- Chemoselective and Tandem Reduction of Arenes Using a Metal–Organic Framework-Supported Single-Site Cobalt Catalyst
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The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal–organic framework (DUT-5 MOF) for chemoselective hydrogenation of arenes. The DUT-5 node-supported cobalt(II) hydride (DUT-5-CoH) is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields. DUT-5-CoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation–hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes. In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory (DFT) studies suggest the insertion of a trisubstituted alkene intermediate into the Co–H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base–metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Begum, Wahida,Chauhan, Manav,Newar, Rajashree,Rawat, Manhar Singh,Manna, Kuntal
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supporting information
p. 1031 - 1040
(2022/01/19)
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- Synthesis method of 4-substituent cyclohexanone
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The invention discloses a synthesis method of 4-substituent cyclohexanone, which comprises the following steps: by taking a 4-substituent phenol compound as a raw material, carrying out catalytic hydrogenation on 4-substituent phenol to obtain 4-substituent cyclohexanol, and then oxidizing the 4-substituent cyclohexanol by taking oxygen-containing gas as an oxidant to prepare the 4-substituent cyclohexanone. The oxygen-containing gas is used as the oxidizing agent, the oxygen-containing gas is low in price, good in reaction selectivity, high in oxidation reaction yield and environment-friendly, and is an ideal clean oxidizing agent; in addition, the whole synthesis process is simple, mild in condition, simple in post-treatment, green, environment-friendly and suitable for large-scale industrial production.
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Paragraph 0034-0035
(2021/05/12)
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- Synthesis method of 4-substituent cyclohexanone liquid crystal intermediate
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The invention discloses a synthesis method of a 4-substituent cyclohexanone liquid crystal intermediate, which comprises the following step: carrying out oxidation catalytic reaction on 4-substituent cyclohexanol under the action of trichloroisocyanide urea to obtain the 4-substituent cyclohexanone liquid crystal intermediate. The method is high in reaction selectivity, high in yield, environment-friendly, simple in post-treatment and suitable for industrial production.
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Paragraph 0048-0049
(2021/05/19)
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- Highly Efficient Cleavage of Ether Bonds in Lignin Models by Transfer Hydrogenolysis over Dual-Functional Ruthenium/Montmorillonite
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Cleavage of ether bonds is a crucial but challenging step for lignin valorization. To efficiently realize this transformation, the development of robust catalysts or catalytic systems is required. In this study, montmorillonite (MMT)-supported Ru (denoted as Ru/MMT) is fabricated as a dual-functional heterogeneous catalyst to cleave various types of ether bonds through transfer hydrogenolysis without using any additional acids or bases. The prepared Ru/MMT material is found to efficiently catalyze the cleavage of various lignin models and lignin-derived phenols; cyclohexanes (fuels) and cyclohexanols (key intermediates) are the main products. The synergistic effect between electron-enriched Ru and the acidic sites on MMT contributes to the excellent performance of Ru/MMT. Systematic studies reveal that the reaction proceeds through two possible reaction pathways, including the direct cleavage of ether bonds and the formation of intermediates with one hydrogenated benzene ring, for all examined types of ether bonds, namely, 4-O-5, α-O-4, and β-O-4.
- Xue, Zhimin,Yu, Haitao,He, Jing,Zhang, Yibin,Lan, Xue,Liu, Rundong,Zhang, Luyao,Mu, Tiancheng
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p. 4579 - 4586
(2020/06/21)
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- Synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid
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The invention provides a synthetic method of cis-4-methoxycyclohexyl-1-carbamic acid. The synthetic method includes the steps of catalytic hydrogenation, oxidative reaction, replacement reaction and hydrolytic reaction; the hydrolytic reaction is carried out in a microreactor, with a Jones reagent acting as an oxidant; barium hydroxide octahydrate is used as an alkaline material in the hydrolyticreaction. The synthetic method has few steps and shorter reaction time; the salt content in reaction wastewater is low, the content of heavy metals is low, and discharged waste is little; the finishedproduct has the content of 98% and above; the total reaction yield is 45% and above.
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Paragraph 0019
(2019/06/27)
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- Elucidating the reactivity of methoxyphenol positional isomers towards hydrogen-transfer reactions by ATR-IR spectroscopy of the liquid-solid interface of RANEY Ni
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In the valorisation of lignin, the application of catalytic hydrogen transfer reactions (e.g. in catalytic upstream biorefining or lignin-first biorefining) has brought a renewed interest in the fundamental understanding of hydrogen-transfer processes in the defunctionalisation of lignin-derived phenolics. In this report, we address fundamental questions underlining the distinct reactivity patterns of positional isomers of guaiacol towards H-transfer reactions in the presence of RANEY Ni and 2-PrOH (solvent and H-donor). We studied the relationship between reactivity patterns of 2-, 3- and 4-methoxyphenols and their interactions at the liquid-solid interface of RANEY Ni as probed by attenuated total reflection infrared (ATR-IR) spectroscopy. Regarding the reactivity patterns, 2-methoxyphenol or guaiacol is predominantly converted into cyclohexanol through a sequence of reactions including demethoxylation of 2-methoxyphenol to phenol followed by hydrogenation of phenol to cyclohexanol. By contrast, for the conversion of the two non-lignin related positional isomers, the corresponding 3- and 4-methoxycyclohexanols are the major reaction products. The ATR-IR spectra of the liquid-solid interface of RANEY Ni revealed that the adsorbed 2-methoxyphenol assumes a parallel orientation to the catalyst surface, which allows a strong interaction between the methoxy C-O bond and the surface. Conversely, the adsorption of 3- or 4-methoxyphenol leads to a tilted surface complex in which the methoxy C-O bond establishes no interaction with the catalyst. These observations are also corroborated by a smaller activation entropy found for the conversion of 2-methoxyphenol relative to those of the other two positional isomers.
- De Castro, Ilton Barros Daltro,Gra?a, Inês,Rodríguez-García, Laura,Kennema, Marco,Rinaldi, Roberto,Meemken, Fabian
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p. 3107 - 3114
(2018/06/29)
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- Preparation method of p-methoxycyclohexanone
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The invention discloses a preparation method of p-methoxycyclohexanone. The preparation method comprises the steps that p-methoxyphenol is subjected to a hydrogenation reduction reaction under existence of a catalyst and a solvent to prepare p-methoxycyclohexanol; and p-methoxycyclohexanol is subjected to an oxidation reaction under existence of an oxidizing agent and a solvent to prepare p-methoxycyclohexanone. The target product can be obtained only by conducting reduction and oxidation reactions on p-methoxyphenol, p-methoxycyclohexanol obtained through the reduction reaction does not needto be purified and is directly used in the oxidation reaction, the technology is simple and easy to operate, the raw materials are wide in source, the production cost is low, and the preparation method is suitable for industrialized production.
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Paragraph 0022; 0024; 0025; 0028; 0031; 0034
(2018/09/11)
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- Oxidation of Secondary Methyl Ethers to Ketones
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We present a mild way of converting secondary methyl ethers into ketones using calcium hypochlorite in aqueous acetonitrile with acetic acid as activator. The reaction is compatible with various oxygen- and nitrogen-containing functional groups and afforded the corresponding ketones in up to 98% yield. The use of this methodology could expand the application of the methyl group as a useful protecting group.
- Gilissen, Pieter J.,Blanco-Ania, Daniel,Rutjes, Floris P. J. T.
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supporting information
p. 6671 - 6679
(2017/07/15)
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- PYRAZOLOPYRIMIDINE DERIVATIVES AS BTK INHIBITORS FOR THE TREATMENT OF CANCER
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This invention relates to novel compounds. The compounds of the invention are tyrosine kinase inhibitors. Specifically, the compounds of the invention are useful as inhibitors of Bruton's tyrosine kinase (BTK). The invention also contemplates the use of t
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- Robustly supported rhodium nanoclusters: Synthesis and application in selective hydrogenation of lignin derived phenolic compounds
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The stabilization of small rhodium nanoclusters (NCs) in a polymer derived silicon carbonitride (SiCN) matrix has been reported to generate highly robust and active solid catalysts for the selective hydrogenation of phenolic compounds. An aminopyridinato Rh complex was used to modify a preceramic polymer (HTT 1800) followed by its pyrolysis at 1100 °C to afford small Rh NCs nicely dispersed over dense SiCN ceramic. For the synthesis of porous catalysts containing Rh NCs, microphase separation (followed by pyrolysis) of a diblock copolymer of HTT 1800 with hydroxy-polyethylene (PE-OH) was used. Both catalysts exhibit high activity in the hydrogenation of substituted phenols at room temperature and under low hydrogen pressure. The catalysts remained highly active and selective for six consecutive catalytic runs.
- Fehn, Sonja,Zaheer, Muhammad,Denner, Christine E.,Friedrich, Martin,Kempe, Rhett
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p. 9252 - 9256
(2016/11/11)
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- Upgrading of aromatic compounds in bio-oil over ultrathin graphene encapsulated Ru nanoparticles
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Fast pyrolysis of biomass for bio-oil production is a direct route to renewable liquid fuels, but raw bio-oil must be upgraded in order to remove easily polymerized compounds (such as phenols and furfurals). Herein, a synthesis strategy for graphene encapsulated Ru nanoparticles (NPs) on carbon sheets (denoted as Ru@G-CS) and their excellent performance for the upgrading of raw bio-oil were reported. Ru@G-CS composites were prepared via the direct pyrolysis of mixed glucose, melamine and RuCl3 at varied temperatures (500-800 °C). Characterization indicated that very fine Ru NPs (2.5 ± 1.0 nm) that were encapsulated within 1-2 layered N-doped graphene were fabricated on N-doped carbon sheets (CS) in Ru@G-CS-700 (pyrolysis at 700 °C). And the Ru@G-CS-700 composite was highly active and stable for hydrogenation of unstable components in bio-oil (31 samples including phenols, furfurals and aromatics) even in aqueous media under mild conditions. This work provides a new protocol to the utilization of biomass, especially for the upgrading of bio-oil.
- Shi, Juanjuan,Zhao, Mengsi,Wang, Yingyu,Fu, Jie,Lu, Xiuyang,Hou, Zhaoyin
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supporting information
p. 5842 - 5848
(2016/05/24)
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- BET BROMODOMAIN INHIBITORS AND THERAPEUTIC METHODS USING THE SAME
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Inhibitors of BET bromodomains and compositions containing the same are disclosed. Methods of using the BET bromodomain inhibitors in the treatment of diseases and conditions wherein inhibition of BET bromodomain provides a benefit, like cancers, also are disclosed.
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Paragraph 0337; 0338
(2014/09/29)
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- Selective production of cyclohexanol and methanol from guaiacol over Ru catalyst combined with MgO
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Selective demethoxylation from aqueous guaiacol proceeded over Ru catalysts at relatively lower temperatures (≤433 K). Addition of MgO to the reaction media suppressed the unselective C-O dissociation. Cyclohexanol and methanol were obtained in high yield (>80%). A reaction route is proposed where partially hydrogenated guaiacol is decomposed into methanol and phenol, which is further hydrogenated to cyclohexanol. the Partner Organisations 2014.
- Nakagawa, Yoshinao,Ishikawa, Momoko,Tamura, Masazumi,Tomishige, Keiichi
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p. 2197 - 2203
(2014/04/17)
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- Catalytic hydrogenation of aromatic rings catalyzed by Pd/NiO
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A simple and efficient heterogeneous palladium catalyst was prepared for aromatic ring hydrogenation. The catalyst was prepared by a reduction-deposition method and exhibited high activity and selectivity for the hydrogenation of a variety of substituted aromatic compounds to the corresponding cyclohexane and cyclohexanol derivatives with up to 99% yields. The catalyst was characterized by BET, TEM, XRD, XPS and ICP. Meanwhile the reusability of the catalyst was investigated, and it can be reused for several runs without significant deactivation.
- Wang, Yanan,Cui, Xinjiang,Deng, Youquan,Shi, Feng
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p. 2729 - 2732
(2014/01/06)
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- DIHYDRO-PYRROLOPYRIDINONE INHIBITORS
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The present invention provides for compounds of formula (I) wherein R1, R2, R3, R4, and R5 have any of the values defined in the specification, and pharmaceutically acceptable salts thereof, that are useful as agents in the treatment of diseases and conditions, including inflammatory diseases, cancer, and AIDS. Also provided are pharmaceutical compositions comprising one or more compounds of formula (I).
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Paragraph 0842
(2014/09/29)
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- Selective reduction of phenol derivatives to cyclohexanones in water under microwave irradiation
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Selective reduction of phenol to cyclohexanone over the Pd/C catalyst in the presence of a hydrogen source of HCOONa/H2O has been studied. Surprisingly, phenol was transformed efficiently to cyclohexanone in an excellent yield of above 98% under microwave irradiation. The influence of some parameters like reaction temperature, time and amount of hydrogen donor, as well as the reaction pathway has been discussed. The combination of microwave irradiation and HCOONa/H2O was certified to be effective for the reduction of phenol as well as its derivatives to their corresponding cyclohexanones. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.
- Cheng, Haiyang,Liu, Ruixia,Wang, Qiang,Wu, Chaoyong,Yu, Yancun,Zhao, Fengyu
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experimental part
p. 1085 - 1090
(2012/07/13)
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- HALOGEN OR CYANO SUBSTITUTED THIENO [2,3-D]PYRIMIDINES HAVING MNK1/MNK2 INHIBITING ACTIVITY FOR PHARMACEUTICAL COMPOSITIONS
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The present invention relates to novel thienopyhmidine compounds of general formula (I), pharmaceutical compositions comprising these compounds and their therapeutic use for the prophylaxis and/or treatment of diseases which can be influenced by the inhib
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Page/Page column 49-50
(2011/09/30)
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- CYCLOALKYL CONTAINING THIENOPYRIMIDINES FOR PHARMACEUTICAL COMPOSITIONS
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The present invention relates to novel thienopyrimidine compounds of general formula pharmaceutical compositions comprising these compounds and their therapeutic use for the prophylaxis and/or treatment of diseases which can be influenced by the inhibition of the kinase activity of Mnk1 and/or Mnk2 (Mnk2a or Mnk2b) and/or variants thereof.
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- 4 - [CYCLOALKYLOXY (HETERO) ARYLAMINO] THIENO [2, 3 - D] PYRIMIDINES HAVING MNKL/ MNK2 INHIBITING ACTIVITY FOR PHARMACEUTICAL COMPOSITIONS
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The present invention relates to novel thienopyrimidine compounds of general formula (I), pharmaceutical compositions comprising these compounds and their therapeutic use for the prophylaxis and/or treatment of diseases which can be influenced by the inhibition of the kinase activity of Mnk1 and/or Mnk2 (Mnk2a or Mnk2b) and/or variants thereof.
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Page/Page column 77-78
(2011/09/30)
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- Ionic-liquid-like copolymer stabilized nanocatalysts in ionic liquids: II. Rhodium-catalyzed hydrogenation of arenes
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Rhodium nanoparticles stabilized by the ionic-liquid-like copolymer poly[(N-vinyl-2-pyrrolidone)-co-(1-vinyl-3-butylimidazolium chloride)] were used to catalyze the hydrogenation of benzene and other arenes in ILs. The nanoparticle catalysts can endure forcing conditions (75 °C, 40 bar H2), resulting in high reaction rates and high conversions compared with other nanoparticles that operate in ILs. The hydrogenation of benzene attained record total turnovers of 20,000, and the products were easily separated without being contaminated by the catalysts. Other substrates, including alkyl-substituted arenes, phenol, 4-n-propylphenol, 4-methoxylphenol, and phenyl-methanol, were studied and in most cases were found to afford partially hydrogenated products in addition to cyclohexanes. In-depth investigations on reaction optimization, including characterization of copolymers, transmission electron microscopy, and an infrared spectroscopic study of nanocatalysts, were also undertaken.
- Zhao, Chen,Wang, Han-zhi,Yan, Ning,Xiao, Chao-xian,Mu, Xin-dong,Dyson, Paul J.,Kou, Yuan
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- Experimental determination of the conformational free energies (A values) of fluorinated substituents in cyclohexane by dynamic 19F NMR spectroscopy. Part 2. Extension to fluoromethyl, difluoromethyl, pentafluoroethyl, trifluoromethylthio and trifluoromethoxy groups
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The synthesis of monosubstituted and 1,4-substituted cyclohexanes bearing one of the title groups is described. The conformational analysis of these compounds was studied by 19F NMR spectroscopy at various temperatures. Chemical shifts for each conformer above the coalescence temperature were obtained by binomial regression from low temperature values, allowing the high precision determination of the equilibrium constants, and the corresponding thermodynamic parameters (ΔG°, ΔH°, ΔS°) of the fluorinated substituents. For A values (-ΔG°298K), the following averaged data were obtained: 1.59 (CFH2), 1.85 (CF2H), 2.67 (C2F5), 0.79 (OCF3) and 1.18 (SCF3) [in kcal mol-1]. the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006.
- Carcenac, Yvan,Tordeux, Marc,Wakselman, Claude,Diter, Patrick
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p. 447 - 457
(2007/10/03)
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- Direct evidence for anchimeric assistance in alcohol elimination from gas-phase MH+ ions of 1,4-dialkoxycyclohexanes under chemical ionisation. Experiment and theory
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trans-1,4-Dialkoxycyclohexanes afford very abundant [MH - ROH]+ ions upon chemical ionisation (CI), in contrast to the cis-isomers, suggesting anchimeric assistance in the alcohol elimination from the MH+ ions of the trans-diethers. Collision induced dissociation (CID) measurements of the [MH - ROH]+ ions, obtained from various suitably deuterium labelled stereoisomeric 1-ethoxy-4-methoxycyclohexanes, indicated fromation of symmetrical bicyclic ethyl and methyl oxonium ions by an anchimerically assisted alcohol elimination from the trans-diethers. On the other hand these measurements suggest that the cis-isomers afford isomeric monocyclic O-protonated 4-alkoxycyclohexene cations, in which the hydrogens at positions 2 and 3 (as well as those at positions 5 and 6, and 1 and 4) are not equivalent. The two results, namely the symmetrical bicyclic structure and the high abundance of the [MH - ROH]+ ions in the CI mass spectra of the trans-diethers, in contrast to the non-symmetrical monocyclic structure and low abundance of these ions in the cis-isomers, are suggested to be direct evidence for anchimeric assistance in a gas-phase ion dissociation process. Ab initio calculations at the MP3/6-31G*//6-31G* level support the anchimerically assisted elimination mechanism observed in trans-1-ethoxy-4-methoxycyclohexane, but also show that the energy difference between the anchimerically assisted and non-assisted elimination mechanisms is small (ca. 2-3 kcal mol-1)(1 cal = 4.184 J).
- Shvily, Ronit,Mueller, Thomas,Apeloig, Yitzhak,Mandelbaum, Asher
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p. 1221 - 1234
(2007/10/03)
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- Improvements in the synthesis of adamantane-2,6-dione and preparation of the novel adamantane-2,6-dione mono-ketal
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A facile seven-step synthesis of adamantane-2,6-dione is presented that involves minimal purification, provides multigram quantities of product, and proceeds in an overall yield of 21%. The mono-ketal of adamantane-2,6-dione is obtained in 18% overall yield.
- Ayres, Fred D.
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p. 7151 - 7154
(2007/10/02)
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- Cardiotonic Agents. 1-Methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and Related Compounds. Synthesis and Activity
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A series of 1-methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinones and related compounds were synthesized and evaluated for positive inotropic activity.Most members of this series exerted a dose-dependent increase in myocardial contractility in the dog acute heart failure model, whereas they caused only slight changes in heart rate and blood pressure.Several derivatives, especially those with cyano, acetyl, and ethyl substituents at the 4-position, were more potent than milrinone, which was used as a reference. 4-Acetyl-1-methyl-7-(4-pyridyl)-5,6,7,8-tetrahydro-3(2H)-isoquinolinone (MS-857) is one of the most potent positive inotropic agents in this series.
- Kaiho, Tatsuo,San-nohe, Kunio,Kajiya, Seitaro,Suzuki, Tsuneji,Otsuka, Kengo,et al.
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p. 351 - 357
(2007/10/02)
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- Isoquinoline derivatives
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Isoquinoline derivatives represented by the general formula (I): STR1 wherein R1 denotes a hydrogen or halogen atom, or a nitro or acetyl group, and R2 denotes a hydrogen atom, or a methyl, methoxy, phenyl, 4-pyridyl or 2-pyridyl group, and therapeutically acceptable salts thereof have high cardiotonic activity and low toxicity.
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- SELECTIVITY OF PALLADIUM AND PLATINUM CATALYSTS IN THE HYDROGENOLYSIS OF 4-HYDROXY- AND 4-METHOXYCYCLOHEXANONES
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Hydrogenolysis of 1,4-cyclohexanedione, 4-hydroxycyclohexanone and 4-methoxycyclohexanone has been studied using palladium and platinum as catalysts.Palladium cleaves the C-O single bond while platinum cleaves the C=O double bond preferentially.
- Teratani, Shousuke,Chihara, Teiji
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p. 807 - 808
(2007/10/02)
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- 1,2-Diphenyl-4,5,6,7-tetrahydroindoles
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This invention relates to novel 1-[4-(R1 R2 N-Cn H2n -O)phenyl]-5-R4 -2-(4-R3 -phenyl)indoles having antifertility and hypocholesterolemic activities and to novel intermediates for their preparation.
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