Tetra methylene di-amine

Imines.—The compounds so formed and containing the group (—NH—), are known as imines. The four carbon imine given above is named pjrrrolidine, and the di-amine from which it is formed, as tetra-methylene di-amine, also as putrescine. It is found as a putrefaction product of animal flesh. The analogous five carbon compounds are, penta-methylene di-amine, or, cadaverine, and the imine is piperidine. The last compound is found in pepper in combination as the alkaloid, piperine. 

Pyrrolidine may be synthesized from tetra-methylene di-amine, putrescine (p. 194), by the loss of ammonia. 

The constitution of pyrridine is established by numerous syntheses. The only one we shall mention is the one from cadaverine or penta-methylene di-amine. The corresponding tetra-methylene di-amine, as already stated (p. 855), loses ammonia and yields pyrrolidine, the saturated hydrogenated pyrrole. By an exactly similar reaction penta-methylene di-amine loses ammonia and yields the saturated hydrogenated pyridine which is known as piperidine. 

These two compounds have been mentioned previously (p. 193). They are respectively tetra-methylene di-amine and penta-methylene di-amine. 

Benzoylation of )V-(2,2-diethoxycarbonylvinyl)-/3-D-galactopyranosy-lamine and -/3-D-gluco analogue in pyridine with benzoyl chloride afforded mixtures of di-, tri-, and tetra-O-benzoyl derivatives. From 2,3,6-tri-O-benzoyl-N-(2,2-ethoxycarbonylvinyl)-j8-D-galatopyranosylamine and -/3-D-glucopyranosylamine the amines were liberated with bromine or chlorine in chloroform or methylene chloride (89MI4). 

As an alternative to the potassium salt, tertiary amines and tetra-alkylammonium salts have been used instead. The acids, e.g. the dried residue from a serum extraction, are treated with an acetonitrile solution of pentafluorobenzyl chloride and di-isopropylethylamine, in a 3 1 molar ratio, at 40 °C for 5 minutes. The reaction mixture is blown dry with nitrogen if necessary the esterification may be repeated (96). lndole-3-acetic acid was similarly esterified, but using acetone as solvent and N-ethylpiperidine as the cation and reaction for 45 minutes at 60 °C [97). Tetrabutylammonium hydrogen sulphate (0.1 mmol) was converted to the hydroxide with sodium hydroxide (0.2 mmol) and added to the dried acids in a serum extract with 1 ml of methylene chloride and 20 pi of pentafluorobenzyl bromide. The mixture was vigorously shaken for 30 minutes and blown down to dryness with nitrogen, and the esters were extracted into hexane for HPLC [98,99). 

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