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Volumn 71, Issue 20, 2006, Pages 7840-7845

On the illusive nature of o-formylazobenzenes: Exploiting the nucleophilicity of the azo group for cyclization to indazole derivatives

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; REACTION KINETICS; SYNTHESIS (CHEMICAL);

EID: 33749150123     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo061288z     Document Type: Article
Times cited : (34)

References (53)
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    • Dürr, H., Bouas-Laurent, H., Eds.; Elsevier: Amsterdam
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    • It should be noted that the formation of azobenzenes from condensation of nitrosobenzenes with anilines in acetic acid, frequently referred to as the Mills reaction: (a) Mills, C. J. Chem. Soc. 1895, 67, 925-933,
    • (1895) J. Chem. Soc. , vol.67 , pp. 925-933
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    • was first described by Baeyer: (b) Baeyer, A. Chem. Ber. 1874, 7, 1638-1640.
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    • See the Supporting Information
    • See the Supporting Information.
  • 21
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    • The synthesis of differently connected oligo(azobenzene)s has been been pioneered by Ruggli and co-workers, who exploited iterative Mills coupling and nitro-reduction sequences. For o-bis(phenylazo)benzenes, see: (a) Ruggli, P.; Rohner, J. HelIv. Chim. Acta 1942, 25, 1533-1542.
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    • Similar synthetic problems have recently been encountered in the construction of oligomers containing m-bis(phenylazo)benzenes: Tie, C.; Gallucci, J. C.; Parquette, J. R. J. Am. Chem. Soc. 2006, 128, 1162-1171.
    • (2006) J. Am. Chem. Soc. , vol.128 , pp. 1162-1171
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    • A potential route via nitration of 2-amino-4-tert-butyltoluene failed in our hands and gave complex product mixtures, contradictory to literature reports: Rosevear, J.; Wilshire, J. F. K. Aust. J. Chem. 1985, 38, 723-733.
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    • Rosevear, J.1    Wilshire, J.F.K.2
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    • The intramolecular coordination of the o-phenylazo group to various heteroatoms has been exploited. For silicon, see: (a) Kano, N.; Komatsu, F.; Kawashima, T. J. Am. Chem. Soc. 2001, 123, 10778-10779.
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  • 38
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    • A thorough literature survey reveals that some initial evidence for this type of rearrangement involving azobenzene precursors carrying either o-aldehyde or o-acetal groups dates back to work by Freundler: (a) Freundler, M. P. Bull. Soc. Chim. Fr. 1904, 31, 862-867.
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    • The formation of 2H-indazolone derivatives from azobenzene precursors has been reported in a few cases with the following ortho substituents. For hydroxymethyl groups, see: (a) Freundler, M. P. Bull. Soc. Chim. Fr. 1903, 29, 742-747.
    • (1903) Bull. Soc. Chim. Fr. , vol.29 , pp. 742-747
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    • A search of the Beilstein database reveals more than 23000 entries of different azobenzene derivatives. In the few cases reporting o-(arylazo)arylaldehydes, an alternative structural assignment to the respective 2H-indazolone derivatives seems plausible: (a) Karamé, I.; Jahjah, M.; Messaoudi, A.; Tommasino, M. L.; Lemaire, M. Tetrahedron: Asymmetry 2004, 15, 1569-1581.
    • (2004) Tetrahedron: Asymmetry , vol.15 , pp. 1569-1581
    • Karamé, I.1    Jahjah, M.2    Messaoudi, A.3    Tommasino, M.L.4    Lemaire, M.5
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    • The oldest literature precedent of controversial assignment of an o-(arylazo)arylaldehyde is related to the so-called "Azoopiansä ure", the product of reducing 2-formyl-5,6-dimethoxy-3-nitrobenzoic acid with zinc under acidic conditions: (a) Prinz, O. J. Prakt. Chem. 1881, 24, 353-374.
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