Reactions of 1,3,5-trinitrobenzene with primary aliphatic alcohols

Journal Article · Tue May 15 04:00:00 EDT 2018 · Russian Chemical Bulletin

DOI:https://doi.org/10.1007/S11172-018-2143-2· OSTI ID:22863343

Aleksanyan, D. R. ^[1]; Serushkina, O. V.; Nesterova, E. N.; Shevelev, S. A. ^[2]

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1. Gubkin Russian State University of Oil and Gas (Russian Federation)
2. Russian Academy of Sciences, N. D. Zelinsky Institute of Organic Chemistry (Russian Federation)

Analysis of reactions of 1,3,5-trinitrobenzene (TNB) with alcoholates of primary aliphatic alcohols (substitution of the nitro group or generation of σ{sup H}-complexes at the unsubstituted position of TNB) leads to the conclusion that high basicity of alcoholates (MeONa, EtONa) of unsubstituted primary alcohols promotes formation of σ{sup H}-complexes, thus preventing nucleophilic substitution of a nitro group. Introduction of electron-withdrawing substitutes (R = HC≡C, H{sub 2}C = CH, pyridyl) into the alcohol molecule (RCH{sub 2}OH) reduces the basicity of their alcoholates which makes substitution of nitro groups possible aff ording the corresponding 1-alkoxy-3,5-dinitrobenzenes in the presence of K{sub 2}CO{sub 3} in N-methylpyrrolidone at 80 °C.

• OSTI ID: 22863343
• Journal Information: Russian Chemical Bulletin, Journal Name: Russian Chemical Bulletin Journal Issue: 5 Vol. 67; ISSN RCBUEY; ISSN 1066-5285
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ALCOHOLS
ALKOXIDES
COMPLEXES
ELECTRONS
NITROBENZENE
POTASSIUM CARBONATES