Benzylfluorocarbene: Reactions and kinetics

Tetrahedron Letters

Volumn 38, Issue 40, 1997, Pages 7049-7052

  Moss, Robert A ^a   Maksimovic, Ljiljana ^a   Merrer, Dina C ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HYDRAZINE DERIVATIVE;

ARTICLE; CHEMICAL REACTION KINETICS; DRUG SYNTHESIS; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; SPECTROPHOTOMETRY; TEMPERATURE; THERMODYNAMICS;

EID: 0030808510     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01709-7     Document Type: Article

References (20)

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2. (b) Liu, M.T.H. Acc. Chem. Res. 1994, 27, 287.
3. (c) Moss, R.A. In Advances in Carbene Chemistry; Brinker, U.H., Ed.; JAI Press: Greenwich, CT, 1994; Vol. 1, pp 59ff.
4. Wierlacher, S.; Sander, W.; Liu, M.T.H. J. Am. Chem. Soc. 1993, 115, 8943.
5. Dix, E.J.; Herman, M.J.; Goodman, J.L. J. Am. Chem. Soc. 1993, 115, 10424.
6. Storer, J.W.; Houk, K.N. J. Am. Chem. Soc. 1993, 115, 10426.
7. Moss, R.A.; Merrer, D.C. Chem. Commun. 1997, 617.
8. (a) Moss, R.A.; Ho, G-J.; Liu, W. J. Am. Chem. Soc. 1992, 114, 959. Moss, R.A. Pure Appl. Chem. 1995, 67, 741.
9. (a) Moss, R.A.; Ho, G-J.; Liu, W. J. Am. Chem. Soc. 1992, 114, 959. Moss, R.A. Pure Appl. Chem. 1995, 67, 741.
10. (b) Evenseck, J.D.; Houk, K.N. J. Phys. Chem. 1990, 94, 5518.
11. Graham, W.H. J. Am. Chem. Soc. 1965, 87, 4396.
12. This procedure is adapted from that of W. Sander and C. Junker, unpublished; private communication from W. Sander, 22 January, 1996. We thank Professor Sander for this information.
13. 1H NMR and high resolution MS. Control experiments showed that 5 and 6 were stable to the photolysis conditions.
14. 358 = 1) at 70 °C in TCE results in only 3.6% decomposition after 18 h.
15. 358 = 0.45, the photolytic yield of 6 is 23% at -40 °C in TCE. The more commonly employed polar solvent MeCN was not useful: 30% of azine formation was observed at 25 °C.
16. Jackson, J.E.; Soundararajan, N.; Platz, M.S.; Liu, M.T.H. J. Am. Chem. Soc. 1988, 110, 5595.
17. max (ylide) = 370 nm.
18. -1.
19. 1c for a related phenomenon, see: Skell, P.S.; Cholod, M.S. J. Am. Chem. Soc. 1969, 91, 7131.
20. It is also possible that the efficiencies of the (intermolecular) carbene + diazirine → azine reactions differ for BFC and BCC, with azine formation favored for BFC. The comparative importance of tunneling in the 1,2-H shifts of BCC and BFC remains to be explored.