Phthalimide minerals

Phenylethylamine has been made by a number of reactions, many of which are unsuitable for preparative purposes. Only the most important methods, from a preparative point of view, are given here. The present method is adapted from that of Adkins,1 which in turn was based upon those of Mignonac,2 von Braun and coworkers,3 and Mailhe.4 Benzyl cyanide has been converted to the amine by catalytic reduction with palladium on charcoal,5 with palladium on barium sulfate,6 and with Adams catalyst 7 by chemical reduction with sodium and alcohol,8 and with zinc dust and mineral acids.9 Hydrocinnamic acid has been converted to the azide and thence by the Curtius rearrangement to /3-phenyl-ethylamine 10 also the Hofmann degradation of hydrocinnamide has been used successfully.11 /3-Nitrostyrene,12 phenylthioaceta-mide,13 and the benzoyl derivative of mandelonitrile 14 all yield /3-phenylethylamine upon reduction. The amine has also been prepared by cleavage of N- (/3-phenylethyl) -phthalimide 15 with hydrazine by the Delepine synthesis from /3-phenylethyl iodide and hexamethylenetetramine 16 by the hydrolysis of the corre-... 

This procedure has found wdde application in the synthesis of aromatic and heteroaromatic azides the yields are usually high and often quantitative. General procedures have been developed by Smith and co-workers the method of choice mainly being determined by the basicity of the amine involved or the solubility of its salts. Weakly basic amines, for example, are diazotized with amyl nitrite in an acetic acid-concentrated sulphuric acid mixture and aqueous sodium azide is subsequently added. Amines which form insoluble salts with common mineral acids zu e converted to the more soluble 2-hydroxyethanesulphonic acid salts prior to diazotization. This procedure has been applied in the diazotization of the N-(aminophenyl)phthalimides (254). Treatment of the resulting diazonium compounds (255) with hydrazoic acid and removal of the protecting phthalimido group affords the otherwise inaccessible azidoanilines (equation 134). Some representative examples of azides recently synthesized by these methods, are shown in Table 11. 

Esterification of acids. The widely used reaction of diazomethane with carboxylic acids was discovered by von Pechmann, who noted also the effectiveness of the reagent for the melhylation of phenols, mineral acids, hydrogen cyanide, and phthalimide. The reagent also methylates tropolones, alkylsulfonic acids, " and arylsulfonic acids. " The fact that neutral alcohols do not react with diuzomethane suggests that an acidic substance supplies a proton required for catalysis of the esteriflcatlon. 

Reaction on a zero oxidation state iron matrix (iron powder) proceeds analogously, with formation of [Fe(L588)] [427]. Zinc(II) tetrabenzoporphinate [Zn(L588)j can also be obtained by interaction of potassium phthalimide with malonic acid or sodium acetate in the presence of zinc(II) acetate [428], as well as by template condensation of isoindolene with a carbonyl component, such as mesoxaUc acid hydrate, paraform, diphenylformamide, or A -methylformanilide at 300-360 C and in the presence of alkali [429]. On treatment of [Zn(L588)] with mineral acid, demetallation takes place with the release of metal-free porphin. This may be then used for synthesis of tetrabenzoporphynates of those metals which are not effective as template agents [427]. 

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