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Volumn 66, Issue 47, 2010, Pages 9171-9174

Active-sodium-promoted reductive cleavage of halogenated benzoic acids

Author keywords

Active sodium; Electron transfer; Hydrodehalogenation; Organic pollutants; Reduction; Vic Diorganometals

Indexed keywords

1,2 DIARYLETHANE; 1,2 DISODIOETHANE; ANION; BENZOIC ACID DERIVATIVE; BROMOBENZOIC ACID DERIVATIVE; CHLOROBENZOIC ACID DERIVATIVE; DIANION; ETHANE; FLUOROBENZOIC ACID DERIVATIVE; IODOBENZOIC ACID DERIVATIVE; SODIUM; UNCLASSIFIED DRUG;

EID: 78049295048     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2010.09.072     Document Type: Article
Times cited : (9)

References (31)
  • 1
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    • R. Weber Chemosphere 67 2007 S109 S117 and references therein
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    • Weber, R.1
  • 2
    • 0036860845 scopus 로고    scopus 로고
    • For a review see: F. Alonso, I.P. Beletskaya, and M. Yus Chem. Rev. 102 2002 4009 4091 for a selection of relevant literature, see:
    • (2002) Chem. Rev. , vol.102 , pp. 4009-4091
    • Alonso, F.1    Beletskaya, I.P.2    Yus, M.3
  • 15
    • 84989479329 scopus 로고
    • One referee suggested that these reducing agents could be better formulated as dianions of the corresponding alkenes, with two electrons located in the LUMO of the starting materials, acting as typical electron carriers. This is an interesting observation, deserving a thorough analysis in the near future. Although we agree that real structures are, most probably, highly delocalized ones, we defined our reducing agents as 1,2-diaryl-1,2- disodioethanes, 1, both because of their clean reactivity as dinucleophiles towards 1,3-dihalogenopropanes (see Ref. 3), as well as of the known reducing properties of other benzylic polycarbanions; see, for example: C.E. Barry III, R.B. Bates, W.A. Beavers, F.A. Camou, B. Gordon III, H.F.-J. Hsu, N.S. Mills, C.A. Ogle, T.J. Siahaan, K. Suvannachut, S.R. Taylor, J.J. White, and K.M. Yager Synlett 1991 207 212 and references cited therein
    • (1991) Synlett , pp. 207-212
    • Barry III, C.E.1    Bates, R.B.2    Beavers, W.A.3    Camou, F.A.4    Iii, G.B.5    Hsu, H.F.-J.6    Mills, N.S.7    Ogle, C.A.8    Siahaan, T.J.9    Suvannachut, K.10    Taylor, S.R.11    White, J.J.12    Yager, K.M.13
  • 16
    • 78049277404 scopus 로고    scopus 로고
    • Few alkali metal mediated reductions of halogenated benzoic acids were already reported
    • Few alkali metal mediated reductions of halogenated benzoic acids were already reported.
  • 18
    • 84977244273 scopus 로고
    • Few very old papers report on the reduction of halogenated benzoic acids with Na/Hg; see, for example: P. Geiner, and F. Beilstein Justus Liebigs Ann. Chem. 139 1866 1 16
    • (1866) Justus Liebigs Ann. Chem. , vol.139 , pp. 1-16
    • Geiner, P.1    Beilstein, F.2
  • 19
    • 78049243698 scopus 로고
    • The reactivity of few mono- and di-halogenobenzenes towards 1,2-disodio-1,2,3,4-tetraphenylethane, 1b, was already reported, see: E. Müller, and G. Röscheisen Chem. Ber. 91 1958 1106 1114
    • (1958) Chem. Ber. , vol.91 , pp. 1106-1114
    • Müller, E.1    Röscheisen, G.2
  • 27
    • 78049310061 scopus 로고    scopus 로고
    • Attempted reduction of the preformed sodium salt of chloroacid 2d (by the reaction of 2d with NaH in THF) with 1.0 equiv of 1b resulted in a very slow reaction, affording a 33% conversion of the starting material after 24 h at rt. It is worth noting the heterogeneity of such a reaction mixture
    • Attempted reduction of the preformed sodium salt of chloroacid 2d (by the reaction of 2d with NaH in THF) with 1.0 equiv of 1b resulted in a very slow reaction, affording a 33% conversion of the starting material after 24 h at rt. It is worth noting the heterogeneity of such a reaction mixture.
  • 29
    • 78049311501 scopus 로고    scopus 로고
    • For selected examples discussing the behaviour of aryl halides under electrochemical reduction conditions and leading to different apparent number of electrons required in the cleavage step, see Ref. 12 and references therein
    • For selected examples discussing the behaviour of aryl halides under electrochemical reduction conditions and leading to different apparent number of electrons required in the cleavage step, see Ref. 12 and references therein.
  • 30
    • 78049281180 scopus 로고    scopus 로고
    • 2O quenching and aqueous work up, led to the quantitative recovery of non deuterated 1,1,2,2-tetraphenylethane, 4
    • 2O quenching and aqueous work up, led to the quantitative recovery of non deuterated 1,1,2,2-tetraphenylethane, 4.
  • 31
    • 78049309629 scopus 로고    scopus 로고
    • Reduction of either 6d or 6e with dianion 1c in a 3:1 M ratio led to the recovery of benzoic acid, 2i, in almost quantitative yield
    • Reduction of either 6d or 6e with dianion 1c in a 3:1 M ratio led to the recovery of benzoic acid, 2i, in almost quantitative yield.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.