4114-28-7Relevant articles and documents
Tuning the electrical and optical properties of dinuclear ruthenium complexes for near infrared optical sensing
Xun, Shidi,LeClair, Gaetan,Zhang, Jidong,Chen, Xin,Gao, Jian Ping,Wang, Zhi Yuan
, p. 1697 - 1700 (2006)
Redox-active dinuclear ruthenium complexes with various 1,2-dicarbonylhydrazido (DCH) ligands are designed and prepared to have intense absorption in the near-infrared region for potential optical sensing in aqueous media, as demonstrated for sensing hydrogen peroxide in this study.
Photooxidation mechanism of nitrogen-containing compounds at TiO2/H2O interfaces: An experimental and theoretical examination of hydrazine derivatives
Waki, Kunio,Zhao, Jincai,Horikoshi, Satoshi,Watanabe, Natsuko,Hidaka, Hisao
, p. 337 - 343 (2000)
The photocatalytic oxidation of oxalyldihydrazide, N,N'- bis(hydrazocarbonyl)hydrazide, N,N'-bis(ethoxycarbonyl)hydrazide, malonyldihydrazide, N-malonyl-bis[(N'-ethoxycarbonyl)hydrazide] was examined in aqueous TiO2 dispersions under UV illumination. The photomineralization of nitrogen and carbon atoms in the substrates into N2 gas, NH4/+ (and/or NO3/-) ions, and CO2 gas was determined by HPLC and GC analysis. The formation of carboxylic acid intermediates also occurred in the photooxidation process. The photocatalytic mechanism is discussed on the basis of the experimental results, and with molecular orbital (MO) simulation of frontier electron density and point charge. Substrate carbonyl groups readily adsorb on the TiO2 surface, and the bonds between carbonyl group carbon atoms and adjacent hydrazo group nitrogen atoms are cleaved predominantly in the initial photooxidation process. The hydrazo groups were photoconverted mainly into N2 gas (in mineralization yields above 70%) and partially to NH+4 ions (below 10%). The formation of NO+3 ions was scarcely recognized. (C) 2000 Elsevier Science Ltd.
Lewis acid catalyzed C-3 alkylidenecyclopentenylation of indoles: An easy access to functionalized indoles and bisindoles
Sarath Chand,Sasidhar,Prakash, Praveen,Sasikumar,Preethanuj,Jaroschik, Florian,Harakat, Dominique,Vasse, Jean-Luc,Radhakrishnan
, p. 38075 - 38084 (2015)
A Lewis acid catalyzed C-3 alkylidenecylopentenylation of indoles through the ring opening of pentafulvene derived diazabicyclic olefins has been developed. The present protocol offers an efficient route toward the synthesis of indole and bisindole derivatives. The role of the hydrazine group, as a reaction carrier in the strategy has also been demonstrated by the stepwise synthesis of functionalized bisindole.
Multiparameter correlation of the rate of a [2 + 2] cycloaddition reaction versus solvophobicity parameter and normalized polarity parameter in aqueous solutions
Gholami,Habibi Yangjeh
, p. 468 - 472 (2000)
The second-order rate constants of the [2 + 2] cycloaddition reaction between diethyl azodicarboxylate and ethyl vinyl ether were obtained spectrophotometrically in various solvents and aqueous solutions of 1,4-dioxane and methanol at 30 ± 0.1 °C. In all media except aqueous solutions, a very good linear correlation of logk2 vs ETN (normalized polarity parameter) was obtained (n = 11, r = 0.991, s = 0.086). Because of the higher polarity of the activated complex relative to the reactants, the rate of the reaction increase with increasing solvent polarity parameter. Dual-parameter correlation of logk2 vs π* (dipolarity/polarizability) and a (hydrogen bonding acidity) also gives good results in various solvents (n = 11, r = 0.985, s = 0.118). Both n* and α have approximately equal effects on the reaction rate. In aqueous solutions of 1,4-dioxane and methanol, the second-order rate constants of the reaction increase dramatically with increasing mole fraction of water. A dual-parameter correlation of logk2 vs Sp (solvophobicity parameter) and ETN was found in aqueous solutions (n = 13, r = 0.988, s = 0.165), in which Sp plays an important role in determining the reaction relative to ETN. This model represents a significant improvement in regression coefficient with respect to the single parameter correlation vs Sp or ETN (r = 0.954 and 0.854, respectively). Similarly to aqueous solutions, a dual-parameter correlation of logk2 vs Sp and ETN was obtained in all media (n = 21, r = 0.987, s = 0.177). Copyright
Catalysis by molybdenum complexes. The reaction of diazenes and acetylenes with thiophenol
McDonald,Corbin,Newton
, p. 2056 - 2061 (1976)
The reaction of diethyl azodicarboxylate with thiophenol to give the appropriate hydrazine and disulfide is catalyzed by various oxomolybdenum compounds, Vaska's compound, and triethylamine. Of these same compounds, only OMo(S2CNR2)
Photocatalytic esterification under Mitsunobu reaction conditions mediated by flavin and visible light
M?rz,Chudoba,Kohout,Cibulka
supporting information, p. 1970 - 1975 (2017/03/11)
The usefulness of flavin-based aerial photooxidation in esterification under Mitsunobu reaction conditions was demonstrated, providing aerial dialkyl azodicarboxylate recycling/generation from the corresponding dialkyl hydrazine dicarboxylate. Simultaneously, activation of triphenylphosphine (Ph3P) by photoinduced electron transfer from flavin allows azo-reagent-free esterification. An optimized system with 3-methylriboflavin tetraacetate (10%), oxygen (terminal oxidant), visible light (450 nm), Ph3P, and dialkyl hydrazine dicarboxylate (10%) has been shown to provide efficient and stereoselective coupling of various alcohols and acids to esters with retention of configuration.
“On-Droplet” Chemistry: The Cycloaddition of Diethyl Azodicarboxylate and Quadricyclane
Bain, Ryan M.,Sathyamoorthi, Shyam,Zare, Richard N.
supporting information, p. 15083 - 15087 (2017/11/20)
Sharpless and co-workers previously studied the [2σ+2σ+2π] cycloaddition of diethyl azodicarboxylate (DEAD) and quadricyclane and reported that the addition of water to the neat reagents caused an acceleration in the reaction rate, giving birth to what has been called “on-water” chemistry. We have examined the same reaction in aqueous microdroplets (ca. 5 μm diameter) and find that the cycloaddition reaction is accelerated even further (by a factor of 102) compared to that of the “on-water” reaction reported previously. The trends of acceleration in solvents other than water demonstrated by Sharpless and colleagues were replicated in the corresponding microdroplet experiments. We also find that DEAD reacts with itself to form a variety of hydrazine carboxylates and intercept intermediates of this reaction in microdroplets to validate a mechanism proposed herein. We suggest that “on-droplet” chemistry, similar to “on-water” chemistry, may be a general process of synthetic interest.
A convergent synthesis of 1,3,4-oxadiazoles from acyl hydrazides under semiaqueous conditions
Tokumaru, Kazuyuki,Johnston, Jeffrey N.
, p. 3187 - 3191 (2017/04/04)
The 1,3,4-oxadiazole is an aromatic heterocycle valued for its low-lipophilicity in drug development. Substituents at the 2- and/or 5-positions can modulate the heterocycle's electronic and hydrogen bond-accepting capability, while exploiting its use as a carbonyl bioisostere. A new approach to 1,3,4-oxadiazoles is described wherein α-bromo nitroalkanes are coupled to acyl hydrazides to deliver the 2,5-disubstituted oxadiazole directly, avoiding a 1,2-diacyl hydrazide intermediate. Access to new building blocks of oxadiazole-substituted secondary amines is improved by leveraging chiral α-bromo nitroalkane or amino acid hydrazide substrates. The non-dehydrative conditions for oxadiazole synthesis are particularly notable, in contrast to alternatives reliant on highly oxophilic reagents to effect cyclization of unsymmetrical 1,2-diacyl hydrazides. The mild conditions are punctuated by the straightforward removal of co-products by a standard aqueous wash.
Tert-Butyl Iodide Mediated Reductive Fischer Indolization of Conjugated Hydrazones
Ito, Yuta,Ueda, Masafumi,Takeda, Norihiko,Miyata, Okiko
supporting information, p. 2616 - 2619 (2016/02/26)
A novel reductive Fischer indolization of readily available N-aryl conjugated hydrazones with tert-butyl iodide has been developed. In this reaction, tert-butyl iodide is used as anhydrous HI source, and the generated HI acts as a Br?nsted acid and a reducing agent. This operationally simple method allows access to various indole derivatives. Furthermore, the procedure can be applied to the synthesis of biologically active compounds.
Method of manufacturing Azodicarboxylic acid diester compd. (by machine translation)
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Paragraph 0026; 0028, (2017/04/28)
PROBLEM TO BE SOLVED: To provide a manufacturing method in which an azodicarboxylate diester compound can be efficiently obtained in a high yield and which is industrially advantageous.SOLUTION: There is provided a manufacturing method for azodicarboxylate diester compound including: a process (a) of obtaining a 1,2-hydrazine dicarboxylate diester compound through reaction between hydrazine and a halocarbonate ester; and a process (b) of obtaining an azodicarboxylate diester compound represented by general formula (2) (where A represents a hydrocarbon or a hydrocarbon which may have an ether bond) by oxidizing the 1,2-hydrazine dicarboxylate diester compound obtained in the process (a), the 1,2-hydrazine dicarboxylate diester compound being neither isolated nor refined.
