- Synthesis, spectroscopic, and structural properties of organogermanyl(IV) complexes of pyridine oximes
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Reactions of triorganogermanyl(IV) chlorides and diorganogermanyl(IV) dichlorides with sodium salts of pyridine-2-carbaldehyde oxime and 2-acetylpyridine oxime, respectively, in 1:1 and 1:2 molar ratio produced organogermanyl(IV) oximates. All the derivat
- Nelson Joseph,Thomas, Raji,Pardasani, Pushpa,Mukherjee, Tulsi
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- Metal ion transport through bulk liquid membrane mediated by cationic ligand surfactants
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A series of N,N,N-trialkyl-2-(hydroxyimino)-2-(pyridin-2-yl)ethan-1-aminium nitrates 3a-3h and N,N,N-trialkyl-4-(hydroxyimino)-4-(pyridin-2-yl)butan-1- aminium nitrates 3i-31 representing cationic surfactants with a powerful 1-(hydroxyimino)-1-(pyridin-2-yl)alkyl chelating subunit were prepared as potential selective metal ion extractants. Their extraction ability was tested in transport of Cu2+, Ni2+, Co2+, and Pd 2+ through a bulk liquid membrane. The introduction of the cationic group into the extractant molecule increases the selectivity and facilitates the metal ion transport as shown by comparing the transports carried out with ligand surfactants 3 and lipophilic alkyl pyridin-2-yl ketoximes 2. The efficiency and selectivity of the metal ion transport mediated by ligand surfactants 3 depends predominantly on their structure and lipophilicity, i.e. on the number and length of hydrophobic alkyl chains and on the length of the spacer connecting the chelating moiety with the cationic head group of the surfactant.
- Svobodova, Eva,Cibulka, Radek,Hampl, Frantisek,Smidrkal, Jan,Liska, Frantisek
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- Investigation of the zinc chloride/methyl(2-pyridyl)ketone oxime reaction system: A mononuclear complex and an inverse 12-metallacrown-4 cluster
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The reactions of methyl(2-pyridyl)ketone oxime, (py)C(Me)NOH, with zinc chloride have been investigated. An excess of the ligand in EtOH/MeCN affords the mononuclear complex [ZnCl2{(py)C(Me)NOH}2] (1) in moderate yield. The metal ion is coordinated by two chloro ligands and two N,N'-chelating (py)C(Me)NOH molecules. The six-coordinate molecule is the cis-cis-trans isomer considering the positions of the coordinated chlorine, pyridyl and oxime nitrogen atoms, respectively. The reaction between equimolar quantities of ZnCl2, (py)C(Me)NOH and LiOH · H2O in EtOH/MeCN leads to the tetranuclear cluster [Zn4(OH) 2Cl2{(py)C(Me)NO}4] (2) in high yield. The molecule lies on a crystallographic inversion center and has an inverse 12-metallacrown-4 topology. Two triply bridging hydroxides are accommodated within the metallacrown ring. Each (py)C(Me)NO- ligand adopts the 2.111 coordination mode (Harris notation), chelating one ZnII ion and bridging a ZnII2 pair. Two metal ions are in a distorted O2N4 octahedral environment, whereas the other two are in a severely distorted tetrahedral O3Cl environment. Complex 2 joins a small family of structurally characterized zinc(II) metallacrown complexes. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes.
- Papatriantafyllopoulou, Constantina,Raptopoulou, Catherine P.,Terzis, Aris,Manessi-Zoupa, Evy,Perlepes, Spyros P.
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- Ligand assisted electrocatalytic water oxidation by a copper(ii) complex in neutral phosphate buffer
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The electrocatalytic water oxidation activity of a copper(ii) complex, 1, [Cu(L1H)(L1)(OH2)](ClO4), with a redox active aryl oxime ligand, L1H [L1H = 1-(pyridin-2-yl) ethanone oxime] has been investigated. Complex 1 shows a remarkably high turnover frequency of ~100 s-1 in neutral phosphate buffer at about 675 mV overpotential with ~94% faradaic efficiency. Electrochemical analysis suggests the involvement of a ligand moiety in a proton-coupled-electron-transfer (PCET) step during the catalytic cycle of complex 1, which in turn provides a route for accumulation of high oxidizing equivalents at the reaction center.
- Kuilya, Hemrupa,Alam, Noohul,Sarma, Debajit,Choudhury, Diganta,Kalita, Apurba
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- AgNO3as Nitrogen Source for Cu-Catalyzed Cyclization of Oximes with Isocyanates: A Facile Route to N-2-Aryl-1,2,3-triazoles
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A versatile copper-catalyzed [3 + 1 + 1] annulation of oximes and isocyanates with AgNO3 is described. In this conversion, AgNO3 and isocyanates instead of conventional azide or diazonium reagents were used as the nitrogen source. This three-component transformation was achieved by cleaving N-O/C-H/C-N bonds and building CN/N-N bonds, which provides a strategy to prepare N-2-aryl-1,2,3-triazoles with a good substrate and functional compatibility.
- Liang, Jingwen,Rao, Yingqi,Zhu, Weidong,Wen, Tingting,Huang, Junjie,Chen, Zhichao,Chen, Lu,Li, Yibiao,Chen, Xiuwen,Zhu, Zhongzhi
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supporting information
p. 7028 - 7032
(2021/09/14)
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- 1-methyl-[1,5-a]-pyridinium imidazole-3-nitrile and chemical synthesis method thereof
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The invention relates to a chemical synthesis method of 1-methyl-[1,5-a]-pyridinium imidazole-3-nitrile. The method comprises the following steps: starting from 2-pyridineethanone as a raw material, carrying out oximation, reduction, substitution, cyclization, hydrolysis, amidation and dehydration to synthesize the 1-methyl-[1,5-a]-pyridinium-3-nitrile, and the method provides an efficient synthesis method for the synthesis of the compound.
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Paragraph 0027-0029; 0040-0042; 0053-0055
(2020/01/25)
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- Synthesis of Functionalized Vinylsilanes via Metal-Free Dehydrogenative Silylation of Enamides
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A novel method of metal-free dehydrogenative silylation of enamides has been developed. The desired functionalized vinylsilane products were obtained in moderate to good yield and with high stereoselectivities. This protocol displays good tolerance of various functionalities. Furthermore, the high chemoselectivity of this reaction enables us to introduce different unsaturated C-C moieties to the products. The ease of further derivatization of the products to other useful compounds also demonstrates the highly synthetic utility of the current methodology.
- Chang, Xi-Hao,Wang, Zi-Lu,Zhao, Meng,Yang, Chao,Li, Jie-Jun,Ma, Wei-Wei,Xu, Yun-He
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supporting information
p. 1326 - 1330
(2020/02/13)
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- Copper-Catalyzed Annulation of Oxime Acetates with α-Amino Acid Ester Derivatives: Synthesis of 3-Sulfonamido/Imino 4-Pyrrolin-2-ones
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A copper-catalyzed annulation of oxime acetates and α-amino acid ester derivatives for the easy preparation of 4-pyrrolin-2-ones bearing a 3-amino group has been developed. This process features the oxidation of amines with oxime esters as the internal oxidant to produce the active 1,3-dinucleophilic and 1,2-dielectrophilic species concurrently. The subsequent nucleophilic cyclization realizes the efficient construction of 4-pyrrolin-2-one derivatives.
- Miao, Chun-Bao,Zheng, An-Qi,Zhou, Li-Jin,Lyu, Xinyu,Yang, Hai-Tao
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supporting information
p. 3381 - 3385
(2020/04/21)
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- SO2F2-Activated Efficient Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
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A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO2F2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with good to nearly quantitative isolated yields (over 90 % yield in most cases) in a short time, including B(OH)2, COOH, NH2, and OH substituted substrates. A tentative mechanism was proposed involving formation and elimination of key intermediate, sulfonyl ester.
- Zhang, Guofu,Zhao, Yiyong,Xuan, Lidi,Ding, Chengrong
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supporting information
p. 4911 - 4915
(2019/07/31)
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- A novel octacyanido dicobalt(iii) building block for the construction of heterometallic compounds
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The first bimetallic octacyanido complex of CoIII, (PPh4)2[Co2(μ-2,5-dpp)(CN)8] (1), was synthesized and used as a metalloligand with [Mn(MAC)(H2O)2]Cl2·4H2
- Alexandru, Maria-Gabriela,Marino, Nadia,Visinescu, Diana,De Munno, Giovanni,Andruh, Marius,Bentama, Abdeslem,Lloret, Francesc,Julve, Miguel
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p. 6675 - 6682
(2019/05/10)
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- Site-Selective Esterifications of Polyol β-Hydroxyamides and Applications to Serine-Selective Glycopeptide Modifications
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The site-selective acylations of β-hydroxyamides in the presence of other hydroxyl groups are described. Central to the success of this modification is the metal-template-driven acylation using pyridine ketoxime esters as acylating reagents in combination
- Takemoto, Kohei,Nishikawa, Yasuhiro,Moriguchi, Shohei,Hori, Yuna,Kamezawa, Yuki,Matsui, Takami,Hara, Osamu
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supporting information
p. 7534 - 7538
(2019/10/08)
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- Copper-catalyzed synthesis of thiazol-2-yl ethers from oxime acetates and xanthates under redox-neutral conditions
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A novel copper-catalyzed annulation of oxime acetates and xanthates for the synthesis of thiazol-2-yl ethers with remarkable regioselectivity has been developed. Various oxime acetates, whether derived from aryl ketones or alkyl ketones, or natural product cores are suitable for this conversion. Unique dihydrothiazoles were also obtained when both reaction sites were methine. Mechanistic studies indicated that imino copper(iii) intermediates were involved. In addition, this protocol proceeded under redox-neutral conditions and did not require additives or ligands.
- Zhu, Zhongzhi,Tang, Xiaodong,Cen, Jinghe,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 3767 - 3770
(2018/04/17)
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- Catalytic Enantio- and Diastereoselective Mannich Addition of TosMIC to Ketimines
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Chiral amines bearing a stereocenter in the α position are ubiquitous compounds with many applications in the pharmaceutical and agrochemical sectors, as well as in catalysis. Catalytic asymmetric Mannich additions represent a valuable method to access such compounds in enantioenriched form. This work reports the first enantio- and diastereoselective addition of commercially available p-toluenesulfonylmethyl isocyanide (TosMIC) to ketimines, affording 2-imidazolines bearing two contiguous stereocenters, one of which is fully-substituted, with high yields and excellent stereocontrol. The reaction, catalyzed by silver oxide and a dihydroquinine-derived N,P-ligand, is broad in scope, operationally simple, and scalable. Derivatization of the products provides enantioenriched vicinal diamines, precursors to NHC ligands and sp3-rich heterocyclic scaffolds. Computations are used to understand catalysis and rationalize stereoselectivity.
- Franchino, Allegra,Chapman, Jack,Funes-Ardoiz, Ignacio,Paton, Robert S.,Dixon, Darren J.
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supporting information
p. 17660 - 17664
(2018/11/10)
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- Synthesis of enaminones via copper-catalyzed decarboxylative coupling reaction under redox-neutral conditions
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A novel copper-catalyzed C(sp3)-H oxidative functionalization of aromatic oxime acetates with α-oxocarboxylic acids was reported. This process involved N-O/C-C bond cleavages and C-C bond formations to furnish substituted enaminones under redox-neutral conditions. The oxime acetates served as both reactants and internal oxidants. Furthermore, this transformation also features good functional group tolerance and needs no ligands or additional bases.
- Zhu, Zhongzhi,Tang, Xiaodong,Li, Jianxiao,Li, Xianwei,Wu, Wanqing,Deng, Guohua,Jiang, Huanfeng
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supporting information
p. 3228 - 3231
(2017/03/20)
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- For the preparation of pyridine [...] and its derivatives (by machine translation)
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A process for preparing pyridine [...] and derivatives thereof, first of all by the compound 2 - acetyl pyridine with hydroxylamine hydrochloride, polar organic solvent under the conditions of reaction [...] intermediate product methyl 2 - pyridyl oxime, then not isolate this intermediate product methyl 2 - pyridyl oxime circumstances, the heating of the reactor mixture, adding alkali to the reaction mixture, and inject the acetylene gas, the acetylene gas and the intermediate product methyl 2 - pyridine [...] generates cyclization reaction, to obtain 2 - (2 '- pyridyl) pyrrole and N - vinyl - 2 - (2' - pyridyl) pyrrole. The present invention is under the normal pressure access C2 H2 , Equipment requirements on the pressure resistance, atom utilization ratio is 100%, the under normal pressure of the glass material instrument reaction apparatus, reaction conditions suitable for ordinary laboratory and plant operation, accord with the green synthetic production technology. By experimental verification, the invention is simple to synthesize, raw materials are easy, separation and purification easy, high yield. (by machine translation)
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Paragraph 0037; 0042; 0043; 0044; 0045
(2018/03/13)
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- Expedient one-pot synthesis of pyrroles from ketones, hydroxylamine, and 1,2-dichloroethane
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2- and 2,3-Substituted pyrroles are readily synthesized in a one-pot procedure from ketones, hydroxylamine hydrochloride, and 1,2-dichloroethane in the KOH/DMSO system (120 °C, 2-4 h), the yields of pyrroles ranging 11-85%. Aliphatic, cycloaliphatic, aromatic, and heteroaromatic ketones tolerate the reaction conditions.
- Trofimov, Boris A.,Mikhaleva, Al'Bina I.,Ivanov, Andrei V.,Shcherbakova, Viktoria S.,Ushakov, Igor A.
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p. 124 - 128
(2015/02/02)
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- Effective conversion of heteroaromatic ketones into primary amines via hydrogenation of intermediate ketoximes
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A process to access heteroaromatic primary amines from the corresponding heteroaromatic ketones has been developed. A broad range of previously reported methods to convert ketones to primary amines was examined on heterocyclic ketones without success, including Leuckart-Wallach conditions, borane reductions, and transition-metal-catalyzed hydrogenations. Unique among the catalysts examined, Raney cobalt produced the desired primary heterocyclic amine. Raney cobalt hydrogenation of structurally varied heterocyclic ketoximes was demonstrated to form primary amines in good selectivity under mild conditions, and the products are easily isolated in high yield. Additionally, this is the first report of a systematic evaluation of the capabilities of Raney cobalt as an oxime hydrogenation catalyst.
- Baucom, Kyle D.,Guram, Anil S.,Borths, Christopher J.
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supporting information
p. 201 - 204
(2015/03/03)
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- TETRAZOLINONE COMPOUND AND USE THEREOF
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The compound represented by formula (1): wherein R4 and R5 each represents a hydrogen atom, a halogen atom, or a C1-C3 alkyl group; R6 represents a C1-C4 alkyl group, a C3-C6 cycloalkyl group, or the like; R7, R8, and R9 each represents a hydrogen atom, a halogen atom, or the like; R10 represents a C1-C3 alkyl group, or the like; R13 represents a C1-C3 alkyl group, or the like; and Q represents a phenyl group, or the like; has an excellent control effect on pests.
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Paragraph 0844; 0922
(2015/11/16)
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- Synthesis of ketoximes via a solvent-assisted and robust mechanochemical pathway
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A versatile and robust mechanochemical route to ketone-oxime conversions has been established for a broad range of ketones via a simple mortar-pestle grinding method. The relative reactivity of aldehydes vs. ketones under these conditions has also been explored, along with an examination of the possible connection between reactivity and electronic substituent effects.
- Aakeroey, Christer B.,Sinha, Abhijeet S.
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p. 8168 - 8171
(2013/09/02)
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- Cobalt-based particles formed upon electrocatalytic hydrogen production by a cobalt pyridine oxime complex
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An open-coordination-sphere cobalt(III) oximato-based complex was designed as a putative catalyst for the hydrogen evolution reaction (HER). Electrochemical alteration in the presence of acid occurs, leading to the formation of cobalt-based particles that
- Ghachtouli, Sanae El,Guillot, Regis,Brisset, Francois,Aukauloo, Ally
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p. 2226 - 2230
(2014/01/06)
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- Solubility and transfer processes of some hydrazones in biologically relevant solvents
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Solubility values of 20 hydrazones in water, 1-octanol and hexane were determined by the isothermal saturation method. Thermophysical characteristics of fusion processes (melting points and fusion enthalpies) of the selected substances were measured by DS
- Perlovich, German L.,Kazachenko, Vladimir P.,Strakhova, Nadezda N.,Schaper, Klaus-J.,Raevsky, Oleg A.
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p. 2659 - 2667
(2013/09/24)
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- First iron-catalyzed synthesis of oximes from styrenes
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Aryl-substituted olefins react with t-butyl nitrite and sodium borohydride in the presence of iron(ii)phthalocyanine to give oximes in moderate to high yields.
- Prateeptongkum, Saisuree,Jovel, Irina,Jackstell, Ralf,Vogl, Nadine,Weckbecker, Christoph,Beller, Matthias
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supporting information; experimental part
p. 1990 - 1992
(2009/09/06)
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- COMPOUNDS FOR TREATING VIRAL INFECTIONS
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The invention relates to compounds, pharmaceutical compositions and methods useful for treating viral infection.
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Page/Page column 80; 86
(2008/12/08)
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- Intermolecular Cope-type hydroamination of alkenes and alkynes using hydroxylamines
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The development of the Cope-type hydroamination as a method for the metal- and acid-free intermolecular hydroamination of hydroxylamines with alkenes and alkynes is described. Aqueous hydroxylamine reacts efficiently with alkynes in a Markovnikov fashion to give oximes and with strained alkenes to give N-alkylhydroxylamines, while unstrained alkenes are more challenging. N-Alkylhydroxy-lamines also display similar reactivity with strained alkenes and give modest to good yields with vinylarenes. Electron-rich vinylarenes lead to branched products while electron-deficient vinylarenes give linear products. A beneficial additive effect is observed with sodium cyanoborohydride, the extent of which is dependent on the structure of the hydroxylamine. The reaction conditions are found to be compatible with common protecting groups, free OH and NH bonds, as well as bromoarenes. Both experimental and theoretical results suggest the proton transfer step of the N-oxide intermediate is of vital importance in the intermolecular reactions of alkenes. Details are disclosed concerning optimization, reaction scope, limitations, and theoretical analysis by DFT, which includes a detailed molecular orbital description for the concerted hydroamination process and an exhaustive set of calculated potential energy surfaces for the reactions of various alkenes, alkynes, and hydroxylamines.
- Moran, Joseph,Gorelsky, Serge I.,Dimitrijevic, Elena,Lebrun, Marie-Eve,Bedard, Anne-Catherine,Seguin, Catherine,Beauchemin, Andre M.
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supporting information; experimental part
p. 17893 - 17906
(2009/07/18)
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- Enantioselective Strecker reaction of phosphinoyl ketoimines catalyzed by in situ prepared chiral N,N′-dioxides
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The enantioselective Strecker reaction of N-diphenylphosphinoyl ketoimines has been achieved by use of in situ prepared chiral N,N′-dioxide catalyst from L-piperidinamide 3f and m-chloroperoxybenzoic acid (m-CPBA). Excellent yields (up to 99%) and high enantioselectivities (up to 92% ee) were obtained. In particular, in situ prepared catalyst with readily available chiral material made the procedure more convenient. Moreover, the L-piperidinamide 3f-derived N,N′-dioxide 9 could be recycled and reused at least five times without any loss of either catalytic activity or enantioselectivity.
- Huang, Jinglun,Liu, Xiaohua,Wen, Yuehong,Qin, Bo,Feng, Xiaoming
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p. 204 - 208
(2007/10/03)
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- Application of aryloximes as solid-phase ketone linkers.
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In both solution and the solid phase, a variety of ketone oxime anions have been treated with 4-substituted-2-fluorobenzonitriles to give the corresponding nucleophilic aromatic substitution aryloxime adducts. Under aqueous acidic conditions, these adducts underwent cyclization to give the corresponding ketones. Suzuki and amide coupling reactions were also successfully performed on two resin-bound oximes followed by subsequent cyclorelease to give ketone product in good yields and purities. [reaction--see text]
- Lepore, Salvatore D,Wiley, Michael R
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- Gamma-hydroxy-2-(fluoroalkylaminocarbonyl)-1-piperazinepentanamides and uses thereof
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γ-Hydroxy-2-(fluoroalkylaminocarbonyl)-1-piperazinepentanamide compounds are inhibitors of HIV protease and inhibitors of HIV replication. These compounds are useful in the prevention or treatment of infection by HV and the treatment of AIDS, either as compounds, pharmaceutically acceptable salts, pharmaceutical composition ingredients, whether or not in combination with other antivirals, immunomodulators, antibiotics or vaccines. Methods of treating AIDS and methods of preventing or treating infection by HIV are also described. These compounds are effective against HIV viral mutants which are resistant to HIV protease inhibitors currently used for treating AIDS and HIV infection.
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Page/Page column 191
(2010/01/31)
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- Diastereoselectivity of Organometallic Additions to Nitrones Bearing Sterogenic N-Substituents
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The diastereoselectivity of organometallic additions to nitrones bearing stereogenic α-arylethyl, β-methoxyalkyl, and β-(silyloxy)alkyl substituents on nitrogen has been investigated.High and complementary diastereoselectivity (90-94percent) was observed in the additions of Grignard reagents to nitrones (e.g. 22 and 23) bearing the potentially chelating β-methoxyalkyl group.However, the opposite selectivity resulted from the reaction of methylmagnesium bromide with the corresponding silyl ether (27).The relative stereochemistry of selected hydroxylamine adducts wasestablished by reduction of their phosphate and carbonate derivatives to known amines (37a,b and 39), by periodate cleavage of a β-hydroxy hydroxylamine (41b), and by various correlations (Scheme II).The high facial diastereoselectivity observed with the N-(β-methoxyalkyl)nitrones is explained by a simple chelation model (Scheme III).
- Chang, Zen-Yu,Coates, Robert M.
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p. 3464 - 3474
(2007/10/02)
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- Oxidative Cleavage of Ketoximes with Iodosobenzene Diacetate
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Hypervalent iodine oxidation of ketoximes (1) using iodosobenzene diacetate leads to cleavage of 1 with the formation of corresponding ketones (2) under neutral conditions in good yields.The scope and limitations of the reaction are discussed as well as the mechanism.
- Moriarty, Robert M.,Prakash, Om,Vavilikolanu, Pushra R.
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p. 1247 - 1254
(2007/10/02)
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