Synthesis and isolation of iodocarbazoles.: Direct iodination of carbazoles by N-iodosuccinimide and N-iodosuccinimide-silica gel system

被引:21
作者
Bonesi, SM [1 ]
Erra-Balsells, R [1 ]
机构
[1] Univ Buenos Aires, Fac Ciencias Exactas & Nat, Dept Quim Organ, RA-1430 Buenos Aires, DF, Argentina
关键词
D O I
10.1002/jhet.5570380111
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Carbazole (1) undergoes electrophilic aromatic substitution with various iodinating reagents. Although, 3-iodocarbazole (1b) and 3,6-diiodocarbazole (1d) obtained by iodination of carbazole were isolated and characterized sometime ago, 1-iodocarbazole (1a), 1,6-diiodocarbazole (1c) and 1,3,6-triiadocarbazole (1e) had never been isolated from the reaction mixture. The preparation and subsequent isolation and characterization of 1a, 1b, 1c, 1d and 1e are reported (mp, t(r), R-f, H-1-nmr, C-13-nmr and ms). As iodinating reagents, NaIO4/I-2 and NaIO4/KI mixtures in (i) ethanol doped with catalytical amount of sulfuric acid and in (ii) acetic acid, and N-iodosuccinimide and N-iodosuccinimide-silica gel in dichloromethane and in chloroform have been used and their uses have been compared. The iodination reaction of different carbazole derivatives such as 2-acetoxycarbazole (2), 3-bromocarbazole (3) and 3-nitrocarbazole (4) was also studied and the corresponding iododerivatives, 2a, 2b, 2c, 3a, 3b, 4a and 4b, are described for the first time. Semiempirical PM3 calculations have been performed in order to predict reactivity of carbazole (1), substituted carbazoles (2-4) and iodocarbazoles (1a-1e, 2a-2c, 3a-3b, 4a and 4b) (Scheme 1). Theoretical and experimental results are discussed briefly.
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页码:77 / 87
页数:11
相关论文
共 33 条
  • [1] ELECTROCHEMICAL AND SPECTROSCOPIC PROPERTIES OF CATION RADICALS .3. REACTION PATHWAYS OF CARBAZOLIUM RADICAL IONS
    AMBROSE, JF
    CARPENTER, LL
    NELSON, RF
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1975, 122 (07) : 876 - 894
  • [2] PHOTOCHEMICAL-REACTION OF FULL-AROMATIC BETA-CARBOLINES IN HALOMETHANES .2. CHCL3 - ELECTRONIC-SPECTRA AND KINETICS
    BIONDIC, MC
    ERRABALSELLS, R
    [J]. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1994, 77 (2-3) : 149 - 159
  • [3] PHOTOCHEMICAL-REACTION OF BETA-CARBOLINES IN CARBON TETRACHLORIDE-ETHANOL MIXTURES
    BIONDIC, MC
    ERRABALSELLS, R
    [J]. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1990, 51 (03) : 341 - 353
  • [4] BIONDIC MC, 1993, AN ASOC QUIM ARGENT, V81, P403
  • [5] PHOTOCHEMICAL-REACTION OF HARMALOL .2. ELECTRONIC-SPECTRA
    BIONDIC, MC
    ERRABALSELLS, R
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (05): : 887 - 903
  • [6] PHOTOCHEMICAL-REACTION OF HARMALINE .1. ELECTRONIC-SPECTRA
    BIONDIC, MC
    ERRABALSELLS, R
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1992, (07): : 1049 - 1058
  • [7] BIONDIC MC, UNPUB EFFECT CCL4 PH
  • [8] BISWAS M, 1982, POLYMER, V23, P1713, DOI 10.1016/0032-3861(82)90112-4
  • [9] BISWAS M, 1986, J MACROMOL SCI R M C, VC26, P249
  • [10] Bonesi SM, 1999, AN ASOC QUIM ARGENT, V87, P127