixtures. I. Thermodynamic characteristics of mixture of n-butylamine and n-butanol. Acta Chim. Acad. Sci. Hung. 1973, 79, 387-393. 

Alcohol Amination. There are many similarities in the process technologies for Methods 1 and 2. In both, an alcohol reacts with ammonia over a fixed catalyst bed at elevated temperature. The reaction section consists of feed systems, vapori2ers, and/or preheaters which pass a Hquid or gaseous feed mixture over the catalyst bed in the desired ratio, temperature, and pressure. Possible amination catalysts for each method are as foUows. 

When aliphatic amines come into contact with cellulose nitrate, this gives rise to charring without ignition. If these amines are replaced by polyamines or amino-alcohols, the mixture combusts spontaneously. 

In a recent example metalloporphyrins are used as the sensing dyes for a wide variety of odorants, including alcohols, amines, arenes, ethers, halocarbons, ketones, phosphines, thioethers and thiols. An array of four different metalloporphyrins are placed on a substrate and exposed to the vapours for 30 s. The various vapour molecules coordinate onto the central metal atoms of the porphyrins, causing them to change colour and producing a unique four-colour array. The resulting colour array is compared with a library of known chemicals or mixtures and identification is achieved. 

Method A Reaction of optically active alcohol (amine) with (i ,5)-PBA-anhydridc in pyridine34 and flash chromatography of the neutral components provides a mixture of diastereomeric esters (amides), which contains predominantly a carbonyl component with the opposite configuration of the liberated free acid. 

The use of an acidic medium, in general, is favorable for the hydrogenation with any of the above catalysts. This is presumably connected with the elimination of the inhibitory effect of the amines formed during the hydrogenation. In imine hydrogenation reactions on Rh, five- to eightfold rate increases are observed when tartaric, phthalic, mandelic, salicylic or formic acids are added to the alcoholic reaction mixture (in a 95 5 mixture of EtOH-MeOH)447. 

Related compounds such as alkanesulfonyl chlorides by treatment with base afford sulfene intermediates, which undergo attack by nucleophiles (H2O, alcohols, amines,. ..) present in the reaction mixture. Although sulfenes have been the subject of intense studies345,346 it has been impossible so far to succeed in the isolation of even one of them. 

The use of sulfur dioxide as the solvent and low temperatures allows efficient and clean formation of the a-chloro nitroso compound4 6. The primary adducts, containing nitroso, nitro, or oxime functions, can be reduced to chlorine-free amines or /i-chloro amines 8. Additionally, chlorine readily undergoes substitution by nucleophiles (hydrides, alcohols, amines, etc.), such that halogen-free and /i-functionalized nitroso and nitro compounds, which can further be reduced to amines, can be prepared by this route. Recently, the conversion of nitroso compounds (RNO) to amines (RNHEt) using a triethylborane/borane mixture has been described9 10, although not applied specifically to /i-chloro nitroso compounds. 

C. G. Balachandran. J. Indian Inst. Sci. 36A, 10-18 (1954). Ultrasonic velocities binary mixtures, alcohols, amines, aromatics. 

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