Kinetics and Mechanism for the Basic Hydrolysis of BIS (2,2- Dinitropropyl) Acetal (BDNPA) and BIS (2,2-Dinitropropyl) Formal (BDNPF)
Abstract
The kinetics for the alkaline homogeneous hydrolysis of bis (2,2- dinitropropyl) acetal (BDNPA) and bis (2,2-dinitropropyl) formal (BDNPF) in water and 53% dioxane-water with sodium hydroxide concentrations between 0.14 and 1.9 molar and temperatures between 40 and 70 C have been investigated. Both BDNPA and BDNPF were found to react with slightly more than four moles of base to yield nitrite, 1,1-dinitroethane, acetate and formate anions. Good second order rate constants were obtained for both BDNPA and BDNPF for the expression - d(BDNPA/dt = k sub 1 (BDNPA) = k sub 2(B(-)) (BDNPA), were k sub 1 is the first order rate constant with excess base, B(-). BDNPA and BDNPF were found to react faster in dioxane-water than in water. The rates of disappearance of both BDNPA and BDNPF were very nearly equal to one half the combined rates for the formation of nitrite and 1,1-dinitroethane anions, and suggest concurrent competing E-2 elimination (78 + for - 5%) and Sn-2 nucleophilic displacement (20 + or - 3%) reactions with base. On the basis of relative K sub 2 values, BDNPA and BDNPF were found to react forty times faster with aqueous base than triethyleneglycol dinitrate (TEGDN), but one thousand times slower than 1,3,5- triaza-1-3,5-trinitrocyclohexane (RDX). The kinetics of the alkaline hydrolysis of BDNPA and BDNPF are discussed in terms of the products formed, and mechanisms are suggested for the formation of these products.
Document Details
- Document Type
- Technical Report
- Publication Date
- Mar 01, 1985
- Accession Number
- ADA153201
Entities
People
- J. C. Hoffsommer
Organizations
- Naval Ordnance Laboratory