THE ALKALINE HYDROLYSIS OF NITRATE ESTERS
Abstract
The stability of nitrate esters in 90% (v/v) ethanol containing sodium hydroxide was studied. Initial rates of decomposition were determined at either 30C or 60C of methyl, n-propyl, n-butyl, n-heptyl, iso-butyl and ethylene glycol mono- nitrates; ethylene glycol, propane 1,3-diol, butane 1,4-diol, pentane 1,5-diol, butane 1,3-diol, butane 2,3-diol, propane 1,2-diol, diethyleneglycol and triethylene glycol dinitrates; glycerol 1- and 2-mono-1,3- di- and trinitrate; metriol and NIBG trinitrates; and PETN and 2-nitro-ethyl nitrate. Alkyl substituents, with retarding inductive effects, stabilize the esters, whereas nitro, nitrate, and hydroxyl groups (with electron attracting properties) increase the rate of hydrolysis by increasing the ionization of alpha-hydrogens. The effects fall off rapidly as the distance between groups increases. Steric effects are more difficult to assess, but increasing the substitution of the beta-carbon appears to decrease the rate of hydrolysis: specific rates range from 0.000044 to 0.000016/M/s (ethyl to isobutyl nitrate) and from 0.0000128 to 0.000034/M/s (NIBG trinitrate to PETN). Ammonium salts decrease reaction rates by combining with hydroxyl ions.
Document Details
- Document Type
- Technical Report
- Publication Date
- May 22, 1968
- Accession Number
- AD0675917
Entities
People
- R. T. Fraser