- Anti-AIDS agents 72. Bioisosteres (7-carbon-DCKs) of the potent anti-HIV lead DCK
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Three 9,10-di-O-(-)-camphanoyl-7,8,9,10-tetrahydro-benzo[h]chromen-2-one (7-carbon-DCK) analogs (3a-c) were synthesized and evaluated for inhibition of HIV-1 replication in H9 lymphocytes. All three new carbon bioisosteres of the anti-HIV lead DCK showed anti-HIV activity. Compound 3a had an EC50 value of 0.068 μM, which was comparable to that of DCK in the same assay. The preliminary results indicated that 7-carbon-DCK analogs merit attention as potential HIV-1 inhibitors for further development into clinical trials candidates.
- Wang, Yang,Huang, Shao-Xu,Xia, Peng,Xia, Yi,Yang, Zheng-Yu,Kilgore, Nicole,Morris-Natschke, Susan L.,Lee, Kuo-Hsiung
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Read Online
- Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
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Paragraph 0094-0095; 0106-0113
(2021/05/29)
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- Enantioselective biomimetic transamination of α-keto acids catalyzed by H4-naphthalene-derived axially chiral biaryl pyridoxamines
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Asymmetric biomimetic transamination is a highly attractive method for synthesis of chemically and biologically important chiral amino acids and chiral amines. Development of chiral pyridoxamines/pyridoxals is the key for the reaction. New axially chiral biaryl pyridoxamines based on H4-naphathene skeleton have been developed. The pyridoxamines display good enantioselectivity and high catalytic activity in asymmetric biomimetic transamination of α-keto acids, affording various optically active unnatural amino acids in 61–98% yields with up to 91% ee's.
- Hou, Chengkang,Zhao, Guoqing,Xu, Dongfang,Zhao, Baoguo
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supporting information
p. 1028 - 1033
(2018/02/15)
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- Benzene and fat ring structure of amino acetyl amine compound and use thereof (by machine translation)
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The invention relates to a fat ring structure containing benzimidazole amino acetyl amine compound and use thereof. The amino acetamide compounds the amino acetamide compounds, the compounds of the formula I, or its optically active isomer or a pharmaceutically acceptable salt: In formula I, R1 Hydrogen, C1 - C6 Straight or branched chain alkyl or phenyl; R2 For C1 - C7 Straight or branched chain alkyl, 5 - 6 membered of aralkyl, heteroaromatic ring group or cycloalkyl, or substituted 5 - 6 membered aromatic ring radical of, aromatic heterocyclic base or cycloalkyl; A is alkylene or carbonyl; n is 1 - 3 of the integer; wherein the substituted 5 - 6 membered of aralkyl, heteroaromatic ring group or cycloalkyl substituted group is selected from the following groups in one or more than two: halogen, C1 - C3 Alkyl or alkoxy, C1 - C3 Fluorine-containing alkyl group or a fluorine-containing alkyl oxy, nitro or cyano; states fragrance heterocyclic radical of the hetero atom as the nitrogen or sulfur; m is 1 - 3 of the integer. The present invention provides amino acetyl amine compound can be used as antiepileptic drug or ion channel blockers. (by machine translation)
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Paragraph 0122; 0123; 0124
(2019/01/06)
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- A naphthoquine salt preparation process
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The invention discloses a novel preparation process for naphthoquine salt. The process comprises the four process steps: (1) carrying out catalytic reduction on 1-naphthol; (2) carrying out a reaction on 5,6,7,8-tetrahydro-1-naphthol and diazonium salt of p-aminobenzene sulfonic acid, carrying out reduction to form a hydrochloride solution in diluted hydrochloric acid, and carrying out reflux reaction and ammonia alkalinization; (3) adding formaldehyde and tert-butyl amine for reflux and carrying out cooling and crystallization; and (4) stirring the mixture for reflux, carrying out cooling and crystallization, and washing the obtained solid by ethanol, and drying the solid to constant weight so as to obtain a target compound, wherein the purity is greater than 99% or even 99.5% or more. The requirements can be met without further recrystallization. Compared to a conventional process, in the novel process, the step of drying 5,6,7,8-tetrahydro-1-naphthol and the step of forming solid hydrochloride by 4-amino-5,6,7,8-tetrahydro-naphthol are cancelled, so that the process is simpler, pollution and corrosion of equipment are avoided to the maximum extent, and the product is high in product and the total yield is improved by over 30%.
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Paragraph 0057; 0066-0068
(2018/03/25)
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- Regioselective and Chemoselective Reduction of Naphthols Using Hydrosilane in Methanol: Synthesis of the 5,6,7,8-Tetrahydronaphthol Core
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A regioselective and chemoselective method for catalytic synthesis of biologically interesting 5,6,7,8-tetrahydronaphthols by reduction of naphthols was described. The side aromatic hydrocarbons in naphthols were site-selectively reduced, using hydrosilanes in methanol, allowing for retaining functional phenol scaffolds intact. It presents a rare example of using low-cost and air-stable hydrosilane for catalytic reduction of unactivated aromatic hydrocarbons under mild conditions. This reaction is scalable and proceeds in high selectivity without the formation of 1,2,3,4-tetrahydronaphthol byproducts with toleration of sensitive functionalities such as bromide, chloride, fluoride, ketone, ester, and amide.
- He, Yuan,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 4159 - 4163
(2018/07/29)
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- Tuning the Reactivity of Peroxo Anhydrides for Aromatic C-H Bond Oxidation
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Phenol moieties are key structural motifs in many areas of chemical research from polymers to pharmaceuticals. Herein, we report on the design and use of a structurally demanding cyclic peroxide (spiro[bicyclo[2.2.1]heptane-2,4′-[1,2]dioxolane]-3′,5′-dione, P4) for the direct hydroxylation of aromatic substrates. The new peroxide benefits from high thermal stability and can be synthesized from readily available starting materials. The aromatic C-H oxidation using P4 exhibits generally good yields (up to 96%) and appreciable regioselectivities.
- Pilevar, Afsaneh,Hosseini, Abolfazl,?ekutor, Marina,Hausmann, Heike,Becker, Jonathan,Turke, Kevin,Schreiner, Peter R.
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p. 10070 - 10079
(2018/09/06)
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- Selective Catalytic Hydrogenation of Arenols by a Well-Defined Complex of Ruthenium and Phosphorus-Nitrogen PN3-Pincer Ligand Containing a Phenanthroline Backbone
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Selective catalytic hydrogenation of aromatic compounds is extremely challenging using transition-metal catalysts. Hydrogenation of arenols to substituted tetrahydronaphthols or cyclohexanols has been reported only with heterogeneous catalysts. Herein, we demonstrate the selective hydrogenation of arenols to the corresponding tetrahydronaphthols or cyclohexanols catalyzed by a phenanthroline-based PN3-ruthenium pincer catalyst.
- Li, Huaifeng,Wang, Yuan,Lai, Zhiping,Huang, Kuo-Wei
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p. 4446 - 4450
(2017/07/24)
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- Selective hydrogenation of 1-naphthol on USY-supported NiB nanocatalyst
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Selective hydrogenation of 1-naphthol to 5,6,7,8-tetrahydro-1-naphthol was investigated over several Ni- and Pd-based supported catalysts such as supported Ni/γ-Al2O3, Pd/C, and NiB/ultrastable Y zeolite (USY). It was found that USY-
- Wang, Bo,Liu, Hui
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p. 3197 - 3204
(2017/04/21)
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- Synthesis of tetraline derivatives through depolymerization of polyethers with aromatic compounds using a heterogeneous titanium-exchanged montmorillonite catalyst
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A novel depolymerization of poly(tetramethylene glycol) (PTMG) with benzene to tetralin using titanium-exchanged montmorillonite (Ti4+-mont) as a solid acid catalyst is described. This catalyst is applicable to depolymerization of PTMG with some aromatic compounds. This is the first demonstration of the potential use of PTMG as a C4 synthon for organic synthesis.
- Maeno, Zen,Torii, Hiroyuki,Yamada, Shota,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro
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p. 89231 - 89233
(2016/10/03)
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- CYCLIC PEROXIDE OXIDATION OF AROMATIC COMPOUND PRODUCTION AND USE THEREOF
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The present invention provides a method for converting an aromatic hydrocarbon to a phenol by providing an aromatic hydrocarbon comprising one or more aromatic C-H bonds and one or more activated C-H bonds in a solvent; adding a phthaloyl peroxide to the solvent; converting the phthaloyl peroxide to a di-radical; contacting the di-radical with the one or more aromatic C-H bonds; oxidizing selectively one of the one or more aromatic C-H bonds in preference to the one or more activated C-H bonds; adding a hydroxyl group to the one of the one or more aromatic C-H bonds to form one or more phenols; and purifying the one or more phenols.
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Page/Page column 9; 10
(2014/10/15)
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- Efficient synthesis of substances related to cinacalcet hydrochloride via heck coupling
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Efficient synthetic methods to process substances related to cinacalcet hydrochloride 1, generated during the preparation, were described. The compounds were identified as [1-(7,8-dihydro-naphthalen-1-yl)-ethyl]-[3-(3- trifluoromethyl-phenyl)-propyl]-amine hydrochloride 2,[1-(5,6,7,8-tetrahydro- naphthalen-1-yl)-ethyl]-[3-(3-trifluoromethyl-phenyl)-propyl]-amine hydrochloride 3 and [1-(naphthalen-2-yl)-ethyl]-[3-(3-trifluoromethyl-phenyl)- propyl]-amine hydrochloride 4. All were prepared from commercially available materials in several linear steps and characterized by their respective spectral data.
- Lei, Fan,Qu, Boyi,Li, Xiaolong,Guo, Li,Guan, Mei,Hai, Li,Jin, Hui,Wu, Yong
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supporting information
p. 2879 - 2885
(2014/09/29)
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- NAPROXEN-BASED CHIRAL COMPOUNDS AND LIQUID CRYSTAL DISPLAY APPLICATIONS
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Naproxen-based ferroelectric liquid crystal (FLC) or nematic liquid crystal chiral compounds, which can be used in liquid crystal compositions useful for electro-optical and display device applications. The liquid crystal can be a ferroelectric liquid crystal. Also provided is a display device that includes the Naproxen-based ferroelectric liquid crystal (FLC) or nematic liquid crystal chiral compound. Also provided is a method of preparing a liquid crystal display device on silicon that includes incorporating the Naproxen-based ferroelectric liquid crystal (FLC) or nematic liquid crystal chiral compound, into a liquid crystal display on silicon by disposing the compound in a liquid crystal, or the liquid crystal, onto a silicon surface.
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Paragraph 0116
(2013/07/19)
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- Quenched skeletal Ni as the effective catalyst for selective partial hydrogenation of polycyclic aromatic hydrocarbons
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Quenched skeletal Ni is an active and selective catalyst for selective partial hydrogenation of polycyclic aromatic hydrocarbons (PAHs). The molecular structure of PAHs significantly dominate the hydrogenation process and furthermore, the distribution of hydrogenated products.
- Liu, Chengyun,Rong, Zeming,Sun, Zhuohua,Wang, Yong,Du, Wenqiang,Wang, Yue,Lu, Lianhai
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p. 23984 - 23988
(2013/11/19)
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- Metal-free oxidation of aromatic carbon-hydrogen bonds through a reverse-rebound mechanism
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Methods for carbon-hydrogen (C-H) bond oxidation have a fundamental role in synthetic organic chemistry, providing functionality that is required in the final target molecule or facilitating subsequent chemical transformations. Several approaches to oxidizing aliphatic C-H bonds have been described, drastically simplifying the synthesis of complex molecules. However, the selective oxidation of aromatic C-H bonds under mild conditions, especially in the context of substituted arenes with diverse functional groups, remains a challenge. The direct hydroxylation of arenes was initially achieved through the use of strong Bronsted or Lewis acids to mediate electrophilic aromatic substitution reactions with super-stoichiometric equivalents of oxidants, significantly limiting the scope of the reaction. Because the products of these reactions are more reactive than the starting materials, over-oxidation is frequently a competitive process. Transition-metal-catalysed C-H oxidation of arenes with or without directing groups has been developed, improving on the acid-mediated process; however, precious metals are required. Here we demonstrate that phthaloyl peroxide functions as a selective oxidant for the transformation of arenes to phenols under mild conditions. Although the reaction proceeds through a radical mechanism, aromatic C-H bonds are selectively oxidized in preference to activated-H bonds. Notably, a wide array of functional groups are compatible with this reaction, and this method is therefore well suited for late-stage transformations of advanced synthetic intermediates. Quantum mechanical calculations indicate that this transformation proceeds through a novel addition-abstraction mechanism, a kind of 'reverse-rebound' mechanism as distinct from the common oxygen-rebound mechanism observed for metal-oxo oxidants. These calculations also identify the origins of the experimentally observed aryl selectivity.
- Yuan, Changxia,Liang, Yong,Hernandez, Taylor,Berriochoa, Adrian,Houk, Kendall N.,Siegel, Dionicio
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p. 192 - 196
(2013/08/23)
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- SUBSTITUTED FNO (2-[FURAN-2-YL] NAPHTHALEN-1-OL) DERIVATIVES AS ANTI-CANCER AGENTS
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Compounds of Formulas I are described, along with methods of using such compounds for the treatment of cancer and pharmaceutical formulations thereof.
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Page/Page column 29
(2010/08/04)
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- Dowex 50WX4-100: An efficient catalyst for the tetrahydropyranylation of alcohols
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The ion-exchange resin Dowex 50WX4-100 has been found to catalyze efficiently the protection reaction of a variety of alcohols with 2,3-dihydro-4H pyran (DHP) and dichloromethane at ambient conditions. Copyright Taylor & Francis Group, LLC.
- Poon,Banerjee, Ajoy K.,Bedoya, Liadis,Laya, Manuel S.,Cabrera, Elvia V.,Albornoz, Karla M.
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body text
p. 3369 - 3377
(2011/03/19)
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- Selective partial hydrogenation of hydroxy aromatic derivatives with palladium nanoparticles supported on hydrophilic carbon
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Selective hydrogenation of phenol to cyclohexanol in the aqueous phase was achieved using a new catalytic system based on palladium particles supported on hydrophilic carbon prepared by one-pot hydrothermal carbonisation. The Royal Society of Chemistry.
- Makowski, Philippe,Demir Cakan, Rezan,Antonietti, Markus,Goettmann, Frederic,Titirici, Maria-Magdalena
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p. 999 - 1001
(2008/09/21)
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- METHOD OF HYDROGENATING PHENOL
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The present invention provides a novel method of hydrogenating a phenol for hydrogenating a phenol industrially advantageously. The present invention relates, in the case of phenol hydrogenation in which carbon dioxide is made to participate in the reaction, to a method of hydrogenating a phenol characterized by using a supported rhodium and/or ruthenium catalyst, whereby the phenol is hydrogenated efficiently at a lower reaction temperature than with prior art; such a method characterized in that carbon dioxide having a temperature of 20 to 250°C and a pressure of 0.1 to 50 MPa is used as the carbon dioxide; and such a method characterized in that hydrogen under conditions of a temperature of 20 to 250°C and a pressure of 0.1 to 50 MPa is used. An environmentally friendly phenol hydrogenation process that uses no harmful organic solvents can be realized.
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Page/Page column 12
(2008/06/13)
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- Selective hydrogenation of naphthols to tetralones over supported palladium catalysts in supercritical carbon dioxide solvent
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Naphthols were selectively hydrogenated to the corresponding tetralones over supported palladium metal catalysts in supercritical carbon dioxide solvent. Copyright
- Mine, Eiichi,Hiyoshi, Norihito,Sato, Osamu,Rode, Chandrashekhar V.,Shirai, Masayuki
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p. 780 - 781
(2007/10/03)
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- Ruthenium-catalyzed aromatization of enediynes via highly regioselective nucleophilic additions on a π-alkyne functionality. A useful method for the synthesis of functionalized benzene derivatives
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TpRu(PPh3)(CH3CN)2PF6 (10 mol %) catalyst effected the nucleophilic addition of water, alcohols, aniline, acetylacetone, pyrroles, and dimethyl malonate to unfunctionalized enediynes under suitable conditions (100 °C, 12-24 h) and gave functionalized benzene products in good yields. In this novel cyclization, nucleophiles very regioselectively attack the internal C1′ alkyne carbon of enediynes to give benzene derivatives as a single regioisomer. Experiments with methoxy substituents exclude the possible involvement of naphthyl cations as reaction intermediates in the cyclization of (o-ethynylphenyl) alkynes. Deuterium-labeling experiments indicate that the catalytically active species is ruthenium-π-alkyne rather than ruthenium-vinylidene species. This hypothesis is further confirmed by the aromatization of o-(2′-iodoethynyl)phenyl alkynes with alcohols. We propose a nucleophilic addition/insertion mechanism for this nucleophilic aromatization on the basis of a series of experiments.
- Odedra, Arjan,Wu, Chang-Jung,Pratap, Taduri Bhanu,Huang, Chun-Wei,Ran, Ying-Fen,Liu, Rai-Shung
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p. 3406 - 3412
(2007/10/03)
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- Synthesis of dihydrobenzo[h]coumarins and their 4-methyl analogs
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Dihydrobenzo[h]coumarins (5a-7a) and their 4-methyl analogs (5b-7b) were synthesized from 1-naphthol via two different synthetic routes. One pathway is the direct condensation of 5,8-dihydro-1-naphthol (9) with malic acid or ethyl acetoacetate, affording 7,10-dihydrobenzo[h]coumarins 7a and 7b, respectively. The other is through the oxidation of 7,8,9,10-tetrahydrobenzo[h] coumarins (15a-b), followed by the reduction of the carbonyl group and dehydration of hydroxyl group, giving 7,8-dihydrobenzo[h]coumarins (5a, b) and 9,10-dihydrobenzo[h]coumarins (6a, b). The regio selectivities for the oxidation reactions of 15a, b were rationalized on the basis of quantum chemical calculations and further confirmed by the X-ray crystallographic analysis of the derivatives of oxidation products. Copyright Taylor & Francis, Inc.
- Wang, Yang,Huang, Shaoxu,Xia, Peng
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p. 3141 - 3156
(2007/10/03)
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- Partial ring hydrogenation of naphthols over supported metal catalysts in supercritical carbon dioxide solvent
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Selective ring hydrogenation of naphthols to tetrahydronaphthols and tetralones proceeded at 323 K over a charcoal supported rhodium catalyst in supercritical carbon dioxide. Copyright
- Mine, Eiichi,Haryu, Eiji,Arai, Kunio,Sato, Takafumi,Sato, Osamu,Sasaki, Akiyoshi,Rode, Chandrashekhar V.,Shirai, Masayuki
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p. 782 - 783
(2007/10/03)
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- Photo-fries rearrangements of phenyl phenylacylates in polyethylene films. Comparison of reactivity and selectivity with 1-naphthyl phenylacylates
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The fates and kinetics of recombination of singlet radical pairs generated by photolyses of three phenyl phenylacylates have been examined in unstretched and stretched polyethylene films. Comparisons with results from photolyses of analogous 1-naphthyl phenylacylates in the same media lead to the conclusions that (1) phenoxy is less reactive overall than 1-naphthoxy toward a common phenylacyl radical but (2) the constrained cages in which the radical pairs reside exert greater control over the movements of the 1-naphthoxy/phenylacyl pairs. The reasons for these observations are discussed in the context of the shapes and van der Waals volumes of the radical pairs, the void volumes of sites in native polyethylene films, and the electronic properties of the aryloxy radicals. The fates and kinetics of recombination of singlet radical pairs generated by photolyses of three phenyl phenylacylates have been examined in unstretched and stretched polyethylene films. Comparisons with results from photolyses of analogous 1-naphthyl phenylacylates in the same media lead to the conclusions that (1) phenoxy is less reactive overall than 1-naphthoxy toward a common phenylacyl radical but (2) the constrained cages in which the radical pairs reside exert greater control over the movements of the 1-naphthoxy/phenylacyl pairs. The reasons for these observations are discussed in the context of the shapes and van der Waals volumes of the radical pairs, the void volumes of sites in native polyethylene films, and the electronic properties of the aryloxy radicals.
- Gu,Weiss
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p. 1775 - 1780
(2007/10/03)
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- Process for the preparation of aldehydes and ketones
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A process for the preparation of vinyl, alkynyl or aryl aldehydes or vinyl, alkynyl or aryl ketones includes reacting vinyl-, alkynyl- and aryl- and -methylene compounds with the aid of a mediator and an oxidant, wherein the mediator is selected from the group of the aliphatic, heterocyclic or aromatic NO or NOH containing compounds.
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- Organic reaction in water. Part 3: A facile method for reduction of aromatic rings using a Raney Ni-Al alloy in dilute aqueous alkaline solution under mild conditions
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Reduction of aromatic rings such as phenol, naphthalenes, biphenyls, acenaphthene, and acenaphthylene was smoothly performed using a Raney Ni-Al alloy in dilute aqueous alkaline solution without any organic solvents at 90°C under atmospheric pressure, and the corresponding reduced compounds were obtained in high yields. (C) 2000 Elsevier Science Ltd.
- Tsukinoki, Takehito,Kanda, Tadashige,Liu, Guo-Bin,Tsuzuki, Hirohisa,Tashiro, Masashi
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p. 5865 - 5868
(2007/10/03)
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- The sliding cyclohexane rearrangement
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6-methoxytetralins may be transformed into 8-methoxytetralins through the action of zirconium tetrachloride. Yields are generally good though turnover is slow. Ultrasonic irradiation, phase transfer catalysts, crown ethers and lithium chloride all accelerate the reaction which proceeds via scission of the C-1 to C-8a bond and cyclisation by intramolecular Friedel-Crafts alkylation.
- Harrowven, David C.,Dainty, Richard F.
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p. 15771 - 15786
(2007/10/03)
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- NOVEL AND FACILE REDUCTION OF PHENOL DERIVATIVES WITH SAMARIUM DIIODIDE-BASE SYSTEM
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Phenol was rapidly reduced with samarium diiodide-base system in the presence of protic solvent at room temperature to afford 3-cyclohexen-1-ol accompanied by cyclohexanol.The similar reduction of 4-methoxyphenol and 2-naphthol gave 4-hydroxycyclohexanone and 1,2,3,4-tetrahydro-2-naphthol in excellent yield, respectively.
- Kamochi, Yasuko,Kudo, Tadahiro
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p. 4169 - 4172
(2007/10/02)
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- Metal Arene Complexes in Organic Synthesis. Hydroxylation, Trimethylsilylation, and Carbethoxylation of Some Polycyclic Aromatic Hydrocarbons Utilizing η6-Arene-Chromium Tricarbonyl Complexes
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The deprotonation of polycyclic aromatic hydrocarbon (PAH) chromium tricarbonyl complexes (PAH = naphthalene, anthracene, phenanthrene, pyrene, fluoranthene) using an in situ technique where the PAH complex, the base (LiTMP or LDA), and the electrophile (trialkyl borate, trimethylsilyl chloride, or ethyl chloroformate) were placed in solution simultaneously resulted in hydroxylation, trimethylsilylation, or carbethoxylation of the PAH after oxidative workup where the regiochemistry was controlled by steric factors.As a result, substitution at positions of the PAHs not readily available by electrophilic substitution were obtained in some cases.Conditions minimizing isomer mixtures and factors affecting the regiochemistry and the scope of the reaction sequence were examined.
- Morley, James A.,Woolsey, Neil F.
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p. 6487 - 6495
(2007/10/02)
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- Synthesis and Solvolysis of a Novel Cyclic Dienynyl Trifluoromethanesulphonate
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Cyclodeca-1,3-dien-5-yn-1-yl trifluoromethanesulphonate (2) has been synthesized and solvolysed in different solvent systems to give cyclized aromatic products exclusively, which are formed mainly via an aryl cation (5) intermediate.
- Hanack, Michael,Rieth, Robert
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p. 1487 - 1489
(2007/10/02)
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- Inverse Electron Demand Diels-Alder Reactions of 3-Carbomethoxy-2-pyrones. Controlled Introduction of Oxygenated Aromatics: Benzene, Phenol, Catechol, Resorcinol, and Pyrogallol Annulation. Regiospecific Total Synthesis of Sendaverine and a Preparation of 6,7-Benzomorphans
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A full investigation of the preparation and Diels-Alder reactions of 3-carbomethoxy-2-pyrones is described.Methods for the preparation of a full range of oxygen-substituted aromatics: benzene, 1-, 2-, or 3-phenol, symmetrical or unsymmetrical o-catechol, resorcinol, and pyrogallol annulation from a common 3-carbomethoxy-2-pyrone intermediate are detailed.A regiospecific total synthesis of sendaverine, a 2-benzyltetrahydroisoquinoline possessing a selectively protected, symmetrical o-catechol, and a preparation of 6,7-benzomorphans are described.
- Boger, Dale B.,Mullican, Michael D.
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p. 4033 - 4044
(2007/10/02)
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- INVERSE ELECTRON DEMAND DIELS-ALDER REACTIONS OF 3-CARBOMETHOXY-2-PYRONES. CONTROLLED INTRODUCTION OF OXYGENATED AROMATICS: BENZENE, PHENOL, CATECHOL, RESORCINOL, PYROGALLOL ANNULATION.
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Implementation of one of four inverse electron demand Diels-Alder reactions of 3-carbomethoxy-2-pyrones with N-vinyl-2-pyrrolidinone, vinylene carbonate, 1,1-dimethoxy-ethylene or 1,1,2-trimethoxyethylene followed by choice of two standard reaction sequences: (1) removal of the carbomethoxy group (NaOH: copper powder, quinoline , Δ) or (2) its conversion to an acetate allows the preparation of a full range of oxygen substituted aromatics from a single intermediate and represent methods of benzene, 1-, 2- or 3-phenol , symmetrical or unsymmetrical catechol, resorcinol and pyrogallol annulation.
- Boger, Dale L.,Mullican, Michael D.
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p. 4939 - 4942
(2007/10/02)
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- Thermolysis of Model Compounds for Coal. 2. Condensation and Hydrogen Transfer during Thermolysis of Naphthols
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The dominant initial products from thermolysis of 1-naphthol in the liquid phase at 400 deg C are 2,2'-binaphthalene-1,1'-diol (2) and 1-tetralone (6).As reaction proceeds, binaphthol 2 undergoes rapid cyclization to dinaphthofuran (1), while ketone 6 is more slowly converted ultimately to naphthalene (8).The initial rate of this ring coupling and hydrogen-transfer reaction shows an apparent kinetic order of ca 2.5 in m-terphenyl diluent.In benzophenone solvent, formation of coupled binaphthol 2 is accelerated, but reduced product 6 is replaced by diphenylmethane.Thermolysis of 2-naphthol behaves similarly except that coupling occurs both between C-1 and C-1' to give dinaphthofuran (3), preceded by 1,1'-binaphthalene-2,2'-diol (4), and between C-1 and C-3' to give dinaphtho(2,1-b:2',3'-d>furan (5).The major reduction product is 2-tetralone (14).The ratio of (3 + 4)/5 decreases with increasing reaction time.Mechanistic hypotheses for this characteristic thermal behavior of phenols are explored.The significance of the reactions involved for conversion processes for coal, which contains significant phenolic functionality, is discussed.
- Poutsma, Marvin L.,Dyer, Catherine W.
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p. 3367 - 3377
(2007/10/02)
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- POPELLANES-LII THE REACTION OF CONJUGATED DIENIC PROPELLANES WITH SINGLET OXYGEN
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The reactions of propellanes containing one or two cyclohexadiene rings with singlet oxygen take the course of exclusive syn-attack with respect to a hetero-ring containing two CO groups.When only one or no CO group is found in the hetero ring, both syn- and anti-attack occur.The former course is interpreted in terms of secondary orbital interactions wich stabilize the transition state for syn-attack.
- Landheer, Iman,Ginsburg, David
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p. 133 - 142
(2007/10/02)
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