- N-Amino-1,8-Naphthalimide is a Regenerated Protecting Group for Selective Synthesis of Mono-N-Substituted Hydrazines and Hydrazides
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A new route to synthesis of various mono-N-substituted hydrazines and hydrazides by involving in a new C?N bond formation by using N-amino-1,8-naphthalimide as a regenerated precursor was invented. Aniline and phenylhydrazines are reproduced upon reacting these individually with 1,8-naphthalic anhydride followed by hydrazinolysis. The practicality and simplicity of this C?N dihalo alkanes; developed a synthon for bond formation protocol was exemplified to various hydrazines and hydrazides. N-amino-1,8-naphthalimide is suitable synthon for transformation for selective formation of mono-substituted hydrazine and hydrazide derivatives. Those are selective mono-amidation of hydrazine with acid halides; mono-N-substituted hydrazones from aldehydes; synthesis of N-aminoazacycloalkanes from acetohydrazide scaffold and inserted to hydroxy derivatives; distinct synthesis of N,N-dibenzylhydrazines and N-benzylhydrazines from benzyl halides; synthesis of N-amino-amino acids from α-halo esters. Ecofriendly reagent N-amino-1,8-naphthalimide was regenerated with good yields by the hydrazinolysis in all procedures.
- Manoj Kumar, Mesram,Venkataramana, Parikibanda,Yadagiri Swamy, Parikibanda,Chityala, Yadaiah
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supporting information
p. 17713 - 17721
(2021/11/10)
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- Synthesis, in-vitro and in-silico studies of triazinoindole bearing bis-Schiff base as β-glucuronidase inhibitors
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Triazinoindole bearing bis-Schiff base analogs (1–20) were synthesized by triazinoindole-thione ring formation, triazinoindole-thiol-phenylethanone, followed by triazinoindole bis-Schiff base formation. Synthesized analogs showed β-glucuronidase potential with IC50 value ranging between 2.60 ± 0.10 to 55.40 ± 1.60 μM as compared to standard D-saccharic acid 1,4-lactone (IC50 = 48.10 ± 1.2 μM). Analog 20 was the most potent one with IC50 value 2.60 ± 0.10 μM. Analogs 17, 4 showed IC50 values 5.20 ± 0.20 and 5.70 ± 0.20 μM respectively and withstand 2nd and 3rd ranked scaffolds among the synthesized analogs. All other sixteen analogs showed many-fold better potency with IC50 values ranging from 7.9 ± 0.2 to 48.1 ± 1.2 μM. The structure-activity relationship was established and confirmed of binding interactions through molecular docking studies.
- Ahmad, Shakeel,Aziz, Aamir,Khan, Fahad,Rahim, Fazal,Sarfraz, Maliha,Taha, Muhammad,Ullah, Hayat,Wadood, Abdul
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- Metal schiff base complexes of tridentate antipyrine based ligand: Synthesis, spectral characterisation, image analysis and biological studies
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Novel tridentate antipyrine based ligand (L) were synthesized and characterized employing analytical, spectral and image processing techniques. The Co(II), Ni(II), Cu(II) and Zn(II) complexes of newly synthesized L is characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, FTIR, UV–visible, 1H NMR, 13C NMR, and mass spectrometry. Octahedral geometry is given to Co(II), Ni(II) and Zn(II) complexes, whereas Cu(II) complex preferred distorted octahedral geometry. The ligand to metal ratio was identified to be 1:1. Thermal stability of the new integrated compounds were inspected by thermogravimetric analysis. Porosity of the complexes is analysed by image processing. The electrochemical deportment of the Schiff base metal complexes was assessed using cyclic voltammetry. In vitro antimicrobial, DNA cleavage and SOD efficacy of the present compounds were determined. The in vitro anticancer potency of the metal complexes were also evaluated against Liver Bilobular cancerous cells (LBir2754).
- Dhanaraj, C. Justin,Jebapriya, M.
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- Diels-Alder Reaction of β-Fluoro-β-nitrostyrenes. Synthesis of Mono-fluorinated Six-Membered Derivatives
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The Diels-Alder reaction of β-fluoro-β nitrostyrenes with some linear dienes was investigated. A number of monofluorinated [4+2]-cycloadducts was prepared in up to 90 % yield. The kinetics of [4+2]-cycloaddition to 2,3-dimethyl-1,3-butadiene was studied i
- Larkovich, Roman V.,Ponomarev, Savva A.,Aldoshin, Alexander S.,Tabolin, Andrey A.,Ioffe, Sema L.,Nenajdenko, Valentine G.
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p. 2479 - 2492
(2020/03/23)
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- Efficient Multigram Approach to Acetylenes and CF3-ynones Starting from Dichloroalkenes Prepared by Catalytic Olefination Reaction (COR)
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A novel approach to terminal acetylenes based on catalytic olefination reaction COR of arylaldehydes to form dichloroalkenes followed by treatment with nBuLi was elaborated. This method is atom economical and displays high yields and effectivity. The corresponding alkynes can be prepared in up to 97 % yield. One pot procedure towards CF3-ynones was elaborated to provide these products in up to 87 % yield starting from dichloroalkenes.
- Muzalevskiy, Vasiliy M.,Sizova, Zoia A.,Diusenov, Arstan I.,Shastin, Alexey V.,Nenajdenko, Valentine G.
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supporting information
p. 4161 - 4166
(2020/07/13)
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- Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2-Trifluoroethyl)arenes
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Reacting hydrazones of arylaldehydes with Togni's CF3-benziodoxolone reagent, in the presence of potassium hydroxide and cesium fluoride, induces a denitrogenative hydrotrifluoromethylation event to produce (2,2,2-trifluoroethyl)arenes. This novel reaction was tolerant to many electronically-diverse functional groups and substitution patterns, as well as naphthyl- and heteroaryl-derived substrates. Advantages of this process include the easy access to hydrazone precursors on a large scale, speed and operational simplicity, and being transition metal-free.
- Zhao, Zhensheng,Ma, Kevin C. Y.,Legault, Claude Y.,Murphy, Graham K.
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supporting information
p. 11240 - 11245
(2019/08/20)
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- Metal-Free Construction of the C(sp3)-CF3 Bond: Trifluoromethylation of Hydrazones with Togni's Reagent under Mild Conditions
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A metal-free trifluoromethylation of hydrazones with Togni's reagent under mild conditions was developed. Various functional groups including ester, methoxy, dimethoxy, nitro, halogen, and heterocyclic compounds were tolerated. This simple and green strategy provides a practical tool to construct C(sp3)-CF3 bonds.
- Zeng, Huiying,Luo, Zhen,Han, Xinlong,Li, Chao-Jun
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supporting information
p. 5948 - 5951
(2019/08/29)
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- Synthesis of Aryldihalomethanes by Denitrogenative Dihalogenation of Benzaldehyde Hydrazones
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We report a denitrogenative dihalogenation reaction of phenyldiazomethanes in which the hypervalent iodine reagents PhICl2 and TolIF2 act as surrogates for elemental chlorine and fluorine. Halogen transfer from iodane to aryldiazomethane is described, as is a tandem oxidative dihalogenation reaction between iodane and hydrazone. This is the first use of non-α-stabilized diazo compounds in this reaction, which provided an efficient synthesis of aryldifluoromethane (ArCHF2) and aryldichloromethane (ArCHCl2) derivatives. (Figure presented.).
- Zhao, Zhensheng,Kulkarni, Kaivalya G.,Murphy, Graham K.
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supporting information
p. 2222 - 2228
(2017/07/07)
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- The diaza-Nazarov cyclization involving a 2,3-diaza-pentadienyl cation for the synthesis of polysubstituted pyrazoles
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An unprecedented iodine-mediated diaza-Nazarov (DAN) type cyclization for the construction of substituted pyrazoles from easily available starting materials via an enamine-iminium ion intermediate is described. The oxidative cyclization worked under green conditions with remarkable regioselectivity. This one-pot, efficient and operationally simple three-component intramolecular regioselective DAN cyclization displayed a wide range of substrate scope. The dichotomy of reaction pathways has been explored with density functional theory in the gas phase and solution phase. Of the possible 1,5-, 1,6-, and 1,7-electrocyclizations, the DAN cyclization, i.e., the 1,5-pathway offers the lowest activation energy barrier supporting our experimental observations.
- Aegurla, Balakrishna,Peddinti, Rama Krishna
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p. 9643 - 9652
(2017/11/30)
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- Denitrogenative hydrofluorination of aromatic aldehyde hydrazones using (difluoroiodo)toluene
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An operationally simple conversion of aromatic aldehyde hydrazones to monofluoromethylated arenes is reported. The hypervalent iodine reagent TolIF2 serves as an oxidant, converting the hydrazone to the corresponding diazo compounds. The by-product of the oxidation process, HF, is consumed in situ by a denitrogenative hydrofluorination reaction of the diazo group.
- Kulkarni, Kaivalya G.,Miokovic, Boris,Sauder, Matthew,Murphy, Graham K.
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supporting information
p. 9907 - 9911
(2016/10/31)
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- Ionic liquids as a reusable media for copper catalysis. Green access to alkenes using catalytic olefination reaction
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It was demonstrated that ionic liquids are superb recyclable media for copper catalyzed reactions using catalytic olefination reaction as an example. As a result a novel green access to the halogenoalkenes was elaborated. Possibility to perform up to five reaction cycles without catalyst leaching and decreasing of the yield was demonstrated. A number of various ionic liquids was screened and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim] [BF4]) was found the solvent with highest efficiency. Mild conditions, high atom economy comparing to other known methods, low amounts of wastes and possibility to recover ionic liquid are the advantages of the proposed method.
- Muzalevskiy, Vasily M.,Shastin, Aleksey V.,Shikhaliev, Namiq G.,Magerramov, Abel M.,Teymurova, Aytekin N.,Nenajdenko, Valentine G.
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p. 7159 - 7163
(2016/10/24)
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- Cyclopropanation using flow-generated diazo compounds
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We have devised a room temperature process for the cyclopropanation of electron-poor olefins using unstabilised diazo compounds, generated under continuous flow conditions. This protocol was applied to a wide range of different diazo species to generate f
- Roda, Nuria M.,Tran, Duc N.,Battilocchio, Claudio,Labes, Ricardo,Ingham, Richard J.,Hawkins, Joel M.,Ley, Steven V.
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supporting information
p. 2550 - 2554
(2015/11/17)
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- Synthesis of 2-aryl-5-oxo-4-[2-(phenylmethylidene)hydrazino]-2,5-dihydro- 1H-pyrrole-3-carboxylates by the reaction between hydrazones, acetylenedicarboxylates, and 1-aryl-N,N′-bis(arylmethylidene) methanediamines
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An efficient approach for the preparation of functionalized 2-aryl-2,5-dihydro-5-oxo-4-[2-(phenylmethylidene)hydrazino]-1H-pyrroles is described. The four-component reaction between aldehydes, NH2NH 2×H2O, dialkyl acetylenedicarboxylates, and 1-aryl-N,N′-bis(arylmethylidene)methanediamines proceeds in EtOH under reflux in good-to-excellent yields (Scheme 1). The structures of 4 were corroborated spectroscopically (IR, 1H- and 13C-NMR, and EI-MS, and, in the case of 4f, by X-ray crystallography). A plausible mechanism for this type of reaction is proposed (Scheme 2). Copyright
- Alizadeh, Abdolali,Saberi, Vahid,Mokhtari, Javad
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p. 1991 - 1996
(2013/11/06)
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- Facile method for the conversion of semicarbazones/thiosemicarbazones into azines (Under Microwave Irradiation) and oxadiazoles (By Grinding)
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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
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experimental part
p. 2607 - 2614
(2011/08/07)
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- Proteolytic studies in liver homogenate in presence of substituted aryl hydrazones
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Hydrazones of different arylaldehydes were synthesized and their effect on endogenous proteolysis in liver was studied. It was observed that different functional groups on the benzene moiety altered the enzymatic activity and para-nitrobenzaldehyde hydrazone exhibited maximum inhibitory effect.
- Raghav,Singh, Mamta,Kaur, Ravinder,Suman,Priyanka
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experimental part
p. 1409 - 1410
(2012/01/03)
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- Novel efficient synthesis of β-fluoro-β-(trifluoromethyl)styrenes
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CF3CFBr2 was employed in catalytic olefination reactions of aromatic aldehydes. In situ prepared hydrazones of aldehydes were transformed to β-fluoro-β-(trifluoromethyl)styrenes by reaction with CF3CFBr2 under CuCl catalysis. Based on this reaction, a novel stereoselective approach towards β-fluoro-β-(trifluoromethyl)styrenes was elaborated. Nucleophilic vinylic substitution of fluorine by secondary amines, thiolates and alkoxides in β-fluoro-β-(trifluoromethyl)styrenes was also tested.
- Goldberg, Aleksey A.,Muzalevskiy, Vasiliy M.,Shastin, Aleksey V.,Balenkova, Elisabeth S.,Nenajdenko, Valentine G.
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experimental part
p. 384 - 388
(2010/04/24)
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- Reaction of CBrF2-CBrF2 with hydrazones of aromatic aldehydes. Novel efficient synthesis of fluorocontaining alkanes, alkenes and alkynes
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An olefination of hydrazones of aromatic aldehydes by CBrF2-CBrF2 under copper catalysis was investigated. In situ prepared aldehydes hydrazones were converted to (3-bromo-2,2,3,3-tetrafluoropropyl)arenes by reaction with CBrF2-CBrF2 in the presence of CuCl. Subsequent elimination of HF by sodium hydroxide resulted in stereospecific formation of fluorocontaining alkenes. Elimination proceeds stereoselectively, only Z -isomers of alkenes are formed. Elimination of two molecules of HF from (3-bromo-2,2,3,3-tetrafluoropropyl)arenes by treatment with potassium tert -butoxide leads to formation of (bromodifluoromethyl)alkynes. As a result a simple and efficient transformation of aromatic aldehydes to range of various fluorinated alkanes, alkenes and alkynes was elaborated.
- Nenajdenko, Valentine G.,Varseev, Georgy N.,Korotchenko, Vasily N.,Shastin, Alexey V.,Balenkova, Elisabeth S.
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p. 1339 - 1345
(2007/10/03)
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- New synthetic approach to α-chlorocinnamates: First example of synthesis of functionally substituted alkenes using catalytic olefination reaction
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A new simple and efficient transformation of carbonyl compounds to α-chlorocinnamates is described. Catalytic olefination reaction with ethyl trichloroacetate gives target alkenes in moderate to good yields. The reaction with aromatic aldehydes proceeds stereoselectively to form preferably Z-isomers.
- Nenajdenko, Valentine G.,Lenkova, Olesya N.,Shastin, Alexey V.,Balenkova, Elizabeth S.
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p. 573 - 577
(2007/10/03)
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- A novel direct synthesis of (2,2-difluorovinyl)benzenes from aromatic aldehydes
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A novel catalytic approach to (2,2-difluorovinyl)benzenes has been developed. It was found that hydrazones of aromatic aldehydes generated in situ could be converted to the corresponding (2,2-difluorovinyl)benzenes by catalytic olefination reaction (COR) with dibromodifluoromethane in the presence of CuCl.
- Nenajdenko, Valentine G.,Varseev, Georgy N.,Korotchenko, Vasily N.,Shastin, Alexey V.,Balenkova, Elisabeth S.
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p. 115 - 118
(2007/10/03)
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- A novel approach to fluoro-containing alkenes
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A new and general one-pot transformation of aromatic aldehydes to fluorinated olefins containing -CH=C(Cl)CF3 or -CH=C(F)CClF2 moieties is described. Freons CCl3CF3 and CCl2FCClF2 were used as trifluoromethyl and difluoromethyl C2-building blocks respectively. A proposed mechanism for the reaction is discussed.
- Korotchenko, Vasily N,Shastin, Alexey V,Nenajdenko, Valentine G,Balenkova, Elisabeth S
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p. 7519 - 7527
(2007/10/03)
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- A novel synthetic approach to dichlorostyrenes
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We found that N-unsubstituted hydrazones of aromatic aldehydes can be easily converted to the corresponding 1,1-dichlorostyrenes in the reaction with carbon tetrachloride using copper (I) chloride as catalyst. Factors affecting the route of the reaction and yields of the products were investigated. A proposed mechanism for the reaction is discussed. (C) 2000 Published by Elsevier Science Ltd.
- Shastin,Korotchenko,Nenajdenko,Balenkova
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p. 6557 - 6563
(2007/10/03)
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