Direct measurements of unimolecular radical kinetics employing ultrafast radical rearrangements as reporters

Journal of the American Chemical Society

Volumn 118, Issue 35, 1996, Pages 8505-8506

  Newcomb, Martin ^a   Tanaka, Noriko ^a   Bouvier, Anne ^a   Tronche, Christopher ^a   Horner, John H ^a   Musa, Osama M ^a   Martinez, Felix N ^a  

^a WAYNE STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; CYCLOALKANE DERIVATIVE;

ARTICLE; CHEMICAL REACTION KINETICS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029840673     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961615s     Document Type: Article

References (18)

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2. Newcomb, M. Tetrahedron 1993, 49, 1151-1176.
3. Newcomb, M.; Johnson, C. C.; Manek, M. B.; Varick, T. R. J. Am. Chem. Soc. 1992, 114, 10915-10921.
4. The acronym PTOC derives from pyridine-2-thione-N-oxycarbonyl. PTOC esters are actually mixed anhydrides of the thiohydroxamic acid N-hydroxypyridine-2-thione and a carboxylic acid. Similarly, PTOC carbamates and N-acyl PTOC carbamates are anhydrides of the thiohydroxamic acid and a carbamic acid or N-acyl carbamic acid, respectively.
5. Barton, D. H. R.; Crich, D.; Motherwell, W. B. Tetrahedron 1985, 41, 3901-3924.
6. -5 M in precursor; increasing the precursor concentration by a factor of 5-10 gave the same rate constants showing that radical - radical reactions were not important.
7. Chatgilialoglu, C.; Ingold, K. U.; Scaiano, J. C. J. Am. Chem. Soc. 1981, 103, 7739-7742.
8. Beckwith, A. L. J.; Blair, I. A.; Phillipou, G. Tetrahedron Lett. 1974, 2251-2254.
9. The upper limit for the kinetics reported here represents the limit of the nanosecond kinetic spectrometer we employed. In principle, the method should be applicable to faster reactions when a picosecond laser unit is employed.
10. Newcomb, M.; Glenn, A. G. J. Am. Chem. Soc. 1989, 111, 275-277.
11. Bowry, V. W.; Lusztyk, J.; Ingold, K. U. J. Am. Chem. Soc. 1991, 113, 5687-5698.
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15. Horner, J. H.; Martinez, F. N.; Musa, O. M.; Newcomb, M.; Shahin, H. E. J. Am. Chem. Soc. 1995, 117, 11124-11133.
16. -1, in general agreement with the kinetic values for 11 at 10-13°C given the rate accelerating effects of the reporter group expected on the basis of the kinetic behavior observed for radicals 3. We thank Dr. Janusz Lusztyk for a helpful discussion of the conflicting data.
17. Wagner, B. D.; Ruel, G.; Lusztyk, J. J. Am. Chem. Soc. 1996, 118, 13-19.
18. Newcomb, M.; Deeb, T. M.; Marquardt, D. J. Tetrahedron 1990, 46, 2317-2328.