- Visible-Light-Mediated Synthesis of Sulfonyl Fluorides from Arylazo Sulfones
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Sulfonyl fluorides are useful motifs for a wide range of applications in organic synthesis including sulfur (VI) fluoride exchange-based “click chemistry.” Herein, a visible-light-mediated synthesis of sulfonyl fluorides from arylazo sulfones is described. In the present study, K2S2O5 and N-fluorobenzenesulfonimide (NFSI) were used as the sulfonyl source and fluorinating agent, respectively, for visible-light-mediated fluorosulfonylation of arylazo sulfones to prepare various sulfonyl fluorides in 60–85% yield. This protocol is a synthetic approach to provide useful sulfonyl fluoride structures at room temperature. (Figure presented.).
- Bui, Tien Tan,Tran, Van Hieu,Kim, Hee-Kwon
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supporting information
p. 341 - 347
(2021/10/14)
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- Fluorination method
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In order to overcome the problems of high cost and low stability of the existing fluorination reagents for preparing acyl fluoride, sulfonyl fluoride and phosphoryl fluoride compounds, the invention provides a fluorination method, which comprises the following operation steps of: adding a fluorination reagent into a substrate, wherein the fluorination reagent comprises cations M and anions, the anions are selected from one or more of perfluoropolyether chain carboxylic acid anions as shown in the specification: CF3(OCF2)nCO2, wherein n is selected from 1-10; the substrate comprises a carboxylic acid compound, a sulfonic acid compound, a phosphoric acid compound and a phosphine oxide compound; and carrying out fluorination reaction to obtain acyl fluoride, sulfonyl fluoride and phosphoryl fluoride products. According to the fluorination method provided by the invention, the perfluoropolyether chain carboxylate is used as a fluorination reagent, so that the dehydroxylation fluorination reaction of the carboxylic acid compound, the sulfonic acid compound and the phosphoric acid compound and the fluorination reaction of the phosphine oxide compound are realized, the product yield isrelatively high, and the fluorination method has relatively good universality for different substrates.
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Paragraph 0130-0163
(2021/01/12)
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- Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides
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This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source andN-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.
- Chen, Qing-Yun,Guo, Yong,Hu, Xiaojun,Liu, Chao,Liu, Yongan,Ma, Xiaoyu,Pan, Qijun,Pang, Wan,Wu, Jingjing
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supporting information
p. 8999 - 9003
(2021/11/04)
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- Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism
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The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.
- Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
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supporting information
p. 8704 - 8708
(2021/05/17)
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- Deoxyfluorination of Carboxylic, Sulfonic, Phosphinic Acids and Phosphine Oxides by Perfluoroalkyl Ether Carboxylic Acids Featuring CF2O Units
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The deoxyfluorination of carboxylic, sulfonic, phosphinic acids and phosphine oxides is a fundamentally important approach to access acyl fluorides, sulfonyl fluorides and phosphoric fluorides, thus the development of inexpensive, stable, easy-to-handle, versatile, and efficient deoxyfluorination reagents is highly desired. Herein, we report the use of potassium salts of perfluoroalkyl ether carboxylic acids (PFECA) featuring CF2O units as deoxyfluorination reagents, which are generated mainly as by-products in the manufacture of hexafluoropropene oxide (HFPO). The synthesis of acyl fluorides, sulfonyl fluorides and phosphoric fluorides can be realized via carbonic difluoride (COF2) generated in situ from thermal degradation of the PFECA salt.
- Zhao, Shiyu,Guo, Yong,Su, Zhaoben,Wu, Chengying,Chen, Wei,Chen, Qing-Yun
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supporting information
p. 1225 - 1232
(2021/05/04)
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- Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
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A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
- Cornella, Josep,Magre, Marc
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supporting information
p. 21497 - 21502
(2022/01/03)
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- A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds
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A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).
- Cornella, Josep,Wang, Lin
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supporting information
p. 23510 - 23515
(2020/10/29)
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- Synthesis of Sulfonyl Fluorides from Sulfonamides
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A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry-BF4 and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late-stage formation of sulfonyl fluorides from densely functionalized molecules.
- Pérez-Palau, Marina,Cornella, Josep
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supporting information
p. 2497 - 2500
(2020/03/11)
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- Nickel(II)-Catalyzed Synthesis of Sulfinates from Aryl and Heteroaryl Boronic Acids and the Sulfur Dioxide Surrogate DABSO
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We report a redox-neutral Ni(II)-catalyzed sulfination of readily available aryl and heteroaryl boronic acids. Using the combination of commercially available, air-stable NiBr2·(glyme), a commercially available phenanthroline ligand, and DABSO, boronic acids are efficiently converted to the corresponding sulfinate salts, which can be further elaborated to valuable sulfonyl-containing groups, including sulfones, sulfonamides, sulfonyl fluorides, and sulfonate esters. The catalyst loading can be reduced to 2.5 mol ?% on a gram scale. This practically simple protocol tolerates an unprecedented range of pharmaceutically relevant and electron-poor (hetero)aryl boronic acids, allowing the direct synthesis of active pharmaceutical ingredients.
- Lo, Pui Kin Tony,Chen, Yiding,Willis, Michael C.
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p. 10668 - 10673
(2019/11/11)
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- Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
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Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
- Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
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supporting information
p. 11832 - 11836
(2019/08/26)
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- One-pot fluorosulfurylation of Grignard reagents using sulfuryl fluoride
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Herein, we report a new method for the one-pot syntheses of sulfonyl fluorides. Addition of an alkyl, aryl, or heteroaryl Grignard to a solution of sulfuryl fluoride at ambient temperature affords the desired sulfonyl fluorides in 18-78% yield. Furthermore, this method is applicable for in situ sequential reactions, whereby the Grignard reagent can be converted to the corresponding diarylsulfone, sulfonate ester, or sulfonamide in a one-pot process.
- Lee, Cayo,Ball, Nicholas D.,Sammis, Glenn M.
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supporting information
p. 14753 - 14756
(2019/12/23)
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- Pd-Catalyzed Conversion of Aryl Iodides to Sulfonyl Fluorides Using SO2 Surrogate DABSO and Selectfluor
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A one-pot Pd-catalyzed conversion of aryl iodide to aryl sulfonyl fluorides using DABSO and Selectfluor has been developed generating aryl sulfonyl fluorides in good to excellent yields. The reaction results in the generation of electronically and sterically diverse sulfonyl fluorides. Additionally, sulfonyl fluorides can be converted to aryl sulfonamides and sulfonic esters using Cs2CO3 under mild conditions.
- Tribby, Ariana L.,Rodríguez, Ismeraí,Shariffudin, Shamira,Ball, Nicholas D.
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p. 2294 - 2299
(2017/02/26)
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- One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides
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A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated.
- Davies, Alyn T.,Curto, John M.,Bagley, Scott W.,Willis, Michael C.
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p. 1233 - 1237
(2017/02/10)
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- Catalyst-free radical fluorination of sulfonyl hydrazides in water
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The first catalyst-free fluorination of sulfonyl hydrazides for the synthesis of sulfonyl fluorides has been developed via a free-radical pathway. This protocol presents a broad substrate scope and does not require any metal catalyst and additive. All these transformations proceed smoothly in water under mild conditions, which enables a straightforward, practical and environmentally benign fluorination for S-F bond formation.
- Tang, Lin,Yang,Wen, Lixian,Yang, Xingkun,Wang, Zhiyong
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p. 1224 - 1228
(2016/03/09)
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- Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
- Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
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p. 2464 - 2471
(2014/04/03)
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- Ascertaining the suitability of aryl sulfonyl fluorides for [18F]radiochemistry applications: A systematic investigation using microfluidics
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Optimization of [18F]radiolabeling conditions and subsequent stability analysis in mobile phase, PBS buffer, and rat serum of 12 aryl sulfonyl chloride precursors with various substituents (electron-withdrawing groups, electron-donating groups, increased steric bulk, heterocyclic) were performed using an Advion NanoTek Microfluidic Synthesis System. A comparison of radiochemical yields and reaction times for a microfluidics device versus a conventional reaction vessel is reported. [18F]Radiolabeling of sulfonyl chlorides in the presence of competing nucleophiles, H-bond donors, and water was also assessed and demonstrated the versatility and potential utility of [18F]sulfonyl fluorides as synthons for indirect radiolabeling. Published 2013 by the American Chemical Society.
- Matesic, Lidia,Wyatt, Naomi A.,Fraser, Benjamin H.,Roberts, Maxine P.,Pham, Tien Q.,Greguric, Ivan
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p. 11262 - 11270
(2013/12/04)
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- The investigation of fluorination reaction of p-substituted benzenesulfonimides with fluorine-nitrogen mixed gas to synthesize NFSI analogues
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This paper studied the fluorination reaction of p-substituted benzenesulfonimides with diluted elemental fluorine to synthesize N-fluoro-benzenesulfonimide (NFSI) analogues. Several synthetic methods were compared and we found that, for many p-substituted
- Yang, Xianjin,Chen, Guanlong,Chen, Fuli,Zhang, Yan,Yang, Xueyan,Yuan, Xiaoming,Wu, Fanhong
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scheme or table
p. 155 - 159
(2012/02/14)
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- Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
- Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
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experimental part
p. 3086 - 3089
(2011/06/26)
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- NOVEL COMPOUNDS
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The present invention relates to novel indole derivatives such as compounds of the formula (I): which possess antagonist potency at the 5-HT6 receptor and the use of such compounds or pharmaceutically acceptable salts or solvates thereof in the treatment of Alzheimer's disease and other CNS disorders.
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Page/Page column 35; 37
(2008/06/13)
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- Cross-interaction Constants as a Measure of the Transition-state Structure. Part 1. The Degree of Bond Formation in Nucleophilic Substitution Reactions
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The kinetic of seven reaction series in methanol involving halides as leaving groups and aromatic amines as nucleophiles are reported.Analyses of various Hammett ρ values, especially the cross-interaction constants ρXY between substituents X in the nucleophile and Y in the substrate, are used to characterize the transition-state structure for the nucleophilic substitution reactions.The degree of bond formation in the transition state as measured by /ρXY/ indicated that the reactions can be classified into two groups according to the magnitude of the cross-interaction constants; the fluoride series gave larger /ρXY/ values indicating a greater degree of bond formation, under the same reactants condition, compared with other series with relatively good leaving groups, e.g.Cl-, Br-, and -OSO2C6H5.When, however, a non-conjugative intervening group such as CO or CH2 is present between the reaction centre and the benzene ring of a reactant, the cross-interaction constant is reduced by a factor of ca. 2, demonstrating the fall-off of the susceptibility of the reaction centres to substituent changes.
- Lee, Ikchoon,Shim, Chang Sub,Chung, Soo Young,Kim, Hyung Yoon,Lee, Hai Whang
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p. 1919 - 1924
(2007/10/02)
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- KINETICS OF THE TRANSFORMATIONS OF AROMATIC SULFO DERIVATIVES TO ACID HALIDES IN CHLORO- AND FLUOROSULFONIC ACID MEDIA
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The pseudofirst-order rate constants for the formation of the corresponding sulfonic acid halides (keff) from sulfo derivatives with the general formula RC6H4SO3X, where X = NH2, Cl, F, and R = H, p-Cl, p-NO2, and m-NO2, were measured by GLC in fluorosulfonic and chlorosulfonic acids.The effect of substituents in the benzene ring on the rate of the transformations of the sulfo derivatives into the halides is similar to the previously investigated effect of substituents on the rate of solvolysis of substituted benzenesulfonyl halides in 100percent sulfuric acid (ρ -4).Com parison of the ratios of the keff values for the transformations of the sulfonamides in chlorosulfonic and fluorosulfonic acids and also the sulfonyl fluorides in 100percent sulfuric acid and chlorosulfonic acid with the ratios of the acidities of the respective media shows that these reactions have acid-catalytic character.The sulfonyl chlorides and sulfonamides in 100percent sulfuric acid are solvolyzed to a significant degree with the participation of H2S2O7.
- Ivanov, S. N.,Gnedin, B. G.
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p. 1909 - 1914
(2007/10/02)
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