Novel syntheses of 3-anilino-pyrazin-2(1H)-ones and 3-anilino-quinoxalin-2-(1H)-ones via microwave-mediated Smiles rearrangement

Tetrahedron Letters

Volumn 49, Issue 11, 2008, Pages 1832-1835

  Christopher Bi, F ^a   Aspnes, Gary E ^a   Guzman Perez, Angel ^a   Walker, Daniel P ^a  

^a PFIZER GLOBAL RESEARCH AND DEVELOPMENT   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

3 ANILINO PYRAZIN 2(1H) ONE DERIVATIVE; 3 ANILINO QUINOXALIN 2 (1H) ONE DERIVATIVE; 4 METHYLSULFONYLPHENOL; HALIDE; PHENOL DERIVATIVE; PYRAZINE DERIVATIVE; QUINOXALINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CRYSTAL STRUCTURE; DRUG STRUCTURE; DRUG SYNTHESIS; MICROWAVE RADIATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

EID: 39149108102     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2008.01.056     Document Type: Article

References (14)

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5. For a review on Smiles rearrangement, see:. Truce W.E., Kreider E.M., and Brand W.W. Org. React. 18 (1970) 99-215
6. For more recent literature examples, see:. Xiang J., Zheng L., Chen F., Dang Q., and Bai X. Org. Lett. 9 (2007) 765-767
7. El Kaim L., Gizolme M., Grimaud L., and Oble J. Org. Lett. 8 (2006) 4019-4021
8. 1H NMR at elevated temperature. Structure of similar Smiles rearrangement products 9, 10, and 11 was confirmed through preparation via an independent chemical route: Reaction of appropriate starting material 5b-d with p-methoxybenzylalcohol (PMB-OH) in the presence of potassium tert-butoxide in hot dioxane gave the 2-PMB ethers 14b-d. Deprotonation of these amines with sodium hydride followed by an addition to 4-fluorophenyl methyl sulfone in DMF at 80 °C yielded the corresponding 3-(4-methylsulfonylphenylamino) compounds 15b-d. Removal of the PMB protecting group with TES/TFA in dichloromethane yielded the equivalent products 9, 10, and 11.{A figure is presented}
9. +): 316.0750, found: 316.0747.
10. 2 = 0.1188 for all data.
11. Jiang B., Yang C.-G., Xiong W.-N., and Wang J. Bioorg. Med. Chem. Lett. 9 (2001) 1149-1154
12. Camerino B., and Palamidessi G. Gazz. Chim. Ital. 90 (1960) 1807
13. 2 = 0.1289.
14. NAr product of the more electron-rich 4-methoxyphenol failed to give any desired rearrangement product, even at higher temperature (T = 250 °C) and prolonged reaction time.