Rearrangement reactions of (hydroxyphenyl)carbenes

Journal of Organic Chemistry

Volumn 61, Issue 13, 1996, Pages 4462-4465

  Kumar, Anil ^a   Narayanan, Ramamurthi ^a   Shechter, Harold ^a  

^a OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000806709     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo952269k     Document Type: Article

References (34)

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2. (a) Joines, R. C.; Turna, A. B.; Jones, W. M. Tetrahedron 1969, 91, 7754. Schissel, P.; Kent, M. E.; McAdoo, D. J.; Hedaya, E. J. Am. Chem. Soc. 1970, 92, 2147.
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7. (g) Tomioka, H.; Takesuji, K. J. Org. Chem. 1993, 58, 4196.
8. (h) For an excellent summary of the products and various mechanisms of benzylidene rearrangements, see: Gasper, P. P.; Hsu, J.-P; Chari, S.; Jones, M., Jr. Tetrahedron 1985, 47, 1479.
9. (a) Wentrup, C. Tetrahedron 1974, 30, 1301.
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11. A. D. Golden and M. Jones, Jr., Princeton University, Princeton, NJ, have found that thermal carbenic decompositions of 9 and 15 under conditions and in equipment different from that of the present study yield phenol, tropone (10), and o-cresol (12). Upon learning that 12 is formed in major amounts in their experiments, we have reopened study of the behavior of 27. We thank Professor Jones for informing us of the results from his laboratory.
12. 4b and products of higher molecular weight are also formed in the present thermolyses of 9. The phenol obtained does not result from loss of carbon monoxide from 4-hydroxybenzaldehyde possibly produced by reaction of 19 with oxygen always present during a flash vacuum pyrolysis experiment. Of particular interest is that phenol may be formed from 9 by hydrogen migration and ipso loss of carbon and nitrogen shown below. (Formula Presented)
13. (b) The structure of the unassigned product is being investigated.
14. (c) On dropping solutions of 9 in ethanol onto vertical glass-packed tubes at 650 °C/0.1 Torr such that very thin films of 9 are deposited on the glass surfaces, thermolyses have been found to give 10 in up to 42% yields on small-scale along with phenol (3%), 12 (2%), and 13 (53%).
15. 5b-e
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20. (f) It is not yet clear whether there will be significant differences in the behaviors of hydroxy-2,4,6-heptatrienylidenes (3, R = OH) and their corresponding hydroxy-1,2,4,6-cycloheptatetraenes (4, R = OH).
21. (a) Cycloheptatrienone 30 is more conjugated and thus may be more stable than is 29.
22. (b) Further, 20-22, 28, and 29 will be quite acidic at 600-800 °C and possibly isomerize to 10 by tautomeric processes.
23. (a) McIntosh, C. L.; Chapman, O. L. J. Chem. Soc., Chem. Commun. 1971, 771.
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27. 7c
28. (9) Slow addition of the dry sodium salt of 4-hydroxybenzaldehyde (p-toluenesulfonyl)hydrazone to a vertical glass-packed column at 800 °C/0.1 Torr results in formation of phenol (49%), 10 (4-5%), 12 (4%), and less volatile products. The dry sodium salt of 2-hydroxybenzaldehyde (p-toluenesulfonyl)hydrazone at 650 °C/0.1 Torr yields phenol (39%), 10 (∼1%), 12 (9%), and high molecular weight derivatives. These systems are based on generation of and decomposition diazo(4-hydroxypheny)methane and diazo(2-hydroxyphenyl)methane and are of interest because of formation of phenol rather than 10 and 12.
29. (a) Brower-Van Straaten, B.; Solinger, D.; Vande Westeringh, C.; Veldstra, H. Recl. Trav. Chim. 1958, 77, 1129.
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