- Synthesis, characterization, crystal structure, and electrochemical properties of three copper(II) complexes with 3,5-dihalosalicylaldehyde Schiff bases derived from amantadine
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Complexes 1-3, C34H36X4CuN2O2 (X = Cl, Br, I), were synthesized with copper chloride dihydrate and three new Schiff base ligands derived from amantadine and 3,5-dihalosalicylaldehydes. They were characterized by IR, UV–VIS, elemental analysis, molar conductance, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that 1 and 2 crystallize in the triclinic system, Pī space group. Each asymmetric unit consists of one copper(II) ion, two corresponding deprotonated Schiff base ligands and one lattice dichloromethane molecule. 3 crystallizes in the monoclinic system, P21/n space group. Each asymmetric unit consists of one copper(II) ion and two deprotonated iodo- Schiff base ligands. The tetra-coordination of the central copper(II) ion in 1-3 is constructed by two nitrogen atoms and two oxygen atoms from the corresponding Schiff base ligands, forming a distorted tetrahedral geometry. Electrochemical properties of the complexes were determined by cyclic voltammetry. (Figure presented.).
- Jin, Xu-Dong,Wang, Han,Xie, Xiao-Kang,Sun, Jia-Yue,Liang, He-Ming
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- Synthesis, characterization, and antibacterial activity of two zinc(II) complexes with Schiff bases from halogenated salicylaldehyde and amantadine
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By a condensation reaction of halogenated salicylaldehyde and amantadine, two new Schiff base ligands (HL1 and HL2) were synthesized, respectively. A followed mixture of the ligands and zinc(II) chloride in the presence of NaOH in an alcoholic medium brought out two novel complexes (ZnL2 1) (I) and (ZnL2 2 (II). These two complexes were characterized by the means of melting point, elemental analysis, IR, UV-Vis, 1H NMR, molar conductance and single-crystal X-ray diffraction analysis. X-ray diffraction analysis reveals that I crystallizes in monoclinic system, P21/c space group, a = 9.7812(5), b = 25.6198(12), c = 27.7381(18) A, β = 105.881(4), F(000) = 1416, R1 = 0.0731, wR2 = 0.1147; II crystallizes in orthorhombic system, Pbca space group, a = 11.1717(10), b = 20.5888(15), c = 27.7381(18) A, F(000) = 2976, R1 = 0.1341, wR2 = 0.1410. Both in I and II, the central zinc(II) atom is four-coordinated via two nitrogen atoms and two oxygen atoms from the corresponding Schiff base ligands, forming a distorted tetrahedral geometry.
- Yang,Xu,Han,Liu,Jin,Wang,Liu,Hu
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- High-relaxivity magnetic resonance imaging (MRI) contrast agent based on supramolecular assembly between a gadolinium chelate, a modified dextran, and poly-β-cyclodextrin
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Nanosized contrast agents have great potential in magnetic resonance molecular imaging applications for clinical diagnosis. This study proposes new nanoparticles spontaneously formed under mild conditions and composed of a noncovalent adduct between a gadolinium complex, a polymer of β-cyclodextrin (pβCD: MW 1.5×106 g mol-1) and a dextran grafted with alkyl chains (MD). The formation of this supramolecular nanoassembly is based upon a "lock-and-key" recognition process in which the hydrophobic alkyl chains of MD and the adamantyl moieties of macrocyclic GdIII chelates are included in the cavities of pβCD. The large number of βCDs contained in the pβCD resulted in the formation of 200 nm diameter nanoparticles, each entrapping 1.8 × 105 molecules of a low-molecular-weight Gd complex. This system, which exhibits a great relaxivity enhancement (48.4 mw-1 s -1, at 20MHz and 37°C) compared to the GdIII chelate itself (5.2 mM-1 s-1), appears to be a promising strategy for the in vivo targeted delivery of GdIII complexes. The mechanisms of particle formation, conjugation strategies, and relaxometric characterizations in the field of contrast-enhanced magnetic resonance imaging are discussed.
- Battistini, Elisa,Gianolio, Eliana,Gref, Ruxandra,Couvreur, Patrick,Fuzerova, Silvia,Othman, Mohammad,Aime, Silvio,Badet, Bernard,Durand, Philippe
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- Comparative proton nuclear magnetic resonance studies of amantadine complexes formed in aqueous solutions with three major cyclodextrins
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Host-guest complexes of alpha-, beta-, and gamma-cyclodextrins (α-CD, β-CD, and γ-CD, respectively) with amantadine (1-aminoadamantane, AMA; an antiviral agent) were characterized in aqueous solutions using proton nuclear magnetic resonance (NMR) spectroscopy. Host-guest molecular interactions were manifested by changes in the chemical shifts of AMA protons. NMR Job's plots showed that the stoichiometry of all the studied complexes was 1:1. Two-dimensional T-ROESY experiments demonstrated that the complexes were formed by different degrees of incorporation of the adamantyl group of AMA into the CD cavity. The mode of AMA binding was proposed. The AMA molecule came into the α-CD cavity (the smallest size) or β-CD cavity (the intermediate size) through its wide entrance to become shallowly or deeply accommodated, respectively. In the complex of AMA with γ-CD (the largest cavity size), the adamantyl group was also quite deeply inserted into the CD cavity, but it arrived there through the narrow cavity entrance. It was found that the adamantyl group of AMA was best accommodated by the β-CD cavity. The binding constants Kaa of the studied complexes (in M-1), determined from DOSY NMR, were fairly high; their values in an ascending order were: α-CD (183) γ-CD (306) a?‰β-CD (5150). 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:274-282, 2014
- Lis-Cieplak, Agnieszka,Sitkowski, Jerzy,Kolodziejski, Waclaw
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- Characterization and solution properties of adamantane-containing quaternary-ammonium-salt-type amphiphilic ionic liquids
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Quaternary-ammonium-salt-type amphiphilic compounds ([CnAdA][X], where n represents the alkyl chain length (n = 1, 2, 4, 6, 8, or 10), X represents a counterion such as [BF4]?, [PF6]?, trifluoromethanesulfonate ([OTf]?), bis(fluorosulfonyl)amide ([FSA]?), or bis(trifluoromethanesulfonyl)amide ([NTf2]?), and Ad and A of AdA represent the adamantane structure and quaternary ammonium group, respectively) were synthesized. The melting points of the prepared compounds were determined by differential scanning calorimetry, and the derivatives with melting points lower than 100 °C were classified as ionic liquids for subsequent analyses. The amphiphilic ionic liquids, [CnAdA][NTf2] (n = 6 and 8), exhibited the lowest melting points (30.6 and 38.7 °C, respectively). Further, the [CnAdA][NTf2] series of amphiphilic ionic liquids exhibited significantly lower conductivities and higher viscosities than the corresponding ionic liquids without the adamantane moiety, [Cn][NTf2]. The viscosities of [CnAdA][NTf2] (n = 6 and 8) decreased significantly with increasing temperature, and showed a larger temperature dependence than that of the viscosities of the [Cn][X] series. The amphiphilic ionic liquids, [C8AdA][X] readily adsorbed at the air/water interface and oriented themselves but did not show the critical micelle concentration in the concentration range over which they could be dissolved in water. The amphiphilic ionic liquids and compounds tended to form ion pairs or premicelles, such as dimers or trimers, in aqueous solutions.
- Kawai, Risa,Yada, Shiho,Yoshimura, Tomokazu
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- The first N-alkyl-N′-polyfluorohetaryl sulfur diimide
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The first Alk-N=S=N-HetF sulfur diimide 6 (Alk = adamant-1-yl, HetF = 2,3,5,6-tetrafluoropyrid-4-yl) was prepared by trapping of the corresponding alkylthiazylamide [AlkNSN]-3 with pentafluoropyridine, followed by X-ray st
- Lork, Enno,Mews, Rüdiger,Shakirov, Makhmut M.,Watson, Paul G.,Zibarev, Andrey V.
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- Method for synthesizing and preparing amantadine dry product
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The invention discloses a synthesis and preparation method of an amantadine dry product, and relates to the technical field of amantadine preparation. The method mainly comprises adamantane, nitrogendioxide, ozone, hydrazine hydrate, ethanol, diethyl ether, ferric chloride hexahydrate and activated carbon, and comprises the following steps: synthesis of a nitro compound: adding adamantane and dichloromethane into a flask according to a ratio of 1g: 120ml, stirring at a certain temperature, introducing 30 equivalents of nitrogen dioxide under a certain condition, introducing ozone at a low speed, reacting for 30 minutes, adding a sodium bicarbonate solution, washing the organic phase to be neutral, performing drying, and carrying out rotary evaporation to obtain the product 1-nitro adamantane. The dry amantadine product is prepared through a hydrazine hydrate reduction method, corresponding purification is conducted, the whole reaction process is mild, the process steps are simple andconvenient, the requirement for equipment is simple, the conversion rate is very high, and the method has the value of industrial batch production popularization.
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Paragraph 0070-0071; 0078-0091; 0098-0115
(2021/03/13)
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- Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
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The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
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Paragraph 0015
(2021/04/17)
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- Preparation method of amantadine
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The invention discloses a preparation method of amantadine, which belongs to the technical field of organic chemical synthesis, and is characterized by comprising the following steps: taking a compound adamantane as an initial raw material, generating an intermediate 1-acetamido adamantane in the presence of acetonitrile, a polyion liquid PIL catalyst and sulfuric acid, and then hydrolyzing the intermediate into amantadine in a system of alcohol and alkali. The preparation method is environment-friendly, post-treatment is convenient, the use amount of sulfuric acid and acetonitrile is greatly reduced through the catalyst polyion liquid, and post-treatment is simple. The ionic liquid catalyst can be recycled, so that the cost is greatly saved, and the method is suitable for large-scale industrial production.
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Paragraph 0074-0092
(2021/06/13)
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- The benzyl can be selectively removed by visible light or near visible light. Method for protecting allyl and propargyl group
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The invention provides a method for selectively removing benzyl, allyl and propargyl protecting groups by visible light or near visible light, namely a substrate containing benzyl, allyl or propargyl protecting groups. The method has the advantages of simple operation, safe and clean visible light or near visible light as excitation conditions, cheap and easily available reagents, high reaction yield, high reaction chemistry and regional selectivity, and is suitable for selective removal of benzyl, allyl and propargyl protecting groups in various substrates.
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Paragraph 0022
(2021/10/16)
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- Cerium-Catalyzed C-H Functionalizations of Alkanes Utilizing Alcohols as Hydrogen Atom Transfer Agents
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Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.
- An, Qing,Chen, Yuegang,Liu, Weimin,Pan, Hui,Wang, Xin,Wang, Ziyu,Zhang, Kaining,Zuo, Zhiwei
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supporting information
p. 6216 - 6226
(2020/04/27)
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- Copper catalyzed reduction of azides with diboron under mild conditions
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We report herein the first Cu catalyzed reduction of azides with B2pin2 (pin = pinacolato) as the reductant under very mild conditions. A series of primary amines and amides were obtained in moderate to excellent yields with high chemoselectivity and good functional group tolerance. This reaction can be performed with a cheap copper salt, a simple NHC ligand and a diboron reagent.
- Chen, Yang,Deng, Shengqi,Gao, Yihua,Liu, Liwen,Liu, Yu,Lu, Da,Wang, Qianwen,Zhang, Xiao
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supporting information
(2020/02/27)
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- Adamantylation of N-aryl and N-arylalkyl acetamides in trifluoroacetic acid
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Alkylation of N-aryl and N-arylalkyl acetamides with hydroxy adamantane derivatives in trifluoroacetic acid was studied. The differentiating effect of trifluoroacetic acid on the regio-selectivity of adamantylation of o-alkyl-substituted acetanilides was established, leading to energetically more stable products of para-substitution with respect to the alkyl group (the content of para-alkyl isomers is 93–94percent). This enabled the synthesis of adamantylaminoarenes in 83–99percent yields and with 95–99percent purity.
- Kireeva, A. V.,Nakhod, M. A.,Novakov, I. A.,Orlinson, B. S.,Pichugin, A. M.,Porkhun, V. I.,Potaenkova, E. A.,Savelyev, E. N.,Vostrikova, O. V.,Zavyalov, D. V.
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p. 1096 - 1101
(2020/07/25)
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- Synthesis, crystallographic studies, molecular modeling and in vitro biological studies of silver(I) complexes with aminoadamantane ligands
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Silver(I) complexes with amantadine (atd) and memantine (mtn) were synthesized and characterized. Elemental, thermogravimetric and mass spectrometric analyses indicated a 1:2 metal/ligand ratio, with the molecular composition AgC20H34N2·NO3 for Ag–atd and AgC24H42N2·NO3·H2O for Ag–mtn. The crystal structures of the silver(I) complexes were determined by single crystal X-ray diffractometric studies and show the coordination of amantadine and memantine to the Ag(I) ion by the nitrogen atom of the NH2 group. The spectral analysis by infrared and 1H, 13C and {15N,1H} nuclear magnetic resonance (NMR) spectroscopies confirmed the coordination sites of the ligands to the silver ions. Computational studies revealed modes of vibration and bond lengths similar to those found experimentally. The in vitro antibacterial activity assays showed that amantadine is not active over the tested strains while memantine showed a low activity against Staphylococcus aureus and Pseudomonas aeruginosa. On the other hand, the complexes had a pronounced antibacterial activity over the same strains with minimum inhibitory concentration (MIC) values in the micromolar range. Biophysical assays based on fluorescence spectroscopy indicated that the silver(I) complexes interact weakly with bovine serum albumin, while agarose gel electrophoresis and competitive binding experiments revealed that the compounds interact with DNA by non-covalent interactions.
- dos Santos Pereira, Anna Karla,Nakahata, Douglas Hideki,Manzano, Carlos Marrote,de Alencar Simoni, Déborah,Pereira, Douglas Henrique,Lustri, Wilton Rogério,Formiga, André Luiz Barboza,Corbi, Pedro Paulo
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- Deacetylative Amination of Acetyl Arenes and Alkanes with C-C Bond Cleavage
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The Br?nsted acid-catalyzed synthesis of primary amines from acetyl arenes and alkanes with C-C bond cleavage is described. Although the conversion from an acetyl group to amine has traditionally required multiple steps, the method described herein, which uses an oxime reagent as an amino group source, achieves the transformation directly via domino transoximation/Beckmann rearrangement/Pinner reaction. The method was also applied to the synthesis of γ-aminobutyric acids, such as baclophen and rolipram.
- Hyodo, Kengo,Hasegawa, Genna,Maki, Hiroya,Uchida, Kingo
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supporting information
p. 2818 - 2822
(2019/04/25)
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- Synthetic method of amantadine
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The invention discloses a synthetic method of amantadine. The method comprises the following steps: adding 1-bromo adamantane and ammonium hydrogen carbonate into a high pressure kettle; uniformly mixing the 1-bromo adamantane and ammonium hydrogen; raising the temperature to the reaction temperature for amination; after the reaction, cooling the mixture to room temperature; then adding water to stir; separating out a solid; filtering the solid; washing a filter cake with water to obtain a yellow amantadine coarse product; and dissolving the coarse product in a recrystallization solvent for recrystallization to obtain a white solid that is the amantadine product. The reaction formula is as shown in a formula shown in the description. Compared with existing industrial common urea as an amination reagent, ammonium hydrogen carbonate is taken as the amination reagent, so that the synthetic method has the advantages of being low in reaction cost, small in three waste amount, convenient forpost-treatment, relatively high in yield and the like.
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Paragraph 0013-0023
(2019/04/13)
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- A Protocol for Direct Stereospecific Amination of Primary, Secondary, and Tertiary Alkylboronic Esters
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The direct, stereospecific amination of alkylboronic and borinic esters can be conducted by treatment of the organoboron compound with methoxyamine and potassium tert -butoxide. In addition to being stereospecific, this process also enables the direct amination of tertiary boronic esters in an efficient fashion.
- Edelstein, Emma K.,Grote, Andrea C.,Palkowitz, Maximilian D.,Morken, James P.
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supporting information
p. 1749 - 1752
(2018/06/26)
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- Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
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A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.
- Chakrabarti, Kaushik,Mishra, Anju,Panja, Dibyajyoti,Paul, Bhaskar,Kundu, Sabuj
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supporting information
p. 3339 - 3345
(2018/07/29)
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- Direct Primary Amination of Alkylmetals with NH-Oxaziridine
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A method for the primary electrophilic amination of primary, secondary, and tertiary organometallic substrates from a bench-stable NH-oxaziridine reagent is described. This facile and highly chemoselective transformation occurs at ambient temperature and without transition metal catalysts or purification by column chromatography to provide alkylamine products in a single step. Density functional theory (DFT) calculations revealed that, despite the basicity of alkylmetals, the direct NH-transfer pathway is favored over proton and O-transfer.
- Behnke, Nicole Erin,Kielawa, Russell,Kwon, Doo-Hyun,Ess, Daniel H.,Kürti, László
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supporting information
p. 8064 - 8068
(2019/01/04)
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- Electrochemical Hofmann rearrangement mediated by NaBr: Practical access to bioactive carbamates
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An electrochemical Hofmann rearrangement is reported. With the mediation of NaBr, highly corrosive and toxic halogens are avoided. Moreover, this efficient and green approach is well compatible with a broad range of amides, including several commercial medicine derivatives, and provides direct access to synthetically useful carbamates. The synthetic utility of this method is also demonstrated by the preparation of 15N labeling carbamate and gram-scale synthesis of Amantadine.
- Li, Lijun,Xue, Mengyu,Yan, Xin,Liu, Wenmin,Xu, Kun,Zhang, Sheng
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supporting information
p. 4615 - 4618
(2018/07/06)
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- Controllable amantadine molecular assembling body
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A controllable amantadine molecular assembling body. The invention relates to an amantadine molecular derivative which can be assembled with beta-cyclodextrin. In the invention, the amantadine molecular derivative is auto-assembled with the beta-cyclodextrin to generate an assembling body that can carry medicines or other molecules. The amantadine derivative, as a guest molecule of the amantadine molecular assembling body, has the molecular structure formula as follows, wherein R1 is a -CnHmO group, n being an integer of 1 to 16 and m being an integer of 2n+1. Through carriage of the medicines, the medicines are improved in stability and reduced in side effects, and are increased in utilization rate. Medicine delivery is carried out just through simple and controllable assemble and disassemble.
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Paragraph 0014; 0015
(2017/09/01)
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- High-Spin Iron Imido Complexes Competent for C-H Bond Amination
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Reduction of previously reported (ArL)FeCl with potassium graphite furnished a low-spin (S = 1/2) iron complex (ArL)Fe which features an intramolecular η6-arene interaction and can be utilized as an FeI synthon (ArL = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin). Treatment of (ArL)Fe with adamantyl azide or mesityl azide led to the formation of the high-spin (S = 5/2), three-coordinate imidos (ArL)Fe(NAd) and (ArL)Fe(NMes), respectively, as determined by EPR, zero-field 57Fe M?ssbauer, magnetometry, and single crystal X-ray diffraction. The high-spin iron imidos are reactive with a variety of substrates: (ArL)Fe(NAd) reacts with azide yielding a ferrous tetrazido (ArL)Fe(κ2-N4Ad2), undergoes intermolecular nitrene transfer to phosphine, abstracts H atoms from weak C-H bonds (1,4-cyclohexadiene, 2,4,6-tBu3C6H2OH) to afford ferrous amido product (ArL)Fe(NHAd), and can mediate intermolecular C-H amination of toluene [PhCH3/PhCD3 kH/kD: 15.5(3); PhCH2D kH/kD: 11(1)]. The C-H bond functionalization reactivity is rationalized from a two-step mechanism wherein each step occurs via maximal energy and orbital overlap between the imido fragment and the C-H bond containing substrate.
- Wilding, Matthew J. T.,Iovan, Diana A.,Betley, Theodore A.
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supporting information
p. 12043 - 12049
(2017/09/07)
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- METHOD FOR PRODUCING TRIMETHYLADAMANTYLAMMONIUM HYDROXIDE
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PROBLEM TO BE SOLVED: To solve a problem in the conventional method for synthesizing trimethyladamantylammonium hydroxide that an equipment cost and a production cost become high. SOLUTION: The problem can be solved by a production method comprising: reacting N,N-dimethyladamantylamine with a quarternarizing agent in a nonpolar solvent having a solubility parameter of less than 10 to obtain N,N,N-trimethyladamantylammonium salt; and, at that time, adding a protic polar solvent to the reaction system before the reaction is started, while the reaction is proceeding, or after the reaction is complete, to selectively obtain N,N,N-trimethyladamantylammonium hydroxide from the reaction system. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0051
(2017/02/09)
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- Process for preparation of amantadine free amine amantadine by use of amantadine hydrochloride
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The present invention discloses a process for preparation of amantadine free amine amantadine by use of amantadine hydrochloride, and the process is characterized as follows: in a reaction vessel, water and the amantadine hydrochloride are added in order, the mass ratio of water to amantadine hydrochloride is 1:4, and after even stirring, the pH value is adjusted to 10 with sodium hydroxide or sodium carbonate; and after solid precipitation, the stirring is continued for 0.5h, and a pure free amine amantadine product can be obtained by filtering, washing with water, and drying.
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Paragraph 0063
(2017/02/09)
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- METHOD FOR PRODUCING TRIMETHYLADAMANTYLAMMONIUM HYDROXIDE
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PROBLEM TO BE SOLVED: To solve a problem in the conventional method for synthesizing trimethyladamantylammonium hydroxide that an equipment cost and a production cost become high. SOLUTION: The problem can be solved by a production method comprising: reacting N,N-dimethyladamantylamine with dimethyl sulfate in an aprotic polar solvent to obtain N,N,N-trimethyladamantylammonium methylsulfate; and subsequently obtaining N,N,N-trimethyladamantylammonium hydroxide from the methylsulfate. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0044
(2017/02/23)
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- A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines
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A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.
- Ohtsuka, Naoya,Okuno, Moriaki,Hoshino, Yujiro,Honda, Kiyoshi
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p. 9046 - 9054
(2016/10/05)
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- One-pot synthesis of primary amines from carboxylic acids through rearrangement of in situ generated hydroxamic acid derivatives
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A one-pot synthesis of primary amines from carboxylic acids through a Lossen rearrangement of hydroxamic acid derivatives, which were in situ generated by the reaction of carboxylic acids with O-trimethylsilylhydroxylamine (NH2OTMS) and carbonyl diimidazole (CDI, 1.5 equiv) in dimethyl sulfoxide at room temperature, has been achieved. This one-pot method could be applied to various carboxylic acids such as aromatic, heteroaromatic, aliphatic, and optically active substrates.
- Hoshino, Yujiro,Ohtsuka, Naoya,Okada, Takuya,Honda, Kiyoshi
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p. 5304 - 5307
(2016/11/16)
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- Photochemical Cleavage of Benzylic C-N Bond to Release Amines
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The 3-(diethylamino)benzyl (DEABn) group has been studied for releasing primary, secondary, and tertiary amines by direct photochemical breaking of the benzylic C-N bond. While photochemical release of primary and secondary amines provides high yields in
- Wang, Pengfei,Devalankar, Dattatray A.,Lu, Wenya
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p. 6195 - 6200
(2016/08/16)
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- PRODUCTION METHOD FOR COMPOUND COMPRISING AMINO GROUP AND/OR HYDROXYL GROUP
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Disclosed is a method for producing a compound having an amino group and/or a hydroxyl group from a substrate compound having an atomic group containing CO or CS by eliminating said atomic group. The substrate compound having an atomic group containing CO or CS (for example, an amide, a carbamate, or the like) is allowed to react with a compound expressed by formula (I) below, at a temperature of 120°C or lower, preferably in the presence of an ammonium salt, to eliminate said atomic group containing CO or CS. In formula (I) A may not be present, and in a case where A is present, A represents an alkyl group having 1 to 6 carbon atoms. ????????H2N-A-NH2?????(I)
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Paragraph 0040; 0060
(2015/01/18)
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- Construction of giant branched nanotubes from cyclodextrin-based supramolecular amphiphiles
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Giant branched nanotubes were successfully constructed using cyclodextrin-based amphiphiles. The 'backbone' of the nanotubes could branch out into two or multiple branches, from which thinner branches grow out.
- Fan, Xiaotong,Wang, Liang,Luo, Quan,Zhao, Linlu,Xu, Jiayun,Liu, Junqiu,Zheng, Qingchuan
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supporting information
p. 6512 - 6514
(2015/04/14)
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- One-Pot Amination of Cage Hydrocarbons
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A one-pot procedure has been proposed for the synthesis of amines directly from cage hydrocarbons. A number of cage amines have been synthesized by treatment of adamantane, its homologs, and structurally related cage hydrocarbons with nitric acid in acetic acid and subsequent addition of urea and heating.
- Leonova,Skomorokhov,Moiseev,Klimochkin
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p. 1703 - 1709
(2016/02/03)
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- Encapsulation of Pt(IV) prodrugs within a Pt(II) cage for drug delivery
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This report presents a novel strategy that facilitates delivery of multiple, specific payloads of Pt(IV) prodrugs using a well-defined supramolecular system. This delivery system comprises a hexanuclear Pt(II) cage that can host four Pt(IV) prodrug guest molecules. Relying on host-guest interactions between adamantyl units tethered to the Pt(IV) molecules and the cage, four prodrugs could be encapsulated within one cage. This host-guest complex, exhibiting a diameter of about 3 nm, has been characterized by detailed NMR spectroscopic measurements. Owing to the high positive charge, this nanostructure exhibits high cellular uptake. Upon entering cells and reacting with biological reductants such as ascorbic acid, the host-guest complex releases cisplatin, which leads to cell cycle arrest and apoptosis. The fully assembled complex displays cytotoxicity comparable to that of cisplatin against a panel of human cancer cell lines, whereas the cage or the Pt(IV) guest alone exhibit lower cytotoxicity. These findings indicate the potential of utilising well-defined supramolecular constructs for the delivery of prodrug molecules.
- Zheng, Yao-Rong,Suntharalingam, Kogularamanan,Johnstone, Timothy C.,Lippard, Stephen J.
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p. 1189 - 1193
(2015/02/19)
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- Self-propagated Lossen rearrangement induced by a catalytic amount of activating agents under mild conditions
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A mild self-propagated Lossen rearrangement induced by a catalytic amount of activating agents in medium to high polar organic solvents has been developed. The rearrangement of aromatic and aliphatic hydroxamic acids in the presence of a catalytic amount (0.01 equiv) of acetic anhydride and an equimolar amount of base such as well-dried potassium carbonate afforded the corresponding amines in high yields. This alternative to traditional Lossen rearrangement provides a simple and mild method for the synthesis of amines from free hydroxamic acids.
- Hoshino, Yujiro,Shimbo, Yuki,Ohtsuka, Naoya,Honda, Kiyoshi
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supporting information
p. 710 - 712
(2015/01/30)
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- Terminal imido rhodium complexes
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Compounds of the late transition metals with M≡X multiple bonds (X=CR2, NR, O) represent a synthetic challenge, partly overcome by preparative chemists, but with noticeable gaps in the second- and third-row elements. For example, there are no isolated examples of terminal imido rhodium complexes known to date. Described herein is the isolation, characterization, and some preliminary reactivity studies of the first rhodium complexes [Rh(PhBP3)(NR)] (PhBP3=PhB{CH2PPh 2}3) with a multiple and terminal Rh≡N bond. These imido compounds result from reactions of organic azides with the corresponding rhodium(I) complex having a labile ligand, and display a pseudo-tetrahedral core geometry with an almost linear Rh-N-C arrangement [177.5(2)°]] and a short Rh-N bond [1.780(2) A]. We also show that the Rh≡N bond undergoes protonation at the nitrogen atom or addition of H2, and also engages in nitrene-group transfer and cycloaddition reactions. A missing link: Terminal imido rhodium complexes with a Rh≡N multiple bond have been prepared, thus providing compounds which have been elusive to synthesis. Preliminary studies indicate rhodium imides are somewhat ambiphilic and can therefore undergo protonation at the nitrogen atom, as well as hydrogenation at the Rh≡N bond. These systems also engage in nitrene-group transfer and cycloaddition reactions.
- Geer, Ana M.,Tejel, Cristina,Lopez, Jose A.,Ciriano, Miguel A.
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p. 5614 - 5618
(2014/06/10)
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- New one-step synthesis of isonitriles
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A new one-step synthesis of isonitriles is described. The starting materials are a primary amine, chloroform, sodium hydride, and the phase-transfer catalyst 15-crown-5 ether, and the solvent is benzene. Five compounds are used to illustrate the features of the new synthesis: 1-adamantyl isocyanide (2a), 2-adamantyl isocyanide (2b), cis-1,8- diisocyano-p-menthane (2c), 2,4,6-trimethylphenyl isocyanide (2d), and trityl isocyanide (2e). The present synthesis is superior to the existing published syntheses because of its yields are good, the by-products are innocuous (H2 gas and NaCl), and its workup is simple. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Bardsley, Kathryn,Hagigeorgiou, Michael,Lengyel, Istvan,Cesare, Victor
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supporting information
p. 1727 - 1733
(2013/05/09)
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- Targeted polysaccharide nanoparticle for adamplatin prodrug delivery
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A series of conjugated hyaluronic acid particles (HAP), composed of a hydrophobic anticancer drug core and hydrophilic cyclodextrin/hyaluronic acid shell, were prepared through self-assembling and characterized by 1H NMR titration, electron microscopy, zeta potential, and dynamic light-scattering experiments. The nanometer-sized HAP thus prepared was biocompatible and biodegradable and was well-recognized by the hyaluronic acid receptors overexpressed on the surface of cancer cells, which enabled us to exploit HAP as an efficient targeted delivery system for anticancer drugs. Indeed, HAP exhibited anticancer activities comparable to the commercial anticancer drug cisplatin but with lower side effects both in vitro and in vivo.
- Yang, Yang,Zhang, Ying-Ming,Chen, Yong,Chen, Jia-Tong,Liu, Yu
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p. 9725 - 9736
(2014/01/06)
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- Selective cleavage of 3,5-bis-(trifluoromethyl)benzylcarbamate by SmI 2-Et3N-H2O
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A novel electron poor protection group for amines has been developed. It undergoes rapid cleavage by SmI2-Et3N-H2O and its orthogonality towards the regular benzyl carbamate group (CBz) under reductive or transfer hydrogenolytic conditions is reported.
- Ankner, Tobias,Said Stalsmeden, Anna,Hilmersson, Goeran
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p. 6867 - 6869
(2013/07/26)
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- Microwave-assisted deacylation of unactivated amides using ammonium-salt-accelerated transamidation
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Easy does it! The chemoselective oxidative ?-C(sp3)H alkylation/cyclization reaction of N-benzyl carbamates using simple mono-, di-, and trisubstituted olefins provides functionalized N-heterocycles such as oxazinones (see picture). A TEMPO oxoammonium salt serves as the oxidant, making it possible to carry out the reaction at low temperatures. Neither a metal catalyst nor preactivation in the ?-position to the nitrogen group are needed.
- Shimizu, Yuhei,Morimoto, Hiroyuki,Zhang, Ming,Ohshima, Takashi
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supporting information; experimental part
p. 8564 - 8567
(2012/09/11)
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- PROCESS FOR PREPARING A PRIMARY AMINE WITH A TERTIARY ALPHA CARBON ATOM BY REACTING A TERTIARY ALCOHOL WITH AMMONIA
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A process for preparing a primary amine with a tertiary alpha-carbon atom by reacting a tertiary alcohol with ammonia in the presence of a heterogeneous catalyst, by performing the reaction in the presence of a non-microporous, non-zeolitic aluminosilicate as a catalyst, where the aluminosilicate has a molar Al/Si ratio in the range from 0.1 to 30.
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Page/Page column 5
(2011/02/15)
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- Reduction of alkyl and aryl azides with sodium thiophosphate in aqueous solutions
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A simple aqueous method for the conversion of alkyl and aryl azides into the corresponding amines using trisodium thiophosphate is presented. Thiophosphate is converted into phosphate during these formal reduction processes.
- Norcliffe, Jennifer L.,Conway, Louis P.,Hodgson, David R.W.
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supporting information; experimental part
p. 2730 - 2732
(2011/06/19)
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- Catalytic C-H bond amination from high-spin iron imido complexes
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Dipyrromethene ligand scaffolds were synthesized bearing large aryl (2,4,6-Ph3C6H2, abbreviated Ar) or alkyl ( tBu, adamantyl) flanking groups to afford three new disubstituted ligands (RL, 1,9-R2-5-mesityldipyrromethene, R = aryl, alkyl). While high-spin (S = 2), four-coordinate iron complexes of the type (RL)FeCl(solv) were obtained with the alkyl-substituted ligand varieties (for R = tBu, Ad and solv = THF, OEt2), use of the sterically encumbered aryl-substituted ligand precluded binding of solvent and cleanly afforded a high-spin (S = 2), three-coordinate complex of the type (ArL)FeCl. Reaction of (AdL)FeCl(OEt2) with alkyl azides resulted in the catalytic amination of C-H bonds or olefin aziridination at room temperature. Using a 5% catalyst loading, 12 turnovers were obtained for the amination of toluene as a substrate, while greater than 85% of alkyl azide was converted to the corresponding aziridine employing styrene as a substrate. A primary kinetic isotope effect of 12.8(5) was obtained for the reaction of (AdL)FeCl(OEt2) with adamantyl azide in an equimolar toluene/toluene-d8 mixture, consistent with the amination proceeding through a hydrogen atom abstraction, radical rebound type mechanism. Reaction of p-tBuC6H4N3 with (ArL)FeCl permitted isolation of a high-spin (S = 2) iron complex featuring a terminal imido ligand, (ArL)FeCl(N(p- tBuC6H4)), as determined by 1H NMR, X-ray crystallography, and 57Fe Moessbauer spectroscopy. The measured Fe-Nimide bond distance (1.768(2) A) is the longest reported for Fe(imido) complexes in any geometry or spin state, and the disruption of the bond metrics within the imido aryl substituent suggests delocalization of a radical throughout the aryl ring. Zero-field 57Fe Moessbauer parameters obtained for (ArL)FeCl(N(p- tBuC6H4)) suggest a FeIII formulation and are nearly identical with those observed for a structurally similar, high-spin FeIII complex bearing the same dipyrromethene framework. Theoretical analyses of (ArL)FeCl(N(p-tBuC 6H4)) suggest a formulation for this reactive species to be a high-spin FeIII center antiferromagnetically coupled to an imido-based radical (J = -673 cm-1). The terminal imido complex was effective for delivering the nitrene moiety to both C-H bond substrates (42% yield) as well as styrene (76% yield). Furthermore, a primary kinetic isotope effect of 24(3) was obtained for the reaction of (ArL)FeCl(N(p- tBuC6H4)) with an equimolar toluene/toluene-d8 mixture, consistent with the values obtained in the catalytic reaction. This commonality suggests the isolated high-spin Fe III imido radical is a viable intermediate in the catalytic reaction pathway. Given the breadth of iron imido complexes spanning several oxidation states (FeII-FeV) and several spin states (S = 0 → 3/2), we propose the unusual electronic structure of the described high-spin iron imido complexes contributes to the observed catalytic reactivity.
- King, Evan R.,Hennessy, Elisabeth T.,Betley, Theodore A.
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supporting information; experimental part
p. 4917 - 4923
(2011/05/16)
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- Giant nanotubes loaded with artificial peroxidase centers: Self-assembly of supramolecular amphiphiles as a tool to functionalize nanotubes
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(Figure Presented) Test tubes: Large-diameter nanotubes have been obtained by direct self-assembly of cyclodextrin-based host-guest superamphiphiles (see picture). By manipulating the surface of the nanotubes with a combination of a molecularimprinting strategy and self-assembly, the main catalytic components of glutathione peroxidase were fabricated on the nanotube scaffold.
- Tang, Yong,Zhou, Lipeng,Li, Jiaxi,Luo, Quan,Huang, Xin,Wu, Ping,Wang, Yongguo,Xu, Jiayun,Shen, Jiacong,Liu, Junqiu
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supporting information; experimental part
p. 3920 - 3924
(2010/09/05)
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- Catalytic C - H amination with unactivated amines through copper(II) amides
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En route to catalysis: Two equivalents of the three-coordinate copper(II) amide [(Cl2NN)Cu]-NHAd participate in stoichiometric C - H amination by a H-atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert-butoxide intermediate to allow for the unprecedented catalytic amination of sp3-C - H bonds with unactivated alkylamines. This method greatly expands the range of amines for catalytic C - H amination since most protocols require N-based electron-withdrawing groups.
- Wiese, Stefan,Badiei, Yosra M.,Gephart, Raymond T.,Mossin, Susanne,Varonka, Matthew S.,Melzer, Marie M.,Meyer, Karsten,Cundari, Thomas R.,Warren, Timothy H.
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supporting information; experimental part
p. 8850 - 8855
(2011/02/24)
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- PROCESS FOR THE PREPARATION OF ADAMANTANAMINES
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The invention relates to a process for preparing certain adamantanamines, of formula (IV) wherein R, R' are each methyl and X is halogen, to intermediates used in the process, and to processes for preparing such intermediates.
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Page/Page column 15
(2010/11/28)
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- Methods and compositions for treating amyloid-related diseases
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Methods, compounds, pharmaceutical compositions and kits are described for treating or preventing amyloid-related disease.
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Page/Page column 142; 145-146
(2010/11/24)
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- Histone deacetylase inhibitors and methods of use thereof
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One aspect of the invention relates to HDAC inhibitors. Methods of sensitizing a cancer cell to the cytotoxic effects of radiotherapy are also provided. The invention also provides methods for treating cancer and methods for treating neurological diseases. Additionally, the invention further provides pharmaceutical compositions comprising an HDAC inhibitor of the invention, and kits comprising a container containing an HDAC inhibitor of the invention.
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- Non-metallocene compounds, method for the production thereof and use of the same for the polymerisation of olefins
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The invention relates to a method for producing special transition metal compounds, to novel transition metal compounds and to the use of the same for the polymerisation of olefins.
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- NMDA receptor antagonists and their use in inhibiting abnormal hyperphosphorylation of microtubule associated protein tau
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Aminocyclohexane and aminoalkylcyclohexane compounds, which are systemic-ally-active as NMDA receptor antagonists, are effective in inhibiting abnormal hyperphosphorylation of microtubule associated protein tau, method of treating disorders resulting from or associated with abnormal hyperphosphorylation of microtubule associated protein tau, and pharmaceutical compositions comprising the same.
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- A direct link between the Passerini reaction and α-lactams
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α-Lactams (aziridinones) can function to replace two of the three reactants, the oxo-compound and the isonitrile, in the Passerini reaction. Four α-lactams (5a-d) were reacted with mono- and dicarboxylic acids of positive pKa values to give 2-acyloxycarboxamides (4) and bis-2-acyloxycarboxamide products 12 and 13, respectively. The same compounds were also prepared via the Passerini reaction. Acids with a negative pK a decarbonylate α-lactams to give immonium salts. The main path of the reaction depends on the pKa of the acid component, the reactivity of the α-lactam, and the reaction conditions.
- Lengyel, István,Cesare, Victor,Taldone, Tony
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p. 1107 - 1124
(2007/10/03)
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- Synthesis of 13-acylamino-huprines: Different behavior of diastereomeric 13-methanesulfonamido-huprines on PPA-mediated hydrolysis
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Two diastereomeric pairs of rationally designed huprines additionally substituted at position 13 with a formamido or an acetamido group have been synthesized as potential high affinity acetylcholinesterase inhibitors. The synthetic sequence involves hydrolysis of two diastereomeric 13-methanesulfonamido-huprines, followed by acylation of the resulting diastereomeric amines. In the hydrolysis reaction, carried out with PPA under harsh conditions, significant amounts of cyclized or rearranged by-products were also formed, depending on the stereochemistry of the starting compound.
- Camps, Pelayo,Gómez, Elena,Mu?oz-Torrero, Diego
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p. 5423 - 5431
(2007/10/03)
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