Acetonitrile → HCID 4149252, compound

Participants

Reaction Steps

Under nitrogen, a mixture of 5.3 g of 2-aminonaphthalene-1-thiol, 6.2 g of trans-3-(p-methoxyphenyl)glycidate and 0.6 g of potassium carbonate in 80 mL of acetonitrile was stirred at reflux for 2 hours. After cooling to room temperature, the mixture was filtered and the filtrate was concentrated to a volume of about 20 mL. The crystals were separated by filtration to give 1.4 g of 2H-naphtho[1,2-b]-1,4-thiazin-3(4H)-one, mp 211°-212°. The mother liquors after removal of 1.4 g of the above compound were concentrated under reduced pressure to give 11.0 g of a mixture of (±)-threo-[(2-amino-1-naphthalenyl)thio]-2-hydroxy-3-(4-methoxyphenyl)propanoic acid methyl ester, 2H-naphtho[1,2-b]-1,4-thiazin-3(4H)-one and p-methoxybenzaldehyde. The mixture was chromatographed on a column using 120 g of silica gel. The column was eluted with 75 mL portions of methylene chloride. The first six portions of which were collected and the solvent was removed under reduced pressure gave 1.1 g of an oil, whose nuclear magnetic resonance spectrum was identical with that of p-methoxybenzaldehyde. Further elution of the column with the same solvent (fractions 7-19) afforded 1.0 g of 2H-naphtho[1,2-b]-1,4-thiazin-3(4H)-one. A sample of this compound was recrystallized from ethanol, mp 211°-212°. (±)-threo-[(2-Amino-1 -naphthalenyl)thio]-2-hydroxy-3-(4-methoxyphenyl)propanoic acid methyl ester was obtained from the column by further elution with methylene chloride. The methylene chloride fractions 20-35 were combined and the solvent was removed under reduced pressure to afford 1.2 g of (±)-threo-[(2-amino-1-naphthalenyl)thio]-2-hydroxy-3-(4-methoxyphenyl)propanoic acid methyl ester, which was treated with hydrogen chloride (anhydrous) in ethyl acetate to afford 1.1 g (85%) of the hydrochloride of (±)-threo-[(2-amino-1-naphthalenyl)thio]-2-hydroxy-3-(4-methoxyphenyl)propanoic acid methyl ester, mp 139°-140°. The hydrochloride salt (1.1 g) on treatment with dilute sodium hydroxide and extraction of the aqueous suspension with ethyl acetate gave after removal of the solvent 1.0 g of (±)-threo-[(2-amino-1-naphthalenyl)thio]-2-hydroxy-3-(4-methoxyphenyl)propanoic acid methyl ester. A sample of this compound was recrystallized from ether--pet. ether, mp. 32°-34°.

Provenance & Evidence