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Organic Synteses vol 69 - Paquette L.A.

Paquette L.A., Boecman R.K. Organic Synteses vol 69 - John Wiley & Sons, 1990. - 174 p.
ISBN 0-471-54560-0
Download (direct link): organicsynthesesvol691990.pdf
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Synthesis of annelated polypyridines or hexagonal lattice receptors from
1,2,3,4,5,6,7,8-octahydroacridines requires oxidative functionalization of the 4-position (CH2 group bonded to the pyridine 2-position). In Step D this is accomplished by "Katada" or "Boekelheide" rearrangement of the N-oxide. This general reaction is commonly used for selective oxidation of alkylated pyridines although the mechanism for conversion of the acetylated N-oxide to the 2-acetoxyalkylpyridine has not been fully elucidated.12 The current procedure reflects an empirical finding that deoxygenation of the acetic anhydride prior to addition results in slightly higher yields.
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Condensation of 2-alkylpyridines with benzaldehyde, followed by ozonolysis of the benzylidene intermediate is a general, alternative route to 2-oxoalkylpyridines.13 The N-oxide rearrangement described here is superior when monofunctionalization is required, because condensation of 9-n-butyl-1,2,3,4,5,6,7,8-octahydroacridine with 1 equivalent of benzaldehyde gives a mixture of monobenzylidene and dibenzylidene derivatives.2 Recent work by Tilichenko has shown that 1,5-diketones may be converted to monobenzylidene derivatives before forming the pyridine ring,14 but overall yields are lower than for the current procedure.
1. Department of Chemistry, State University of New York, Stony Brook, New York 11794-3400.
2. (a) Bell, T. W.; Firestone, A. J. Org. Chem. 1986, 51, 764-765; (b) Bell, T. W.; Firestone, A. J. Am. Chem. Soc. 1986, 108, 8109-8111; (c) Bell, T. W.; Firestone, A.; Guzzo, F.; Hu, L. Y. J. Inclusion Phenom. 1987, 5, 149-152; (d) Bell, T. W.; Liu, J. J. Am. Chem. Soc. 1988, 110, 3673-3674.
3. Review: Thummel, R. P. in "Pyridine and its Derivatives," Newkome, G. R.; Ed.; Wiley-lnterscience: New York, 1984; Chapters.
4. (a) Gill, N. S.; James, K. B.; Lions, F.; Potts, K. T. J. Am. Chem. Soc. 1952, 74, 4923-4928; (b) Colonge, J.; Dreux, J.; Delplace, H. Bull. Soc. Chim. Fr. 1957, 447-449; (c) Hall, G. E.; Walker, J. J. Chem. Soc. (C) 1968, 2237-2244; (d) Vysotskii, V. I.; Tilichenko, M. N. Khim. Geterotsikl. Soedin. (Eng. Trans.) 1969, 560-561; Chem. Abstr. 1970, 72, 31579m; (e) Moskovkina, T. V.; Kaminskii, V. A.; Vysotskii, V. I.; Tilichenko, M. N. Khim. Geterotsikl. Soedin. (Eng. Trans.) 1973, 759-762; Chem. Abstr. 1973, 79, 91958p; (f) Thummel, R. P.; Jahng, Y. J. Org. Chem. 1985, 50, 2407-2412.
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5. (a) Newkome, G. R.; Fishel, D. L. J. Org. Chem. 1972, 37, 1329-1336; (b) Partch, R. E.; Andrews, R. R.; Luellen, P.; Forsyth, D. A. Tetrahedron Lett. 1982,
23, 4447-4448.
6. (a) Thummel, R. P.; Kohli, D. K. J. Org. Chem. 1977, 42, 2742-2747; (b) Katritzky, A. R.; Marson, C. M. J. Am. Chem. Soc. 1983, 105, 3279-3283; (c) Ransohoff, J. E. B.; Stabb, H. A. Tetrahedron Lett. 1985, 26, 6179-6182; (d) Risch, N.; Esser, A. Synthesis 1988, 337-339.
7. Tilichenko, M. N. Uch. Zap. Saratovsk. Gos. Univ. 1962, 75, 60-65; Chem. Abstr. 1964, 60, 419a.
8. Bell, T. W.; Rothenberger, S. D. Tetrahedron Lett. 1987, 28, 4817-4820.
9. Katritzky, A. R.; Lagowski, J. M. "Chemistry of the Heterocyclic N-Oxides" Academic Press: New York, 1971.
10. Klimov, G. A.; Tilichenko, M. N. Khim. Geterotsikl. Soedin. Sb. 1: Azotsoderzhashchie Geterotsikey 1967, 306-309; Chem. Abstr. 1969, 70, 87539z.
11. (a) Trost, B. M.; Curran, D. P. Tetrahedron Lett. 1981, 22, 1287-1290; (b) Gallopo, A. R.; Edwards, J. O. J. Org. Chem. 1981, 46, 1684-1688; (c) Cicala,
G.; Curci, R.; Fiorentino, M.; Laricchiuta, O. J. Org. Chem. 1982, 47, 2670-2673; (d) Jeyaraman, R.; Murray, R. W. J. Am. Chem. Soc. 1984, 106, 2462-2463; (e) Murray, R. W.; Jeyaraman, R. J. Org. Chem. 1985, 50, 2847-2853; (f) Davis, F. A.; Chattopadhyay, S.; Towson, J. C.; Lai, S.; Reddy, T. J. Org. Chem. 1988, 53, 2087-2089.
12. (a) Cohen, T.; Deets, G. L. J. Am. Chem. Soc. 1972, 94, 932-938; (b) McKillop,
A.; Bhagrath, M. K. Heterocycles 1985, 23, 1697-1701, and references therein.
13. Lodde, N.; Reimann, E. Arch. Pharm. (Weinheim, Ger.) 1979, 312, 940-950; Chem. Abstr. 1980, 163822h.
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14. Minaeva, N. N.; Tilichenko, M. N. Khim. Geterotsikl. Soedin. (Eng. Trans.) 1986,
22, 1720-1724.
Appendix
Chemical Abstracts Nomenclature (Collective Index Number); (Registry Number)
9-n-Butyl-1,2,3,4,5,6,7,8-octahydroacridin-4-ol; 4-Acridinol, 9-butyl-1,2,3,4,5,6,7,8-octahydro- (11); (99922-91-5)
8-n-Butyl-2-hydroxytricyclo[7.3.1.02-7]tridecan-13-one; 5,9-Methanobenzocycloocten-11-one, 10-butyldodecahydro-4a-hydroxy- (8,9); (24133-22-0)
Cyclohexanone (8,9); (108-94-1)
Pentanal: Valeraldehyde (8); Pentanal (9); (110-62-3)
9-n-Butyl-1,2,3,4,5,6,7,8-octahydroacridine: Acridine, 9-butyl-1,2,3,4,5,6,7,8-octahydro- (11); (99922-90-4)
Ammonium acetate: Acetic acid, ammonium salt (8,9); (631-61-8)
Cupric acetate monohydrate: Acetic acid, copper(2+) salt, monohydrate (8,9); (6046-93-1)
Oxone: Peroxymonosulfuric acid, monopotassium salt, mixt. with dipotassium sulfate and potassium hydrogen sulfate (9); (37222-66-5)
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