2,2′‐ジヒドロキシ‐3,3′‐ジメチル‐5,5′‐メチレン二安息香酸のニトロ化による開裂
Nitrative Cleavage of 2, 2'-Dihydroxy-3, 3'-dimethyl 5, 5'-methylenedibenzoic Acid

Misao SHINODA, Tadatomo ASAOKA, Choichiro SHIMASAKI, Hitomi SUZUKI
1974 NIPPON KAGAKU KAISHI  
Reactions of the title compound Cl J with nitric acid (d=1. 38) have been investigated in chloroform, carbon tetrachloride, nitromethane, methanol, and acetic acid. In every case, C 1] underwent facile nitrative cleavage and nitrodecarboxylation to yield 2-hydroxy-3-methy1-5nitrobenzoic acid C 2] as the major isolable product. Other products obtained include 4, 4'dihydroxy-3, 3'-dimethyl-5, 5'-dinitrodiphenylmethane C 3 D, 4-hydroxy-3-methyl-5-nitrobenzyl nitrate C 4 ), and 4,
more » ... 5 J. Substantial amounts of C 3 J were formed in the reactions in acetic acid. In addition to these, 4-hydroxy-3-methy1-5-nitrobenzyl methyl ether C 7 ) and 4-hydroxy-3-methyl-5-nitrobenzyl acetate C 8 J were obtained from the reactions in methanol and acetic acid, respectively. These benzylic compounds probably arose from the solvolysis of the initial product C 4D. With increase in the amount of nitric acid, formation of C 5 ] and unidentified carbonyl compounds became prominent. Further addition of nitiric acid upon C 3 3 in chloroform led to similar cleavage, giving C 4], C 5], and 4-hydroxy-3-methyl-5-nitrobenzaldehyde C 9]. By heating in acetic acid under , gentle reflux, C 4] was readily converted into a mixture of C 5] and C 8]. Possible pathway from C . ID to C 2 has been suggested.
doi:10.1246/nikkashi.1974.2375 fatcat:o7cxeru2xvaoxloctohoodmtxe