cas 5350-57-2, Benzophenone hydrazone | Articles data

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Keto-salicylaldehyde azine: Asymmetric substituent effect on their optical properties via electron-donating group insertion
Organic fluorescent probes have attracted increasing attention owing to their high sensitivity and recognition ability, structurally adjustable flexibility and manifestation in the form of visualization. Salicylaldehyde azine (SAA) and its derivatives exhibit a great potential for practical applications, but the synthesis of SAA asymmetric compounds in low yields, serving multiple functions, is cumbersome. As an alternative building block, Keto-Salicylaldehyde Azine (KSA) was developed by our group for constructing various AIEgens via an excited state intramolecular proton transfer (ESIPT) process to detect some cellular organelles and specific metal ions. For illuminating the structure-property relationship of the two asymmetric sides in a KSA unit, DPAS was employed as a model and the N,N-diethyl group with electron-donating effects was introduced on its salicylaldehyde side (S-terminal) and diphenylketone side (K-terminal). Three new derivatives were obtained and showed different photophysical properties, particularly in AIE performance and metal ion responsiveness, implying that their intrinsic electronic structure can be easily affected by the asymmetric substitution effect. Therefore, this study is a meaningful and valuable reference for KSA modification on expanding fluorescent probes with various functions via the purposeful regulation of their chemical structure, by either modifying the K-terminal or the S-terminal.
Tong, Jialin,Zhang, Kexin,Wang, Jing,Li, Hui,Zhou, Fan,Wang, Zhiming,Zhang, Xiaojuan,Tang, Ben Zhong
p. 996 - 1001
(2020)
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Anti-glycemic potential of benzophenone thio/semicarbazone derivatives: synthesis, enzyme inhibition and ligand docking studies
Inhibition of dipeptidyl peptidase-IV (DPP-IV) has been identified as a promising approach for the treatment of type 2 diabetes mellitus (T2DM). Therefore, development of DPP-IV inhibitors with new chemical scaffold is of utmost importance to medicinal chemistry. In the present study, we identified benzophenone thio- and semicarbazone scaffolds as novel DPP-IV inhibitors. For that purpose, benzophenone thio- and semicarbazone were synthesized through a 2-step reaction. These newly synthetic derivatives were characterized by different spectroscopic techniques, including HREI-MS and NMR. whereas stereochemistry of the iminic bond was predicted by NOESY experiments. Thio- and semicarbazones derivatives were evaluated for their DPP-IV inhibitory potential and found to exhibit a good to moderate enzyme inhibitory activity. Most active and non-cytotoxic derivatives were further evaluated for their DPP-IV inhibitory potential in in cellulo model. The binding sites as well as affinity of active compounds for DPP- IV enzyme were predicted by in silico studies, and compared to a standard drug, sitagliptin. Pharmacophore studies of thio- and semicarbazones derivatives 1–29 suggest that substitution of aryl group, particularly a lipophilic substituents at C-4″ of benzene ring, and a hydroxyl at C-4′ strongly influenced the DPP-IV inhibitory activity. Compound 9 showed the highest inhibitory activity (IC50 = 15.0 ± 0.6 μM), whereas compounds 10, 17, 12, 14 and 23 showed a moderate activity with IC50 values in the range of 28.9–39.2 μM. This study identifies thio- and semicarbazones as new classes of DPP-IV inhibitors which may translate into safe and effective therapeutics for a better management of type 2 diabetes. Communicated by Ramaswamy H. Sarma.
Arshia,Fayyaz, Sharmeen,Shaikh, Muniza,Khan, Khalid Mohammed,Choudhary, M. Iqbal
(2021)
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Electrochemical Studies of Diazoalkanes: The Formation and Decomposition of Ph2C=N2(radical-anion) and Ph2C=N22-
Ph2C=N2 undergoes successive one-electron reductions in DMF-0.1 M (CH3)4NBF4 at subambient temperatures to give a relatively stable anion radical and an unstable dianion.In the absence of added proton donors, Ph2C=N22- undergoes rapid reaction to give an unobserved intermediate, believed to be Ph2CH-, that reacts with Ph2C=N2 to give Ph2CHN-N=CPh2(radical) (k = 5*104 M*s-1 at -37 deg C).Ph2C=N2(radical-anion) reacts under these conditions by abstraction of a hydrogen atom from a component of the solvent-electrolyte system (k = 0.4 s-1 at -23 deg C) to give Ph2C=NNH- as a longer lived intermediate.This species subsequently reacts with Ph2C=N2, giving first Ph2CHN-N=CPh2 and then the final product, Ph2C=NN=CPh2.The transformation of Ph2C=N2 into Ph2C=NN=CPh2 occurs by a chain process and is initiated by both Ph2C=NNH- and Ph2CHN-N=CPh2.Ph2C=NNH- and Ph2CHN-N=CPh2 are proposed to react with Ph2C=N2 by pathways that transfer hydride ion, either directly or indirectly, from the anion to the central carbon of Ph2C=N2.The final steps in the propagation cycle involve the loss of N2 from Ph2CHN2- and the subsequent coupling of Ph2CH- with Ph2C=N2 to regenerate Ph2CHN-N=CPh2.Ph2C=N2(radical-anion) and Ph2(C=N22- behave as ambient bases in the presence of Broensted acids which can effect their protonation and afford, depending upon whether the central carbon or the terminal nitrogen is protonated, Ph2CH2 or Ph2C=NNH2, respectively.The fraction of Ph2C=NNH2 formed increases with decreasing pKa of the proton donor.
Cheng, Spencer,Hawley, M. Dale
p. 3799 - 3804
(1986)
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Synthesis and physical studies of coumarin-based chemosensor for cyanide ions
A series of novel coumarin-based chemosensor azine derivatives L1, L2 and L3 were synthesized and characterized by various spectroscopic methods such as 1H NMR, mass spectrometry, FT-IR and elemental analysis. The sensing property of the sensor L derivatives was confirmed by the UV–Vis absorption, emission spectra and the naked eye sensing. The sensor L derivatives showed the absorption band at 320–330 nm. The fluorescence emission band was observed at 550–560 nm. In the presence of CN? ions, the chemosensor L derivatives show the “turn-on” fluorescence response over the other competing anions such as Br?, I?, HSO4?, ClO4? and PF6?, and the new absorption band appeared at 385 nm and the emission band also shifted to the blue region at 440 nm. The sensor L derivatives bind to cyanide ions in a 1:1 binding stoichiometry calculated from the job's plot experiments. The detection limit of sensor L1 towards CN? was 5.79 × 10?8 M. Additionally, the binding constant was determined to be 1.0209 × 106 M?1 from the Benesi-Heilbrand equation. The theoretical calculations were performed by Gaussian 9 software. The sensing mechanism of the interaction between the cyanide ion and imine carbon was confirmed by the 1H NMR titration method and mass spectra.
Devendhiran, Tamiloli,Kumarasamy, Keerthika,Lin, Mei-Ching,Yang, Yu Xuan
(2021/10/12)

POLYAROMATIC UREA DERIVATIVES AND THEIR USE IN THE TREATMENT OF MUSCLE DISEASES
The current invention provides urea derivatives, in particular compounds having the core structure heteroaryl-NH-CO-NH-aryl-O- heteroaryl, for use in treating, ameliorating, delaying, curing and/ or preventing a disease or condition associated with muscle cells and/or satellite cells, such as Duchenne muscular dystrophy, Becker muscular dystrophy, cachexia or sarcopenia.
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(2021/01/29)

Dehalogenative Cross-Coupling of gem-Difluoroalkenes with Alkyl Halides via a Silyl Radical-Mediated Process
Herein, we describe a convenient general protocol for monofluoroalkenylation reactions of alkyl bromides involving cooperative visible-light photoredox catalysis and halogen abstraction. Mechanistic experiments showed that the products were generated by selective cross-coupling of aliphatic radicals with fluoroalkenyl radicals. Silyl radical-mediated halogen abstraction enabled the protocol to be used for the monofluoroalkenylation of a broad range of alkyl and heteroaryl halides. The protocol could be carried out on a gram scale and was applied to cholesterol, indicating its utility for late-stage monofluoroalkenylation reactions.
Tian, Hao,Yang, Shaoxiang,Wang, Xiaochen,Xu, Wentao,Liu, Yuxiu,Li, Yongqiang,Wang, Qingmin
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p. 12772 - 12782
(2021/09/13)

Photochemical Carbene Transfer Reactions of Aryl/Aryl Diazoalkanes—Experiment and Theory**
Controlling the reactivity of carbene intermediates is a key parameter in the development of selective carbene transfer reactions and is usually achieved by metal complexes via singlet metal-carbene intermediates. In this combined experimental and computational studies, we show that the reactivity of free diaryl carbenes can be controlled by the electronic properties of the substituents without the need of external additives. The introduction of electron-donating and -withdrawing groups results in a significant perturbation of singlet triplet energy splitting of the diaryl carbene intermediate and of activation energies of consecutive carbene transfer reactions. This strategy now overcomes a long-standing paradigm in the reactivity of diaryl carbenes and allows the realization of highly chemoselective carbene transfer reactions with alkynes. We could show that free diaryl carbenes can be readily accessed via photolysis of the corresponding diazo compounds and that these carbenes can undergo highly chemoselective cyclopropenation, cascade, or C?H functionalization reactions. Experimental and theoretical mechanistic analyses confirm the participation of different carbene spin states and rationalize for the observed reactivity.
Jana, Sripati,Pei, Chao,Empel, Claire,Koenigs, Rene M.
supporting information
p. 13271 - 13279
(2021/05/10)

Oxime Ether Synthesis through O-H Functionalization of Oximes with Diazo Esters under Blue LED Irradiation
A green and sustainable oxime ether formation method via the visible-light-promoted O-H functionalization of oximes with diazo esters is described. The reaction occurs under very mild conditions (catalyst- and additive-free) with a high yield and a high functional group tolerance. When the reaction was performed with a cyclic ether as the solvent (e.g., THF, 1,4-dioxane, tetrahydropyran, ect.), an interesting photochemical three-component reaction product was obtained in good yields.
Li, Qian,Cai, Bao-Gui,Li, Lei,Xuan, Jun
supporting information
p. 6951 - 6955
(2021/09/02)

Copper-Mediated Cross-Coupling of Diazo Compounds with Sulfinates
A copper-mediated cross-coupling reaction between a diazo compound and a sodium alkane(arene)sulfinate gives a sulfone as the product. This reaction proceeds under mild conditions and features excellent functional group compatibility. A wide range of sodium alkane(arene)sulfinates were successfully applied in this chemistry. Mechanistic studies revealed that the overall reaction efficiency of the sulfinates was in line with their nucleophilicity in this reaction.
Wang, Qian,Liu, An,Wang, Yan,Ni, Chuanfa,Hu, Jinbo
supporting information
p. 6919 - 6924
(2021/09/11)

Silver-Catalyzed N-H Functionalization of Aryl/Aryl Diazoalkanes with Anilines
Herein, we report on the N-H functionalization reaction of primary and secondary anilines with diaryldiazoalkanes using simple AgPF6 as catalyst. We demonstrated broad applicability in the reaction of diaryldiazoalkanes with different anilines (31 examples, up to 97% yield). Furthermore, we propose a possible reaction mechanism for the N-H functionalization.
He, Feifei,Empel, Claire,Koenigs, Rene M.
supporting information
p. 6719 - 6723
(2021/09/13)

All-Carbon Tetrasubstituted Olefins Synthesis from Diazo Compounds and Iodonium Ylides under Blue LED Irradiation
A route for the construction of all-carbon tetra-substituted olefins through visible-light promoted coupling of diazo compounds with iodonium ylides was developed. A wide range of all-carbon tetra-substituted olefins was obtained in moderate to good yields. The synthetic values of the current method were further approved by the synthesis of natural isolates modified alkenes and the successful transformation of final olefins into important heterocycles. (Figure presented.).
Li, Lei,Xu, Guo-Yong,Xuan, Jun,Zhao, Yan-Rui
supporting information

(2021/12/08)

Azine hydrazine compound containing diethylamine as well as preparation method and application thereof
The invention discloses an azine hydrazine compound containing diethylamine as well as a preparation method and application thereof. The method comprises the following steps: carrying out a heating reaction on a diphenyl hydrazine derivative and diethylamine-containing aryl in a solvent, and separating and purifying the reaction product to obtain the diethylamine-containing azine hydrazine compound. The invention further discloses application of the compound, the fluorescence intensity of the azine hydrazine compound is adjusted by adjusting the strength of interaction between the azine hydrazine compound and microorganisms, and fungus recognition and selective antibiosis are achieved. The azine hydrazine compound containing diethylamine has remarkable capability of generating active oxygen due to aggregation-induced emission (AIE) property, shows selective bacterial fluorescence staining capability and antibacterial activity, and has a good application prospect.
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(2020/11/25)

Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation
Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemical formation of carbenes from diazoalkanes has not been proposed. Synergies of experiments and computations demonstrate the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazoalkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1) drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.
Pite?a, Tomislav,Ale?kovi?, Marija,Becker, Kristin,Basari?, Nikola,Do?li?, Nada
supporting information
p. 9718 - 9724
(2020/07/02)

Direct Observation of Aggregation-Induced Emission Mechanism
The mechanism of aggregation-induced emission, which overcomes the common aggregation-caused quenching problem in organic optoelectronics, is revealed by monitoring the real time structural evolution and dynamics of electronic excited state with frequency and polarization resolved ultrafast UV/IR spectroscopy and theoretical calculations. The formation of Woodward–Hoffmann cyclic intermediates upon ultraviolet excitation is observed in dilute solutions of tetraphenylethylene and its derivatives but not in their respective solid. The ultrafast cyclization provides an efficient nonradiative relaxation pathway through crossing a conical intersection. Without such a reaction mechanism, the electronic excitation is preserved in the molecular solids and the molecule fluoresces efficiently, aided by the very slow intermolecular charge and energy transfers due to the well separated molecular packing arrangement. The mechanisms can be general for tuning the properties of chromophores in different phases for various important applications.
Corminboeuf, Clémence,Guan, Jianxin,Han, Han,Lin, Kun-Han,Liu, Jitian,Peng, Jie,Prlj, Antonio,Wei, Rong,Yu, Zhihao,Zhao, Dahui,Zheng, Junrong
supporting information
p. 14903 - 14909
(2020/07/04)

Organocatalytic Nucleophilic Substitution Reaction of gem-Difluoroalkenes with Ketene Silyl Acetals
An organocatalytic nucleophilic substitution reaction of gem-difluoroalkenes with ketene silyl acetals was developed. Phosphazene P4-tBu effectively catalyzed the reaction under mild conditions to provide monofluoroalkenes possessing an alkoxycarbonylmethyl group in high yields with high Z selectivities.
Kondoh, Azusa,Koda, Kazumi,Terada, Masahiro
supporting information
p. 2277 - 2280
(2019/03/26)

Trifluoromethylation and Monofluoroalkenylation of Alkenes through Radical–Radical Cross-Coupling
The first visible-light-induced trifluoromethylation and monofluoroalkenylation of simple alkenes via a challenging radical–radical cross-coupling step was achieved. This method provided a mild, step-economical and redox-neutral route to privileged two different fluorinated difunctionalized allyl compounds. The utility of this method is illustrated by late-stage modification of medically important molecules.
Wang, Qiang,Qu, Yi,Tian, Hao,Liu, Yuxiu,Song, Hongjian,Wang, Qingmin
supporting information
p. 8686 - 8690
(2019/06/17)

Direct α-Monofluoroalkenylation of Heteroatomic Alkanes via a Combination of Photoredox Catalysis and Hydrogen-Atom-Transfer Catalysis
In this study, a new C(sp3)-H monofluoroalkenylation reaction involving cooperative visible-light photoredox catalysis and hydrogen-atom-transfer catalysis to afford products generated by selective hydrogen abstraction and radical-radical cross-coupling was described. This mild, efficient reaction shows high regioselectivity for the α-carbon atoms of amines, ethers, and thioethers and thus allows the preparation of monofluoroalkenes bearing various substituents. The reaction was applied to two bioactive molecules, indicating its utility for late-stage monofluoroalkenylation of compounds with inert C(sp3)-H bonds.
Tian, Hao,Xia, Qing,Wang, Qiang,Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin
supporting information
p. 4585 - 4589
(2019/06/17)

Reactions of hydrazones and hydrazides with Lewis acidic boranes
The reaction of (diphenylmethylene)hydrazone or 1,4-bis-hydrazone-ylidene(phenylmethyl)benzene with Lewis acidic boranes B(2,4,6-F3C6H2)3 or B(3,4,5-F3C6H2)3 generates the Lewis acid-base adducts. Alternatively, when (9H-fluoren-9-ylidene)hydrazone is employed several products were isolated including 1,2-di(9H-fluoren-9-ylidene)hydrazone, the 2:1 borane adduct of NH2-NH2 and the 1-(diarylboraneyl)-2-(9H-fluoren-9-ylidene)hydrazone in which one ArH group has been eliminated. The benzhydrazide starting material also initially gives an adduct when reacted with Lewis acidic boranes which upon heating eliminates ArH generating a CON2B heterocycle.
Gazis, Theodore A.,Dasgupta, Ayan,Hill, Michael S.,Rawson, Jeremy M.,Wirth, Thomas,Melen, Rebecca L.
supporting information
p. 12391 - 12395
(2019/08/26)

2,2-diphenylcyclopropyl compound and synthesis method thereof
The present invention provides a 2,2-diphenylcyclopropyl compound, which has a chemical name 2,2-diphenyl methyl cyclopropanecarboxylate compound, wherein the structure formula is defined in the specification, and the group R in the structure formula represents C1-C4 short-chain alkane, cycloalkane, halogenated alkane or halogenated cycloalkane. The present invention further provides a synthesis method of the 2,2-diphenylcyclopropyl compound, wherein the system method comprises: synthesizing Benzophenone hydrazone, synthesizing diphenyldiazomethane, and synthesizing the target product. According to the present invention, the three-membered ring of the 2,2-diphenyl methyl cyclopropanecarboxylate compound contains a chiral center, which can be used as a chiral precursor to introduce the chiral carbon atom into the reaction product so as to provide more possibility for the development of active compounds; and the synthesis method is simple, easy to operate, and suitable for industrial production.
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(2019/10/01)

Synthesis and biological imaging of fluorescent polymeric nanoparticles with AIE feature via the combination of RAFT polymerization and post-polymerization modification
In recent years, florescent polymeric nanoparticles (FPNs) containing aggregation-induced emission (AIE) fluorogens have received great intention for their potential applications in biological imaging and theranostic nanomedicine. Herein, we have developed AIE-active FPNs through a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and post-polymerization modification strategies. The salicylaldehyde (SA) containing zwitterionic copolymers are fabricated via RAFT polymerization and further modified by benzophenone hydrazone (BPH) via Schiff base reaction. The obtained AIE-active amphiphilic copolymers BPH-poly(FHMA-co-MPC) can self-assemble in aqueous solution with the hydrophobic fluorogens aggregating together to form the core and the hydrophilic chains to form the protective shell. BPH-poly(FHMA-co-MPC) and the resulting FPNs are characterized by 1H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy. Results demonstrate that BPH-poly(FHMA-co-MPC) are successfully synthesized and as-prepared BPH-poly(FHMA-co-MPC) FPNs exhibit desirable morphology and size, good dispersibility, high brightness, remarkable photostability and large Stokes shifts. More importantly, through cytotoxicity test and cell uptake behavior, these BPH-poly(FHMA-co-MPC) FPNs show low toxicity and excellent cell dyeing behavior. Taken together, we have developed a facile and effective method for the fabrication of AIE-active FPNs, which display great potential for biomedical applications.
Liu, Yanzhu,Mao, Liucheng,Yang, Saijiao,Liu, Meiying,Huang, Hongye,Wen, Yuanqing,Deng, Fengjie,Li, Yongxiu,Zhang, Xiaoyong,Wei, Yen
p. 79 - 87
(2018/05/26)

Mechanism of generation of: Closo -decaborato amidrazones. Intramolecular non-covalent B-H?π(Ph) interaction determines stabilization of the configuration around the amidrazone CN bond
Three types of N(H)-nucleophiles, viz. hydrazine, acetyl hydrazide, and a set of hydrazones, were used to study the nucleophilic addition to the CN group of the 2-propanenitrilium closo-decaborate cluster (Ph3PCH2Ph)[B10H9NCEt], giving N-closo-decaborato amidrazones. A systematic mechanistic study of the nucleophilic addition is provided and included detailed synthetic, crystallographic, computational and kinetic work. As a result, two possible mechanisms have been proposed, which consist of firstly a consecutive incorporation of two Nu(H) nucleophiles, with the second responsible for a subsequent rapid proton exchange. The second possible mechanism assumes a pre-formation of a dinuclear [Nu(H)]2 species which subsequently proceeds with the nucleophilic attack on the boron cluster. The activation parameters for hydrazones indicate a small dependence on bond formation [ΔH? = 6.8-15 kJ mol-1], but significantly negative entropies of activation [ΔS? ranges from -139 to -164 J K-1 mol-1] with the latter contributing some 70-80% of the total Gibbs free energy of activation, ΔG?. In the X-ray structure of (Z)-(Ph3PCH2Ph)[B10H9N(H)C(Et)NHNCPh2], very rare intramolecular non-covalent B-H?π(Ph) interactions were detected and studied by DFT calculations (M06-2x/6-311++G?? level of theory) and topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method). The estimated strength of these non-covalent interactions is 0.8-1.4 kcal mol-1.
Burianova, Valeria K.,Bolotin, Dmitrii S.,Mikherdov, Alexander S.,Novikov, Alexander S.,Mokolokolo, Pennie Petrus,Roodt, Andreas,Boyarskiy, Vadim P.,Dar'In, Dmitry,Krasavin, Mikhail,Suslonov, Vitalii V.,Zhdanov, Andrey P.,Zhizhin, Konstantin Yu.,Kuznetsov, Nikolay T.
p. 8693 - 8703
(2018/06/08)

Palladium-Catalyzed Fluoroarylation of gem-Difluoroalkenes
A Pd-catalyzed fluoroarylation of gem-difluoroalkenes with aryl halides is reported. By taking advantage of the in situ generated α-CF3-benzylsilver intermediates derived from the nucleophilic addition of silver fluoride to gem-difluoroalkenes, this strategy bypasses the use of a strong base, thus enabling a mild and general synthetic method for ready access to non-symmetric α,α-disubstituted trifluoroethane derivatives.
Tang, Hai-Jun,Lin, Ling-Zhi,Feng, Chao,Loh, Teck-Peng
supporting information
p. 9872 - 9876
(2017/08/08)

Visible light photocatalytic decarboxylative monofluoroalkenylation of α-amino acids with: Gem -difluoroalkenes
α-Amino acids are among the most common biologically active molecules in nature, and their functionalization has attracted much attention. In this communication, a novel, efficient and general visible-light photocatalytic decarboxylative monofluoroalkenylation of N-protected α-amino acids with gem-difluoroalkenes is reported, affording the corresponding α-amino monofluoroalkenes which might find applications in medical chemistry and materials science. The reaction proceeded at room temperature with high efficiency and tolerance of various functional groups.
Li, Jingjing,Lefebvre, Quentin,Yang, Haijun,Zhao, Yufen,Fu, Hua
supporting information
p. 10299 - 10302
(2017/09/25)

Synthesis and urease inhibitory activities of benzophenone semicarbazones/thiosemicarbazones
Twenty-five benzophenone semicarbazones and thiosemicarbazones 3–27 were synthesized starting from benzophenones via hydrazones treated with different aryl isocyanates and isothiocyantes under reflux. All synthetic derivatives were evaluated for their urease inhibitory potential. Good to moderate inhibition trend against urease was observed with the IC50 values in the range of 8.7–119.5 μM, when compared with the standard thiourea (IC50 = 21.2 ± 1.3 μM). Compound 15 showed better inhibition than the standard having the IC50 value of 8.7 ± 0.6 μM. Compounds 3, 4, 8, 11–14, 16, and 17 with the IC50 values within the range of 26.1 to 43.6 μM, demonstrated good to moderate activities while compound 9 (IC50 = 119.5 ± 1.6 μM) displayed very weak activity. The enzyme kinetic studies on the most active compounds 15 and 17 were performed to deduce their modes of inhibition and dissociation constants Ki.
Arshia, Arshia,Khan, Ajmal,Khan, Khalid Mohammed,Saad, Syed Muhammad,Siddiqui, Nida Iqbal,Javaid, Sumaira,Perveen, Shahnaz,Choudhary, M. Iqbal
p. 2666 - 2679
(2016/10/25)

Microwave assisted solvent-free C-H amination by silica-supported manganese dioxide
An effective and convenient method has been developed for the preparation of 1-unsubstituted 1H-indazoles via C-H amination of N-acetylhydrazones in the presence of a catalytic amount of manganese dioxide under microwave irradiation. This new method featured easy operation and relatively short reaction-time.
Cao, Sufen,Duan, Wenhu
supporting information
p. 2390 - 2394
(2016/05/19)

Hypervalent-iodine(iii) oxidation of hydrazones to diazo compounds and one-pot nickel(ii)-catalyzed cyclopropanation
A one-pot process for the catalytic cyclopropanation of various alkenes with unsubstituted hydrazones is described. Iodosobenzene (Ph = O) was found to be a competent oxidant of hydrazones to diazo compounds. Ni(OH)2 was chosen as an effective and cheap metal catalyst. The cyclopropane products can be generated efficiently (5 min-4 h) in moderate to good yields (42-91%) under mild (80°C) and neat conditions.
Liu, Haixuan,Wei, Yunyang,Cai, Chun
supporting information
p. 674 - 678
(2016/01/12)

New applications of hetaryl thioketones for the synthesis of hetaryl-substituted ethenes via 'two-fold extrusion reaction'
A series of aryl/hetaryl thioketones was applied for the reactions with aryl/hetaryldiazomethanes yielding, after elimination of N2, the corresponding thiiranes. The relatively unstable dihetaryldiazomethanes were generated in situ from the corresponding hydrazones by oxidation with DMSO. The obtained thiiranes were converted into tetraaryl/hetaryl-substituted ethenes in good yields by desulfurization performed with tris(diethylamino)phosphine ((Et2N)3P).
Mlostoń, Grzegorz,Urbaniak, Katarzyna,Pawlak, Aneta,Heimgartner, Heinz
p. 127 - 139
(2017/03/14)

A General Approach towards NH-Pyrazoles That Bear Diverse Fluoroalkyl Groups by Means of Fluorinated Iminium Salts
A new and general approach to important fluoroalkyl-substituted pyrazoles has been developed. The approach is based on the use of fluoroalkyl amino reagents and their Lewis acid activation to form a fluoroalkyl iminium salt that acts as a formal "fluoroacyl transfer reagent". Their interaction with readily available fluoroalkyl azines followed by spontaneous cyclization of the formed intermediates under acidic conditions leads to the formation of 3,5-disubstituted pyrazoles. The reaction is extremely versatile, high yielding, and allows quick access to pyrazoles that bear two fluoroalkyl functionalities (identical or different). These compounds are otherwise difficult to prepare. The reaction is scalable and suitable for industrial production.
Schmitt, Etienne,Landelle, Grégory,Vors, Jean-Pierre,Lui, Norbert,Pazenok, Sergiy,Leroux, Frédéric R.
supporting information
p. 6052 - 6060
(2015/09/22)

PROCESS FOR PREPARING 3,5-BIS(HALOALKYL)PYRAZOLE DERIVATIVES VIA ACYLATION OF HYDRAZONES
Process for preparing 3,5-bis(haloalkyl)pyrazole derivatives of the formula (I), via acylation of Hydrazones.
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(2016/01/01)

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors
A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.
Hu, Mingyou,Ni, Chuanfa,Li, Lingchun,Han, Yongxin,Hu, Jinbo
supporting information
p. 14496 - 14501
(2015/11/27)

Cross-Coupling between Difluorocarbene and Carbene-Derived Intermediates Generated from Diazocompounds for the Synthesis of gem-Difluoroolefins
Cross-coupling between difluorocarbene and carbene-derived intermediates generated from diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gem-difluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper-difluorocarbene complex was proposed.
Zheng, Jian,Lin, Jin-Hong,Yu, Liu-Ying,Wei, Yun,Zheng, Xing,Xiao, Ji-Chang
supporting information
p. 6150 - 6153
(2016/01/09)

Fluorogenic Strain-Promoted Alkyne-Diazo Cycloadditions
Fluorogenic reactions, in which non- or weakly fluorescent reagents produce highly fluorescent products, are attractive for detecting a broad range of compounds in the fields of bioconjugation and material sciences. Herein, we report that a dibenzocyclooctyne derivative modified with a cyclopropenone moiety (Fl-DIBO) can undergo fast strain-promoted cycloaddition reactions under catalyst-free conditions with azides, nitrones, nitrile oxides, as well as mono- and disubstituted diazo-derivatives. Although the reaction with nitrile oxides, nitrones, and disubstituted diazo compounds gave cycloadducts with low quantum yield, monosubstituted diazo reagents produced 1H-pyrazole derivatives that exhibited an approximately 160-fold fluorescence enhancement over Fl-DIBO combined with a greater than 10 000-fold increase in brightness. Concluding from quantum chemical calculations, fluorescence quenching of 3H-pyrazoles, which are formed by reaction with disubstituted diazo-derivatives, is likely due to the presence of energetically low-lying (n,π?) states. The fluorogenic probe Fl-DIBO was successfully employed for the labeling of diazo-tagged proteins without detectable background signal. Diazo-derivatives are emerging as attractive reporters for the labeling of biomolecules, and the studies presented herein demonstrate that Fl-DIBO can be employed for visualizing such biomolecules without the need for probe washout.
Friscourt, Frédéric,Fahrni, Christoph J.,Boons, Geert-Jan
supporting information
p. 13996 - 14001
(2015/09/28)

Facile Synthesis of Isoindolinones via Rh(III)-Catalyzed One-Pot Reaction of Benzamides, Ketones, and Hydrazines
A Rh(III)-catalyzed one-pot reaction of benzamides, ketones, and hydrazines for facile access to isoindolinones is reported. In this method, various ketones are transformed into donor-donor diazo compounds, which sequentially engage in insertion with benzamides under Rh(III) catalysis to generate N-substituted quaternary isoindolinones. (Chemical Presented).
Zhang, Yan,Wang, Dahai,Cui, Sunliang
supporting information
p. 2494 - 2497
(2015/05/27)

A Versatile Room-Temperature Route to Di- and Trisubstituted Allenes Using Flow-Generated Diazo Compounds
A copper-catalyzed coupling reaction between flow-generated unstabilized diazo compounds and terminal alkynes provides di- and trisubstituted allenes. This extremely mild and rapid transformation is highly tolerant of several functional groups. Well tolerated: A mild copper-catalyzed coupling reaction between unstabilized diazo compounds (generated in flow) and terminal alkynes is reported. The method provides di- and trisubstituted allenes with high functional-group tolerance.
Poh, Jian-Siang,Tran, Duc N.,Battilocchio, Claudio,Hawkins, Joel M.,Ley, Steven V.
supporting information
p. 7920 - 7923
(2015/06/30)

Cu(I)-catalyzed coupling of diaryldiazomethanes with terminal alkynes: An efficient synthesis of tri-aryl-substituted allenes
A highly efficient method for the synthesis of tri-aryl-substituted allenes has been developed through Cu(I)-catalyzed coupling of diaryldiazomethanes with terminal alkynes. The reaction is under mild conditions and uses simple and inexpensive CuI as the catalyst. Mechanistically, the reaction follows a pathway involving Cu(I) carbene migratory insertion.
Wu, Chenggui,Hu, Fangdong,Liu, Zhenxing,Deng, Guisheng,Ye, Fei,Zhang, Yan,Wang, Jianbo
p. 9196 - 9201
(2015/11/27)

PROCESS FOR PREPARING 3,5-BIS(FLUOROALKYL)PYRAZOLE DERIVATIVES FROM α,α-DIHALOAMINES
The present invention relates to a novel process for preparing 3,5-bis(fluoroalkyl)pyrazole derivatives from α,α-dihaloamines.
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(2014/12/12)

NOVEL CEPHALOSPORIN DERIVATIVE AND PHARMACEUTICAL COMPOSITION THEREOF
The present invention relates to novel cephalosporin derivatives represented by Chemical Formula 1. Wherein, X, Y, L, R1, and R2 are as same as defined in the description of the invention. The present invention also relates to pharmaceutical antibiotic compositions comprising a novel celphalosporin derivative represented by Chemical Formula 1, a prodrug thereof, a hydrate thereof, a solvate thereof, an isomer thereof, or a pharmaceutically acceptable salt thereof as an effective ingredient. According to the present invention, novel cephalosporin derivatives, a prodrug thereof, a hydrate thereof, a solvate thereof, an isomer thereof, or a pharmaceutically acceptable salt thereof as an effective ingredient for the broad spectrum of antibiotic resistant, low toxicity, particularly in Gram-negative bacteria, which can be useful with strong antimicrobial activity.
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Paragraph 0181

(2014/03/25)

Diversity-oriented synthesis of azapeptides with basic amino acid residues: Aza-lysine, aza-ornithine, and aza-arginine
Aza-peptides with basic amino acid residues (lysine, ornithine, arginine) and derivatives were synthesized by an effective approach featuring alkylation of a hydrazone-protected aza-glycine residue with α-bromo ω-chloro propane and butane to provide the corresponding alkyl chloride side chains. Displacement of the chloride with azide and various amines gave entry to azaOrn, azaLys, and azaArg containing peptides as demonstrated by the solution and solid-phase syntheses of 29 examples, including an aza-library of Growth Hormone Releasing Peptide-6 analogs.
Traore, Mariam,Doan, Ngoc-Duc,Lubell, William D.
supporting information
p. 3588 - 3591
(2014/07/21)

An easy route to N,N-diarylhydrazines by Cu-catalyzed arylation of pyridine-2-carbaldehyde hydrazones with aryl halides
A copper-catalyzed C-N coupling reaction is described for the preparation of pyridine-2-carbaldehyde N,N-diarylhydrazones by the arylation of N-mono- or -non-substituted hydrazones with aryl bromides/iodides, and the subsequent conversion of the hydrazones into N,N-diarylhydrazines by a transimination process with an aqueous solution of H2NNH2. The reaction features the use of CuI as the catalyst without the need for external ligands. This methodology provides a convenient alternative to the synthesis of structurally diverse N,N-diarylhydrazines from simple, easily accessible precursors. Copyright
Wu, Wei,Li, Xin-Le,Fan, Xin-Heng,Yang, Lian-Ming
supporting information
p. 862 - 867
(2013/03/28)

Copper-catalyzed gem -difluoroolefination of diazo compounds with TMSCF3 via C-F bond cleavage
A novel Cu-catalyzed gem-difluoroolefination of diazo compounds is described. This transformation starts from readily available TMSCF3 and diazo compounds, via trifluoromethylation followed by C-F bond cleavage, to afford the desired 1,1-difluoroalkene products.
Hu, Mingyou,He, Zhengbiao,Gao, Bing,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
supporting information
p. 17302 - 17305
(2014/01/06)

Evaluation of some classical hydrazones of ketones and 1,2-diketones as antileishmanial, antibacterial and antifungal agents
The paper describes the synthesis and antimicrobial (antileishmanial, antibacterial and antifungal) activity of some classical hydrazones of benzophenones and of 1,2-diketones. N-(Diaryl) acyl derivatives of these hydrazones have also been synthesized and evaluated. 4,4,- Demthoxybenzil monohydrazone and 4,4'-dimethoxybenzophenone hydrazone showed significant antileishmanial activity. The effect of substituents on the bioactivity is discussed.
Al-Kahraman, Yasser M.S.A.,Yasinzai, Masoom,Singh, Girija S.
experimental part
p. 1009 - 1013
(2012/10/08)

NOVEL CEPHALOSPORIN DERIVATIVES AND PHARMACEUTICAL COMPOSITIONS THEREOF
The present invention relates to novel cephalosporin derivatives represented by Chemical Formula 1. Wherein, X, Y, L, R1, and R2 are as same as defined in the description of the invention. The present invention also relates to pharmaceutical antibiotic compositions comprising a novel celphalosporin derivative represented by Chemical Formula 1, a prodrug thereof, a hydrate thereof, a solvate thereof, an isomer thereof, or a pharmaceutically acceptable salt thereof as an effective ingredient. According to the present invention, novel cephalosporin derivatives, a prodrug thereof, a hydrate thereof, a solvate thereof, an isomer thereof, or a pharmaceutically acceptable salt thereof as an effective ingredient for the broad spectrum of antibiotic resistant, low toxicity, particularly in Gram-negative bacteria, which can be useful with strong antimicrobial activity.
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Page/Page column 50

(2012/10/23)

Research on the synthesis of aromatic hydrazone in ionic liquids
Aromatic hydrazones are important intermediates for pesticides cibenzoline and cefxime. The methodology of synthesis of aromatic hydrazone from aromatic ketone and hydrazine hydrate in ionic liquid, was described and various aromatic hydrazones were prepared by the reaction of aromatic ketone with hydrazine hydrate in ionic 1iquid at 100C with good yields. The ionic liquids could be recycled and reused after the reaction. The influences of the various ionic liquids on the reaction are discussed. The product structure was characterized by infrared, mass spectrometry, NMR spectra, and elemental analysis. Copyright
Wang, Haibin,Sun, Li,Li, Xiaonian,Duan, Jiangli,Pei, Wen
experimental part
p. 3223 - 3227
(2011/09/30)

Facile method for the conversion of semicarbazones/thiosemicarbazones into azines (Under Microwave Irradiation) and oxadiazoles (By Grinding)
In an effective transformation, semicarbazones/thiosemicarbazones are smoothly converted into azines under microwave irradition. Oxadiazoles are also obtained from semicarbazones by reaction with bromine generated in situ via a grinding reaction in the solid phase. Taylor &Francis Group, LLC.
Chattopadhyay, Gautam,Ray, Partha Sinha
experimental part
p. 2607 - 2614
(2011/08/07)

Surprising secondary photochemical reactions observed on conventional photolysis of diazotetrahydrofuranones
The formation of C-H insertion products of the terminal N-atom of a diazo group into the α-S{cyrillic}N{cyrillic}-bond of tetrahydrofuran during direct photolysis of regioisomeric 2,2-dimethyl-5,5-diphenyl and 5,5-dimethyl-2,2-diphenyl-substituted 3-diazotetrahydrofuran-4-ones in THF is dictated by photochemical cycloelimination of the originally formed (1,1-dimethyl-2-oxa-3,3-diphenyl-propano)ketene and oxetanecarboxylic acid derivatives to yield benzophenone. The latter, under subsequent UV irradiation of the reaction mixture, initiates sensitized photolysis of the starting diazoketones resulting in the appearance of the insertion products with the solvent.
Nikolaev, Valerij A.,Galkina, Olesja S.,Sieler, Jochim,Rodina, Ludmila L.
experimental part
p. 2713 - 2716
(2010/06/19)

Synthesis and biological activity of some 2-imidazolinylhydrazone derivatives
A series of N-(imidazolidin-2-ylidene)hydrazones and N-(4,5-dihydro-1H- imidazol-2-yl)-N-methylhydrazones were prepared and examined for α1-, α2-adrenergic and imidazoline I 1, I2 receptors binding affinities as well as cytotoxic activity against human tumor cell lines. Among the compounds tested, 2-naphthaldehyde N-(imidazolidin-2-ylidene)hydrazone (3e) exhibited a significant affinity for both α2-adrenergic and imidazoline I1 receptors (Ki = 94.3 nM and IC50 = 51.7 nM, respectively). Moreover, pyridine-2-carboxaldehyde N-(imidazolidin-2-ylidene) hydrazone (3l) showed the highest binding affinity to α1- adrenoceptors (Ki = 24.6 nM), while quinoline-2-carboxaldehyde N-(imidazolidin-2-ylidene)hydrazone (3m) displayed the highest I2 affinity with a Ki value of 26.7 nM and a high selectivity with respect to α2-adrenergic and imidazoline I1 receptors (Ki = 22470.0 nM and IC50 = 6145.0 nM, respectively). None of the tested N-(4,5-dihydro-1H-imidazol-2-yl)-N- methylhydrazones 4p-u displayed cytotoxic activity.
Kornicka, Anita,Hudson, Alan L.,Bednarski, Patrick J.
experimental part
p. 523 - 534
(2010/02/27)

Facile and efficient way to synthesize the radical cyclization precursor methyl 3-(tert-butyl((E)-3-(2,2-diphenylcyclopropyl)-2-propenyl)amino)-3-oxo-2- (phenylseleno)propanoate for kinetic research
Methyl 3-(tert-butyl((E)-3-(2,2-diphenylcyclopropyl)-2-propenyl)amino)-3- oxo-2-(phenylseleno)propanoate was prepared in 10 steps in good to excellent yield using benzophenone and hydrazine hydrate as the starting materials. Copyright Taylor & Francis Group, LLC.
Yu, Jindi,Lian, Gaoyan,Zhang, Danwei
p. 37 - 46
(2007/10/03)

Reductive deoximation of aryloximes into hydrocarbons by hydrazine/KOH: A novel application of the wolff-kishner reduction
We report the reductive deoximation of different substituted aryl, diaryl, and aralkyloximes into the respective methyl or methylene derivatives by hydrazine hydrate/KOH at reflux in satisfactory yields. Copyright Taylor & Francis Group, LLC.
Nanjundaswamy,Pasha
p. 2183 - 2187
(2007/10/03)

A chemical method for the convenient surface functionalisation of polymers
A method for the application of carbenes as reactive intermediates for surface modification of polymeric substrates has been developed; the efficacy of the process has been demonstrated by irreversible dyeing of polystyrene, polythene, nylon, silica, and controlled pore glass, and to a limited extent, polytetrafluoroethylene. The Royal Society of Chemistry 2005.
Awenat, Karim M.,Davis, Philip J.,Moloney, Mark G.,Ebenezer, Warren
p. 990 - 992
(2007/10/03)

A novel transformation of oximes into hydrazones by hydrazine hydrate
We report a novel transformation of different substituted aryl, diaryl, and aralkyloximes into the respective hydrazones using hydrazine hydrate in ethanol at reflux in excellent yields.
Pasha,Nanjundaswamy
p. 3827 - 3831
(2007/10/03)

Microwave induced synthesis of hydrazones and Wolff-Kishner reduction of carbonyl compounds
Carbonyl compounds 1 are converted to hydrazones 3 and then to hydrocarbons 4 by Wolff-Kishner reductions under microwave irradiations within 25-30 mins in excellent yields.
Gadhwal, Sunil,Baruah, Mukulesh,Sandhu, Jagir S.
p. 1573 - 1574
(2007/10/03)