- Nucleophilic addition to a p-benzyne derived from an enediyne: A new mechanism for halide incorporation into biomolecules
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Biosynthesis of haloaromatics ordinarily occurs by electrophilic attack of an activated halogen species on an electron-rich aromatic ring. We now present the discovery of a new reaction whereby a nucleophilic halide anion can be attached even to an aromatic ring without activating substituents. We show that the enediyne cyclodeca-1,5-diyn-3-ene, in the presence of lithium halide and a weak acid, is converted to 1-halotetrahydronaphthalene. The kinetics are consistent with rate-limiting cyclization to a p-benzyne biradical that rapidly adds halide and is then protonated. This reaction has interesting mechanistic features and important implications for incorporation of halide into biomolecules.
- Perrin, Charles L.,Rodgers, Betsy L.,O'Connor, Joseph M.
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Read Online
- 13C scrambling of [5-13C]5-cyclodecynone
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Scrambling of [5-13C]5-cyclodecynone occurs as a result of acidic conditions that preclude its rapid consumption. (C) 2000 Elsevier Science Ltd.
- Wempe, Michael F.,Grunwell, John R.
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Read Online
- Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation Using N-Halosuccinimides
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A Lewis base catalyst Trip-SMe (Trip = triptycenyl) for electrophilic aromatic halogenation using N-halosuccinimides (NXS) is introduced. In the presence of an appropriate activator (as a noncoordinating-anion source), a series of unactivated aromatic compounds were halogenated at ambient temperature using NXS. This catalytic system was applicable to transformations that are currently unachievable except for the use of Br2 or Cl2: e.g., multihalogenation of naphthalene, regioselective bromination of BINOL, etc. Controlled experiments revealed that the triptycenyl substituent exerts a crucial role for the catalytic activity, and kinetic experiments implied the occurrence of a sulfonium salt [Trip-S(Me)Br][SbF6] as an active species. Compared to simple dialkyl sulfides, Trip-SMe exhibited a significant charge-separated ion pair character within the halonium complex whose structural information was obtained by the single-crystal X-ray analysis. A preliminary computational study disclosed that the πsystem of the triptycenyl functionality is a key motif to consolidate the enhancement of electrophilicity.
- Nishii, Yuji,Ikeda, Mitsuhiro,Hayashi, Yoshihiro,Kawauchi, Susumu,Miura, Masahiro
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supporting information
p. 1621 - 1629
(2020/02/04)
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- GLYCOLATE OXIDASE INHIBITORS FOR THE TREATMENT OF DISEASE
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Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with a defect in glyoxylate metabolism, for example a disease or disorder associated with the enzyme glycolate oxidase (GO) or alterations in oxalate metabolism. Such diseases or disorders include, for example, disorders of glyoxylate metabolism, including primary hyperoxaluria, that are associated with production of excessive amounts of oxalate.
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Paragraph 001287
(2021/01/22)
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- GLYCOLATE OXIDASE INHIBITORS FOR THE TREATMENT OF DISEASE
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Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with the enzyme glycolate oxidase (GO). Such diseases or disorders include, for example, disorders of glyoxylate metabolism, including primary hyperoxaluria, that are associated with production of excessive amounts of oxalate.
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Paragraph 001329; 001330; 001331
(2019/07/17)
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- New organic compounds and organic light emitting device using the same
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The present invention relates to a polycyclic aromatic hydrocarbon compound in which a substituted or unsubstituted C2-30 cycloalkane, or a substituted or unsubstituted C5-50 polycycloalkane is fused to a substituent of said polycyclic aromatic hydrocarbon as represented by formula (3). Furthermore, the present invention relates to an organic light emitting device comprising a first electrode, at least one organic layer and a second electrode, laminated successively, in which at least one organic layer comprises said polycyclic aromatic hydrocarbon compound.
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Paragraph 0077
(2016/10/07)
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- ORGANIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
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The present invention provides an organic light emitting device comprising a first electrode, at least one organic layer and a second electrode, laminated successively, in which at least one layer of the organic layer has a polycyclic aromatic hydrocarbon as a core and comprises at least one of a derivative in which a substituted or unsubstituted C2-30 cycloalkane, or a substituted or unsubstituted C5-50 polycycloalkane is directly fused to the core or fused to a substituent of the core: and a new organic compound usable in the organic light emitting device. Furthermore, the present invention provides a charge carrier extracting, injecting or transporting material which has a polycyclic aromatic hydrocarbon as a core and comprises a derivative in which a substituted or unsubstituted C2-30 cycloalkane, or a substituted or unsubstituted C5-50 polycycloalkane is directly fused to the core or fused to a substituent of the core.
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Paragraph 0108-0109
(2014/04/03)
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- ORGANIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
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The present invention provides an organic light emitting device comprising a first electrode, at least one organic layer and a second electrode, laminated successively, in which at least one layer of the organic layer has a polycyclic aromatic hydrocarbon as a core and comprises at least one of a derivative in which a substituted or unsubstituted C2-30 cycloalkane, or a substituted or unsubstituted C5-50 polycycloalkane is directly fused to the core or fused to a substituent of the core; and a new organic compound usable in the organic light emitting device. Furthermore, the present invention provides a charge carrier extracting, injecting or transporting material which has a polycyclic aromatic hydrocarbon as a core and comprises a derivative in which a substituted or unsubstituted C2-30 cycloalkane, or a substituted or unsubstituted C5-50 polycycloalkane is directly fused to the core or fused to a substituent of the core.
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Paragraph 0108-0110
(2014/04/03)
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- SUBSTITUTED PARA-BIPHENYLOXYMETHYL DIHYDRO OXAZOLOPYRIMIDINONES, PREPARATION AND USE THEREOF
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The present invention relates to a series of substituted para-biphenyloxymethyl dihydro oxazolopyrimidinones of formula (I) as defined herein. This invention also relates to methods of making these compounds including novel intermediates. The compounds of
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Page/Page column 43
(2011/04/19)
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- Regioselective haloaromatization of 1,2-bis(ethynyl)benzene via halogen acids and PtCl2. Platinum-catalyzed 6-π electrocyclization of 1,2-bis(1′-haloethenyl)benzene intermediates
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Treatment of 1,2-bis(ethynyl)benzene (1) with aqueous HX (X = Br, I) in hot 3-pentanone (100-105 °C, 2 h) afforded 1,2-bis(1′-haloethenyl)benzene species 2-Br and 2-I in 98% and 95% yields, respectively. The hydrochlorination of endiyne 1 failed to proceed at elevated temperature but was implemented efficiently by PtCl2 (5 mol %) in hot 3-pentanone (100 °C, 2 h) to give 1,2-bis(1′-chloroetheny)benzene 2-Cl in 80% yield. In the presence of PtCl2 (5 mol %), these halides 2-Cl, 2-Br, and 2-I were subsequently converted to 1-halonaphthalenes 3-Cl, 3-Br, and 3-I in the mother solution via sequential 6-π electrocyclization and dehalogenation reactions. PtCl2 (5 mol %) also effected direct haloaromatization of endiyne 1 with HX (X = Cl, Br, I) and gave 1-halonaphthalenes 3-Cl, 3-Br, and 3-I in 64-71% yields. This investigation reports the scope and the regioselectivity of haloaromatization of various enediynes catalyzed by PtCl2.
- Lo, Ching-Yu,Kumar, Manyam Praveen,Chang, Hsu-Kai,Lush, Shie-Fu,Liu, Rai-Shung
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p. 10482 - 10487
(2007/10/03)
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- A PROCESS FOR THE PREPARATION OF 3-CYANO-1-NAPHTHOIC ACID AND SOME ANALOGUES THEREOF
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The present invention is related to a process for the preparation of 3-cyano-1-naphthoic acid and some analogues thereof of formula (1), the intermediate 1-halo-3-cyano naphthalene and some analogues thereof used in this process and a process for the preparation of said intermediate.
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- Substituted phenyl farnesyltransferase inhibitors
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Compounds of formula (I) or pharmaceutically acceptable salts thereof, inhibit farnesyltransferase. Methods for making the compounds, pharmaceutical compositions containing the compounds, and methods of treatment using the compounds are disclosed.
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- The Transannular Rearrangement of 5-Cyclodecynone
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The acid-catalyzed rearrangement of 5-cyclodecynone (1) to bicyclo-1(6)-decen-2-one (5) has been investigated via 13C and deuterium labeling experiments, which showed that the transannular rearrangement proceeds by a mechanism not involving an enol
- Wempe, Michael F.,Grunwell, John R.
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p. 2714 - 2720
(2007/10/02)
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- A simple and improved procedure for selective ring bromination of alkyl-substituted aromatic hydrocarbons on the surface of alumina
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Highly selective ring bromination of alkyl-substituted aromatic hydrocarbons has been achieved using molecular bromine adsorbed on the surface of alumina without any solvent.
- Ranu,Sarkar,Chakraborty
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p. 1095 - 1099
(2007/10/02)
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- Thermolabile Hydrocarbons, 31. - Stereoselective Formation and Cleavage of the Dimers of the 1-(5,6,7,8-Tetrahydro-1-naphthyl)neopentyl Radical
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The 1,2-diaryl-1,2-di-t-butylethanes meso- and DL-6 are synthesised by partial catalytic hydrogenation of the parent dinaphthylethanes 5.The crystal structure of meso-6 was obtained experimentally and calculated by molecular mechanics methods (MM2).It is shown, that 1-(5,6,7,8-tetrahydro-1-naphthyl)neopentyl radical 8 forms its dimers 6 with high stereoselectivity, e.g.DL-6: meso-6 = 45 (at -20 deg C) and 7.07 (at 100 deg C).The selectivity was measured over a range of 300 K by using several radical precursors.The difference of the enthalpy of activation has been derived for the two dimerisation reactions: ΔH(excit.)dim (DL - meso) = -2.8 +/- 0.2 kcal/mol.The cleavage of DL-6 and meso-6 into 8 was measured kinetically, and the enthalpies of activation ΔH(excit.)dis = 46.2 +/- 0.6 (DL-6) and 52.6 +/- 1.3 kcal/mol (meso-6) and the entropies of activation ΔS(excit.)dis = 8.4 +/- 0.6 (DL-6) and 20.0 +/- 2.5 e.u. (meso-6) have been obtained.A complete thermodynamic cycle is constructed by using the calculated (MM2) heats of formation ΔHf0 = -27.6 (DL-6) and -30.0 kcal/mol (meso-6).Thus, the diastereomer (DL-6), which is formed preferentially, appears to be the thermodynamically and kinetically less stable one.It turns out, that the high stereoselectivity of the dimerisation of 8, compared to the parent 1-phenyl-neopentyl radical (2a), is mainly caused by the steric repulsions between the approaching radicals. Key words: Bond-formation, C-C, stereoselectivity of; bond cleavage, C-C, kinetics of; calculations, force field.
- Peyman, Anuschirwan,Beckhaus, Hans-Dieter,Kramer, Dirk,Peters, Karl,Schnering, Hans Georg von,Ruechardt, Christoph
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p. 1989 - 1996
(2007/10/02)
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- Synthesis of the Angular Ring Tetrahydro Epoxides of the Carcinogens 7- and 12-Methylbenzanthracene and 7,12-Dimethylbenzanthracene
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Tetrahydro epoxide derivatives at the 1,2-and 3,4-positions on the angular ring of carcinogens 7- and 12-methylbenzanthracene (7- and 12-MeBA) and 7,12-dimethylbenzanthracene (7,12-DMBA) have been synthesized in order to probe the basis for the tumorigenicity-enhancing effects of methyl groups on polycyclic aromatic hydrocarbons (PAH).The epoxides were prepared from the corresponding dihydro PAH.For the 7-MeBA and 12-MeBA derivatives, access to the dihydro derivatives was achieved by acetoxylation at the 1- and 4-positions of the tetrahydro ring of 7-and 12-acetoxy-1,2,3,4-tetrahydrobenzanthracene, respectively (Scheme II).For the 7,12-DMBA derivatives, oxidation of 1,2,3,4-tetrahydrobenzanthracene-7,12-quinone afforded the 1- and 4-oxo derivatives, which were converted to the respective dihydro compounds (Scheme III).Alkenes 13 and 22, both of which have a 12-methyl group and C1-C2 double bond, were higly susceptible to endoperoxide formation.The dihydro compounds were converted to the epoxides via cyclization of the bromohydrin or bromoacetate derivatives (Scheme IV).The 1,2-bromohydrin and/or bromoacetate derivatives of 3,4-dihydro-12-methylbenzanthracene and 3,4-dihydro-7,12-dimethylbenzanthracene were highly labile and required special handling in order to be purified and converted into the epoxide derivatives.
- Lehr, Roland E.,Kole, Panna L.,Singh, Mahatam,Tschappat, Kathryn D.
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p. 850 - 857
(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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- Hydrocarbures arylaliphatiques. Partie VII. Orientation dans la reaction de bromation de benzocyclenes bi- et tricycliques superieurs
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The bromination of 1,2,3-trimethylbenzene, and bi- and tricyclic fused ring systems (i.e. indan, tetralin, benzosuberan, 2a,3,4,5-tetrahydroacenaphthen and higher homologues) is described in this paper.This work is part of a research project studying the ring size influence of peri-fused semi-aromatic ring system on benzene reactivity.This study was started in a first step on acetylation and was continued on bromination.Forthcoming studies (now underway) concern the kinetic measurement of protodesilylation of univocal silyl derivatives.The synthesis of the starting bromo derivatives used for this latter study is described here.These bromides were used for the attribution via NMR spectroscopy of the electrophile reaction site in the direct bromination of the fused ring unsymmetrical systems (the reactive sites are obvious in symmetrical molecules). Thus, meta substitution is predominant in the case of tetraline and benzosuberan, but ortho substitution is relatively more important in tetralin.In 1,2,3-trimethylbenzene and the fused tricyclic compounds, substitution takes place in an ortho position respective to the substituent or the ring system, the meta position being totally deactivated.In the special case of a five-membered ring, the ortho position this ring is always non reactive.The reactivity differences between these compounds are explained by hyper conjugation and the stabilities of the transition states.
- Gruber, Rene,Cagniant, Denise,Cagniant, Paul
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