Catalytic pathways in the ethanolysis of fenitrothion, an organophosphorothioate pesticide. A dichotomy in the behaviour of crown/cryptand cation complexing agents

• Published in: Canadian journal of chemistry Vol. 79; no. 2; pp. 157 - 173
• Main Authors: Balakrishnan, Vimal K, Dust, Julian M, vanLoon, Gary W, Buncel, Erwin
• Format: Journal Article
• Language: English
• Published: Ottawa, Canada NRC Research Press 01.02.2001; Canadian Science Publishing NRC Research Press
• Subjects: Alkali metals; Catalysis; Catalysts; Chemical reactions; Chemistry; Esters; Ethanol; Herbicides & pesticides; Organometallic compounds; Pesticides; Phosphorus compounds; R&D; Research & development
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/v01-006

The rates of displacement of 3-methyl-4-nitrophenoxide ion from the pesticide, fenitrothion, by alkali metal ethoxides in anhydrous ethanol were followed spectrophotometrically. Through product analysis experiments, which included 31 P NMR and GC-MS, as well as spectrophotometric analysis, three reaction pathways were identified: nucleophilic attack at the phosphorus centre, attack at the aliphatic carbon, and a minor S N Ar route ( 7%). Furthermore, a consecutive process was found to occur on the product of attack at the phosphorus centre. For purposes of kinetic treatment, the processes at the aliphatic and aromatic carbon were combined (i.e., the minor S N Ar pathway was neglected), and the observed reaction rate constants were dissected into rate coefficients for nucleophilic attack at phosphorus and at aliphatic carbon. Attack at phosphorus was found to be catalyzed by the alkali metal ethoxides in the order KOEt > NaOEt > LiOEt. Catalysis arises from alkali metal ethoxide aggregates in the base solutions used (0–1.8 M); treatment of the system as a mixture of free ethoxide, ion-paired metal ethoxide, and metal ethoxide dimers resulted in a good fit with the kinetic data. An unexpected dichotomy in the kinetic behaviour of complexing agents (e.g., DC-18-crown-6, [2.2.2]cryptand) indicated that the dimers are more reactive than free ethoxide anions, which are in turn more reactive than ion-paired metal ethoxide. The observed relative order of reactivity is explained in the context of the Eisenman theory in which the free energy of association of the metal ion with the rate-determining transition state is largely determined by the solvent reorganization parameter. In contrast with displacement at the phosphorus centre, attack at the aliphatic carbon was not found to be catalyzed by alkali metals. In this case, the free ethoxide anion was more reactive than either the ion-paired metal ethoxide or the dimeric aggregate. The differing effects of alkali metals on the two pathways is ascribed largely to the leaving group pK a . For carbon attack, the pK a value estimated for demethyl fenitrothion, 2.15, is sufficiently low that metal ions are not required to stabilize the rate-determining transition state. In contrast, for phosphorus attack, 3-methyl-4-nitrophenoxide, with a pK a of 7.15, requires stabilization by metal ion interactions. Hence, alkali metal ions catalyze attack at phosphorus, but not attack at the carbon centres.Key words: organophosphorothioate, pesticide, fenitrothion, ethanolysis, alkali metal ethoxide, ion-pair reactivity, dimers, catalysis, competitive pathways.