The action of hypochlorite on m-cresol. Part 2. Muconic acid derivatives

Abstract

2765 (1980). Two new crystalline products were isolated from the chlorination of m-cresol in cold alkaline solution. These products have been identified as E,Z-2-chloro-5-methyl muconic acid and 5Z-carboxymethylene-3-chloro-4-methyl-2(5H) furanone. GEORGE M. STRUNZ, MASATOSHI KAKUSHIMA, ALAN D. GIBSON, ARCHIBALD W. MCCULLOCH et PETER S. WHITE. Can. J. Chem. 58,2765Chem. 58, (1980. Deux nouveaux produits cristallins ont ete isoles de la reaction du m-cresol avec chlore en milieu alkalin froid. On a identifie ces produits comme I'acide E,Z-2-chloro-5-methyle muconique et la furfuranone-2(5H)-5Z-carboxymCthyl~ne-3-chloro-Cmethyle.The reaction of phenol with hypochlorite in al-exploited as the key step in the total synthesis ofthe kaline solution gives rise, inter alia, to 3,5,5-tri-fungal metabolite4 cryptosporiopsin (5). chloro-l,4-dihydroxy-2-cyclopentene-l-carboxy-The capricious nature of the reaction, resulting lic acid (1, R=H) (2-4). Mechanisms advanced for from its sensitivity to minor variations in experithis transformation invoked Favorskii-type ring mental conditions, has been noted (3, 4). In the contraction, involving intermediates such as 2 (3) course of studies with m-cresol aimed at optimizaor 3 (4). It was demonstrated that meta alkyl sub-tion of yields of 1 (R = methyl), cf. ref. 1, the effects stituted phenols afforded the corresponding 2-alkyl of variations in temperature, pH, chlorine flow derivatives (1, R = methyl or n-propyl) under rate, etc. were explored. Under certain conditions similar conditions (1, 5), and the reaction was (see Experimental), two additional crystalline compounds were obtained as minor products. We report here on the structures of these compounds, C7H704Cl and C7H,04Cl, which are prod-