Methvl formate

Methylethylallyacetophenone Methyl ethyl ketone Methvl formate Methylfumaric acid... 

A mixture of 4.0 grams of N-methyl-3-toluidine and 2.8 grams of sodium hydrogencarbon-ate in 50 cc of acetone was stirred at 0° to 10°C and 7.4 grams of 2-naphthyl chlorothiono-formate was added in small portions thereto and the mixture was heated under reflux for 30 minutes. The cooled mixture was poured into about 150 cc of cold water and 2-naphthvl-N-methvl-N-(3-tolyl)thionocarbamate was obtained as white crystals. Yield is 9.1 grams (90 o). Recrystallization from alcohol gave colorless needle crystals, MP 110.5° to 111.5°C. 

Goto et al. (386) have qualitatively studied the relationship between the structure and the ease of formation of some 2-aryl- and 2-heteroarvl-A-2-thiazolin-4-one derivatives. It is found that 2-pyridyl. 2-benzimidazoyl, and 2-(6 hydroxy-5 -methvl)-benzothiazolyl derivatives are too unstable to be isolated. 6 -Hydroxy-, 6 -methyl-, and unsubsti-ruted 2-benzothiazolyl derivarives. as well as naphtothiazoiyl derivatives are unstable but isolable. On the other hand, 6 -methoxy-. 6 -acetoxy-. and 5, 7 -dimethyl-6 -hvdroxybenzothiazolyl derivatives as well as most of their 5-methyl substituted derivatives are stable and easily prepared. 

The biosynthesis of novobiocin has been reviewed 52, and the formation in cell-free extracts of novobiocic acid has been described 53. The latter can be formed from 3-am1no-4, 7-dihydroxy-8-methvl coumarin (B ring) and 4-hydroxy-3(3-methyl-2-butenyl)benzoic acid (A ring) by an enzyme that forms an amide bond between these precursors. Energy (ATP) is required but the mode of activation of the carboxyl group is unknown. Novobiocin itself possesses a sugar (noviose) but its biosynthesis and the formation of the glycosidic link are little studied 52. 

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