PDF herunterladen
Synthesis 2003(3): 0413-0425
DOI: 10.1055/s-2003-37344
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Reactions of 1,2,3-Triazinium Salts

Michael Mättner, Hans Neunhoeffer*
Darmstadt University of Technology, Clemens Schöpf Institute of Organic Chemistry and Biochemistry, Petersenstr. 22, 64289 Darmstadt, Germany
Fax: +49(6151)166016; e-Mail: di88@hrzpub.tu-darmstadt.de;
Weitere Informationen

Publikationsverlauf

Received 22 August 2002
Publikationsdatum:
19. Februar 2003 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

The synthesis of monosubstituted 1,2,3-triazinium salts 7-9 and their reactivity towards C-nucleophiles is described. The nucleophilic attack at 7-9 is regioselective at position 5, isolation of dihydroproducts was possible and an unusual ring contraction was observed.

Key words

1,2,3-triazines - cations - nucleophilic additions - π-deficient heterocycles - regioselectivity

    References

  • 1a Chupakhin ON. Charushin VN. van der Plas HC. In Nucleophilic Aromatic Substitution of Hydrogen   Academic Press; San Diego: 1994. ; and references cited therein
    CrossrefGoogle Scholar
  • 1b Chupakhin ON. Charushin VN. van der Plas HC. Tetrahedron  1988,  44:  1 
    CrossrefGoogle Scholar
  • 2 Charushin VN. Chupakhin ON. Sidorov EO. Beiles YI. Zh. Org. Khim.  1978,  14:  140 
    Google Scholar
  • 3a Rusinov VL. Zyryanov GV. Pilicheva TL. Chupakhin ON. Neunhoeffer H. J. Heterocycl. Chem.  1997,  34:  1013 
    CrossrefGoogle Scholar
  • 3b Kojevnikov DN. Ulomsky EN. Rusinov VL. Chupakhin ON. Neunhoeffer H. Mendeleev Commun.  1997,  116 
    CrossrefGoogle Scholar
  • 3c Chupakhin ON. Rusinov VL. Ulomsky EN. Kojevnikov DN. Neunhoeffer H. Mendeleev Commun.  1997,  66 
    CrossrefGoogle Scholar
  • 4 Stupnikova TV. Petrenko VV. Khim. Geterotskil. Soedin.  1984,  1383 
    Google Scholar
  • 5 Pozharskii AF. Gulevskaya AV. Chem. Heterocycl. Cmpds.  2001,  37:  1480 ; and references cited therein
    Google Scholar
  • For a review on 1,2,3-triazines see:
  • 6a Ohsawa A. Itoh T. In Comprehensive Heterocyclic Chemistry II   Boulton AJ. Elsevier; Oxford: 1996.  p.483-505  
    Google Scholar
  • 6b Ohsawa A. Itoh T. In Comprehensive Heterocyclic Chemistry II   Boulton AJ. Elsevier; Oxford: 1996.  p.1177-1307  
    Google Scholar
  • 7a Okatani T. Koyama J. Tagahara K. Heterocycles  1989,  29(9):  1809 
    Google Scholar
  • 7b Neunhoeffer H. Bopp R. Diehl W. Liebigs Ann. Chem.  1993,  367 
    Google Scholar
  • 8 Neunhoeffer H. Clausen M. Vötter H.-D. Ohl H. Krüger C. Angermund K. Liebigs Ann. Chem.  1985,  9:  1732 
    Google Scholar
  • 9 Ohsawa A. Arai H. Ohnishi H. Kaihoh T. Itoh T. Yamaguchi K. Igeta H. Iitaka Y. Yakugaku Zasshi  1985,  105:  1122 
    Google Scholar
  • 10 Ohsawa A. Itoh T. Hasegawa H. Nagata K. Okada M. J. Chem. Soc., Perkin. Trans. I  1996,  20:  2511 
    Google Scholar
  • 11 Meerwein H. Angew. Chem.  1970,  72:  927 
    Google Scholar
  • 13 Frisch MJ. Trucks GW. Schlegel HB. Gill PMW. Johnson BG. Robb JR. Cheeseman JR. Keith T. Peterson GA. Montgomery JA. Ragharachari K. Al-Laham MA. Zakrzewski VG. Ortiz JV. Foresman JB. Cioslowski J. Stefanov BB. Nanayakkara A. Challacombe M. Peng CY. Ayala PJ. Chen W. Wang MW. Andres JL. Replogle ES. Gomperts R. Martin RL. Fox DJ. Binkley JS. Defrees DJ. Baker J. Stewart JP. Head-Gordon M. Gonzalez C. Pople JA. Gaussian 94 Rev. D.4   Gaussian Inc.; Pittsburgh PA: 1995. 
    Google Scholar
  • 14a Pople JA. Schlegel HB. Krishnan R. DeFrees D. Binkley JS. Frisch MJ. Whiteside RF. Hout RF. Hehre WJ. Int. J. Quantum Chem. Quantum Chem. Symp  1981,  15:  269 
    Google Scholar
  • 14b Foresman JB. Frisch MJ. In Exploring Chemistry with Electronic Structures Methods: A Guide to Using Gaussian   Gaussian Inc.; Pittsburgh: 1993. 
    Google Scholar
  • 16 Varvoglis A. In The Organic Chemistry of Polycoordinated Iodine   VCH Publishers Inc.; New York: 1992. 
    Google Scholar
  • 17a Moriarty RM. Vaid RK. Synthesis  1990,  431 
    Google Scholar
  • 17b Varvoglis A. Synthesis  1984,  709 
    Google Scholar
  • 17c Jacobsen SA. Rodbotten S. Benneche T. J. Chem. Soc., Perkin Trans.1  1999,  22:  3265 
    Google Scholar
  • 18 Kang S.-K. Lee S.-H. Lee D. Synlett  2000,  1022 
    Artikel in Thieme ConnectGoogle Scholar
  • 19 Neßlers reagent for ammonium salts from Merck VWR International Inc. Darmstadt, see: Burns EA. Streuli CA. Averell PR. In The Analytical Chemistry of Nitrogen and its Compounds   Wiley-Intersience; New York: 1970. 
    Google Scholar
  • 20a Itoh T. Okada M. Nagata K. Yamaguchi K. Ohsawa A. Chem. Pharm. Bull.  1990,  38:  2108 
    Google Scholar
  • 20b Itoh T. Nagata K. Kaihoh T. Okada M. Kawabata C. Arai H. Ohnishi H. Yamaguchi K. Igeta H. Ohsawa A. Iitaka Y. Heterocycles  1992,  33:  631 
    Google Scholar
  • 21 Ohsawa A. Itoh T. Nagata K. Okada M. Chem. Pharm. Bull.  1992,  40:  2283 
    Google Scholar
12

Ab initio calculations done with Gaussian 94 [12] with standard basic set 6-311G*, geometries were optimized on HF/6-31G* level and characterized as minima by vibrational frequency analysis (number of imaginary frequencies = zero for minima). These provided the zero-point vibrational energies (ZPEs) which were scaled for the calculation of relative energies by an empirical factor of 0.89. [13]

15

Energies for N-2 ethylated and N-2 protonated 1,2,3-triazines 7 and 8 were defined as 0 kJmol-1