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

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.

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

References

<A NAME="RT09402SS-1A">1a</A> Chupakhin ON. Charushin VN. van der Plas HC. In Nucleophilic Aromatic Substitution of Hydrogen   Academic Press; San Diego: 1994. ; and references cited therein

<A NAME="RT09402SS-1B">1b</A> Chupakhin ON. Charushin VN. van der Plas HC. Tetrahedron  1988,  44:  1 

<A NAME="RT09402SS-2">2</A> Charushin VN. Chupakhin ON. Sidorov EO. Beiles YI. Zh. Org. Khim.  1978,  14:  140 

<A NAME="RT09402SS-3A">3a</A> Rusinov VL. Zyryanov GV. Pilicheva TL. Chupakhin ON. Neunhoeffer H. J. Heterocycl. Chem.  1997,  34:  1013 

<A NAME="RT09402SS-3B">3b</A> Kojevnikov DN. Ulomsky EN. Rusinov VL. Chupakhin ON. Neunhoeffer H. Mendeleev Commun.  1997,  116 

<A NAME="RT09402SS-3C">3c</A> Chupakhin ON. Rusinov VL. Ulomsky EN. Kojevnikov DN. Neunhoeffer H. Mendeleev Commun.  1997,  66 

<A NAME="RT09402SS-4">4</A> Stupnikova TV. Petrenko VV. Khim. Geterotskil. Soedin.  1984,  1383 

<A NAME="RT09402SS-5">5</A> Pozharskii AF. Gulevskaya AV. Chem. Heterocycl. Cmpds.  2001,  37:  1480 ; and references cited therein

For a review on 1,2,3-triazines see:

<A NAME="RT09402SS-6A">6a</A> Ohsawa A. Itoh T. In Comprehensive Heterocyclic Chemistry II   Boulton AJ. Elsevier; Oxford: 1996.  p.483-505  

<A NAME="RT09402SS-6B">6b</A> Ohsawa A. Itoh T. In Comprehensive Heterocyclic Chemistry II   Boulton AJ. Elsevier; Oxford: 1996.  p.1177-1307  

<A NAME="RT09402SS-7A">7a</A> Okatani T. Koyama J. Tagahara K. Heterocycles  1989,  29(9):  1809 

<A NAME="RT09402SS-7B">7b</A> Neunhoeffer H. Bopp R. Diehl W. Liebigs Ann. Chem.  1993,  367 

<A NAME="RT09402SS-8">8</A> Neunhoeffer H. Clausen M. Vötter H.-D. Ohl H. Krüger C. Angermund K. Liebigs Ann. Chem.  1985,  9:  1732 

<A NAME="RT09402SS-9">9</A> Ohsawa A. Arai H. Ohnishi H. Kaihoh T. Itoh T. Yamaguchi K. Igeta H. Iitaka Y. Yakugaku Zasshi  1985,  105:  1122 

<A NAME="RT09402SS-10">10</A> Ohsawa A. Itoh T. Hasegawa H. Nagata K. Okada M. J. Chem. Soc., Perkin. Trans. I  1996,  20:  2511 

<A NAME="RT09402SS-11">11</A> Meerwein H. Angew. Chem.  1970,  72:  927 

<A NAME="RT09402SS-12">12</A>

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]

<A NAME="RT09402SS-13">13</A> 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. 

<A NAME="RT09402SS-14A">14a</A> 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 

<A NAME="RT09402SS-14B">14b</A> Foresman JB. Frisch MJ. In Exploring Chemistry with Electronic Structures Methods: A Guide to Using Gaussian   Gaussian Inc.; Pittsburgh: 1993. 

<A NAME="RT09402SS-15">15</A>

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

<A NAME="RT09402SS-16">16</A> Varvoglis A. In The Organic Chemistry of Polycoordinated Iodine   VCH Publishers Inc.; New York: 1992. 

<A NAME="RT09402SS-17A">17a</A> Moriarty RM. Vaid RK. Synthesis  1990,  431 

<A NAME="RT09402SS-17B">17b</A> Varvoglis A. Synthesis  1984,  709 

<A NAME="RT09402SS-17C">17c</A> Jacobsen SA. Rodbotten S. Benneche T. J. Chem. Soc., Perkin Trans.1  1999,  22:  3265 

<A NAME="RT09402SS-18">18</A> Kang S.-K. Lee S.-H. Lee D. Synlett  2000,  1022 

<A NAME="RT09402SS-19">19</A> 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. 

<A NAME="RT09402SS-20A">20a</A> Itoh T. Okada M. Nagata K. Yamaguchi K. Ohsawa A. Chem. Pharm. Bull.  1990,  38:  2108 

<A NAME="RT09402SS-20B">20b</A> 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 

<A NAME="RT09402SS-21">21</A> Ohsawa A. Itoh T. Nagata K. Okada M. Chem. Pharm. Bull.  1992,  40:  2283