Abstract
The reactions of 2,4,6-trinitrotoluene (TNT) and TNT-d3 (deuterated methyl group) with tetra-n-butylammonium tert-butoxide and with potassium tert-butoxide (KOBut), in the absence and presence of the crown ethers 18-crown-6, and dicyclohexyl-18-crown-6, have been studied kinetically in tert-butanol at 30.0 °C. Evidence is presented to support the suggestion that, at ratios of crown ether to base > 1, the reactive base species is free tert-butoxide ion and that this rapidly reacts with TNT or TNT-d3 to form, in each case, a mixture of σ-complex and purple anion. Specific rate constants for the reactions of free tert-butoxide ion and ion-paired KOBut with TNT and TNT-d3 to form both σ-complex and purple anion are compared.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
9 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献
1. Detection of dinitrotoluene isomers using reactions with bases: A structural, spectroscopic, kinetic, and computational study;Sensors and Actuators B: Chemical;2015-09
2. Speciation of the Products of and Establishing the Role of Water in the Reaction of TNT with Hydroxide and Amines: Structure, Kinetics, and Computational Results;The Journal of Physical Chemistry A;2013-10-30
3. Amidinate Salt of Hexafluoroacetone Hydrate for the Preparation of Fluorinated Compounds by the Release of Trifluoroacetate;Organic Letters;2012-12-14
4. The versatile electrophilic reactivity of 4,6-dinitrobenzo[d]isoxazole-3-carbonitrile;Organic & Biomolecular Chemistry;2009
5. Equilibrium data, visible absorption spectra and1H NMR studies for 1,8-Diazabicyclo [5,4,0]undec-7-ene (DBU) and sodium alkoxide addition to 1-x-2,4,6-trinitrobenzenes;Journal f�r Praktische Chemie/Chemiker-Zeitung;1992