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Volumn , Issue 15, 2010, Pages 2954-2970

An efficient synthesis of substituted meta-halophenols and their methyl ethers: insight into the reaction mechanism

Author keywords

Grob type fragmentation; Ketones; Meta halophenols; Oxidation; Reaction mechanisms

Indexed keywords


EID: 77952183947     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.201000071     Document Type: Article
Times cited : (7)

References (80)
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    • For the usefulness of phenolic derivatives as synthetic intermediates, see: a
    • For the usefulness of phenolic derivatives as synthetic intermediates, see: a) C. H. Burgos, T. E. Barder, X. Huang, S. L. Buchwald, Angew. Chem. Int. Ed, 2006 45, 4321-4326;
    • (2006) Angew. Chem. Int. Ed , vol.45 , pp. 4321-4326
    • Burgos, C.H.1    Barder, T.E.2    Huang, X.3    Buchwald, S.L.4
  • 33
    • 8844263009 scopus 로고    scopus 로고
    • For various chlorination and bromination methods, see: a) J. M. Gnaim, R. A. Sheldon, Tetrahedron Lett. 2004 45, 9397-9399;
    • (2004) Tetrahedron Lett. , vol.45 , pp. 9397-9399
    • Gnaim, J.M.1    Sheldon, R.A.2
  • 74
    • 77952151871 scopus 로고    scopus 로고
    • To examine whether the formation of the methyl ethers 11 was intermolecular or intramolecular in nature, the fragmentation reaction was carried out with substrate 7b under optimized conditions at two different molar concentrations. It was observed that with dilution the yield of 11b decreases (37% in 0.07 M to 19% in 0.027 M) with a consequent proportionate increase in the yield of 10b (53% to 67%), the overall yield remaining almost the same. These results are clearly indicative of an intermolecular reaction, mechanism.
    • To examine whether the formation of the methyl ethers 11 was intermolecular or intramolecular in nature, the fragmentation reaction was carried out with substrate 7b under optimized conditions at two different molar concentrations. It was observed that with dilution the yield of 11b decreases (37% in 0.07 M to 19% in 0.027 M) with a consequent proportionate increase in the yield of 10b (53% to 67%), the overall yield remaining almost the same. These results are clearly indicative of an intermolecular reaction, mechanism.
  • 75
    • 77952175302 scopus 로고    scopus 로고
    • Decomposition of 7e or 7f took place in tightly stoppered RB flasks on prolonged storage at room, temperature. Slow decomposition was observed, from the gradual color change from white to reddish-brown, resulting in the formation, of MeBr together with the usual, products (i.e. 10e and. 11e, or 10f and 11f). Decomposition took place even in a refrigerator (5-10 °C), but the time required was much longer;
    • a) Decomposition of 7e or 7f took place in tightly stoppered RB flasks on prolonged storage at room, temperature. Slow decomposition was observed, from the gradual color change from white to reddish-brown, resulting in the formation, of MeBr together with the usual, products (i.e. 10e and. 11e, or 10f and 11f). Decomposition took place even in a refrigerator (5-10 °C), but the time required was much longer;
  • 76
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    • 1H NMR sample preparation.
    • 1H NMR sample preparation.
  • 77
    • 77952164680 scopus 로고    scopus 로고
    • 1H NMR spectrum of the reaction mixture and in order to facilitate easy detection of the ethyl ether product.
    • 1H NMR spectrum of the reaction mixture and in order to facilitate easy detection of the ethyl ether product.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.