Kinetics and Mechanism of the Nucleophilic Displacement Reactions of Chloroacetanilide Herbicides: Investigation of α-Substituent Effects

Journal of Agricultural and Food Chemistry

Volumn 52, Issue 10, 2004, Pages 3010-3021

  Lippa, Katrice A ^a   Demel, Sandra ^a   Lau, Irvin H ^a   Roberts, A Lynn ^a  

^a The Johns Hopkins University   (United States)

Author keywords

Activation parameters; Alachlor; Anchimeric assistance; Chloroacetamidea; Chloroacetanilidea; Intramolecular substitution; Metolachlor; Neighboring group participation; Nucleophilic aliphatic substitution; Propachlor; S N2

Indexed keywords

ACETANILIDE DERIVATIVE; ALACHLOR; ALPHA CHLOROACETANILIDE; ALPHA CHLOROTHIOACETANILIDE; ANILINE; HERBICIDE; NITROGEN; PROPACHLOR; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; HERBICIDAL ACTIVITY; IONIC STRENGTH; KINETICS; MOLECULAR INTERACTION; NUCLEOPHILIC DISPLACEMENT REACTION; REACTION ANALYSIS; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS;

ACETAMIDES; ACETANILIDES; ANIONS; CHEMISTRY, PHYSICAL; KINETICS; OSMOLAR CONCENTRATION; SOLUTIONS; SULFUR COMPOUNDS; WATER;

EID: 2442439021     PISSN: 00218561     EISSN: None     Source Type: Journal    
DOI: 10.1021/jf030290d     Document Type: Article

References (58)

1. 2-). Environ. Sci. Technol. 2002, 36, 4065-4073.
2. Gan, J.; Wang, Q.; Yates, S. R.; Koskinen, W. C.; Jury, W. A. Dechlorination of chloroacetanilide herbicides by thiosulfate salts. PNAS 2002, 99, 5189-5194.
3. Lebaron, H. M.; McFarland, J. E.; Simoneaux, B. J. Metolachlor. In Herbicides. Chemistry, Degradation, and Mode of Action; Kearney, P. C., Kaufman, D. D., Eds.; Marcel Dekker: New York, 1975; Vol. 3, pp 335-382.
4. Scarponi, L.; Perucci, P.; Martinetti, L. Conjugation of 2-chloroacetanilide herbicides with glutathione: role of molecular structures and of gluthathione S-transferase enzymes. J. Agric. Food Chem. 1991, 39, 2010-2013.
5. Lippa, K. A. Reactions of Chloro-s-triazine and Chloroacetanilide Agrochemicals with Reduced Sulfur Nucleophiles. Ph.D. Dissertation. The Johns Hopkins University: Baltimore, MD, 2002; p 474.
6. Kearney, P. C.; Kaufman, D. D. Chloroacetamides. In Herbicides: Chemistry, Degradation, and Mode of Action, 2nd ed.; Jaworski, E. G., Ed., Marcel Dekker: New York, 1975; pp 349-376.
7. Feng, P. C. Soil transformation of acetochlor via glutathione conjugation. Pestic. Biochem. Physiol. 1991, 40, 136-142.
8. Fuerst, E. P. Understanding the mode of action of the chloro-acetamide and thiocarbamate herbicides. Weed Technol. 1987, 1,270-277.
9. Copping, L. G.; Hewitt, H. G. Chemistry and Mode of Action of Crop Protection Agents; The Royal Society of Chemistry: Cambridge, 1998.
10. Hamm, P. C. Discovery, development and current status of the chloroacetamide herbicides. Weed Sci. 1974, 22, 541-545.
11. U. S. EPA. R. E. D. Facts. Alachlor. EPA-738-F-98-018; 1998. http://www.epa.gov/oppsrrd1/REDs/factsheets/0063fact.pdf (accessed Oct. 7, 2003).
12. U. S. EPA. Acetochlor. http://www.epa.gov/oppefed1/aceto/index.htm (accessed Oct. 7, 2003).
13. U. S. EPA. R. E. D. Facts. Metolachlor. EPA-738-F-95-007; 1995. http://www.epa.gov/oppsrrd1/REDs/factsheets/0001fact.pdf (accessed Oct. 7, 2003).
14. Dearfield, K. L.; McCarroll, N. E.; Protzel, A.; Stack, H. F.; Jackson, M. A.; Waters, M. D. A survey of EPA/OPP and open literature on selected pesticide chemicals. II. Mutagenicity and carcinogenicity of selected chloroacetanilides and related compounds. Mutat. Res. 1999, 443, 183-221.
15. Boulègue, J.; Lord, C. J.; Church, T. M. Sulfur speciation and associated trace metals (Fe, Cu) in the pore waters of Great Marsh, Delaware. Geochim. Cosmochim. Acta 1982, 46, 453-464.
16. Zheng, H.; Ye, C. Hydrolysis of chloroacetanilide herbicides acetochlor and butachlor. Huanjing Huaxue 2001, 20, 168-171.
17. Moelwyn-Hughes, E. A. The hydrolysis of the methyl halides. Proc. R. Soc. London, Ser. A 1938, 164, 295-306.
18. N2 reactions. J. Am. Chem. Soc. 1964, 4645-4650.
19. McLennan, D. J.; Pross, A. The mechanism for nucleophilic substitution of α-carbonyl derivatives. Application of the valence-bond configuration mixing model. J. Chem. Soc., Perkin Trans. 2 1984, 981-984.
20. N2 nucleophilic substitution reactions: a theoretical comparison. J. Org. Chem. 1986, 51, 1030-1033.
21. Ross, S. D.; Finkelstein, M.; Peterson, R. C. Rates and salt effects in the reactions of phenacyl bromide with N-ethylaniline and triethylamine in chloroform. J. Am. Chem. Soc. 1968, 90, 6411-6415.
22. Chupp, J. P.; Olin, J. F.; Landwehr, H. K. Structural features influencing rotational isomerism and alkylation properties in some α-haloacetanilides. J. Org. Chem. 1968, 34, 1192-1197.
23. N2 reactions. 2. Tetrahedron 1997, 53, 10513-10516.
24. Mukerjee, A. K.; Singh, A. K. β-Lactams: retrospect and prospect. Tetrahedron 1978, 34, 1731-1767.
25. L'abbé, G. Heterocyclic analogues of methylenecyclopropanes. Angew. Chem., Int. Ed. Engl. 1980, 19, 276-289.
26. Gupta, R. R.; Kumar, M.; Gupta, V. Four-Membered Heterocycles. In Heterocyclic Chemistry I; Springer: Berlin, 1998; pp 360-410.
27. Hoffman, R. V. Stereospecificity in the α-Lactam (Aziridinone) Synthon. In The Amide Linkage. Structural Significance in Chemistry, Biochemistry, and Material Science; Greenberg, A., Breneman, C. M., Liebman, J. F., Eds.; Wiley-Interscience: New York, 2000; pp 137-155.
28. Lippa, K. A.; Roberts, A. L. Nucleophilic displacement reactions of chloroacetanilide herbicides: a DFT computational study of α-substituent effects. J. Agric. Food Chem. 2004, in preparation.
29. N2 reactions of chloroacetanilide herbicides and their structural analogs with environmentally relevant nucleophiles. Environ. Toxicol. Chem. 2004, in preparation.
30. Carlson, D. L. Environmental Transformations of Chloroacetamide Herbicides: Hydrolysis and Reactions with Iron Pyrite. Ph.D. Dissertation. The Johns Hopkins University: Baltimore, MD, 2003; p 256.
31. 2-). Environ. Sci. Technol. 2002, 36, 2008-2018.
32. Stumm, W.; Morgan, J. J. Aquatic Chemistry. Chemical Equilibria and Rates in Natural Waters; Wiley and Sons: New York, 1996.
33. Montgomery, J. H., Ed. Agrochemicals Desk Reference: Environmental Data; Lewis Publishers: Boca Raton, FL, 1993; p 450.
34. EPA. Health and Environmental Effects Document for Chloro-acetic Acid. ECAO-CIN-G038. Environmental Criteria and Assessment Office, Office of Health and Environmental Assessment, Office of Research and Development: Cincinnati, OH, 1988.
35. Jeffers, P. M.; Wolfe, N. L. Homogeneous hydrolysis rate constants. Part II: additions, correction, and halogen effects. Environ. Toxicol. Chem. 1996, 15, 1066-1070.
36. Swain, C. R.; Scott, C. B. Quantitative correlation of relative rates. Comparison of hydroxide ion with other nucleophilic reagents towards alkyl halides, esters, epoxides and acyl halides. J. Am. Chem. Soc. 1953, 75, 141-147.
37. O'Conner, C. J.; Denny, W. A.; Fan, J.-Y.; Gravatt, G. L.; Grigor, B. A. ; McLennan, D. J. Hydrolysis and alkylating reactivity of aromatic nitrogen mustards. J. Chem. Soc., Perkin Trans. 2 1991, 1933-1939.
38. Cullis, P. M.; Green, R. E.; Malone, M. E. Mechanism and reactivity of chlorambucil and chlorambucil-spermidine conjugate. J. Chem. Soc., Perkin Trans. 2 1995, 1503-1511.
39. Pettersson-Fernholm, T.; Vilpo, J.; Kosonen, M.; Hakala, K.; Hovinen, J. Reactions of 4-bis(2-chloroethyl)aminophenylacetic acid (phenylacetic acid mustard) in physiological solutions. J. Chem. Soc., Perkin Trans. 2 1999, 2183-2187.
40. Benn, M. H.; Kazmaier, P.; Watanatada, C. The mechanism of the reaction of aryl nitrogen mustards with nucleophiles. J. Chem. Soc., Chem. Commun. 1970, 1685-1686.
41. Fainberg, A. H.; Winstein, S. Salt effects and ion pairs in solvolysis and related reactions. IV. Salt effects in acetolysis of neophyl and p-methoxyneophyl halides and arylsulfonates. J. Am. Chem. Soc. 1955, 78, 2763-2767.
42. Duynstee, E. F. J.; Grunwald, E.; Kaplan, M. L. Salt-induced medium effects. II. Kinetic salt effects in the solvolysis of neophyl p-toluenesulfonate and in the racemization of 1-(+)-threo-3-phenyl-2-butyl p-toluenesulfonate in 50 wt % dioxane-water. J. Am. Chem. Soc. 1960, 82, 5654-5660.
43. Winstein, S.; Klinedinst, P. E.; Robinson, G. C. Salt effects and ion pairs in solvolysis and related reactions. XVII. Induced common ion rate depression and the mechanism of the special salt effect. J. Am. Chem. Soc. 1961, 83, 885-895.
44. Ritchie, C. D. Salt and Solvent Effects on Reaction Rates. In Physical Organic Chemistry: the Fundamental Concepts; Marcel Dekker: New York, 1990; pp 59-66.
45. Smith, M. B.; March, J. Aliphatic Nucleophilic Substitution. In March's Advanced Organic Chemistry. Reactions, Mechanisms, and Structure; Wiley-Interscience: New York, 2001; pp 389-674.
46. Mackay, D.; Shiu, W.-Y.; Ma, K.-C., Ed. Illustrated Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals. Oxygen, Nitrogen and Sulfur Containing Compounds; Lewis Publishers: Chelsea, 1992; Vol. IV.
47. Pross, A. Theoretical and Physical Principles of Organic Reactivity; John Wiley and Sons: New York, 1995.
48. Koivurinta, J.; Kyllonen, A.; Leinonen, L.; Valaste, K.; Koskikallio, J. Nucleophilic reactivity. Part VIII. Kinetics of reactions of methyl iodide with nucleophiles in water. Finn. Chem. Lett. 1974, 239-243.
49. Moelwyn-Hughes, E. A. The kinetics of certain reactions between methyl halides and anions in water. Proc. R. Soc. London, Ser. A 1949, 196, 540-553.
50. N2 and E2 reactions of β-substituted ethyl chlorides with sodium acetate in aqueous solution. Bull. Chem. Soc. Jpn. 1967, 40, 1913-1916.
51. Bathgate, R. H.; Moelwyn-Hughes, E. A. The kinetics of certain ionic exchange reactions of the four methyl halides in aqueous solutions. J. Chem. Soc. 1959, 2642-2648.
52. Alexander, R.; Ko, E. C. F.; Parker, A. J.; Broxton, T. J. Solvation of ions. XIV. Protic-dipolar aprotic solvent effects on rates of bimolecular reactions. Solvent activity coefficients of reactants and transition states at 25 °C. J. Am. Chem. Soc. 1968, 90, 5049-5069.
53. Turnquist, C. R.; Taylor, J. W.; Grimsrud, E. P.; Williams, R. C. Temperature dependence of chlorine kinetic isotope effects for aliphatic chlorides. J. Am. Chem. Soc. 1973, 95, 4133-4138.
54. Bel'skii, V. E. Isokinetic relationships for nucleophilic substitution reactions at the saturated carbon atom. Reactions in aqueous solution. Russ. Chem. Bull. (Engl. Transl.) 2000, 49, 806-811.
55. Galli, C.; Illuminati, G.; Mandolini, L.; Tamborra, P. Ring-closure reactions. 7. Kinetics and activation parameters of lactone formation in the range of 3- to 23-member rings. J. Am. Chem. Soc. 1977, 99, 2591-2597.
56. Edwards, J. O. Correlation of relative rates and equilibria with a double basicity scale. J. Am. Chem. Soc. 1954, 76, 1540-1547.
57. Edwards, J. O.; Pearson, R. G. The factors determining nucleophilic reactivities. J. Am. Chem. Soc. 1962, 84, 16-24.
58. O'Reilly, K. T.; Moir, M. E.; Taylor, C. D.; Smith, C. A.; Hyman, M. R. Hydrolysis of tert-butyl methyl ether (MTBE) in dilute aqueous acid. Environ. Sci. Technol. 2001, 35, 3954-3961.