Reactivity of activated phenyl groups in supercritical water

Journal Article · Thu Aug 01 04:00:00 EDT 1996 · High Temperature and Materials Science

OSTI ID:538290

Hibbs, M R; Yao, J; Evilia, R F ^[1]

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1. Univ. of New Orleans, LA (United States). Dept. of Chemistry

The reactivities of phenol, anisole, aniline, and N,N-dimethylaniline in deuterium oxide and sodium deuteroxide solution at 400 C and 250 bar are reported. Ortho/para deuteration characteristic of electrophilic substitution is found for phenol in both media and for all of the compounds in deuterium oxide. However, under basic conditions, only ortho deuteration of anisole and aniline and no deuteration of N,N-dimethylaniline is observed. These latter results in basic media suggest that, in these cases, the reaction proceeds via attack by deuteroxide ion at the site closest to the inductively electron withdrawing group, rather than by the more common electrophilic mechanism. N,N-dimethylaniline undergoes electrophilic substitution under neutral conditions, but does not react in basic media because either the acidity of its ortho hydrogen is too weak and/or it is sterically hindered by the presence of the methyl groups. N,N,N-trimethyl ammonium chloride decomposes to uncharacterized products under the reaction conditions employed.

• OSTI ID: 538290
• Journal Information: High Temperature and Materials Science, Journal Name: High Temperature and Materials Science Journal Issue: 1 Vol. 36; ISSN HTMSFP; ISSN 1080-1278
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
54 ENVIRONMENTAL SCIENCES
ACTIVATION ENERGY
ANILINE
ANISOLE
CHEMICAL REACTION KINETICS
DEUTERATION
HEAVY WATER
INDUSTRIAL WASTES
PHENOL
POLYCYCLIC AROMATIC AMINES
SUPERCRITICAL STATE
WATER