Syntheses of mono-, di- and triethynylazulenes

Tetrahedron Letters

Volumn 41, Issue 16, 2000, Pages 2855-2858

  Fabian, Kai H H ^a   Elwahy, Ahmed H M ^a   Hafner, Klaus ^a  

^a DARMSTADT UNIVERSITY OF TECHNOLOGY   (Germany)

Author keywords

Corey Fuchs reaction; Ethynylazulenes; Pd cross coupling reaction

Indexed keywords

AZULENE DERIVATIVE; DIETHYNYLAZULENE; MONOETHYNYLAZULENE; TRIETHYNYLAZULENE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; COMPLEX FORMATION; COUPLING FACTOR; CRYSTAL STRUCTURE; DRUG SYNTHESIS; PROTON NUCLEAR MAGNETIC RESONANCE; SIALYLATION;

EID: 0034656152     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00308-7     Document Type: Article

References (29)

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7. Müllen, K. Pure & Appl. Chem. 1993, 65, 89-96; Diederich, F.; Martin, R. E. Angew. Chem. 1999, 111, 1440-1469; Angew. Chem., Int. Ed. 1999, 38, 1350-1377; Scherf, U., Müllen, K. Synthesis 1992, 23-38; Tour, J. M. Chem. Rev. 1996, 96, 537-553; Nelson, J. C.; Saven, J. G.; Moore, J. S.; Wolynes, P.G. Science 1997, 277, 1793-1796; Electronic Materials: The Oligomer Approach; Müllen, K.; Wegner, G.; Eds.; Wiley-VCH: Weinheim, 1997.
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16. 1- and 2-ethynylazulenes (72%) as well as 1,2- and 1,3-diethynylazulenes (23-26%) were also recently prepared from the corresponding aldehydes with lithium trimethylsilyldiazomethane; Fujimori, K. Abstract 1P31, 13th Symposium on Fundamental Organic Chemistry; Nagoya University, Japan Nov. 1-3, 1996, and personal communication.
17. The mono- and diiodoazulenes 2a, b and 3a, b were obtained by reacting the corresponding azulenes with 1 and 2.2 equiv. NIS, respectively, in dichloromethane. The solvent was then removed in vacuo below 10°C followed by chromatography on alumina (BII-III) using n-hexane as an eluent. The greenish blue residue was immediately resolved in triethylamine for further cross-coupling reactions. For the synthesis of 1-iodo-and 1-bromoazulene as well as 1,3-dibromoazulene see also: Hafner, K.; Patzelt, H.; Kaiser, H. Liebigs Ann. Chem. 1962, 656, 24-33. For the synthesis of 2-iodoazulene (4) see: Nozoe, T.; Seto, S.; Matsumura, S. Bull. Chem. Soc. Jpn. 1962, 35, 1990-1998.
18. The mono- and diiodoazulenes 2a, b and 3a, b were obtained by reacting the corresponding azulenes with 1 and 2.2 equiv. NIS, respectively, in dichloromethane. The solvent was then removed in vacuo below 10°C followed by chromatography on alumina (BII-III) using n-hexane as an eluent. The greenish blue residue was immediately resolved in triethylamine for further cross-coupling reactions. For the synthesis of 1-iodo-and 1-bromoazulene as well as 1,3-dibromoazulene see also: Hafner, K.; Patzelt, H.; Kaiser, H. Liebigs Ann. Chem. 1962, 656, 24-33. For the synthesis of 2-iodoazulene (4) see: Nozoe, T.; Seto, S.; Matsumura, S. Bull. Chem. Soc. Jpn. 1962, 35, 1990-1998.
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21. 9 with TMSA in refluxing triethylamine.
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26. Attempts to synthesize 1a, b, d, f and g by the Corey-Fuchs method, starting from the corresponding formylazulenes were unsuccessful presumably due to the deactivation of the carbonyl function at the five-membered ring.
27. Depending on the number and position of the ethynyl groups in the azulene-system the bathochromic shift ranged from 3-48 nm.
28. The described new compounds gave correct elemental analyses.
29. 3 with tetramethylsilane as internal standard. UV-vis spectra were recorded with a Beckman UV-5240 spectrometer. Mass spectra (MS) were obtained with a Varian 311A instrument.