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The reaction of acetyl-containing furan-3-carboxylates with substituted hydrazines in an alcohol solution leads to the formation of substituted furan-3-carboxylate hydrazones. The resulting hydrazones have E-configuration, as determined by NMR spectroscopy and X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The reaction of 1-(3-(furan-2-yl)-5-methyl-1-(4-nitrophenyl)-1H-pyrazol-4-yl)ethan-1-one 1 with dimethylformamide dimethyl acetal (DMF-DMA) afforded 3-(dimethylamino)-1-(3-(furan-2-yl)-5-methyl-1-(4-nitrophenyl)-1H-pyrazol-4-yl)prop-2-en-1-one 2. Then the treatment of enaminone 2 with the appropriate hydrazonoyl halides 3a–f in chloroform in the presence of triethylamine at reflux gave novel bipyrazolyl methanone derivatives 4a–f. The novel bipyrazole derivatives 4a–c and 4d–f reacted with hydrazine hydrate in ethanol at reflux to give the corresponding pyrazolopyridazinones 9a–c and pyrazolopyridazines 10d–f, respectively. Stirring of hydroximoyl chlorides 11a,b with enaminone 2 in chloroform in the presence of triethylamine at room temperature afforded isoxazole derivatives 12a,b. The reaction of isoxazoles 12a,b with hydrazine hydrate in refluxing ethanol gave the corresponding isoxazolopyridazines 14a,b. [ABSTRACT FROM AUTHOR]

Background: The production of a variety of chalcones (1-Aryl/Alkyl amino substituted-dene-2-(-1,3-diphenylallylidene) hydrazine (ABSa-e) was brought about as a result of the condensation of hydrazide compound and Aryl/Alkyl substituted aldehyde/ketone in ethanol as a solvent with the help of two drops of conc. hydrochloric acid as a catalyst followed by neutralization. All synthesized derivatives were identified with different spectroscopic techniques and biologically evaluated by microorganisms. Materials and Methods: The in vitro antibacterial and antifungal activity of all synthesised compounds was evaluated. In the microbial studies, the five strains of selected bacteria and two strains of fungi have been used to evaluate the synthesized compounds, DMSO used as the solvent, and amoxicillin and griseofulvin used as control drugs. Results and Conclusion: Derivatives exhibited the highest potency (17mm, 18mm, 16mm, 18mm, 15mm) (MIC) with the electron donating groups (CH3) in position 4 of the phenyl ring (ABSc). On the other hand, the withdrawing group (NO2, Cl) of compounds ABSb & ABSe showed the most negligible potency against selected microorganisms. The unsubstituted phenyl ring (ABSa) showed moderate activity (17mm, 15mm, 15mm, 16mm, 14mm) at 100 µg/mL. The oxygen-containing furan compound ABSd proved as the second-highest potency (16mm, 17mm, 15mm, 17mm, 14mm) of this series. All of the results pointed to compound ABSc as a potential antibacterial lead molecule, and efforts are currently being made to increase the potency of amino chalcone derivatives. [ABSTRACT FROM AUTHOR]

Hydrazine‐assisted water electrolyzer is a promising energy‐efficient alternative to conventional water electrolyzer, offering an appealing path for sustainable hydrogen (H2) production with reduced energy consumption. However, such electrolyzer is presently impeded by lacking an efficient catalyst to accelerate the kinetics of pivotal half‐reaction, that is, hydrazine oxidation reaction (HzOR). Herein, a ruthenium (Ru) single‐atom on an octahedral cobalt oxide (Co3O4) substrate (Ru‐Co3O4) catalyst, guided by theoretical calculations is developed. Those lattice‐confined Ru sites within octahedral structure of spinel Co3O4 effectively lower the energy barrier required for the formation of N2H2* intermediate and desorption of H* species in HzOR. As a result, the Ru‐Co3O4 catalyst achieves superior HzOR performance with a low potential of −0.024 V versus (vs.)reversible hydrogen electrode (RHE) at 100 mA cm−2 and remarkable stability for over 200 h at 200 mA cm−2. Importantly, a modular H2 production achieves an output of 0.48 kWh electricity per m3 H2 by decoupling and pairing the HzOR and hydrogen evolution reaction (HER) half‐reaction with a Zinc (Zn) redox reservoir. The work represents a significant advancement in the field, offering substantial flexibility for on‐demand H2 production and energy output. [ABSTRACT FROM AUTHOR]

Improving the dispersion of metal nanoparticles and suppressing metal aggregation have long been the keys to constructing efficient metal-loaded catalysts. Herein, catalysts of cobalt (Co) supported on nitrogen (N)-doped carbon were prepared by a simple hydrothermal method using folic acid (FA) as the carbon source. Surprisingly, hydrazine hydrate not only facilitated the loading of metal Co, but also regulated the morphology of the catalyst, promoted the uniform distribution of metal Co, and effectively improved the catalytic hydrogenation activity of the catalyst. It was found that the catalyst mediated with 10 mL hydrazine hydrate and pyrolyzed at 900 °C exhibited the best catalytic performance (99.6% conversion of quinoline and 98.0% selectivity for 1,2,3,4-tetrahydroquinoline). In addition, it exhibited satisfying adaptability for diverse substrates. This study can provide great theoretical significance and practical guidance for the preparation of Co–N–C catalysts. [ABSTRACT FROM AUTHOR]

In organic synthesis, azodicarboxylates are frequently used as an aza‐dienophile and electrophilic amination agent. To create carbon–nitrogen bonds, azodicarboxylates typically react with nucleophiles or radicals. This report explores its reactivity as a co‐monomer towards radical polymerization to introduce nitrogen–nitrogen single bonds into the polymer chain. Azodicarboxylates are capable of copolymerizing with styrenic monomers to achieve linear polymers with 40% feed. [ABSTRACT FROM AUTHOR]

Azines are organic molecules with a C=N−N=C functional range of applications. But the conventional azines synthesis process requires a high reaction temperature and long reaction time combined with complex reaction facilities, so the synthesis process needs to be further improved in terms of economic efficiency and process simplification. Here, we demonstrate a structurally well‐defined inorganic ligand Ni compound, (NH4)4[NiMo6O18(OH)6](Ni‐POMs). The catalysts show good activity towards the reaction of carbonyl compounds, and the corresponding products can be obtained in yields up to about 90 %. In this condition, the majority of the aldehydes (aromatic and aliphatic) can be reacted, and the products are obtained in high yields. Density functional theory (DFT) looked into the process by which benzaldehyde and hydrazine hydrate reacted on the surface of Ni‐POMs. It was calculated that the whole reaction goes through two stages and the activation energy of the whole reaction is −6.72 kcal/mol. Thus, from experiment to calculation, a complete structure of the catalytic reaction cycle has been constructed. [ABSTRACT FROM AUTHOR]

An N‐allylation of monosubstituted acyl hydrazines with allylic alcohols has been developed by using B(C6F5)3 catalysis. This protocol allows for convenient access to various synthetically useful N‐allylated hydrazine products in 48–96% yields with broad substrate scope and wide functional group compatibility. The operationally simple reaction proceeds without calling for stringent removal of air and moisture, and can be readily scaled up to gram scale. Preliminary mechanistic studies support the generation of an allylic carbon cation that is involved in the catalytic cycle, and the reaction proceeds via the in situ formation of diallyl ethers as intermediates. [ABSTRACT FROM AUTHOR]

In this study, MXene Ti 3 C 2 X 2 and BaMnO 3 nanoparticle-doped MXene particles were prepared by HF etching mechanism and hydrothermal method. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), transmission electron microscopy (TEM), and X-ray diffraction (XRD) methods were utilized for the characterization of as-synthesized catalysts. The presence of BaMnO 3 nanoparticles in the catalyst system was confirmed by XRD and EDX spectra. The catalytic activity of the BaMnO 3 /MXene catalyst for hydrazine electrooxidation was investigated by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in a basic medium. The mass activities of bare MXene and BaMnO 3 /MXene for hydrazine electrooxidation were determined as 309.5 and 731.7 mA mg−1, respectively. Increasing specific activity attributed to the improvement of the kinetics for the hydrazine electrooxidation reaction on MXene with the addition of BaMnO 3. BaMnO 3 /MXene has been found to have lower charge transfer resistance and higher electrocatalytic activity than MXene. Novel BaMnO 3 /MXene catalyst showed super performance for hydrazine electrooxidation. • BaMnO 3 nanoparticle-doped MXene particles were prepared by HF etching mechanism and hydrothermal method. • Mass activity of BaMnO 3 /MXene for hydrazine electrooxidation was 731.7 mA cm−2. • Presence of BaMnO 3 reduced the mass transfer limitations of MXene. [ABSTRACT FROM AUTHOR]

Tailoring the d‐orbital electron of Fe (III) in oxyhydroxide is highly expected to realize an efficient hydrazine oxidation reaction (HzOR) for assisting seawater electrolysis. Although interface engineering can effectively change electron states on Fe sites by charge injection or extraction, most interfaces have a directional electric field for inaccessible regulation. Herein, the combination of iron oxyhydroxide and biphasic nickel phosphide is established to obtain a dual built‐in electric field (BEF) with opposite direction, which aims to manipulate the d‐orbital electron configuration of Fe (III) sites, thereby optimizing the binding strength and activating of N2H4 intermediates. Both computational and experimental analyses reveal that the moderate Fe─*N2H4 binding strength originating from tailored electron injection plays the key role in accelerating dehydrogenation. Impressively, such a promising promotion endows the catalyst with a remarkable HzOR activity, realizing working potentials of −8 and 44 mV for 10 and 100 mA cm−2 in alkaline seawater, respectively, and achieving outstanding long‐term stability for over 100 h. H2 production from a hybrid seawater electrolyzer (HSE) requires a dramatically low power consumption of 16.4 Wh L−1 H2 with ≈100% Faraday efficiency. It is believed that the work sheds new inspiration on d‐orbital regulation for obtaining advanced HzOR electrocatalysts. [ABSTRACT FROM AUTHOR]

The reaction of acyl isothiocyanates of 2-allyl- and 2-benzylmaleopimarimides with ethyl-, benzylhydrazine, or ethyl ester of hydrazinoacetic acid leads to the formation of maleopimarimides containing the fragment of 5-thioxo-2,5-dihydro-1H-1,2,4-triazole. The structures of the synthesized compounds were determined by 1H, 13C, 1H–13C HSQC, 1H–13C HMBC, COSY, NOESY, and 1H-15N HMBC NMR spectroscopy methods. [ABSTRACT FROM AUTHOR]

The condensation of 3-benzyl-2-sulfanylidene-2,3-dihydro-1H-spiro[benzo[h]quinazoline-5,1′-cyclo-heptan]-4(6H)-one with 5,5-dialkyl-2-(chloromethyl)benzo[h]quinazolines gave bis-benzo[h]quinazoline compounds in which the spiro[benzo[h]quinazoline-5,1′-cycloheptane] fragment is linked through the 2-position to another benzo[h]quinazoline moiety via a SCH2 spacer. 3-Benzyl-2-sulfanylidene-2,3-dihydro-1H-spiro-[benzo[h]quinazoline-5,1′-cycloheptan]-4(6H)-one reacted under similar conditions with methylene iodide to produce 2,2′-[methylenebis(sulfanediyl)]bis{3-benzyl-3H-spiro[benzo[h]quinazoline-5,1′-cycloheptan]-4(6H)-one}. The initial benzo[h]quinazoline was converted to 2-hydrazinyl derivative which underwent elimination of the hydrazine moiety by the action of alkali with the formation of 3-benzyl-3H-spiro[benzo[h]quinazoline-5,1′-cycloheptan]-4(6H)-one. The 2-hydrazinyl derivative was used to obtain the corresponding phenylhydrazone, thiosemicarbazide, and 4-benzyl-4H-spiro[benzo[h][1,2,4]triazolo[4,3-a]quinazoline-6,1′-cycloheptanone]-5(7H)-one. The alkylation of 4-benzyl-1-sulfanyl-4H-spiro[benzo[h][1,2,4]triazolo[4,3-a]quinazoline-6,1′-cycloheptan]-5(7H)-one with alkyl halides afforded the corresponding 1-alkylsulfanyl derivatives. The synthe-sized compounds were tested for antibacterial activity. [ABSTRACT FROM AUTHOR]

Previously synthesized ethyl 2-benzamido-4-(1,4-benzodioxan-2-yl)thiophene-3-carboxylates were cyclized to 2-aryl-3-aminothieno[2,3-d]pyrimidin-4(1H)-ones by the action of hydrazine hydrate. The con-densation of ethyl 2-amino-4-(1,4-benzodioxan-2-yl)thiophene-3-carboxylate with chloroacetyl chloride gave the corresponding N-substituted 2-chloroacetamide which reacted with piperidine and morpholine to produce 2-aminoacetamides, and the latter were also subjected to cyclization with hydrazine hydrate to obtain 3-amino-thienopyrimidin-4-one derivatives. The synthesized compounds were tested for antihypoxic activity. [ABSTRACT FROM AUTHOR]

The reaction of a mixture of equimolar quantities of 2-acetylbenzofuran and (2,4,6-trichlorophenyl)hydrazine in ethanol containing concentrated hydrochloric acid (0.2 mL; 37%) as a catalyst under reflux for two hours yielded 1-(1-(benzofuran-2-yl)ethylidene)-2-(2,4,6-trichlorophenyl)hydrazine. The crude product was purified by crystallization using dimethylformamide to provide the title heterocycle in a 90% yield. The structure of the new heterocycle was confirmed through X-ray diffraction and spectral analyses. [ABSTRACT FROM AUTHOR]

The reaction of (E)-2-(4-fluorobenzylidene)-3,4-dihydronaphthalen-1(2H)-one and (2,4-dinitrophenyl)hydrazine in boiling ethanol containing hydrochloric acid (0.2 mL; 37%) for 1.5 h gave 1-(2,4-dinitrophenyl)-2-(2-(4-fluorobenzylidene)-3,4-dihydronaphthalen-1(2H)-ylidene)hydrazine in a 90% yield. Various spectral analyses, including NMR, and X-ray crystallography established the structure of the newly synthesized hydrazone. [ABSTRACT FROM AUTHOR]

The two-step method for the synthesis of previously unknown 1-hydroxy-2,3-dihydropyrazolo[1,2-c]-benzo-1,3,4-thiadiazepin-11(5H)-one has been developed based on 2-mercaptobenzoic acid hydrazide and commercially available formaldehyde and acrolein. The synthesized compound, which has a targeted antitumor effect, is a promising bioactive co-ligand for obtaining gold glyco-nanoparticles for biomedical purposes. [ABSTRACT FROM AUTHOR]

PurposeAntitumor activity in preclinical models and a phase I study of patients with dedifferentiated liposarcoma (DD-LPS) was observed with selinexor. We evaluated the clinical benefit of selinexor in patients with previously treated DD-LPS whose sarcoma progressed on approved agents.MethodsSEAL was a phase II-III, multicenter, randomized, double-blind, placebo-controlled study. Patients age 12 years or older with advanced DD-LPS who had received two-five lines of therapy were randomly assigned (2:1) to selinexor (60 mg) or placebo twice weekly in 6-week cycles (crossover permitted). The primary end point was progression-free survival (PFS). Patients who received at least one dose of study treatment were included for safety analysis (ClinicalTrials.gov identifier: NCT02606461).ResultsTwo hundred eighty-five patients were enrolled (selinexor, n = 188; placebo, n = 97). PFS was significantly longer with selinexor versus placebo: hazard ratio (HR) 0.70 (95% CI, 0.52 to 0.95; one-sided P = .011; medians 2.8 v 2.1 months), as was time to next treatment: HR 0.50 (95% CI, 0.37 to 0.66; one-sided P < .0001; medians 5.8 v 3.2 months). With crossover, no difference was observed in overall survival. The most common treatment-emergent adverse events of any grade versus grade 3 or 4 with selinexor were nausea (151 [80.7%] v 11 [5.9]), decreased appetite (113 [60.4%] v 14 [7.5%]), and fatigue (96 [51.3%] v 12 [6.4%]). Four (2.1%) and three (3.1%) patients died in the selinexor and placebo arms, respectively. Exploratory RNA sequencing analysis identified that the absence of CALB1 expression was associated with longer PFS with selinexor compared with placebo (median 6.9 v 2.2 months; HR, 0.19; P = .001).ConclusionPatients with advanced, refractory DD-LPS showed improved PFS and time to next treatment with selinexor compared with placebo. Supportive care and dose reductions mitigated side effects of selinexor. Prospective validation of CALB1 expression as a predictive biomarker for selinexor in DD-LPS is warranted.

PURPOSE: Selinexor is the first selective inhibitor of nuclear export to be approved for the treatment of relapsed or refractory multiple myeloma (MM). Currently, there are no known genomic biomarkers or assays to help select MM patients at higher likelihood of response to selinexor. Here, we aimed to characterize the transcriptomic correlates of response to selinexor-based therapy. METHODS: We performed RNA sequencing on CD138+ cells from the bone marrow of 100 patients with MM who participated in the BOSTON study, followed by differential gene expression and pathway analysis. Using the differentially expressed genes, we used cox proportional hazard models to identify a gene signature predictive of response to selinexor, followed by validation in external cohorts. RESULTS: The three-gene signature predicts response to selinexor-based therapy in patients with MM in the BOSTON cohort. Then, we validated this gene signature in 64 patients from the STORM cohort of triple-class refractory MM and additionally in an external cohort of 35 patients treated in a real-world setting outside of clinical trials. We found that the signature tracks with both depth and duration of response, and it also validates in a different tumor type using a cohort of pretreatment tumors from patients with recurrent glioblastoma. Furthermore, the genes involved in the signature, WNT10A, DUSP1, and ETV7, reveal a potential mechanism through upregulated interferon-mediated apoptotic signaling that may prime tumors to respond to selinexor-based therapy. CONCLUSION: In this study, we present a present a novel, three-gene expression signature that predicts selinexor response in MM. This signature has important clinical relevance as it could identify patients with cancer who are most likely to benefit from treatment with selinexor-based therapy.

Hydrazine hydrate (N 2 H 4 ·H 2 O) is one of the compounds that can be used to produce hydrogen through a dehydrogenation reaction. The use of trimetallic nanoparticles can increase the catalytic activity and selectivity of the hydrogen produced. Ordered mesoporous silica SBA-15 was synthesized to be used as a support for NiPtAg trimetallic nanoparticles. NiPtAg/SBA-15 was synthesized from NiCl 2.6H 2 O, K 2 PtCl 6 , AgNO 3 , and SBA-15 by wet impregnation method and then reduced by NaBH 4. To determine the best variation of metal composition, optimization of the trimetallic composition was carried out. Ni 0.6 Pt 0.2 Ag 0.2 /SBA-15 catalyst demonstrates a good catalytic activity with selectivity of 94% and TOF of 321.9 h−1 at 343 K. The activation energy required by the Ni 0.6 Pt 0.2 Ag 0.2 /SBA-15 catalyst in the dehydrogenation reaction of hydrazine hydrate is 55.6 kJ/mol. [Display omitted] • NiPtAg catalysts on SBA-15 are prepared for dehydrogenation of hydrazine hydrate. • The Ni 0.6 Pt 0.2 Ag 0.2 /SBA-15 shows the highest activity towards the HDO of guaiacol. • The role of Ag dopant towards dehydrogenation of hydrazine hydrate activity is elucidated. • The certain amount of Ag is correlated with increasing the activity of the catalysts. [ABSTRACT FROM AUTHOR]

Nitrite (NO2−) and hydrazine (N2H4) are common N‐pollutants in groundwater. The electrochemical method can realize the treatment of N‐pollutants and the synthesis of energy substance ammonia (NH3). Designing and synthesizing efficient electrocatalysts is of great significance. Herein, ultrathin Co0.5NiS nanosheets attached on nickel foam (Co0.5NiS‐NSs/NF) are synthesized via cyanogel‐NaBH4 hydrolysis process and succedent sulfurization approach. Owing to the ultrathin nanosheet structure and the interaction between Ni and Co, Co0.5NiS‐NSs/NF exhibits high activity for NO2− reduction reaction (NO2−RR), in which the Faraday efficiency is 92.2% and the NH3 yield is 0.25 mmol h−1 cm−2 at −0.15 V potential. Meanwhile, Co0.5NiS‐NSs/NF also displays remarkable activity for N2H4 oxidation reaction in KOH electrolyte. Therefore, a symmetrical Co0.5NiS‐NSs/NF||Co0.5NiS‐NSs/NF electrolyzer is assembled, which only needs the operating voltage of 0.36 V to reach 10 mA cm−2 for NO2−‐to‐NH3 conversion in the presence of N2H4. This work reports a promising and efficient strategy for NH3 production at a small operating voltage and treatment of the N‐pollutants. [ABSTRACT FROM AUTHOR]

Developed here is a robust electrochemical cross‐coupling reaction between aroyl hydrazine and NH‐sulfoximine via concomitant cleavage and formation of C(sp2)−N bonds with the evolution of H2 and N2 as innocuous by‐products. This sustainable protocol avoids the use of toxic reagents and occurs at room temperature. The reaction proceeds via the generation of an aroyl and a sulfoximidoyl radical via anodic oxidation under constant current electrolysis (CCE), affording N‐aroylated sulfoximine. The strategy is applied to late‐stage sulfoximidation of L‐menthol, (−)‐borneol, D‐glucose, vitamin‐E derivatives, and marketed drugs such as probenecid, ibuprofen, flurbiprofen, ciprofibrate, and sulindac. In addition, the present methodology is mild, high functional group tolerance with broad substrate scope and scalable. [ABSTRACT FROM AUTHOR]

A palladium-catalyzed allylation of hydrazines with allyl alcohols and aldehydes was developed, enabling the syntheses of a series of allylhydrazones in good to excellent yields with high regioselectivity. Furthermore, the four-component tandem allylation carbonylation of hydrazines with allyl alcohols and aldehydes was established using the catalytic system, producing various allyl acylhydrazones. Additionally, the functionalized allyl acylhydrazones could be smoothly constructed with the catalytic system employing allylhydrazones as a partner. The catalytic system exhibited good functional tolerance with excellent regioselectivities and scaled-up capability, overcoming the limitations of chemoselectivity of the multicomponent transformation and poor conversion of the weak nucleophile. [ABSTRACT FROM AUTHOR]

An effective synthesis of four potentially biologically active O- and N-containing 23-, 28-, 30-, and 31-membered macroheterocycles from undec-10-enal was carried out. First, undec-10-enal was converted to undec-10-enyl undec-10-enoate via the Tishchenko disproportionation reaction catalyzed by Al(i-PrO)3. The subsequent Wacker–Tsuji oxidation of undec-10-enyl undec-10-enoate gave 10-oxoundecanyl 10-oxoundecanoate. Finally, the [1+1]-condensation of 10-oxoundecanyl-10-oxoundecenoate with hydrazine hydrate or malonic, glutaric, or adipic acid dihydrazides resulted in the synthesis of four macroheterocycles. [ABSTRACT FROM AUTHOR]

Herein, Ir/CeO2 catalysts were prepared using the deposition–precipitation method with NaOH or urea as the precipitating agent or using sol immobilization with tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the protective and reducing agent. The effect of the preparation method on Ir catalyst activity was evaluated in the liquid-phase catalytic decomposition of hydrous hydrazine to hydrogen. Ir/CeO2 prepared using sol immobilization and DP NaOH showed the best activity (1740 h−1 and 1541 h−1, respectively) and yield of hydrogen (36.6 and 38.9%). Additionally, the effect of the support was considered, using TiO2 and NiO in addition to CeO2. For this purpose, the sol immobilization of preformed nanoparticles technique was considered because it allows the same morphology of the immobilized particles to be maintained, regardless of the support. Ir deposited on NiO resulted in the most selective catalyst with a H2 yield of 83.9%, showing good stability during recycling tests. The catalysts were characterized using different techniques: X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) equipped with an X-ray detector (EDX) and inductively coupled plasma–mass spectroscopy (ICP-MS). [ABSTRACT FROM AUTHOR]

The recyclizations of 5‐amino‐ and 5‐hydrazine‐1,3‐oxazoles mainly with electron‐withdrawing group in 4th position are considered. The chemical behavior of these heterocycles is due to the presence of two hidden amide fragments; therefore, the recyclization processes include a stage of nucleophile attack on 2nd or 5th position of the oxazole cycle. When the nitrile group is present in 4th position, it is often involved in the recyclization forming α‐aminoazoles. 5‐Amino/hydrazine‐1,3‐oxazoles undergo recyclization both in nucleophilic (amines, hydrazine, thionating agents) and electrophilic medium ((trifluoro)acetic acid, other acylating agents). The numerous types of functionalized heterocycles can be easily obtained with the usage of these recyclizations, such as the derivatives of 3‐amino‐6,7‐dihydro‐5H‐pyrrolo[1,2–a]imidazole, imidazolidine‐2,4‐dione, 1H‐pyrazole‐3,4,5‐triamine, 5,6‐diamino‐2,3‐diphenylpyrimidin‐4(3H)‐one, 2‐(2‐R‐7‐oxo‐5‐(trifluoromethyl)oxazolo[5,4–d]pyrimidin‐6(7H)‐yl)acetic acid, 2‐R‐4‐(5‐R′‐1,3,4‐oxadiazol‐2‐yl)oxazol‐5‐amine, (amino(5‐amino‐1,3,4‐thiadiazol‐2‐yl)methyl)phosphonate. [ABSTRACT FROM AUTHOR]

The corresponding pyridyl chalcones were synthesized by the aldol-crotonic condensation of the acetyl derivative of epoxybenzo[7,8]-oxocino[4,3-b]pyridine with aromatic aldehydes. A subsequent cyclization with hydrazine hydrate in acetic acid led to the corresponding 4,5-dihydro-1H-pyrazole derivatives. An assessment of the resulting derivatives for antitubercular activity was carried out. [ABSTRACT FROM AUTHOR]

Integrating hydrogen evolution reaction (HER) with hydrazine oxidation reaction (HzOR) has an encouraging prospect for the energy‐saving hydrogen production, demanding the high‐performance bifunctional HER/HzOR electrocatalyst. Ruthenium phosphide/doped carbon composites have exhibited superior activity toward multiple electrocatalytic reactions. To explore the decent water‐soluble precursors containing both N and P elements is highly attractive to facilely prepare metal phosphide/doped carbon composites. Herein, as one kind ecofriendly biomolecules, adenine nucleotide was first employed to selectively fabricate the highly pure RuP nanoparticles embedded into porous N,P‐codoped carbons (RuP/PNPC) with a straightforward "mix‐and‐pyrolyze" approach. The newly prepared RuP/PNPC only requires 4.0 and −83.0 mV at 10 mA/cm2 separately in alkaline HER and HzOR, outperforming most of reported electrocatalysts, together with the outstanding neutral bifunctional performance. Furthermore, the two‐electrode alkaline and neutral overall hydrazine splitting both exhibit significant power‐efficiency superiority to the corresponding overall water splitting with the voltage difference of larger than 2 V, which can be also easily driven by the fuel cells and solar cells with considerable H2 generation. Our report innovates the N‐ and P‐bearing adenine nucleotide to effortlessly synthesize the high‐quality RuP/doped carbon composite catalysts, highly potential as a universal platform for metal phosphide‐related functional materials. [ABSTRACT FROM AUTHOR]

The catalytic deoxygenative reduction of hydrazides to the corresponding alkyl hydrazine with PhSiH3 via B(C6F5)3‐catalyzed hydrosilylation is reported. This metal‐free protocol is compatible with various acylhydrazides and diacylhydrazides, giving rise to a variety of structurally diverse alkyl hydrazine products in 63–95% yields. The proper selection of borane catalyst and hydrosilane reductant is essential for catalysis. Mechanistic investigations reveal that the reaction involves a hydrazone intermediate. [ABSTRACT FROM AUTHOR]

This review mainly focused on the synthesis of 3(5)-trifluoromethylpyrazoles via condensation of trifluoromethyl-β-diketones with hydrazines. Also, a special emphasis is led on the biological potential of fluorine containing compounds and pyrazoles in introduction section. We have covered all the literature reported condensation reactions of trifluoromethyl-β-diketones with hydrazines. [ABSTRACT FROM AUTHOR]

5‐N,N‐diarylaminothiazoles containing cyano and nitro groups were synthesized using the Pd‐catalyzed Buchwald‐Hartwig amination reaction with good yields. The cyano group in the resultant thiazole was reduced to a formyl group. This was then subjected to the Knoevenagel condensation reaction, leading to the formation of thiazoles with a dicyanovinyl group. The nitro group in the thiazole was reduced to an amino group, which was subsequently reacted with triphosgene, yielding a thiazole with an isocyanate group. These thiazoles, with their electron‐accepting properties, demonstrated absorption and emission spectra at longer wavelengths. Notably, the thiazole containing the dicyanovinyl group displayed a red emission. Tests for the detection of hydrazine, a hazardous volatile organic compound, were conducted using the synthesized thiazoles. The results showed that the dicyanovinyl group effectively responded to hydrazine hydrate, evidenced by changes in the absorption and emission spectra. This change in color was also visibly detectable to the naked eye. [ABSTRACT FROM AUTHOR]

Replacing sluggish anodic oxygen evolution reaction by hydrazine oxidation reaction in seawater electrolysis is one of the smartest ways of getting multiple benefits as it offers an energy saving route for hydrogen production keeping the cell voltage way smaller than responsible voltage for corrosive chloride oxidation. Here, we report iron-doped Co 3 N as highly active electrocatalyst towards hydrazine oxidation reaction and hydrogen evolution reaction in wide pH range of 7–14. The two-electrode electrolyser system reached industry scale current density of 1000 mA cm−2 at ultralow cell voltage of 0.65 V, and found sustainable at 500 mA cm−2 over 95 h in hydrazine assisted alkaline seawater splitting. The electrolyser system also achieved 200 mA cm−2 current density at 0.75 V in hydrazine assisted neutral seawater medium. Interestingly, a thin amorphous iron oxide layer formed in Fe-doped Co 3 N provided much needed protection during electrocatalysis offering long term stability at industry level current density. [Display omitted] • Amorphous Fe-oxide surface layer protected Fe–Co 3 N developed as electrocatalyst. • HzOR-assisted seawater splitting offers an efficient way to avoid corrosive CER. • The electrocatalyst achieved 1000 mA cm−2 current density at 0.65 V in HzOS. • The electrocatalyst is efficient in wide pH range of seawater splitting. [ABSTRACT FROM AUTHOR]

This article provides a comprehensive overview of the synthesis and characterization of luminescent substances containing azole motifs, specifically focusing on pyrazole derivatives. The authors explore different synthetic routes and reactions with hydrazines to develop more efficient methods for the synthesis of ethynylpyrazoles and ethynylpyrazolines. They also discuss the potential applications of the synthesized compounds in medicinal, agricultural, and materials science fields. The article includes experimental results, discusses reaction mechanisms, and provides data to support their findings. This resource is valuable for library patrons conducting research on azole compounds and their applications. [Extracted from the article]

The development of an effective molecular catalyst to reduce hydrazine efficiently to ammonia using a suitable reductant and proton source is demanding. Herein, an unprecedented air-stable, phosphine-free ruthenium complex is used as a potent catalyst for hydrazine hydrate reduction to generate ammonia using SmI2 and water under ambient reaction conditions. Maximizing the flow of electrons from the reductant to the hydrazine hydrate via the metal centre results in a greater yield of ammonia while minimizing the evolution of H2 gas as a competing product. [ABSTRACT FROM AUTHOR]

Controllable hydrogen generation through catalytic decomposition of hydrazine monohydrate (N 2 H 4 ·H 2 O) holds promise for mobile and portable applications. However, the existing catalysts (such as Ni 60 Pt 40 /CeO 2 , CoPt/CeO x) often suffer from poor stability, and active site poisoning appears an important cause of deactivation. Here, we present a simple yet effective method to address this issue. By adding a Ce3+ salt during the precipitation-deposition process, we observed enhanced interactions between Ni–Pt alloy and CeO 2 matrix, impacting the electronic structure and dispersion of Ni–Pt nanoparticles. Thus-obtained Ni 4 Pt/CeO 2 catalyst exhibited an over two-fold increase in activity and an 80% retention after 10 cycles, outperforming conventional methods. The novel approach simultaneously improved activity and stability while maintaining a constant alloy composition. This catalyst demonstrated high activity, 100% H 2 selectivity, and good stability in N 2 H 4 ·H 2 O decomposition. Additionally, it enabled the construction of a high-capacity N 2 H 4 ·H 2 O-based hydrogen generation system with rapid dynamic response. Integrating Ce3+ salt during the precipitation-deposition process in the fabrication of Ni–Pt/CeO 2 catalysts yields enhanced metal-support interactions, which results in a marked improvement in both activity and stability for hydrogen production from hydrazine monohydrate when contrasted with conventional approaches. [Display omitted] • New approach for Ni–Pt/CeO 2 catalysts towards N 2 H 4 ·H 2 O decomposition is proposed. • Enhanced metal-support interactions using Ce3+ during precipitation-deposition. • New method improves both the intrinsic activity and Ni–Pt dispersion. • Thus-obtained Ni 4 Pt/CeO 2 catalyst showed remarkable activity and high stability. [ABSTRACT FROM AUTHOR]

Herein, we report that bulky alkylphosphines such as PtBu3 can switch the roles from actor to spectator ligands to promote the FeCl2‐catalyzed N‐amidation reaction of arylamines with dioxazolones, giving hydrazides in high efficiency and chemoselectivity. Mechanistic studies indicated that the phosphine ligands could facilitate the decarboxylation of dioxazolones on the Fe center, and the hydrogen bonding interactions between the arylamines and the ligands on Fe nitrenoid intermediates might play a role in modulating the delicate interplay between the phosphine ligand, arylamine, and acyl nitrene N, favoring N−N coupling over N−P coupling. The new ligand‐promoted N‐amidation protocols offer a convenient way to access various challenging triazane compounds via double or sequential N‐amidation of primary arylamines. [ABSTRACT FROM AUTHOR]

Exploiting low-cost and bifunctional electrodes for the hydrogen evolution reaction (HER) and hydrazine hydrate oxidation (HzOR) is significant for the efficient generation of H 2 , but still some challenges remain. In this work, the in-situ growth of the Co-modified bimetallic hydroxysulfide (NiFeSOH) nanosheet arrays is realized by a simple aging method. The NiFe foam (NFF) is used as self-sacrificing Ni and Fe sources and happens coupling reaction with the surface-modified Co2+, resulting in the self-reconstruction of hydroxysulfide on NFF. Remarkably, the catalytic active sites and reaction kinetics are optimized by the introduction of Co centers, which endows the catalyst with greatly improved catalytic activity for both HER and HzOR. As a consequence, the Co–FeNiSOH/NFF sample shows low potentials toward HER (−0.266 V) and HzOR (0.355 V) at 100 mA cm−2 in an alkaline medium. In addition, the Co–FeNiSOH/NFF-based electrolyzer realizes small cell voltages of 0.26 V and 0.64 V at the current density of 10 mA cm−2 and 100 mA cm−2, respectively, that outperforms most reported hydroxide materials. Our work develops efficient bifunctional HER/HzOR electrodes, which may provide a promising way for the preparation of the other catalysts in H 2 generation. A novel type of Co-modified bimetallic hydroxysulfide (NiFeSOH) nanosheet arrays are developed by a rapid two-step oxidation approach. Benefiting from multiple synergistic advantages, the Co–FeNiSOH/NFF shows the excellent bifunctional activity and high stability for HzOR-assisted water splitting. [Display omitted] • The Co–FeNiSOH nanosheet arrays are first synthesized on NiFe foam. • NiFe foam used as supporter and Ni/Fe sources for the reconstruction of catalyst. • Superior bifunctional catalytic activity of HER/HzOR are demonstrated. • The multiple synergistic advantages improve the catalytic performance. • The constructed electrolyzer realizes small cell voltage of 0.26 V at 10 mA cm−2. [ABSTRACT FROM AUTHOR]

The reaction of hydrazine hydrate, N2H4 ⋅ H2O, and SO3 leads to hydrazine sulfonic acid (Pca21, a=849.59(4) pm, b=482.18(2) pm, c=832.17(4) pm). Structure elucidation reveals the zwitter‐anionic nature of the compound according to NH3NH(SO3). With the barium salt Ba[NH2NH(SO3)]2(H2O), a first salt of hydrazine sulfonic acid has been prepared (P1‾ $\bar 1$ , a=489.75(5) pm, b=737.52(7) pm, c=1317.4(1) pm, α=88.238(4)°, β=84.761(4)°, γ=79.701(4)°). The compounds were characterized by vibrational spectroscopy, DFT calculations and thermal analyses. [ABSTRACT FROM AUTHOR]

In this study, two lab-scale reactors were operated to evaluate the impact of exogenous folate on the start-up process of single-stage partial nitritation-anammox (SPNA). Folate at a dose of 0.5, 1.0, and 1.5 mg/L was continuously added into the experimental reactor (RI) at different operation stages. The highest nitrogen removal rate was 0.26 kg N/(m3•d) in RI with a nitrogen loading rate of 0.45 kg N/(m3•d), which was higher than that in the control reactor (RII) of 0.20 kg N/(m3•d). Moreover, the extracellular polymeric substances production in RI with 1.5 mg/L folate dosage was 264.24 ± 6.74 mg/gVSS, enhancing by 0.5-fold that of the RII, and the activity of hydrazine oxidase increased to the highest level of 0.37 ± 0.01 μmol cyt- c /(gVSS•s). Meanwhile, the activity of dehydrogenase in RI was enhanced from 796.39 ± 2.19 μg/(gVSS•min) to 819.17 ± 24.47 μg/(min•gVSS). The relative abundance of Candidatus Brocadia was 0.64 % at the end of phase 5 in RI whereas it remained at 0.25 % in RII. Function prediction showed that the nitrogen-related genes highly increased with the folate addition. [Display omitted] [ABSTRACT FROM AUTHOR]

The development of efficient and environmentally friendly catalysts for the electro-oxidation of hydrazine derivatives is of great importance in various industrial applications. In this study, we report the utilization of graphite-based catalysts for the electro-oxidation of hydrazine derivatives, using sodium chloride as a green and sustainable chemical approach. Graphite, a two-dimensional carbon material with exceptional properties, offers numerous advantages as a catalyst, including its high surface area, excellent electrical conductivity, and chemical stability. These characteristics make graphite an ideal candidate for promoting electrochemical reactions. Sodium chloride (NaCl), a readily available and cost-effective salt, serves as a green alternative to traditional oxidants used in hydrazine oxidation processes. By replacing conventional oxidizing agents with NaCl, we aim to reduce the environmental impact associated with the production and disposal of hazardous chemicals. This process enables the transformation of the HN-NH bond within hydrazines, leading to the formation of azo compounds (N = N). Azo compounds are important organic molecules with diverse applications in organic synthesis. This novel approach has successfully showcased the efficacy of utilizing various azo compounds in 13 different examples, yielding excellent or moderate to good results. The method capitalizes on electricity as the final oxidizing agent, providing an environmentally friendly oxidation strategy. Its high efficiency and gentle reaction conditions make this technique valuable for synthesizing azo derivatives, even when working with hydrazines containing diverse functional groups, resulting in yields ranging from moderate to excellent. Through systematic experiments, we evaluated the catalytic performance of graphite-based catalysts in the electro-oxidation of hydrazine derivatives. The catalysts demonstrated remarkable catalytic activity due to their efficient conversion of hydrazine derivatives into desired products. Moreover, the system exhibited good stability and recyclability, suggesting its suitability for practical applications. [ABSTRACT FROM AUTHOR]

[Display omitted] The low-potential hydrazine oxidation reaction (HzOR) can replace the oxygen evolution reaction (OER) and thus assemble with the hydrogen evolution reaction (HER), consequently achieving energy-saving hydrogen (H 2) production. Notably, developing sophisticated bifunctional electrocatalysts for HER and HzOR is a prerequisite for efficient H 2 production. Alloying noble metals with eligible non-precious ones can increase affordability, catalytic activity, and stability, alongside rendering bifunctionality. Herein, RuNi alloy deposited onto carbon (RuNi/C) was directly prepared by a simple and highly practical co-reduction method, showing excellent performance for HER and HzOR. Interestingly, to achieve 10 mA cm−2, RuNi/C only required an ultralow potential of 24 mV for HER, on par with commercial 20 wt% platinum in carbon (Pt/C), and −65 mV for HzOR, surpassing most reported counterparts. Moreover, the two-electrode electrolyzer only required small operation voltages of 57.8 and 327 mV to drive 10 and 100 mA cm−2, respectively. Driven by a homemade hydrazine (N 2 H 4) fuel cell and solar panel, appreciable H 2 yields of 1.027 and 1.406 mmol h−1 were achieved, respectively, exhibiting the energy-saving advantages alongside robust practicability. Moreover, theoretical calculations revealed that alloying with Ru endows bifunctional Ni sites not only with a lower H 2 O dissociation barrier but also with more favorable H* adsorption alongside the reduced energy barrier between HzOR intermediates. [ABSTRACT FROM AUTHOR]

We report the formation of NHC complexes of mono‐ and bis‐hydrazino boranes with N−N−B and N−N−B−N−N chains via the reaction of NHC‐boranes with electrophilic azo reagents. The influence of steric hindrance on the carbene and on the azo reagent has been shown to be crucial for the reactivity. The hydroboration of dissymmetric azo reagents is regioselective only when the latter is sufficiently electronically twisted. Bis‐hydrazino borane complexes with two different hydrazine arms could be obtained via sequential addition. [ABSTRACT FROM AUTHOR]

Pd-containing catalysts (1% Pd/Al2O3 and 5% Pd/Al2O3) supported on aluminum oxide were studied in the decomposition reaction of hydrazine monohydrate. According to in situ IR-spectroscopic data, hydrazine monohydrate was adsorbed in a linear form on the coordinatively unsaturated sites of the catalyst surface. As the temperature was increased, the adsorbed hydrazine monohydrate lost a water molecule with a change in the geometry of the molecular complex. The adsorption of hydrazine on a support and its diffusion onto palladium clusters is a more advantageous process than direct adsorption on active sites. This circumstance shows that the hydrazine adsorbed on the support can be an intermediate in the process of its decomposition. The test catalysts had a maximum activity at a temperature of about 100°C. At temperatures in a range of 100−120°C, the ratio between hydrogen and nitrogen concentrations in the reaction products was 2, which corresponds to 100% selectivity for hydrogen. The selectivity decreased significantly with the reaction temperature. The high selectivity for hydrogen at low temperatures was explained by the fact that N2H4 was chemisorbed through the formation of hydrogen–metal bonds. The hydrogen–metal bond strength in such a complex is higher than the nitrogen–metal bond strength; hence, the N−H bond breaking barrier is lower than the N−N bond breaking barrier, and this fact led to the breaking of an N–H bond and the preservation of an N–N bond. At elevated temperatures, some of the formed hydrogen atoms recombined, and the other reacted with the surface complexes of hydrazine to form the intermediate NH3−NH3, in which N–N bond breaking led to the appearance of ammonia molecules in the gas phase. [ABSTRACT FROM AUTHOR]

The kinetics and mechanism of the oxidation of hydrazine by [RuIII(pic)3] (pic- = picolinate anion) were studied spectrophotometrically as a function of hydrazine concentrations at a constant pH of 5.5. The rate of the reaction was followed by monitoring the appearance of the MLCT band of [RuII(pic)3]- at 466 nm. The reaction rate was found to be first-order for Ru(III)-complex concentration. The observed rate constant (kobs) values increased linearly with increase in the hydrazine concentration. The oxidation reaction was studied at varied temperature (20–40 °C). The ΔH≠ (73 ± 3 kJ mol−1 kJ·mol−1) and the negative ΔS≠ (34 ± 7 J·deg−1mol−1) values are consistent with the proposed outer-sphere electron transfer process operative in the oxidation of hydrazine with [RuIII(pic)3]. A working mechanism involving the formation of an active diazene (HN = NH) intermediate followed by its rapid two-electron oxidation by [RuIII(pic)3] in a kinetically inconsequential step producing N2 as sole product is proposed for an overall four-electron oxidation of hydrazine to dinitrogen. [ABSTRACT FROM AUTHOR]

In this study, MWCNT supported Pd (Pd/MWCNT) was synthesized by NaBH4 reduction method as catalyst for hydrazine electrooxidation reaction (HEOR). Characterization methods namely inductively coupled plasma mass spectrometry (ICP-MS), elemental mapping, and scanning electron microscopy with energy dispersive X-ray (SEM-EDX) were used to analyze the surface morphology and metal composition of the catalysts. The Pd/MWCNT catalyst's average particle size is estimated to be 6.35 nm based on SEM images. Glassy carbon electrode (GCE) modification parameters namely the amount of catalyst ink transferred to the GCE surface (Vs), ultrasonication time of the catalyst ink (tu), and the drying time of the Pd/MWCNT/GCE (td) were optimized by using response surface methodology as 4.92 µL, 1 min and 19.52 min, respectively. Experimental specific activity value for HEOR was obtained as 7.13 mA cm-2 with 2.59% deviation under optimum conditions. Optimization of electrode preparation conditions is an inexpensive and facile method that could be used to improve the performance of anode catalysts for fuel cells. [ABSTRACT FROM AUTHOR]

An efficient, unprecedented, catalyst‐free, and rapid synthesis of substituted 3‐hydroxy‐2‐oxindoles is described by the one‐pot, three‐component reaction of hydrazine hydrate, ethyl acetoacetate, and isatins in water. The reported protocol is a green and general route for the simple preparation of new heteroaromatic substituted 3‐hydroxy‐2‐oxindoles in quantitative yields under very mild reaction conditions by using simple, cheap, and readily available materials. The developed method is effectively applicable to a variety of isatin substrates. Operational simplicity, mild and greener reaction conditions, short reaction time, a wide scope of substrates, good isolated yields of the products, and environmentally benign reaction medium are the distinctive features of the present method. [ABSTRACT FROM AUTHOR]

The interaction of 1,3-propanedithiolate with propargyl chloride leads to the formation of a mixture of products. After completion of the reaction (40–42 °C, 6.5 h), two main compounds were isolated: 2-methyl-6,7-dihydro-5H-1,4-dithiepin (62%) and 4,8-dithioundecadiin-2.9 (12%). Quantum chemical modeling of the mechanism of interaction between propargyl chloride and potassium 1,3-propanedithiolate in the hydrazine hydrate–KOH system was carried out using the combined approach CCSD(T)/6–31 + G*//B3LYP/6–311 + + G**. It was shown that the interaction of potassium propane dithiolate with propargyl chloride, leading to the formation of 2-methyl-6,7-dihydro-5H-1,4-dithiepine, proceeds sequentially via several stages. They include the nucleophilic substitution of the chlorine atom of propargyl chloride by one of the sulfide anions 1,3-propanedithiolate leading to the formation of a monosubstitution product. Under the influence of the medium, the latter undergoes an acetylene-allene rearrangement and turns into a more stable cumulated diene. The resulting diene derivative transforms into a dithiepine cycle due to the nucleophilic attack of the second sulfide anion of propane dithiolate on the sp-hybridized carbon atom. The formation of 4,8-dithioundecadiin-2,9 occurs when potassium propane dithiolate replaces chlorine atoms in two molecules of propargyl chloride, which is followed by the isomerization of the triple bond. [ABSTRACT FROM AUTHOR]

BackgroundProteasome inhibitors (PIs), including carfilzomib, potentiate the activity of selinexor, a novel, first-in-class, oral selective inhibitor of nuclear export (SINE) compound, in preclinical models of multiple myeloma (MM).MethodsThe safety, efficacy, maximum-tolerated dose (MTD) and recommended phase 2 dose (RP2D) of selinexor (80 or 100 mg) + carfilzomib (56 or 70 mg/m2) + dexamethasone (40 mg) (XKd) once weekly (QW) was evaluated in patients with relapsed refractory MM (RRMM) not refractory to carfilzomib.ResultsThirty-two patients, median prior therapies 4 (range, 1-8), were enrolled. MM was triple-class refractory in 38% of patients and 53% of patients had high-risk cytogenetics del(17p), t(4;14), t(14;16) and/or gain 1q. Common treatment-related adverse events (all/Grade 3) were thrombocytopenia 72%/47% (G3 and G4), nausea 72%/6%, anaemia 53%/19% and fatigue 53%/9%, all expected and manageable with supportive care and dose modifications. MTD and RP2D were identified as selinexor 80 mg, carfilzomib 56 mg/m2, and dexamethasone 40 mg, all QW. The overall response rate was 78% including 14 (44%) ≥ very good partial responses. Median progression-free survival was 15 months.ConclusionsWeekly XKd is highly effective and well-tolerated. These data support further investigation of XKd in patients with MM.