Methyl -phenylglycinate hydrochloride

Determined by optical rotation of methyl phenylglycinate hydrochloride. 

SCHEME 4. Sodium borohydride reduction of methyl (S )-phenylglycinate hydrochloride. 

The aqueous layer on usual workup gave optically active phenylglycine methyl ester hydrochloride in 83.4% yield [ee% = 45.9 (1 excess [a]D° -60.59°) based on pure (/ )-phenylglycine methyl ester hydrochloride [a] ° -132.13°] (Scheme 3). 

An analogous enzymatic acylation of the 3-chloro-3-cephem nucleus for the preparation of cefaclor and derivatives was also reported by Toyo Jozo Company, Inc. (Jpn. Patent 38,693, 1978). A reaction of the 3-chloro-3-cephem nucleus (124, R = Cl) with methyl D-phenylglycinate hydrochloride (125) in 0.1 M acetate (pH 6.0) buffer is catalyzed by a cell suspension of Achromobacter sp. B-402-2 at 37°C for 3 hr. After removal of the cells, the filtrate is chromatographed. The antibiotic frac-... 

To a 1 liter flask containing dimethylformamide at 0°C, was added 24.8 g sodium N-(2-methoxycarbonyl-l-methylvinyl)-D-a-phenylglycine (prepared from sodium D-a-phenylglycine and methyl acetoacetate). The mixture was cooled to -40°C and methyl chloroformate (7.5 ml) and dimethylbenzylamine (0.26 ml) added. After stirring for 25 minutes, p-nitrobenzyl 7-aminodesacetoxycephalosporanate (32.8 g) in the form of its hydrochloride salt was added, followed by triethylamine (12.1 ml) and dimethylformamide (140 ml) over a period of 20 minutes. The reaction mixture was stirred for 2 hours at -25°C to -35°C, then warmed to 0°C and water (32 ml) added. To the resultant solution, hydrochloric acid (54 ml) was added followed by zinc (21.8 g) in portions over a period of 5 minutes, the temperature being maintained at 5°C to 10°C. Further hydrochloric acid (35 ml) was added and the solution stirred at 15°C to 20°C for 7 hours. 

Application of the Mettler RC1 Reaction Calorimeter in Optimizing a Process for the Reduction of Methyl (S)-Phenylglycinate. The sodium borohydride reduction of methyl (S )-phenylglydnate (hydrochloride salt) to the corresponding primary amino alcohol (Scheme 4) had been worked out in the laboratory and taken to a pilot plant scale where an unexpected exotherm was observed. 

D-( —)-a-Dihydrophenylglycine chloride hydrochloride D-(—)-a-Dihydrophenylglycine Dane salt methyl sodium D-(3.4-Dihydroxy)-a-phenylglycine... 

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