Synthesis and some reactions of 1,2-diamino-1,3-diaza- and 1,2-diamino-1-azaazulenium salts

Abe, Noritaka; Odagiri, Kunihiko; Otani, Miki; Fujinaga, Etsuko; Fujii, H.; Kakehi, Akikazu

doi:10.1039/a900688e

Cited by 12 publications

(5 citation statements)

References 10 publications

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“…Salts derived from N-amino-substituted nitrogencontaining heterocycles are widely used as reagents for the amination of arenes [3] and for the preparation of imines [4] and various heterocyclic and other compounds [5][6][7][8][9][10][11][12][13][14][15][16][17]. Such salts having several nitrogen atoms in the ring are also promising as energetic materials [18][19][20].…”

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Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine

et al. 2011

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Treatment of 2-X-substituted pyrazines [X = H, Me, Et, Pr, i-Pr, t-Bu, MeCH(OH), H 2 N, AcNH] with O-mesitylenesulfonylhydroxylamine gave the corresponding 2-X-and 3-X-(1-amino)pyrazin-1-ium mesitylenesulfonates. 2-Alkylpyrazines (X = Me, Et, Pr, i-Pr) displayed a correlation between the logarithms of the concentration ratio of 2-and 3-substituted cations and substituent steric constants. Wider series of substituted pyrazines [X = H, Me, Et, Pr, i-Pr, MeCH(OH), H 2 N, AcNH] conformed to a multiparameter correlation between the logarithms of the concentration ratio of 2-and 3-substituted cations, on the one hand, and substituent constants σ I , σ R o , and E s o , on the other. The obtained data on the regioselectivity of amination of pyrazines were interpreted in terms of DFT/PBE/3Z quantum-chemical calculations. * For preliminary communications, see [1, 2].Salts derived from N-amino-substituted nitrogencontaining heterocycles are widely used as reagents for the amination of arenes [3] and for the preparation of imines [4] and various heterocyclic and other compounds [5][6][7][8][9][10][11][12][13][14][15][16][17]. Such salts having several nitrogen atoms in the ring are also promising as energetic materials [18][19][20]. Salts of N-amino cations are usually prepared by direct amination of nitrogen-containing heterocycles with various aminating agents; among the latter, O-mesitylenesulfonylhydroxylamine (MSH) is used most widely [11][12][13].If a heteroaromatic compounds contains nitrogen atoms with different environments, amination regioselectivity problem arises [13,21]. We previously studied reactions of 3-bromo-, 4-methyl-, and 5-nitro-1,10-phenanthrolines with MSH and found that the ratio of the resulting isomeric amino cations is determined by their relative stability [21]. The goal of the present work was to reveal factors responsible for regioselectivity in the amination of pyrazine derivatives. The latter were selected as substrates, taking into account that pyrazines are widely used in the synthesis of N-amino derivatives [13]. In addition, unlike 1,10-phenanthroline derivatives listed above, the substituent in 2-X-pyrazines is contiguous to the reaction center, and the nitrogen atoms are present in a single ring, which could endow the amination process with some specificity.The reaction of 2-substituted pyrazines Ia-Ii with MSH in methylene chloride resulted in the formation

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Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine

et al. 2011

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“…N-Amino-substituted azinium salts are widely used as reagents for amination of arenes [1][2][3][4][5] and synthesis of imines [6][7][8] and various heterocyclic and other compounds [6][7][8][9][10]. In the synthesis of N-amino derivatives of azines having several heteroatoms, the problem arises as to whether the amination will occur at one or another nitrogen atom [11].…”

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Regioselectivity in the amination of azines. Reaction of 1,10-phenanthroline derivatives with O-mesitylsulfonylhydroxylamine

et al. 2004

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“…). 13 C NMR spectrum (DMSO-d6 ), δ C , ppm: cation: 39.7 (CH 3 ), 107.3, 139.6, 154.Found, %: C 57.23; H 6.85: N 12.33. C 16 H 23 N 3 O 3 S. Calculated, %: C 56.95; H 6.87; N 12.45.…”

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“…Salts containing N-amino cations derived from nitrogen-containing heteroaromatic compounds are widely used as reagents for amination of arenes [1] and for the synthesis of various heterocyclic compounds through the corresponding imines [2][3][4][5][6][7][8][9][10][11][12]. Salts containing a large number of nitrogen atoms are promising as energetic compounds [13][14][15].…”

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Structure-kinetics relations holding in the amination of six-membered nitrogen-containing heterocyclic compounds

2011

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Relative rates of the amination of 3-X-and 4-X-substituted pyridines (X = H, 3-Me, 4-Me, 3-F 3 C, 3-CN, 4-CN, 3-Cl, 3-Br, 4-MeO, 4-Me 2 N), pyrazine, quinoline, isoquinoline, 2,2′-and 4,4′-bipyridines, and 1,10-phenanthroline with O-mesitylenesulfonylhydroxylamine were estimated by NMR spectroscopy. Correlations were found between logarithms of the relative amination rate constants and substituent constants σ or σ I and σ R for X-substituted pyridines. A wide series of nitrogen-containing heterocyclic compounds turned out to fit correlations between logarithms of the relative amination rate constants, on the one hand, and relative stabilities of N-aminoazinium cations, energies of activation of the amination process, and gas-phase proton affinities, calculated by the DFT/PBE/3z and DFT/B3LYP/L2 methods, on the other.

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Synthesis and some reactions of 1,2-diamino-1,3-diaza- and 1,2-diamino-1-azaazulenium salts

Cited by 12 publications

References 10 publications

Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine

Regioselectivity in the amination of azines: Reaction of pyrazine derivatives with O-mesitylenesulfonylhydroxylamine

Regioselectivity in the amination of azines. Reaction of 1,10-phenanthroline derivatives with O-mesitylsulfonylhydroxylamine

Structure-kinetics relations holding in the amination of six-membered nitrogen-containing heterocyclic compounds

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