Glycine, copper derivative preparation

A Methylamino)phenol. This derivative, also named 4-hydroxy-/V-methy1ani1ine (19), forms needles from benzene which are slightly soluble in ethanol andinsoluble in diethyl ether. Industrial synthesis involves decarboxylation of A/-(4-hydroxyphenyl)glycine [122-87-2] at elevated temperature in such solvents as chlorobenzene—cyclohexanone (184,185). It also can be prepared by the methylation of 4-aminophenol, or from methylamiae [74-89-5] by heating with 4-chlorophenol [106-48-9] and copper sulfate at 135°C in aqueous solution, or with hydroquinone [123-31 -9] 2l. 200—250°C in alcohoHc solution (186). 

Ames and Ribeira (75JCS(Pl)1390) described a method for the preparation of thieno[2,3-c]pyridin-7-ones (Scheme 68). The sodium salt of 3-bromothiophene-2-carboxylic acid reacts with carbanions in the presence of copper or copper(II) acetate to give condensation products (274) by displacement of bromide ion, often with simultaneous deacetylation. Cyclization of (274) provides a convenient route to thieno[2,3-c]pyridin-7-ones. Thieno[2,3-c]pyridin-4-ones and thieno[3,2-c]pyridin-7-ones have been prepared by Friedel-Crafts cyclization of AT-(2-thenyl)- and A-(3-thenyl)-glycine derivatives (81H(l6)127l). 

V-D-Gluconylglycine, a pseudopeptide derivative of D-glucono-S-lactone and glycine, was prepared according to ref. 7. The equilibrium constants of its copper coordination, determined according to ref. 1 (Table 1), were used to calculate the concentration distribution curves in Fig. 1, which show the compositions and protonation states of the different species in solutions of different pH. 

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