- 1,3-Bis(4-methylphenyl)triazene, 1-(4-chlorophenyl)-3-(4-fluorophenyl)- triazene and 1-(4-fluorophenyl)-3-(4-methylphenyl)triazene
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The title 4,4′-disubstituted diphenyl-1,3-triazines, C 14H15N3, (I), C12H 9ClFN3, (II), and C13H12FN 3, (III), each contain a triazene group (-N=N-NH-) having an extended conformation. The dihedral angles between the two benzene rings in (I), (II) and (III) are 4.3, 3.4 and 6.5°, respectively. The molecules are almost entirely planar, with maximum deviations from the mean planes of 0.1087 (2), -0.1072 (7) and 0.1401 (3) A, respectively. In each compound, the molecules are linked by N-H...N hydrogen bonds to form chains and pack similarly in the crystal structures.
- Karadayi, Nevzat,Cakmak, Suekriye,Odabasoglu, Mustafa,Bueyuekguengoer, Orhan
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- N2 extrusion and co insertion: A novel palladium-catalyzed carbonylative transformation of aryltriazenes
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A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H. Nitrogen was released from the substrates and CO formally inserted. Aryl bromides, iodides, alkynes, and free hydroxyl groups can be tolerated in this transformation.
- Li, Wanfang,Wu, Xiao-Feng
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supporting information
p. 1910 - 1913
(2015/04/27)
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- Manganese complexes with triazenido ligands encapsulated in NaY zeolite as heterogeneous catalysts
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Two different methods were described for the preparation of manganese complexes with triazenido derivative ligands encapsulated in NaY zeolite. The catalytic behaviour of the heterogeneous catalysts was evaluated for styrene and cyclohexanol oxidation rea
- Ku?niarska-Biernacka, Iwona,Fonseca, António M.,Neves, Isabel C.
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p. 591 - 597
(2013/03/13)
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- Novel one-pot synthesis of thiophenols from related triazenes under mild conditions
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In this work, at first, triazenes were synthesized from primary aryl amines. Afterwards, triazenes were converted into the corresponding thiophenols in one-pot using sodium sulfide in acidic media, by in situ generation of diazonium counterion beside hydrogen sulfide as anionic sulfur nucleophile at room temperature. The procedure can be a convenient shortcut for the preparation of thiophenols from primary aryl amines. Georg Thieme Verlag Stuttgart · New York.
- Khazaei, Ardeshir,Kazem-Rostami, Masoud,Moosavi-Zare, Ahmadreza,Bayat, Mohammad,Saednia, Shahnaz
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experimental part
p. 1893 - 1896
(2012/09/22)
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- Pd-catalyzed C-H activation/C-N bond formation: A new route to 1-aryl-1H-benzotriazoles
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A method for the C-H activation of aryl triazene compounds followed by intramolecular amination is described. It involves the use of a catalytic amount of Pd(OAc)2 that efficiently effects the cyclization to provide 1-aryl-1H-benzotriazoles at moderate temperature.
- Kumar, Rapolu Kiran,Ali, Md Ashif,Punniyamurthy, Tharmalingam
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supporting information; experimental part
p. 2102 - 2105
(2011/06/25)
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- Substituent effects on the thermal cis-to-trans isomerization of 1,3-diphenyltriazenes in aqueous solution
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The thermal cis-to-trans isomerization of some symmetrically p,p′-disubstituted 1,3-diphenyltriazenes has been studied by means of laser-flash photolysis techniques. The geometric isomerization is catalyzed by general acids and general bases as a result of acid/base-promoted 1,3-prototropic rearrangements. Acid catalysis becomes more prominent as the electron-donating character of the para substituent increases, while base catalysis becomes more important as the electron-withdrawing character of the para substituent increases. In addition, the rate ascribed to the interconversion of neutral cis rotamers through hindered rotation around the nitrogen-nitrogen single bond is found to decrease as the electron-withdrawing character of the para substituent increases. Rates of interconversion of neutral cis rotamers are also found to decrease with decreasing solvent polarity, which is indicative of the involvement of a polar transition state. On the other hand, kinetic investigations of the acid-catalyzed decomposition of target triazenes are consistent with an A1 mechanism.
- Chen, Nan,Barra, Monica,Lee, Ivan,Chahal, Navjot
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p. 2271 - 2277
(2007/10/03)
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- Nitrogen dioxide - Sodium iodide as an efficient reagent for the one- pot conversion of aryl amines to aryl iodides under nonaqueous conditions
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Successive treatment of aromatic amines with liquid nitrogen dioxide and powdered sodium iodide in acetonitrile at -20 °C, followed by usual work- up, gave the corresponding aryl iodides in good yield. This method worked especially well for less basic amines bearing electron-withdrawing substituents.
- Suzuki, Hitomi,Nonoyama, Nobuaki
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p. 4533 - 4536
(2007/10/03)
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- Reactions of Nitric Oxide with Amines in the Presence of Dioxygen
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Nitric oxide (NO), a multifaceted bioregulatory agent and an environmental pollutant, can effectively convert aromatic amines to the corresponding triazenes under aerobic conditions, but not under anaerobic conditions.Nucleic acid bases and nucleosides are also determinated via hydrolysis of the diazonium ion products with exposure to aerobic NO solution.A peroxynitrite radical or nitrogen dioxide is suggested to be the ultimate reactive species.
- Nagano, Tetsuo,Takizawa, Hiromasa,Hirobe, Masaaki
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p. 8239 - 8242
(2007/10/02)
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- Triazene Drug Metabolites. Part 13. The Decomposition of 3-Acyl-3-alkyl-1-aryltriazenes in Aqueous Sulfuric Acid
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The hydrolysis of 1-aryl-3-acyl-3-methyltriazenes in aqueous sulfuric acid si described.The 3-formyl derivative undergoes an acid-catalysed deacylation reaction, characterised by a monotonic rise in the pseudo-first-order rate constant ko with increasing acidity, solvent deuterium isotope effects, kH2SO4/kD2SO4, of 0.9 (at 0.95 mol dm-3 H2SO4) and 0.8 (at 2.85 mol dm-3 H2SO4) and an entropy of activation of -80 J mol-1 K-1.The 3-alkanoyl derivatives also undergo acid-catalysed decomposition involving cleavage of either the N3-C acyl bond or the N2-N3 triazene bond.Below 3 mol dm-3 H2SO4, only acyl bond cleavage is observed.At higher acidities the extent of N2-N3 bond cleavage increases.The reaction is characterised by (i) solvent deuterium isotope effects of ca. 0.6 at 2 and 5 mol dm-3 H2SO4 and ca. 0.4 at 8 mol dm-3 H2SO4, (ii) ΔS(excit.) values of -6.7 and 51 J mol-1 K-1 at 2 and 6.1 mol dm-3 H2SO4, respectively, (iii) Hammett ρ values for the substituent in the triazene N-aryl ring of -0.7 and -0.9 at 3 and 9 mol dm-3 H2SO4, respectively, and (iv) an increase in reactivity with electron donating ability of the alkyl substituent of the acyl group.The 3-trifluoroacetyl triazenes are subject to solvolysis of the neutral, as well as the protonated, substrate.The hydrolysis of the neutral substrate involves N-acyl bond cleavage and is characterised by a solvent deuterium isotope effect, kH2O/kD2O, of 2.4, and a Hammett ρ value of +0.8 for the substituent in the N-aryl ring.The reactivity of the neutral substrate diminishes with increasing acidity until 6 mol dm-3 H2SO4, beyond which acid-catalysed N-acyl bond cleavage predominates, for which the solvent isotope effect, kH2SO4/kD2SO4, is 0.8 and the Hammett ρ value -0.5.The 3-aroyl substrates suffer acid-catalysed decomposition, the extent of the N2-N3 bond cleavage process being greater than for the N-alkanoyl counterparts.The reactions are rationalised in terms of a process that involves pre-equilibrium protonation of the substrate either at the N1 triazene atom or the amide oxygen atom, followed by subsequent decomposition of the protonated substrate via either N3-C bond cleavage, involving attack of water at the amide carbonyl, or unimolecular N2-N3 bond cleavage.The relative extents of the N3-C and N2-N3 bond cleavage processes depend on the reactivity of the acyl group and the water acitivity; the higher the water activity and the more reactive the acyl group, the more deacylation is favoured.
- Carvalho, Emilia,Iley, Jim,Rosa, Eduarda
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p. 865 - 870
(2007/10/02)
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- A New Reaction of Aryl Isocyanates with Nitrite Ion
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Reaction of nitrite ion with excess aryl isocyanate in organic solvents at 0 deg C rapidly produces 1,3-diaryltriazenes in good yields via an aryldiazotate ion intermediate reacting with a second molecule of the aryl isocyanate.
- Botting, Nigel P.,Challis, Brian C.
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p. 1585 - 1586
(2007/10/02)
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- SUBSTITUENT EFFECT ON SOLVOLYSIS OF 3-ACETYL-1,3-DIPHENYLTRIAZENES
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Eleven symmetrically disubstituted 3-acetyl-1,3-diphenyltriazenes have been synthetized by a new method.The solvolysis kinetics of title compounds has been measured in 20percent aqueous ethanol at several temperatures.The results are discussed from the point of view of temperature and substituent effects on the solvolysis rate constant of the 3-acetyl-1,3-diphenyltriazenes and conclusions are drawn about the reaction mechanism.
- Pytela, Oldrich,Pilny, Miroslav,Vecera, Miroslav
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p. 1173 - 1181
(2007/10/02)
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