Formation of a σ-complex from dicyanopyridinyl and hydroxyalkyl radicals. An ESR study of the photoinitiated complex forming reactions of aryl ketones with 2,4-pyridinedicarbonitrile and alcohols

Journal of Heterocyclic Chemistry

Volumn 37, Issue 1, 2000, Pages 131-136

  Vittimberga, Bruno M ^a   Rieger, Anne L ^b  

^a University of Rhode Island   (United States)

^b BROWN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; KETONE DERIVATIVE; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; PYRIDINE DERIVATIVE; RADICAL;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BINDING; CHEMICAL REACTION; COMPLEX FORMATION; ELECTRON SPIN RESONANCE; IRRADIATION; REACTION ANALYSIS; STEREOCHEMISTRY; TEMPERATURE SENSITIVITY;

EID: 0034024688     PISSN: 0022152X     EISSN: None     Source Type: Journal    
DOI: 10.1002/jhet.5570370122     Document Type: Article

References (17)

1. T. Caronna, S. Morrocchi, and B. M. Vittimberga, J. Am. Chem. Soc., 108, 2205 (1986).
2. D. Rehm and A. Weller, Isr. J. Chem. 8, 259 (1970).
3. S. L. Murov, I Carmichael, and G. L. Hug, Handbook of Photochemistry, Marcel Dekker: New York, NY, 1993, p 85.
4. 4.4′-Dimethylbenzhydrol was prepared by the reduction of 4,4′-dimethylbenzophenone using a procedure adapted from one described in R. L. Dannley and J. D. Crum, Experimental Organic Chemistry, Macmillan: New York, NY, 1968, 47.
5. M. W. D. Cohen, Rec. Trav. Chim., 38, 113 (1919).
6. W. E. Feeley and E. M. Beavers, J. Am. Chem. Soc., 81, 4004 (1959).
7. The time required to reach the α steady-state level ranged from 10 s for methanol to 27 s for 2-propanol. To reach the β level, the time required ranged from 3 s for methanol to 11 s for 2-propanol. All other alcohols tested had values within these ranges.
8. -1..
9. For examples see K. Akiyama, S. Tero-Kubota, and Y. Ikegami, J. Am. Chem. Soc., 105, 3601 (1983).
10. 2OH, may decay by disproportionation, dimerization, or reaction with benzophenone.
11. One decay route of 2, equation (7), is substitution of the cyano groups in the 2 and 4 positions by diphenylmethanol groups.
12. eq value, an observation that is under further study.
13. This work was presented at the 14th IUPAC Symposium on Photochemistry, Leuven, Belgium, 1992 and appears in the book of abstracts for that meeting.
14. P. McDevitt, and B. M. Vittimberga, J. Heterocyclic Chem., 27, 1903 (1990).
15. Reference 5, pp 284-287.
16. E. M. Kosower, J. Chim. Phys., 61, 230 (1964).
17. M. Charton, J. Am. Chem. Soc., 97, 1552 (1975).