Kinetic and Spectroscopic Studies on the Thermal Decomposition of 2,2,6-Trimethyl-4H-1,3-dioxin-4-one: Generation of Acetylketene

Journal of the American Chemical Society

Volumn 111, Issue 6, 1989, Pages 2186-2193

  Clemens, Robert J ^a   Witzeman, J Stewart ^a  

^a EASTMAN KODAK COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845184134     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00188a037     Document Type: Article

References (15)

1. (a) Clemens, R. J. Chem. Rev. 1986, 86, 241–317, and references therein. (b) Maujean, A.; Chuche, J. Tetrahedron Lett. 1976, 16, 2905–2908.
2. (a) Jäger, G.; Wenzelburger, J. Liebigs Ann. Chem. 1976, 16, 1689–1712. (b) Sato, M.; Kanuma, N.; Kato, T. Chem. Pharm. Bull. 1982, 30, 1315–1321. (c) Sato, M.; Ogasawara, H.; Yoshizumi, E.; Kato, T. Chem. Pharm. Bull. 1983, 31, 1902–1910.
3. Hyatt, J. A.; Feldman, P.; Clemens, R. J. J. Org. Chem. 1984, 49, 5105–5108.
4. Clemens, R. J.; Hyatt, J. A. J. Org. Chem. 1985, 50, 2431–2435.
5. Acetylketene generation; see ref 3–5. Other acylketenes: Sato, M.; Ogasawara, H.; Komatsu, S. Kato, T. Chem. Pharm. Bull. 1984, 32, 3848–3856.
6. Several other reactions appear to proceed via the generation of α-oxoketene intermediates. From 5-acyl Meldrum's acids, see: Oikawa, Y.; Sugano, K.; Yonemitsu, O. J. Org. Chem. 1978, 43, 2087–2088. Yamamoto, Y.; Watanabe, Y. Chem. Pharm. Bull. 1987, 35, 1860–1870, 1871–1879. From a-diazoketones, see: Jager, G. Chem. Ber. 1972, 105, 137–149. Hyrstak, M.; Durst, T. Heterocycles 1987, 26, 2393–2409. Stetter, H.; Kiehs, K. Chem. Ber. 1965, 98, 1181–1187, 2099–2102. From diacid chlorides, see: Borrmann, D.; Wegler, R. Chem. Ber. 1966, 99, 1245–1252, From 2,3-furandiones, see: Murai, S.; Hasegawa, K.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1975, 14, 636–637.
7. (a) Dehmlow, E. V.; Shamout, A. R. Liebigs Ann. Chem. 1982, 1753–1755. (b) Sato, M.; Ogasawara, H.; Oi, K.; Kato, T. Chem. Pharm. Bull. 1983, 31, 1896–1901. (c) Sato, M.; Sekiguchi, K.; Ogasawara, H.; Kaneko, C. Synthesis 1985, 224. (d) Henegar, K. E.; Winkler, J. D. Tetrahedron Lett. 1987, 28, 1051–1054. (e) Sato, M.; Ogasawara, H.; Sekiguchi, K.; Kaneko, C. Heterocycles 1984, 22, 2563–2568.
8. These references include only those reactions which probably proceed via ketene intermediates. The (2 + 2) cycloaddition chemistry of 1,3-dioxinones is also extensive. (a) Baldwin, S. W.; Martin, G. F.; Jr.; Nunn, D. S. J. Org. Chem. 1985, 50, 5720–5723. (b) Boeckman, R. K., Jr.; Perni, R. B. J. Org. Chem. 1986, 51, 5486–5489. (c) Boeckman, R. K., Jr.; Thomas, A. J. J. Org. Chem. 1982, 47, 2823–2824. (d) Demuth, M.; Palomer, A.; Sluma, H. D.; Dey, A. K.; Kruger, C.; Tsay, Y. H. Angew. Chem., Int. Ed. Engl. 1986, 25, 1117–1118. (e) Sato, M.; Ogasawara, H.; Kato, K.; Sakai, M.; Kato, T. Chem. Pharm. Bull. 1983, 31, 4300–4305. (f) Sato, M.; Ogasawara, H.; Yoshizumi, E.; Kato, T. Heterocycles 1982, 17, 297–300. (g) Seebach, D.; Zimmermann, J. Helv. Chim. Acta. 1986, 69, 1147–1152. (h) Sato, M.; Ogasawara, H.; Kato, T. Chem. Pharm. Bull. 1984, 32, 2602–2608. (i) Sato, M.; Yoneda, N.; Kaneko, C. Chem. Pharm. Bull. 1986, 34, 621–627, 4577–4584. (j) Sato, M.; Kanuma, N.; Kato, T. Chem. Pharm. Bull. 1984, 32, 106–116.
9. The exact nature and order of the reaction of various ketenes with nucleophiles is the subject of some debate (for example, see ref 10a,c,i). The reaction order in nucleophile could be first order or higher: the important point is that there would be a dependence on the nucleophile concentration. (a) Allen, A. D.; Tidwell, T. T. J, Am. Chem. Soc. 1987, 109, 2774–2780. (b) Bothe, E.; Meier, H.; Schulte-Frohlinde, D.; von Sonntag, C. Angew. Chem., Int. Ed. Engl. 1976, 15, 380–381. (c) Poon, N. L.; Satchell, D. P. N. J. Chem. Soc., Perkin Trans. 2, 1986, 1485–1490. (d) Lillford, P. J.; Satchell, D. P. N. J. Chem. Soc. B 1968, 889–897. (e) Brady, W. T.; Vaughn, W. L.; Hoff, E. F. J. Org. Chem. 1969, 34, 843–845. (f) Tille, A; Pracejus, H. Chem. Ber. 1967, 100, 196–210. (g) Pracejus, H.; Samtleben, R. Tetrahedron Lett. 1970, 2189–2194. (h) The reaction of acetylketene with a nucleophile to give 3 may, under certain conditions, be reversible. However, this process is slow relative to the rate of decomposition of dioxinone 1. (i) Seikaly, H. R.; Tidwell, T. T. Tetrahedron 1986, 42, 2587–2613.
10. (14) Hyatt, J. A. J. Org. Chem. 1984, 49, 5102–5104.
11. This reaction has precedence in the reactions of isopropenyl esters. Nelson, S. D.; Kasparian, D. J.; Trager, W. F. J. Org. Chem. 1972, 37, 2686–2688. Rothman, E. S. J. Am. Oil Chem. Soc. 1968, 45, 189–193.
12. (a) Tsang, W. Int. J. Chem. Kinet. 1973, 5, 651–662. (b) Limmie, J. Int. J. Chem. Kinet. 1978, 10, 227. (c) Tsang, W. J. Chem. Phys. 1965, 42, 1805–1809.
13. (a) Moore, C. B.; Pimental, G. C. J. Chem. Phys. 1963, 38, 2816. (b) Maquestiau, A.; Pauwels, P.; Flammang, R.; Lorenčak, P.; Wentrup, C. Org. Mass Spectrum 1986, 21, 259–265. (c) Wentrup, C.; Gross, G.; Berstermann, H.-M.; Lorenčak, P. J. Org. Chem. 1985, 50, 2877–2881.
14. (a) Semiempirical (MNDO) calculations predict that the s-trans form of 2 is more stable. Hyatt, J. A.; Foster, C. H., personal communication. (b) Other explanations for these two bands are possible; additional work is being conducted in this area. (c) The IR absorption frequency for ketene is known to be sensitive to the surrounding medium. See ref 17a and Gano, J. E.; Jacob, E. J. Spectrochem. Acta 1987, 43A, 1023–1025. Arendale, W. F.; Fletcher, W. H. J. Chem. Phys. 1957, 26, 793–797.
15. (a) Benson, S. W.; Cruickshank, F. R.; Golden, D. M.; Haugen, G. R.; O'Neal, H. E.; Rodgers, A. S.; Shaw, R.; Walsh, R. Chem. Rev. 1969, 69, 279. (b) Thermochemical Data of Organic Compounds; Pedley, J. B., Naylor, R. D., Kirby, S. P., Eds.; Chapman and Hall: 1986. (c) Deming, R. L.; Wulff, C. A., In The Chemistry of Ketenes Allenes and Related Compounds; Patai, S., Ed.; John Wiley and Sons: 1980; Vol 1, pp 155–164. (d) Vilcu, R.; Persianu, S. Rev. Roum. Chim. 1979, 24, 237. (e) Qunchant, M. Ann. Chem. 1918, 10, 30. Nuttall, R. L.; Laufer, A. H.; Kilday, M. V. J. Chem. Thermodyn. 1971, 3, 167–174. (g) These thermodynamic cycles assume that the heat of reaction for the exchange process is zero (ref 21c). The similarity of the values obtained from the three cycles suggests that this assumption is valid.