Use of linear free energy relationships (LFERS) to elucidate the mechanisms of reaction of a γ-methyl-β-alkynyl and an ortho-infstituted aryl chloroformate ester

International Journal of Molecular Sciences

Volumn 13, Issue 1, 2012, Pages 665-682

  D'Souza, Malcolm J ^a   Knapp, Jaci A ^a   Fernandez Bueno, Gabriel A ^a   Kevill, Dennis N ^b  

^a Wesley College   (United States)

^b NORTHERN ILLINOIS UNIVERSITY   (United States)

Author keywords

methyl alkynyl chloroformate; 2 butyn 1 yl chloroformate; 2 methoxyphenyl chloroformate; Aryl chloroformate; Grunwald winstein equation; Ionizing power; Linear free energy relationships (LFERS); Nucleophilicity; Solvolysis

Indexed keywords

2 BUTYN 1 YL CHLOROFORMATE; 2 METHOXYPHENYL CHLOROFORMATE; SOLVENT; UNCLASSIFIED DRUG; ALKYNE; ANISOLE DERIVATIVE; CHLOROCARBONIC ACID; ESTER; FORMIC ACID DERIVATIVE; WATER;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONTROLLED STUDY; HYDROGEN BOND; IONIZATION; NUCLEOPHILICITY; SOLVOLYSIS; TEMPERATURE; CHEMISTRY; KINETICS; THERMODYNAMICS;

ALKYNES; ANISOLES; ESTERS; FORMATES; KINETICS; SOLVENTS; TEMPERATURE; THERMODYNAMICS; WATER;

EID: 84856250797     PISSN: None     EISSN: 14220067     Source Type: Journal    
DOI: 10.3390/ijms13010665     Document Type: Article

References (76)

1. Rinehart, J.K. Symmetrical alkynyl ureas. U.S. Patent 4,066,440, 3 January 1978.
2. Hirao, G.; Totani, Y.; Itou, T.; Nakatsuka, M.; Yamaguchi, T. Aromatic chloroformate compound. Jpn. Patent JP3394057, 31 January 2003.
3. Wang, W.; Xu, B.; Hammond, G.B. Synthesis of functionalized α,α-diinfstituted β-alkynyl esters from allenoates through an alkynylenolate intermediate. Org. Lett. 2008, 10, 3713-3716.
4. Lepore, S.D.; He, Y.; Damisse, P. Studies on the base-promoted conversion of conjugated alkynyl esters to α-infstituted α-allenyl esters. J. Org. Chem. 2004, 69, 9171-9175.
5. Fathalla, O.A.; Zeid, I.F.; Haiba, M.E.; Soliman, A.M.; Abd-Elmoez, Sh.I.; El-Serwy, W.S. Synthesis, antibacterial and anticancer evaluation of some pyrimidine derivatives. World J. Chem. 2009, 4, 127-132.
6. Wells, P.R. Linear Free Energy Relationships; Academic Press: New York, NY, USA, 1968; pp. 8-35.
7. Roberts, I.; Johnson, C.D.; Taylor, P.G. Linear free energy and solvolysis reactions. Tetrahedron 1977, 33, 2123-2126.
8. Shorter, J. Correlations Analysis of Organic Reactivity; with Particular Reference to Multiple Regression Analysis; John Wiley & Sons, Inc.: Somerset, NJ, USA, 1982; pp. 1-235.
9. Winstein, S.; Grunwald, E.; Jones, H.W. The correlation of solvolyses rates and the classification of solvolysis reactions into mechanistic categories. J. Am. Chem. Soc. 1951, 73, 2700-2707, and references there in.
10. Bentley, T.W.; Garley, M.S. Correlations and predictions of solvent effects on reactivity: some limitations of multi-parameter equations and comparisons with similarity models based on one solvent parameter. J. Phys. Org. Chem. 2006, 19, 341-349.
11. Bentley, T.W.; Harris, H.C.; Ryu, Z.-H.; Lim, G.T.; Sung, D.D.; Szajda, S.R. Mechanisms of solvolyses of acid chlorides and chloroformates. Chloroacetyl and phenylacetyl chloride as similarity models. J. Org. Chem. 2005, 70, 8963-8970.
12. Kevill, D.N.; D'Souza, M.J. Sixty years of the Grunwald-Winstein equation: development and recent applications. J. Chem. Res. 2008, 2008, 61-66, and references therein.
13. Bentley, T.W.; Carter, G.E. The SN2-SN1 spectrum. 4. Mechanism for solvolyses of tert-butyl chloride: A revised Y scale of solvent ionizing power based on solvolyses of 1-adamantyl chloride. J. Am. Chem. Soc. 1982, 104, 5741-5747.
14. Bentley, T.W.; Llewellyn, G. Yx scales of solvent ionizing power. Prog. Phys. Org. Chem. 1990, 17, 121-158.
15. Kevill, D.N.; D'Souza, M.J. Additional YCl values and correlation of the specific rates of solvolysis of tert-butyl chloride in terms of NT and YCl scales. J. Chem. Res. Synop. 1993, 174-175.
16. Lomas, J.S.; D'Souza, M.J.; Kevill, D.N. Extremely large acceleration of the solvolysis of 1-adamantyl chloride upon incorporation of a spiro adamantane infstituent: Solvolysis of 1-chlorospiro[adamantane-2, 2'-adamantane]. J. Am. Chem. Soc. 1995, 117, 5891-5892.
17. Kevill, D.N.; Ryu, Z.H. Additional solvent ionizing power values for binary water-1,1,1,3,3,3,-hexafluoro-2-propanol solvents. Int. J. Mol. Sci. 2006, 7, 451-455.
18. Schadt, F.L.; Bentley, T.W.; Schleyer, P.v.R. The SN2-SN1 spectrum. 2. Quantitative treatments of nucleophilic solvent assistance. A scale of solvent nucleophilicities. J. Am. Chem. Soc. 1976, 98, 7667-7674.
19. Kevill, D.N.; Anderson, S.W. An improved scale of solvent nucleophilicity based on the solvolysis of the S-methyldibenzothiophenium Ion. J. Org. Chem. 1991, 56, 1845-1850.
20. Kevill, D.N. Development and Uses of Scales of Solvent Nucleophilicity. In Advances in Quantitative Structure-Property Relationships; Charton, M., Ed.; JAI Press: Greenwich, CT, USA, 1996; Volume 1, pp. 81-115.
21. D'Souza, M.J.; Ryu, Z.-H.; Park, B.-C.; Kevill, D.N. Correlation of the rates of solvolysis of acetyl chloride and α-infstituted derivatives. Can. J. Chem. 2008, 86, 359-367.
22. Bentley, T.W. Structural effects on the solvolytic reactivity of carboxylic and sulfonic acid chlorides. Comparisons with gas-phase data for cation formation. J. Org. Chem. 2008, 73, 6251-6257.
23. D'Souza, M.J.; Yaakoubd, L.; Mlynarski, S.L; Kevill, D.N. Concerted solvent processes for common sulfonyl chloride precursors used in the synthesis of sulfonamide-based drugs. Int. J. Mol. Sci. 2008, 9, 914-925.
24. D'Souza, M.J.; Shuman, K.E.; Carter, S.E.; Kevill, D.N. Extended Grunwald-Winstein analysis-LFER used to gauge solvent effects in p-nitrophenyl chloroformate solvolysis. Int. J. Mol. Sci. 2008, 9, 2231-2242.
25. Ryu, Z.-H.; Lee, S.W.; D'Souza, M.J.; Yaakoubd, L.; Feld, S.E.; Kevill, D.N. Correlation of the rates of solvolysis of two arenesulfonyl chlorides and of trans-β-styrenesulfonyl chloride-Precursors in the development of new pharmaceuticals. Int. J. Mol. Sci. 2008, 9, 2639-2657.
26. D'Souza, M.J.; Reed, D.N.; Erdman, K.J.; Kyong, J.B.; Kevill, D.N. Grunwald-Winstein analysis-isopropyl chloroformate solvolysis revisited. Int. J. Mol. Sci. 2009, 10, 862-879.
27. Bentley, T.W.; Jones, R.O.; Kang, D.H.; Koo, I.S. The SN3-SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols. J. Phys. Org. Chem. 2009, 22, 799-806.
28. D'Souza, M.J.; Hailey, S.M.; Kevill, D.N. Use of empirical correlations to determine solvent effects in the solvolysis of S-methyl chlorothioformate. Int. J. Mol. Sci. 2010, 11, 2253-2266.
29. D'Souza, M.J.; Mahon, B.P.; Kevill, D.N. Analysis of the nucleophilic solvation effects in isopropyl chlorothioformate solvolysis. Int. J. Mol. Sci. 2010, 11, 2507-2611.
30. Koh, H.J.; Kang, S.J.; Kevill, D.N. Kinetic studies of the solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate. Bull. Korean Chem. Soc. 2010, 31, 835-839.
31. Koh, H.J.; Kang, S.J. Kinetic studies of the solvolyses of isopropenyl chloroformate. Bull. Korean Chem. Soc. 2010, 31, 1793-1796.
32. D'Souza, M.J.; Darrington, A.M.; Kevill, D.N. On the importance of the aromatic ring parameter in studies of the solvolyses of cinnamyl and cinnamoyl halides. Org. Chem. Int. 2010, 2010, doi:10.1155/2010/130506.
33. Moon, D.H.; Seong, M.H.; Kyong, J.B.; Lee, Y.; Lee, Y.-W. Correlation of the rates of solvolysis of 1- and 2-naphthyl chloroformates using the extended Grunwald-Winstein equation. Bull. Korean Chem. Soc. 2011, 32, 2413-2417.
34. D'Souza, M.J.; Carter, S.E.; Kevill, D.N. Correlation of the rates of solvolysis of neopentyl chloroformate-A recommended protecting agent. Int. J. Mol. Sci. 2011, 12, 1161-1174.
35. D'Souza, M.J.; Darrington, A.M.; Kevill, D.N. A study of solvent effects in the solvolysis of propargyl chloroformate. ISRN Org. Chem. 2011, 2011, 767141:1-767141:6.
36. D'Souza, M.J.; McAneny, M.J.; Kevill, D.N.; Kyong, J.B.; Choi, S.H. Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters. Beilstein J. Org. Chem. 2011, 7, 543-552.
37. D'Souza, M.J.; Shuman, K.E.; Omondi, A.O.; Kevill, D.N. Detailed analysis for the solvolysis of isopropenyl chloroformate. Eur. J. Chem. 2011, 2, 130-135.
38. D'Souza, M.J.; Hailey, S.M.; Mahon, B.P.; Kevill, D.N. Understanding solvent effects in the solvolyses of 4-fluorophenyl chlorothionoformate. Chem. Sci. J. 2011, CSJ-35, 1-9.
39. Koh, H.J.; Kang, S.J. A kinetic study on solvolysis of 9-fluorenylmethyl chloroformate. Bull. Korean Chem. Soc. 2011, 32, 3799-3801.
40. Ruff, F.; Farkas, Ö. Concerted SN2 mechanism for the hydrolysis of acid chlorides: Comparisons of reactivities calculated by the density functional theory with experimental data. J. Phys. Org. Chem. 2011, 24, 480-491.
41. Park, K.-H.; Kevill, D.N. Influence of the ortho effect in the solvolyses of dichlorobenzoyl chlorides. J. Phys. Org. Chem. 2011, doi:10.1002/poc.1851.
42. Park, K.-H.; Kevill, D.N. The importance of the ortho effect in the solvolyses of 2,6-difluorobenzoyl chloride. J. Phys. Org. Chem. 2011, doi:10.1002/poc.1906.
43. Bentley, T.W.; Harris, H.C. Solvolyses of benzoyl chlorides in weakly nucleophilic media. Int. J. Mol. Sci. 2011, 12, 4805-4818.
44. Kevill, D.N.; Ismail, N. H.J.; D'Souza, M.J. Solvolysis of the (p-methoxybenzyl)dimethylsulfonium Ion. Development and use of a scale to correct for dispersion in Grunwald-Winstein plots. J. Org. Chem. 1994, 59, 6303-6312.
45. Kevill, D.N.; D'Souza, M.J. Use of the simple and extended Grunwald-Winstein equations in the correlation of the rates of solvolysis of highly hindered tertiary alkyl derivatives. Cur. Org. Chem. 2010, 14, 1037-1049.
46. Queen, A. Kinetics of the hydrolysis of acyl chlorides in pure water. Can. J. Chem. 1967, 45, 1619-1629.
47. Butler, A.R.; Robertson, I.H.; Bacaloglu, R. Kinetics and mechanism of the base-catalysed hydrolysis of some infstituted phenyl chloroformates. J. Chem. Soc. Perkin Trans 2 1974, 1733-1736.
48. Yew, K.H.; Koh, H.J.; Lee, H.W.; Lee, I. Nucleophilic infstitution reactions of phenyl chloroformate. J. Chem. Soc. Perkin Trans. 2 1995, 2263-2268.
49. Koo, I.S.; Yang, K.; Kang, K.; Oh, H.K.; Lee, I. Stoichiometric solvation effects. Product-rate correlation for the solvolyses of phenyl chloroformate in alcohol-water mixtures. Bull. Korean Chem. Soc. 1996, 17, 520-524.
50. Kevill, D.N.; D'Souza, M.J. Correlation of the rates of solvolysis of phenyl chloroformate. J. Chem. Soc. Perkin Trans. 2 1997, 1721-1724.
51. Koo, I.S.; Yang, K.; Koo, J.C.; Park, J.-K.; Lee, I. Stoichiometric solvation effects. Part 4. Product-Rate correlations for solvolyses of p-methoxyphenyl chloroformate in alcohol-water mixtures. Bull. Korean Chem. Soc. 1997, 18, 1017-1021.
52. Koo, I.S.; Yang, K.; Kang, K.; Lee, I.; Bentley, T.W. Stoichiometric solvation effects. Part 3. Product-Rate correlations for solvolyses of p-nitrophenyl chloroformate in alcohol-water mixtures. J. Chem. Soc. Perkin Trans 2 1998, 1179-1183.
53. Koo, I.S.; Yang, K.; Kang, K.; Lee, I. Transition-state variation in the solvolyses of para-infstituted phenyl chloroformates in alcohol-water mixtures. Bull. Korean Chem. Soc. 1998, 19, 968-973.
54. Kevill, D.N.; Koyoshi, F.; D'Souza, M.J. Correlation of the specific rates of solvolysis of aromatic carbamoyl chlorides, chloroformates, chlorothionoformates, and chlorodithioformates revisited. Int. J. Mol. Sci. 2007, 8, 346-352.
55. D'Souza, M.J.; Reed, D.; Koyoshi, F.; Kevill, D.N. Consideration of the factors influencing the specific rates of solvolysis of p-methoxyphenyl chloroformate. Int. J. Mol. Sci. 2007, 8, 788-796.
56. Castro, E.A.; Ruiz, M.G.; Salinas, S.; Santos, J.G. Kinetics and mechanism of the aminolysis of phenyl and 4-nitrophenyl chloroformates in aqueous solution. J. Org. Chem. 1999, 64, 4817-4820.
57. Castro, E.A.; Ruiz, M.G.; Santos, J.G. Structure-reactivity correlations in the aminolysis of aryl chloroformates. Int. J. Chem. Kinetics 2001, 281-287.
58. Crugerias, J.; Leis, J.R.; Ríos, A. Micellar effects on the spontaneous hydrolysis of phenyl chloroformate. J. Chem. Educ. 2001, 78, 1538-1540.
59. Muňoz, M.; Rodríguez, A.; Graciani, M.d.M.; Moyá, M.L. Micellar medium effects on the hydrolysis of phenyl chloroformate in ionic, zwitterionic, nonionic, and mixed micellar solutions. Int. J. Chem. Kinetics 2002, 34, 445-451.
60. Graciani, M.d.M.; Rodríguez, A.; Muňoz, M.; Moyá, M. Water-ethylene glycol alkyltrimethylammonium bromide micellar solutions as reaction media: Study of spontaneous hydrolysis of phenyl chloroformate. Langmuir 2003, 19, 8685-8691.
61. McManus, S.P.; Safavy, A. Solvolysis in mixed solvents with complementary electrophilic and nucleophilic properties. Hexafluoro-2-propanol and 1,3-propanedithiol. J. Org. Chem. 1986, 51, 3532-3535.
62. Doherty, R.M.; Abraham, M.H.; Harris, J.M.; Taft, R.W.; Kamlet, M.J. Linear solvation energy relationships. 39. A double-difference method for estimating electrophilic solvent assistance effects in solvolysis reactions. J. Org. Chem. 1986, 51, 4872-4875.
63. Koo, I.S.; Lee, J.S.; Yang, K.; Kang, K.; Lee, I. The studies on infstituent and kinetic solvent isotope effect in solvolyses of phenyl chloroformates. Bull. Korean Chem. Soc. 1999, 20, 573-576.
64. Kim, R.; Ali, D.; Lee, J.P.; Yang, K.; Koo, I.S. Correlation of the rates of solvolysis of 4-morpholinecarbonyl chloride using the extended Grunwald-Winstein equation. Bull. Korean Chem. Soc. 2010, 31, 1963-1967.
65. Choi, H.; Ali, D.; Lee, J.P.; Yang, K.; Park, J.K.; Koo, I.S. Correlation of the rates of solvolysis of 1-piperidincarbonyl chloride using the extended Grunwald-Winstein equation. Bull. Korean Chem. Soc. 2011, 32, 3941-3946.
66. Kevill, D.N.; Casamassa, A.J.; D'Souza, M.J. Rates and product selectivities for the solvolyses of 4-(chloroformyl)morpholine. J. Chem. Res. S. 1996, 472-473.
67. Chemical Compounds Database. Available online: http://www.chembase.com/cbid_84810.htm (accessed on 8 October 2010).
68. Kevill, D.N.; D'Souza, M.J. Concerning the two reaction channels for the solvolyses of ethyl chloroformate and ethyl chlorothioformate. J. Org. Chem. 1998, 63, 2120-2124.
69. Kyong, J.B.; Won, H.; Kevill, D.N. Application of the extended Grunwald-Winstein equation to solvolyses of n-propyl chloroformate. Int. J. Mol. Sci. 2005, 6, 87-96.
70. Kevill, D.N.; Kim, J.C.; Kyong, J.B. Correlation of the rates of solvolysis of methyl chloroformate and solvent properties. J. Chem. Res. S. 1999, 150-151.
71. Frost, A.A.; Pearson, R.G. Kinetics and Mechanism-a Study of Homogeneous Chemical Reactions, 2nd Ed.; Wiley: New York, NY, USA, 1961; pp. 49-50.
72. Kevill, D.N.; Abduljaber, M.H. Correlation of the rates of solvolysis of cyclopropylcarbinyl and cyclobutyl bromides using the extended Grunwald-Winstein equation. J. Org. Chem. 2000, 65, 2548-2554.
73. Microsoft Office, Excel 2010; Microsoft Corporation: Redmond, WA, USA, 2010.
74. SigmaPlot, version 9.0; SYSTAT Software Inc.: San Jose, CA, USA, 2005.
75. ® Informatics System, ADME/Tox 2008; BioRad Laboratories, Philadelphia, PA, USA, 2008.
76. D'Souza, M.J.; Dwyer, P.; Allison, B.E.; Miller, J.M.; Drohan, J. Wesley College ignites potential with undergraduate student research program. CUR Quart. 2011, 32, 41-45.