Kinetic study of reactions of a ketone with a dialkylmagnesium compound and with organomagnesate species

Organometallics

Volumn 21, Issue 17, 2002, Pages 3661-3666

  Chubb, John E ^a   Richey Jr , Herman G ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL SHIFTS;

ABSORPTION; BENZENE; KETONES; MAGNESIUM COMPOUNDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SOLUTIONS; SOLVENTS; SYNTHESIS (CHEMICAL);

ORGANOMETALLICS;

EID: 0037741062     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om020324r     Document Type: Article

References (44)

1. Some of this work is taken from: Chubb, J. E. Ph.D. Dissertation, The Pennsylvania State University, 1997.
2. 2Mg see: Wakefield, B. J. Organomagnesium Methods in Organic Synthesis; Academic: London, 1995. Refs 3 and 4. Silverman, G. S.; Rakita, P. E. Handbook of Grignard Reagents; Marcel Dekker: New York, 1996.
3. 2Mg see: Wakefield, B. J. Organomagnesium Methods in Organic Synthesis; Academic: London, 1995. Refs 3 and 4. Silverman, G. S.; Rakita, P. E. Handbook of Grignard Reagents; Marcel Dekker: New York, 1996.
4. Richey, H. G., Jr. Grignard Reagents: New Developments, Wiley: Chichester, 2000.
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6. Lindsell, W. E. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon: Oxford, 1982; Chapter 4. Lindsell, W. E. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 1, Chapter 3.
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8. 7
9. Holm, T.; Grassland, I. In ref 4, Chapter 1.
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14. To the extent that the equilibrium constant for formation of a 2:1 complex is small, dilution would reduce its amount, causing the NMR absorptions to move closer to those of the reactants. Within the limits of the precision of the spectra, however, the absorptions were not altered significantly.
15. Kinetic behavior was more complex at lower ratios.
16. Squiller, E. P.; Whittle, R. R.; Richey, H. G., Jr. J. Am. Chem. Soc. 1985, 707, 432. Richey, H. G., Jr.; Kushlan, D. M. J. Am. Chem. Soc. 1987, 709, 2510. Pajerski, A. D.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 2660. Richey, H. G., Jr. In Comprehensive Supramolecular Chemistry; Atwood, J. L., Davies, J. E. D., MacNicol. D. D. Vögtle, F., Eds.; Pergamon: Oxford, 1996; Vol. 1 (Gokel, G. W., Ed.), Chapter 21.
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18. Squiller, E. P.; Whittle, R. R.; Richey, H. G., Jr. J. Am. Chem. Soc. 1985, 707, 432. Richey, H. G., Jr.; Kushlan, D. M. J. Am. Chem. Soc. 1987, 709, 2510. Pajerski, A. D.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 2660. Richey, H. G., Jr. In Comprehensive Supramolecular Chemistry; Atwood, J. L., Davies, J. E. D., MacNicol. D. D. Vögtle, F., Eds.; Pergamon: Oxford, 1996; Vol. 1 (Gokel, G. W., Ed.), Chapter 21.
19. Squiller, E. P.; Whittle, R. R.; Richey, H. G., Jr. J. Am. Chem. Soc. 1985, 707, 432. Richey, H. G., Jr.; Kushlan, D. M. J. Am. Chem. Soc. 1987, 709, 2510. Pajerski, A. D.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 2660. Richey, H. G., Jr. In Comprehensive Supramolecular Chemistry; Atwood, J. L., Davies, J. E. D., MacNicol. D. D. Vögtle, F., Eds.; Pergamon: Oxford, 1996; Vol. 1 (Gokel, G. W., Ed.), Chapter 21.
20. Tang, H.; Parvez, M.; Richey, H. G., Jr. Organometallics 2000, 19, 4810.
21. Pajerski, A. D. Ph.D. Dissertation, The Pennsylvania State University, 1990.
22. Also see: Pajerski, A. D.; Chubb, J. E.; Fabicon. R. M.; Richey, H. G., Jr. J. Org. Chem. 2000, 65, 2231. Tang, H.; Richey, H. G., Jr. Organometallics 2001, 20, 1569.
23. Also see: Pajerski, A. D.; Chubb, J. E.; Fabicon. R. M.; Richey, H. G., Jr. J. Org. Chem. 2000, 65, 2231. Tang, H.; Richey, H. G., Jr. Organometallics 2001, 20, 1569.
24. + ions show magnesium to be so enveloped by 14N4 that specific interactions with donor molecules must be minimal [ref 16 and Tang, H.; Parvez, M.; Richey. H. G., Jr. Organometallics 1996, 15, 52811.
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26. 19
27. 2Mg or RMgX to the ketone (R′R″C=O), and transition metal impurities.
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33. 2Mg and p-methylthioacetophenone was extracted from kinetic observations [Rudolph, S. E.; Charbonneau, L. F.; Smith, S. G. J. Am. Chem. Soc. 1973, 95, 7083].
34. Bikales, N. M.; Becker, E. I. Can. J. Chem. 1963, 41, 1329. Holm, T. Acta Chem. Scand. 1966, 20, 1139. Also see: Holm, T. Acta Chem. Scand. 1966, 20, 2821.
35. Bikales, N. M.; Becker, E. I. Can. J. Chem. 1963, 41, 1329. Holm, T. Acta Chem. Scand. 1966, 20, 1139. Also see: Holm, T. Acta Chem. Scand. 1966, 20, 2821.
36. Bikales, N. M.; Becker, E. I. Can. J. Chem. 1963, 41, 1329. Holm, T. Acta Chem. Scand. 1966, 20, 1139. Also see: Holm, T. Acta Chem. Scand. 1966, 20, 2821.
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40. 2Mg in THF.
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