Chemical and Spectroscopic Studies of the Decomposition of Bicyclic Azo Compounds Derived from Isopyrazoles

Journal of the American Chemical Society

Volumn 92, Issue 21, 1970, Pages 6218-6231

  Evnin, A B ^a   Arnold, D R ^a   Karnischky, L A ^a   Strom, E ^a  

^a Union Carbide Research Institute ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0343658020     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00724a021     Document Type: Article

References (73)

1. R. J. Crawford, R. J. Dummel, and A. Mishra, J. Amer. Chem. Soc., 87, 3023 (1965);
2. T. H. McGee, J. Phys. Chem., 72, 1621 (1968);
3. I. S. Krull and D. R. Arnold, Tetrahedron Lett., 1247 (1969).
4. G. L. Closs, W. A. Boll, H. Heyn, and V. Dev, J. Amer. Chem. Soc., 90, 173 (1968);
5. R. Anet and F. A. L. Anet, J. Amer. Chem. Soc., 86, 525 (1964).
6. R. Criegee and A. Rimmelin, Chem. Ber., 90, 414 (1957);
7. C. Steel, J. Phys. Chem., 67, 1779 (1963).
8. T. S. Chambers and G. B. Kistiakowsky, J. Amer. Chem. Soc., 56, 399 (1934);
9. P. J. Wagner and G. S. Hammond, Advan. Photochem., 5, 21 (1968);
10. J. P. Chesick, J. Amer. Chem. Soc., 84, 3250 (1962).
11. R. J. Crawford and A. Mishra, J. Amer. Chem. Soc., 88, 3963 (1966);
12. R. J. Crawford and D. M. Cameron, Can. J. Chem., 45, 691 (1967);
13. Basil H. Al-Sader and R. J. Crawford, Can. J. Chem., 46, 3301 (1968).
14. S. Seltzer, J. Amer. Chem. Soc., 85, 14 (1963);
15. S. Seltzer and F. T. Dunne, J. Amer. Chem. Soc., 87, 2628 (1965); and
16. S. Seltzer and S. G. Mylonakis, J. Amer. Chem. Soc., 89, 6584 (1967).
17. E. Allred and R. L. Smith, J. Amer. Chem. Soc., 89, 7133 (1967);
18. W. R. Roth and M. Martin, Justus Liebigs Ann. Chem., 702, 1 (1967);
19. W. R. Roth and M. Martin, Tetrahedron Lett., 4695 (1967).
20. R. Hoffmann, J. Amer. Chem. Soc., 90, 1475 (1968);
21. Chem. Commun., 240 (1969).
22. H. E. Simmons, private communication.
23. C. G. Overberger and J. P. Anselme, J. Amer. Chem. Soc., 86, 658 (1964).
24. W. R. Roth, private communication.
25. P. Dowd, J. Amer. Chem. Soc., 88, 2587 (1966);
26. P. Dowd and K. Sachdev, J. Amer. Chem. Soc., 89, 715 (1967);
27. P. Dowd, A. Gold, and K. Sachdev, J. Amer. Chem. Soc., 90, 2715 (1968).
28. G. L. Closs, L. R. Kaplan, and V. I. Bendall, J. Amer. Chem. Soc., 89, 3367 (1967).
29. S. D. Andrews and A. C. Day, Chem. Commun., 667 (1966);
30. J. Chem. Soc. B, 1271 (1968);
31. T. Sanjiki, H. Kato, and M. Ohta, Chem. Commun., 496 (1968).
32. A. B. Evnin and D. R. Arnold, J. Amer. Chem. Soc., 90, 5330 (1968).
33. The subject has been recently reviewed in “1,4-Cycloaddition Reactions,” J. Hamer, Ed., Academic Press, New York, N. Y., 1967, p 182.
34. G. Ya Kondrat'yeva, Izo. Akad. Nauk SSSR, Old. Khim. Nauk, 484 (1959).
35. R. A. Carboni and R. V. Lindsey, Jr., J. Amer. Chem. Soc., 81, 4342 (1959);
36. J. Sauer and D. Lang, Angew. Chem., 76, 603 (1964).
37. K. N. Zelenin and Z. M. Matveeva, Zh. Org. Khim., 4, 532 (1967).
38. R. C. Cookson, S. S. H. Gilani, and I. D. R. Stevens, J. Chem. Soc C, 1905 (1967), and earlier publications by this group.
39. A. B. Evnin, A. Y. Lam, J. J. Maher, and J. J. Blyskal, Tetrahedron Lett., 4497 (1969).
40. This dienophile has also been described recently by other groups: B. T. Gillis and R. A. Izydore, J. Org. Chem., 34, 3181 (1969);
41. H. Stetter and P. Woernle, Justus Liebigs Ann. Chem., 724, 150 (1969).
42. R. A. Clement, J. Org. Chem., 27, 1115 (1962).
43. S. G. Cohen, R. Zand, and C. Steel, J. Amer. Chem. Soc., 83, 2895 (1961).
44. L. J. Bellamy, “Infrared Spectra of Complex Molecules,” Methuen, London, 1969, p 271–272.
45. The anisotropy of the azo linkage has been previously remarked upon: J. J. Uebel and J. C. Martin, J. Amer. Chem. Soc., 86, 4618 (1964);
46. R. J. Crawford, A. Mishra, and R. J. Dummcl, J. Amer. Chem. Soc., 88, 3959 (1966).
47. V. F. Bystrov, A. U. Stepanyants, and V. A. Mironov, J. Gen. Chem. USSR, 34, 4099 (1964).
48. The lack of concern is especially surprising in light of the considerable interest in conformational studies of N,N-disubstttutecl piperazines and bridged derivatives of this system: for a summary of work in this area, sec J. M. Lehn and J. Wagner, Tetrahedron, 25, 677 (1969).
49. B. T. Gillis and J. D. Hagarty, J. Org. Chem., 32, 330 (1967).
50. The exo conformation should be significantly destabilized by interactions between the urazole ring and the methyl group syn to it on the bridging methylene. Studies of the adducts of 5- and 5,5-dimethyl-cyclopcntadiencs with maleic anhydride provide no examples of compounds in which the anhydride is exo and the bridging methyl syn: ref 28 and C. F. Wilcox, Jr., and M. Mesirov, J. Org. Chem., 25, 1841 (1960).
51. A. B. Evnin, R. D. Miller, and G. R. Evanega, Tetrahedron Lett., 5963 (1968)
52. II and XXVII should be significantly more strained than norbornene itself due to interactions of the methyl groups, compression due to shortened N-N linkages, and the additional rigidity resulting from the third ring (and fourth in XXIII). Norbornene has ∼25 kcal of strain energy: P. R. von Schleyer, J. Amer. Chem. Soc., 80, 1700 (1958).
53. Acyclic diacyl hydrazines have been shown by X-ray studies to be transoid and planar: R. Shintani, Acta Crystallogr., 13, 609 (1960). It is uncertain, however, whether this result pertains to our system because of the presence of the cisoid conformation, the imide nitrogen and ring strain.
54. P. G. Gassman, K. T. Mansfield, and T. J. Murphy, J. Amer. Chem. Soc., 91, 1684 (1969), and previous papers by these authors.
55. The results were previously communicated in preliminary form: D. R. Arnold, A. B. Evnin, and P. Kasai, J. Amer. Chem. Soc., 91, 784 (1969).
56. For a discussion of diradical esr spectra see: P. B. Ayscough, “Electron Spin Resonance in Chemistry,” Methuen, London, 1967, pp 401–413.
57. S. Forsén and R. A. Hoffman, J. Chem. Phys., 39, 2892 (1963).
58. S. Forsén and R. A. Hoffman, J. Chem. Phys., 40, 1189 (1964).
59. R. B. Woodward and R. Hoffmann, Angew. Chem., 81, 797 (1967);
60. Angew. Chem., Int. Ed. Engl., 8, 781 (1969).
61. A. Rodgman and G. F. Wright, J. Org. Chem., 18, 465 (1953);
62. J. Sauer and B. Schroder, Chem. Ber., 100, 678 (1967).
63. Attempts to generate and carry out 4 + 2 cycloadditions with less highly substituted isopyrazoles were unsuccessful: G. Gubelt and J. Warkentin, Chem. Ber., 102, 2481 (1969).
64. H. M. Frey, J. Amer. Chem. Soc., 82, 5947 (1960).
65. Several examples of nonplanar alkyl radicals have been reported in the literature. A relevant one is the 2,4,6-trimethyltrioxanyl radical: A. J. Dobbs, B. C. Gilbert, and R. O. C. Norman, Chem. Commun., 1353 (1969).
66. Trimethylenemethane (IV) is one such case. A. Streitwieser, “Molecular Orbial Theory for Organic Chemists,” Wiley, New York, N. Y., 1961, p 43.
67. K. B. Wiberg, Advan. Alicyclic Chem., 2, 185 (1967).
68. R. B. Turner, P. Goebel, B. J. Mallon, W. E. von Doering, J. F. Coburn, Jr., and M. Pomerantz, J. Amer. Chem. Soc., 90, 4315 (1968).
69. R. Walsh, D. M. Golden, and S. W. Benson, J. Amer. Chem. Soc., 88, 650 (1966).
70. M. J. Jorgenson, T. J. Clark, and J. Corn, J. Amer. Chem. Soc., 90, 7020 (1968).
71. J. J. Bloomfield, J. Org. Chem., 26, 4112 (1961).
72. I. I. Grandberg, A. P. Krasnoshchek, A. N. Kost, and G. K. Faizova, J. Gen. Chem. USSR, 33, 2521 (1963).
73. B. M. Fung, J. Chem. Phys., 49, 2973 (1968).