Accession Number : AD0473679

Title :   THE MICHAEL REACTION IN NON-ALKALINE MEDIA. IX. KINETICS AND MECHANISMS OF THE REACTIONS IN THE NITROFORM-METHYL ACRYLATE SYSTEM.

Descriptive Note : Technical rept.,

Corporate Author : NAVAL ORDNANCE LAB WHITE OAK MD

Personal Author(s) : Kaplan, Lloyd A. ; Glover, Donald J.

Report Date : 24 SEP 1965

Pagination or Media Count : 42

Abstract : The kinetics of the addition of nitroform to methyl acrylate to form methyl 4,4,4-trinitrobutyrate (MeTNB) and methyl 4,4-dinitro- 2-hydroxybutyrate (DNS) in 50% dioxane were studied in perchloric acid and acetic acid buffers. The reaction forming MeTNB is subject to general acid catalysis except at high acidities where the addition of trinitromethide ion to methyl acrylate becomes rate determining. The reaction forming DNS was found to compete with the protonation reaction for the intermediate carbanion. This reaction is kinetically first order in the intermediate carbanion. From the results of O-18-tracer experiments, a mechanism for the formation of DNS is suggested. (Author)

Descriptors :   *REACTION KINETICS), (*ORGANIC NITROGEN COMPOUNDS, (*ESTERS, REACTION KINETICS), SYNTHESIS(CHEMISTRY), ORGANIC SOLVENTS, SOLUTIONS(MIXTURES), PERCHLORIC ACID, CARBOXYLIC ACIDS, TRACER STUDIES, IONS, PH FACTOR, BUFFERS, CATALYSTS.

Distribution Statement : APPROVED FOR PUBLIC RELEASE