New reactions of hydrazides. Part 1: Directed ortho- and lateral metalation of aromatic carbocyclic and heterocyclic systems

Tetrahedron Letters

Volumn 40, Issue 50, 1999, Pages 8767-8770

  McCombie, Stuart W ^a   Lin, Sue Ing ^a   Vice, Susan F ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID; AROMATIC COMPOUND; CARBOXYLIC ACID DERIVATIVE; ESTER DERIVATIVE; HYDRAZIDE DERIVATIVE; MANGANESE DIOXIDE; METHANOL; ORGANOLITHIUM COMPOUND; WATER;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; OXIDATION; REACTION ANALYSIS;

EID: 0033544748     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01876-6     Document Type: Article

References (15)

1. Snieckus, V. Chem. Rev. 1990, 90, 879.
2. Kusurkar, R. S.; Patil, R. N. Indian J. Chem., Sect. B 1990, 29, 64; Bestmann, H. J.; Kern, F.; Schaefer, D.; Witschel, M. C. Angew. Chem. 1992, 104, 757.
3. Kusurkar, R. S.; Patil, R. N. Indian J. Chem., Sect. B 1990, 29, 64; Bestmann, H. J.; Kern, F.; Schaefer, D.; Witschel, M. C. Angew. Chem. 1992, 104, 757.
4. de Oliviera Baptista, M. J. V.; Barrett, A. G. M.; Barton, D. H. R.; Girijavallabhan, M.; Kelly, J.; Turner, J. V.; Usher, N. A. J. Chem. Soc., Perkin Trans. 1 1977, 1477.
5. Fisher, L. E.; Caroon, J. M.; Jahangir; Stabler, S. R.; Lundberg, S.; Muchowski, J. M. J. Org. Chem. 1993, 58, 3643.
6. All of the hydrazides were prepared from the appropriate aroyl chloride with 2.5 equiv. of the hydrazine in dichloromethane at 10°C, followed by aqueous workup and recrystallization.
7. For this oxidation on an analogous N,N-diethylbenzamide, see: de Silva, S. O.; Reed, J. N.; Billedeau, R. J.; Wang, X.; Norris, D. J.; Snieckus, V. Tetrahedron 1992, 48, 4863.
8. For pertinent examples, see: Ref. 1, pp. 924-928 and references cited therein.
9. 2-Furoic acid selectively forms the O,C-5 dilithio species: Knight, D. W.; Nott, A. P. J. Chem. Soc., Perkin Trans. 1 1981, 1125. The corresponding oxazoline gives up to a :1 ratio of C-3 to C-5 metalation products, depending upon theconditions: Chadwick, D. J.; McKnight, M. V.; Ngochindo, R. J. Chem. Soc., Perkin Trans. 1, 1982, 1343. The N,N-diethylamide undergoes ring scission: Doadt, E. G.; Snieckus, V. Tetrahedron Lett. 1985, 26, 1149.
10. 2-Furoic acid selectively forms the O,C-5 dilithio species: Knight, D. W.; Nott, A. P. J. Chem. Soc., Perkin Trans. 1 1981, 1125. The corresponding oxazoline gives up to a :1 ratio of C-3 to C-5 metalation products, depending upon theconditions: Chadwick, D. J.; McKnight, M. V.; Ngochindo, R. J. Chem. Soc., Perkin Trans. 1, 1982, 1343. The N,N-diethylamide undergoes ring scission: Doadt, E. G.; Snieckus, V. Tetrahedron Lett. 1985, 26, 1149.
11. 2-Furoic acid selectively forms the O,C-5 dilithio species: Knight, D. W.; Nott, A. P. J. Chem. Soc., Perkin Trans. 1 1981, 1125. The corresponding oxazoline gives up to a :1 ratio of C-3 to C-5 metalation products, depending upon theconditions: Chadwick, D. J.; McKnight, M. V.; Ngochindo, R. J. Chem. Soc., Perkin Trans. 1, 1982, 1343. The N,N-diethylamide undergoes ring scission: Doadt, E. G.; Snieckus, V. Tetrahedron Lett. 1985, 26, 1149.
12. 3 group. (Formula Presented) Preliminary experiments indicate that N-methoxyamides can also induce ortho-methoxy displacement, and this and related reactions are currently being investigated in our laboratories.
13. Nate, H.; Sekine, Y.; Honma, Y.; Nakai, H.; Wada, H. Chem. Pharm. Bull. 1987, 35, 1953; Flippin, L. A.; Carter, D. S.; Dubree, N. J. P. Tetrahedron Lett. 1993, 34, 3255.
14. Nate, H.; Sekine, Y.; Honma, Y.; Nakai, H.; Wada, H. Chem. Pharm. Bull. 1987, 35, 1953; Flippin, L. A.; Carter, D. S.; Dubree, N. J. P. Tetrahedron Lett. 1993, 34, 3255.
15. 2: requires: C, 73.62; H, 7.98; N, 8.59%. By chromatographing the mother liquors, an additional 7% of pure product could be isolated.