122-66-7Relevant articles and documents
Highly efficient and selective photocatalytic hydrogenation of functionalized nitrobenzenes
Yang, Xiu-Jie,Chen, Bin,Zheng, Li-Qiang,Wu, Li-Zhu,Tung, Chen-Ho
, p. 1082 - 1086 (2014)
We report a simple but efficient photocatalytic nitrobenzene reduction method employing eosin Y as the photocatalyst and TEOA as the reducing agent. With green LED light irradiation, the nitro group in the nitrobenzenes containing other reducible groups was chemoselectively reduced into an amino group, and the corresponding anilines were isolated in quantitative yields. The photoinduced electron transfer mechanism suggests that the high chemoselectivity originates from the better electron-withdrawing ability of the nitro group.
Catalytic Hydrogenation of Azobenzene in the Presence of a Cuboidal Mo3S4Cluster via an Uncommon Sulfur-Based H2Activation Mechanism
Guillamón, Eva,Oliva, Mónica,Andrés, Juan,Llusar, Rosa,Pedrajas, Elena,Safont, Vicent S.,Algarra, Andres G.,Basallote, Manuel G.
, p. 608 - 614 (2021)
Azobenzene hydrogenation is catalyzed under moderate conditions by a cuboidal Mo3(μ3-S)(μ-S)3 diamino complex via a cluster catalysis mechanism. Dihydrogen activation by the molecular [Mo3(μ3-S)(μ-S)3Cl3(dmen)3]+ cluster cation takes place at the μ-S bridging atoms without direct participation of the metals in clear contrast with classical concepts. The reaction occurs with the formation of 1,2-diphenylhydrazine as an intermediate with similar appearance and disappearance rate constants. On the basis of DFT calculations, a mechanism is proposed in which formation of 1,2-diphenylhydrazine and aniline occurs through two interconnected catalytic cycles that share a common reaction step that involves H2 addition to two of the bridging sulfur atoms of the catalyst to form a dithiolate Mo3(μ3-S)(μ-SH)2)(μ-S) adduct. Both catalytic cycles have similar activation barriers, in agreement with the experimental observation of close rate constant values. Microkinetic modeling of the process leads to computed concentration-time profiles in excellent agreement with the experimental ones providing additional support to the calculated reaction mechanism. Slight modifications on the experimental conditions of the catalytic protocol in combination with theoretical calculations discard a direct participation of the metal on the reaction mechanism. The effect of the ancillary ligands on the catalytic activity of the cluster fully agrees with the present mechanistic proposal. The results herein demonstrate the capability of molybdenum sulfide materials to activate hydrogen through an uncommon sulfur based mechanism opening attractive possibilities toward their applications as catalysts in other hydrogenation processes.
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Urey,Lavin
, p. 3288 (1929)
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Newsom, H. C.,English, W. D.,McCloskey, A. L.,Woods, W. G.
, p. 4134 - 4138 (1961)
μ-imido, μ-(η2,η2-N,N-hydrazido) and μ-(η1-C:η2-C,N-isocyanido) dinuclear (fulvalene)zirconium derivatives
Gonzalez-Maupoey, Marta,Rodriguez, Gema M.,Cuenca, Tomas
, p. 2057 - 2063 (2002)
Treatment of the chloro (fulvalene)zirconium(III) compound [Zr(η5-C5H5)(μ-Cl)]2 [μ-(η5,η5-C10H8)] with an equimolar amount of azobenzene in toluene, under extremely anhydrous conditions, gives the μ-[bis(imido)] derivative [Zr(η5- C5H5)(μ-NPh)]2[μ-(η5, η5-C10H8)] (1). However, when this reaction is carried out under insufficiently dry conditions a mixture of the previously reported μ-oxo complex [Zr(η5- C5H5)Cl]2(μ-O)[μ-(η5, η5-C10H8)] and 1,2-diphenylhydrazine is obtained. When the chloro(fulvalene)zirconium(III) compound reacts with benzo[c]cinnoline the μ-(η2,η2-N,N-hydrazido) complex [Zr(η5-C5H5)Cl]2[μ- (NC6H4C6H4N)][μ (η5,η5-C10H8)] (2a) is obtained, which rearranges to the thermodynamically more stable 2b. Addition of an equimolar amount of RNC (R = nBu, C6H11) to a toluene solution of [Zr(η5-C5H5)(μ-Cl)]2 [μ-(η5,η5-C10H8)] gives [Zr(η5- C5H5)Cl]2(μ-CNR)[μ- (η5,η5-C10H8)] [R = nBu (3), C6H11 (4)]. Reaction of [Zr(η5-C5H5)Cl]2(μ-CNtBu) [μ-(η5,η5-C10H8)] with 1 equiv, of PhCH2MgCl or (PhCH2)2Mg(THF)2 afforded the monobenzyl derivatives [Zr(η5-C5H5)]2 (CH2Ph)(Cl)(μ-CNtBu) [μ-(η5,η5-C10H8)] (5 and 6). When this reaction was carried out with 2 equiv. or an excess of PhCH2MgCl, a mixture of the monobenzyl and dibenzyl compounds [Zr(η5- C5H5)]2(CH2Ph)(Cl) (μ-CNtBu)[μ-(η5,η5- C10H8)] (5) and [Zr(η5-C5H5) (CH2Ph)]2(μ-CNtBu)[μ-(η5, η5-C10H8)] (7) is obtained. Similar reactions with 1 or 2 equiv. of (CH3)3SiCH2Li afford a mixture of the monoalkyl and dialkyl compounds [Zr(η5-C5H5)]2 [CH2Si(CH3)3](Cl)(μ-CNtBu) [μ-(η5,η5-C10H8)] (8) and {Zr(η5-C5H5)[CH2Si (CH3)3]}2(μ-CNtBu) [μ-(η5,η5- C10H8)] (9) compounds. Moreover, methylation of [Zr(η5- C5H5)Cl]2(μ-CNnBu) [μ-(η5,η5-C10H8)] gives the analytically pure tetramethyl derivative [Zr(η5-C5H5) (CH3)]2(μ-CNnBu) [μ-(η5,η5-C10H8)] (10), whereas [Zr(η5-C5H5)Cl]2(μ- CNC6H11)[μ-(η5, μ5-C10H8)] reacts with MeLi to give a mixture of the monomethyl derivatives [Zr(η5C5H5)]2 (CH3)(Cl)(μ-CNC6H11)[μ- (η5,η5-C10H8)] (11 and 12), as well as the dimethyl compound [Zr(η5-C5H5) (CH3)]2(μ- CNC6H11)[μ-(η5, η5-C10H8)] (13). Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
N=N bond cleavage of azobenzene through Pt/TiO2 photocatalytic reduction
Tada, Hiroaki,Kubo, Masanobu,Inubushi, Yoichi,Ito, Seishiro
, p. 977 - 978 (2000)
TiO2 photocatalytic 2e--reduction of azobenzene to hydrazobenzene is found to occur at λ(ex) > 300 nm while loading of nanometer-sized Pt particles on TiO2 induces N=N bond cleavage via 4e--reduction; only photoisomerization occurs in the absence of TiO2.
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Banthorpe et al.
, p. 2054 (1971)
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Shine et al.
, p. 3719,3721,3722 (1977)
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Hashimoto,S.,Kano,K.
, p. 852 - 855 (1972)
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Wawzonek
, p. 285,290 (1971)
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Reduction of Azo-, Azoxy-, and Nitrobenzenes by Dihydrolipoamide-Iron(II)
Kijima, Masashi,Nambu, Yoko,Endo, Takeshi,Okawara, Makoto
, p. 2407 - 2409 (1983)
Dihydrolipoamide (DHLAm) was found to be an effective reagent for the reduction of nitrobenzene derivatives in the presence of a catalytic amount of ferrous ion.Azo- and azoxybenzenes were reduced to hydrazobenzene without the formation of aniline, and nitrobenzene, nitrosobenzene, and phenylhydroxylamine were also reduced to aniline in good yields under mild conditions.The reduction was presumed to proceed through the complex formation between DHLAm, ferrous ion, and substrates.
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Pratt,Swinden
, p. 1321 (1969)
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Synthesis of Functionalized Hydrazines: Facile Homogeneous (N-Heterocyclic Carbene)-Palladium(0)-Catalyzed Diboration and Silaboration of Azobenzenes
Ansell, Melvyn B.,Kostakis, George E.,Braunschweig, Holger,Navarro, Oscar,Spencer, John
, p. 3765 - 3769 (2016)
The bis(N-heterocyclic carbene)(diphenylacetylene)palladium complex [Pd(ITMe)2(PhC≡CPh)] (ITMe=1,3,4,5-tetramethylimidazol-2-ylidene) acts as a highly active pre-catalyst in the diboration and silaboration of azobenzenes to synthesize a series of novel functionalized hydrazines. The reactions proceed using commercially available diboranes and silaboranes under mild reaction conditions. (Figure presented.).
Convenient semihydrogenation of azoarenes to hydrazoarenes using H2
Sahoo, Manoj K.,Sivakumar, Ganesan,Jadhav, Sanjay,Shaikh, Samrin,Balaraman, Ekambaram
supporting information, p. 5289 - 5293 (2021/06/30)
The high atom-economical and eco-benign nature of hydrogenation reactions make them much more superior to conventional reduction and transfer hydrogenation. Herein, a convenient and highly selective hydrogenation reaction of azoarenes using molecular hydrogen to access diverse hydrazoarenes is reported. The present catalytic method is general and operationally simple, and it operates under exceedingly mild conditions (room temperature and 1 atm of hydrogen pressure). The reusability of catalysts used in this method is also successfully demonstrated.
Visible-light-promoted decarboxylative addition cyclization of: N -aryl glycines and azobenzenes to access 1,2,4-triazolidines
Ma, Ben,Qi, Yanfang,Song, Menghui,Wang, Xi-Cun,Yang, Jingya,Zhou, Hongyan
supporting information, p. 5806 - 5811 (2021/08/23)
Methods for the synthesis of 1,2,4-triazolidines are scarce. Herein, we report a visible-light-promoted decarboxylative addition cyclization of N-aryl glycines and azobenzenes to access such important compounds. Using commercially available methylene blue (MB) as an organic photocatalyst, the reaction proceeded smoothly in the absence of transition-metal catalysts at ambient temperature, affording the corresponding products, 1,2,4-triaryl 1,2,4-triazolidines, in good to excellent yields. This work demonstrates a new synthetic application of readily available azobenenes and provides a novel strategy for constructing 1,2,4-triazolidines.