627-70-3Relevant academic research and scientific papers
Effect of intercalants inside birnessite-type manganese oxide nanosheets for sensor applications
Wuamprakhon, Phatsawit,Krittayavathananon, Atiweena,Kosasang, Soracha,Ma, Nattapol,Maihom, Thana,Limtrakul, Jumras,Chanlec, Narong,Kidkhunthod, Pinit,Sawangphruk, Montree
, p. 15595 - 15605 (2020)
Hydrazine is a common reducing agent widely used in many industrial and chemical applications; however, its high toxicity causes severe human diseases even at low concentrations. To detect traces of hydrazine released into the environment, a robust sensor with high sensitivity and accuracy is required. An electrochemical sensor is favored for hydrazine detection owing to its ability to detect a small amount of hydrazine without derivatization. Here, we have investigated the electrocatalytic activity of layered birnessite manganese oxides (MnO2) with different intercalants (Li+, Na+, and K+) as the sensor for hydrazine detection. The birnessite MnO2 with Li+ as an intercalant (Li-Bir) displays a lower oxidation peak potential, indicating a catalytic activity higher than the activities of others. The standard heterogeneous electron transfer rate constant of hydrazine oxidation at the Li-Bir electrode is 1.09- and 1.17-fold faster than those at the Na-Bir and K-Bir electrodes, respectively. In addition, the number of electron transfers increases in the following order: K-Bir (0.11 mol) Na-Bir (0.17 mol) Li-Bir (0.55 mol). On the basis of the density functional theory calculation, the Li-Bir sensor can strongly stabilize the hydrazine molecule with a large adsorption energy (-0.92 eV), leading to high electrocatalytic activity. Li-Bir also shows the best hydrazine detection performance with the lowest limit of detection of 129 nM at a signal-to-noise ratio of ~3 and a linear range of 0.007-10 mM at a finely tuned rotation speed of 2000 rpm. Additionally, the Li-Bir sensor exhibits excellent sensitivity, which can be used to detect traces of hydrazine without any effect of interference at high concentrations and in real aqueous-based samples, demonstrating its practical sensing applications.
Ammonia and Hydrazine from Coordinated Dinitrogen by Complexes of Iron(0)
Field, Leslie D.,Li, Hsiu L.,Dalgarno, Scott J.,McIntosh, Ruaraidh D.
, p. 2006 - 2011 (2019)
The iron(0) dinitrogen complexes [Fe(N2)(PP3R)] (PP3R = P(CH2CH2PR2)3, R = Ph, iPr, Cy) were synthesized by reduction of the precursor chloro complexes with potassium graphite. On reaction with triflic acid, [Fe(N2)(PP3R)] complexes afforded ammonia and hydrazine in yields of up to 23 and 16 % respectively. The complex [Fe(N2)(PP3Ph)] which has only been previously synthesized in situ, has now been isolated and fully characterized by 15N NMR spectroscopy and by X-ray crystallography.
Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction
Davis II, William E.,Li, Yongtao
, p. 5449 - 5453 (2008)
A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-15N2 used as the surrogate standard formed acetone azine and acetone azine-15N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine- 15N2. The extracted acetone azine was quantified against the extracted acetone azine-15N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine- 15N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.
Hydrogenative metathesis of enynes via piano-stool ruthenium carbene complexes formed by alkyne gem-hydrogenation
Peil, Sebastian,Bistoni, Giovanni,Goddard, Richard,Fürstner, Alois
supporting information, p. 18541 - 18553 (2020/11/17)
The only recently discovered gem-hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp?RuCl]4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis, and a prototypical example of such a reactive intermediate with an olefin ligated to the ruthenium center has been isolated and characterized by X-ray diffraction. It is the substitution pattern of the olefin that determines whether metathesis or cyclopropanation takes place: a systematic survey using alkenes of largely different character in combination with a computational study of the mechanism at the local coupled cluster level of theory allowed the preparative results to be sorted and an intuitive model with predictive power to be proposed. This model links the course of the reaction to the polarization of the double bond as well as to the stability of the secondary carbene complex formed, if metathesis were to take place. The first application of "hydrogenative metathesis"to the total synthesis of sinularones E and F concurred with this interpretation and allowed the proposed structure of these marine natural products to be confirmed. During this synthesis, it was found that gem-hydrogenation also provides opportunities for C-H functionalization. Moreover, silylated alkynes are shown to participate well in hydrogenative metathesis, which opens a new entry into valuable allylsilane building blocks. Crystallographic evidence suggests that the polarized [Ru-Cl] bond of the catalyst interacts with the neighboring R3Si group. Since attractive interligand Cl/R3Si contacts had already previously been invoked to explain the outcome of various ruthenium-catalyzed reactions, including trans-hydrosilylation, the experimental confirmation provided herein has implications beyond the present case.
Hydrogenative Cyclopropanation and Hydrogenative Metathesis
Peil, Sebastian,Guthertz, Alexandre,Biberger, Tobias,Fürstner, Alois
supporting information, p. 8851 - 8856 (2019/05/28)
The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap.
Unprecedented synthesis of symmetrical azines from alcohols and hydrazine hydrate using nickel based NNN-pincer catalyst: An experimental and computational study
Shiekh, Bilal Ahmad,Kaur, Damanjit,Godara, Sachin Kumar
, p. 19 - 23 (2019/03/02)
Azines are having widespread applications in both industry as well as synthetic chemistry. Thus new catalytic synthetic protocols are desirable as they are greener alternatives than traditional methods of synthesis. Thus, herein a novel earth abundant nickel based NNN-pincer catalyst Ni(BPEA)(Cl2) is synthesized for the first time for the direct transformation of alcohols and hydrazine hydrate into symmetrical azines. This catalytic reaction is accompanied by dehydrogenative coupling of alcohols and hydrazine hydrate and is carried out in presence of a base. Theoretical calculations supported by experimental evidence have been performed for understanding the mechanistic insights of the reaction.
Ruthenium(ii)-catalysed direct synthesis of ketazines using secondary alcohols
Kishore, Jugal,Thiyagarajan, Subramanian,Gunanathan, Chidambaram
supporting information, p. 4542 - 4545 (2019/04/26)
Direct one-pot synthesis of ketazines from secondary alcohols and hydrazine hydrate catalyzed by a ruthenium pincer complex is reported, which proceeds through O-H bond activation of secondary alcohols via amine-amide metal-ligand cooperation in the catalyst. Remarkably, liberated molecular hydrogen and water are the only byproducts.
Chromatographic component of identification of the transformation products of 1,1-dimethylhydrazine in the presence of sulfur
Zenkevich,Ul'Yanov,Golub,Buryak
, p. 1106 - 1114 (2014/08/05)
The gas-chromatographic retention indices of the products of 1,1-dimethylhydrazine transformations in the presence of sulfur allows one to confirm and, in ceratin cases, make more exact the results of their gas chromatography-mass spectrometry identificat
METHOD FOR PRODUCING KETAZINE COMPOUND
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Page/Page column 7, (2009/12/07)
A process for preparing a ketazine compound of the formula (1) from a ketone compound of the formula (2), ammonia and an oxidizing agent, wherein a solution containing the ketone compound of the formula (2) and ammonia is brought into contact with an aqueous solution of the oxidizing agent in a tubular reactor having a flow channel width of 2 to 10000 μm wherein R1 and R2 are the same or different and are each a C1-6 alkyl group, or R1 and R2 are combined with each other into a straight-chain C2-7 alkylene group wherein R1 and R2 are the same as above.
Diaryloxycarbenes from oxadiazolines
Lu,Reid,Warkentin
, p. 319 - 327 (2007/10/03)
Symmetric and unsymmetric 2,2-diaryloxy-5,5-dimethyl-Δ3-1,3,4-oxadiazolines were synthesized by oxidative cyclization of aryloxycarbonyl hydrazones of acetone with lead tetraacetate and subsequent treatment of the product mixture with a phenol in acidic solution. Thermolysis of the oxadiazolines in benzene solution at 110°C afforded carbonyl ylide intermediates that cyclize, in part, to the corresponding 2,2-diaryloxyoxirane intermediates. The oxiranes, which were not observed, are required to account for the 1,1-diaryloxy-2-methylpropenes (ketene acetals) that were isolated. Most of the carbonyl ylides fragment to acetone and diaryloxycarbenes. The latter form dimers (tetraaryloxyethenes) or they can be trapped with phenols to form orthoformates. Diphenoxycarbene was also trapped with dimethyl acetylenedicarboxylate (DMAD). The method appears to be the first for generating the parent diphenoxycarbene under relatively mild conditions in solution, and the only one to date for generating unsymmetrically substituted diaryloxycarbenes. Minor competing fragmentations of the oxadiazolines to 2-diazopropane and the appropriate diaryl carbonates, were also observed.
