Methyl, alcohol amines

P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

Secondary and tertiary amines are not generally prepared in the laboratory. On the technical scale methylaniline is prepared by heating a mixture of aniline hydrochloride (55 parts) and methyl alcohol (16 parts) at 120° in an autoclave. For dimethylaniline, aniline and methyl alcohol are mixed in the proportion of 80 78, 8 parts of concentrated sulphuric acid are added and the mixture heated in an autoclave at 230-235° and a pressure of 25-30 atmospheres. Ethyl- and diethyl-anihne are prepared similarly. One method of isolating pure methyl- or ethyl-aniline from the commercial product consists in converting it into the Y-nitroso derivative with nitrous acid, followed by reduction of the nitroso compound with tin and hydrochloric acid ... 

The catalyst is inactive for the hydrogenation of the (isolated) benzene nucleus and so may bo used for the hydrogenation of aromatic compounds containing aldehyde, keto, carbalkoxy or amide groups to the corresponding alcohols, amines, etc., e.g., ethyl benzoate to benzyl alcohol methyl p-toluate to p-methylbenzyl alcohol ethyl cinnamate to 3 phenyl 1-propanol. 

They show good to excellent resistance to highly aromatic solvents, polar solvents, water and salt solutions, aqueous acids, dilute alkaline solutions, oxidative environments, amines, and methyl alcohol. Care must be taken in choice of proper gum and compound. Hexafluoropropylene-containing polymers are not recommended for use in contact with ammonia, strong caustic (50% sodium hydroxide above 70°C), and certain polar solvents such as methyl ethyl ketone and low molecular weight esters. However, perfluoroelastomers can withstand these fluids. Propylene-containing fluorocarbon polymers can tolerate strong caustic. 

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. 

This formula was confirmed hy Haworth and Perkin s synthesis of a-flZZocryptopine from herherine, the first application of a process, of which examples have heen given already in the syntheses of cryptopine (p. 298) and protopine (p. 301) hy the same authors. Anhydrotetrahydromethyl-herherine (I cf. hase (a), p. 346) in dry chloroform was added to a solution of perhenzoic acid in ether cooled helow 5°. The amine oxide, C21H23O5N (II), separated as an oil, which after shaking with sodium hydroxide solution, solidified and was crystallised from water in slender prisms, m.p. 135°. It was dissolved in acetic acid, hydrochloric acid added, the mixture heated in boiling water for an hour and the hase precipitated hy addition of potassium hydroxide. The precipitate was dissolved in methyl alcohol, ether added, the alcohol washed out with water and the ethereal... 

Q. CO. C(COaEt). N(CO. Ph). CH. CHj. CHPr. CH, was hydrolysed and decarboxylated and the unstable keto-amine hydrogenated in methyl alcohol with palladised charcoal as catalyst to the... 

An interesting question is the effect of unshared pairs of electrons on an axial atom. Pauling states that they appear to contribute little to three fold barriers, basing this on the observed fact that methyl amine with two N—H bonds and one pair has about 2/3 the barrier of ethane while methyl alcohol with one O—H bond and two pairs has approximately one third the ethane value. He explains this by pointing out that the unshared pairs, not forming bonds, have not the same reason to acquire / character, without which they will not contribute to a threefold barrier. 

Alcohols, flavors, fragrances, fatty acid methyl esters, amines, acids... 

Conveniently prepared by the method here described, diazomethane is much used in scientific work, since it enables valuable acids and phenols to be elegantly and smoothly methylated. Alcoholic OH-groups are practically never attacked by diazomethane, nor are amines affected. 

A.S.H. Ong, K. Y. Cheah u. Y.M. Choo, Elaeis 1, 31-51 (1989) . .Oleochemicals from Palm Oil and Palm Kernel Oil [Production and Uses of Acids, Methyl Esters, Amines, and Alcohols derived from Palm and Palm Kernel Oils, and their Derivatives]". 

Diethyl(trifluoromethyl)amine (19) and [difluoro(phenyl)methyl](dimethyl)amine (21) are mild reagents which can fluorinate alcohols to their corresponding fluorides. They can also fluorinate carboxylic acids to their corresponding fluorides however, good yields are only obtained when the product is sufficiently volatile to be distilled off during the course of the reaction. 

The amine (121 gms.) is added slowly to a solution of tartaric acid (150 gms.) in 750 c.cs. methyl alcohol. After cooling, the complex is immediately filtered and recrystallised from boiling methyl alcohol (2 litres). The complex is decomposed in the usual manner, when pure amine, a.fm = — 38-7°, is obtained. 

The methyl alcohol is removed from the filtrate and the residue recrystallised from water. In this crystallisation it may be necessary to concentrate and cool the solution in ice. Two or three re-crystallisations from water may be necessary. The complex obtained yields amine of C, = + 37°-38°. 

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