- Practical access to aromatic thiocyanates by CuCN-mediated direct aerobic oxidative cyanation of thiophenols and diaryl disulfides
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The practical and mild aerobic oxidative CuCN-mediated cyanation of thiophenols and diaryl disulfides was investigated. The reaction was performed in air at room temperature and reached aromatic thiocyanates in moderate to good yields starting from a broad range of diversely functionalized substrates.
- Castanheiro, Thomas,Gulea, Mihaela,Donnard, Morgan,Suffert, Jean
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- NEW METHODS AND REAGENTS IN ORGANIC SYNTHESIS. 23. DIETHYL PHOSPHOROCYANIDATE(DEPC): A USEFUL REAGENT FOR AN UNPRECEDENTED TRANSFORMATION OF SULFINIC ACIDS TO THIOCYANATES
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Diethyl phosphorocyanidate(DEPC) can be efficiently used for a simple, one-step transformation of sulfinic acids to thiocyanates.
- Harusawa, Shinya,Shioiri, Takayuki
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- Temperature-Controlled Chemoselective Synthesis of Thiosulfonates and Thiocyanates: Novel Reactivity of KXCN (X=S, Se) towards Organosulfonyl Chlorides
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An efficient chemoselective protocol has been developed for the synthesis of thiosulfonates and thiocyanates by employing cost effective and commercially available organosulfonyl chlorides with potassium thio-/selenocyanate. The strategy offered the thiosulfonates and thiocyanates selectively by tuning the equivalents of KSeCN and optimizing the reaction temperature. On the other hand, thiosulfonates were obtained as sole products when organosulfonyl chlorides were treated with KSCN. Furthermore, the syntheses of diarylthioethers and aryl(heteroaryl) thioethers were carried out as a part of synthetic application of newly prepared arylthiocyanates.
- Kalaramna, Pratibha,Goswami, Avijit
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supporting information
p. 5359 - 5366
(2021/10/25)
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- Synthesis of Thio-/Selenopyrrolines via SnCl4-Catalyzed (3+2)-Cycloadditions of Donor-Acceptor Cyclopropanes with Thio-/Selenocyanates
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A straightforward protocol has been developed to access thio-/selenopyrrolines through a (3+2)-cycloaddition of aryl thio-/selenocyanates with donor-acceptor cyclopropanes (DACs) in the presence of SnCl4 as a Lewis acid catalyst. Further, good chemoselectivity was observed when DACs were treated with 3-cyano phenyl thiocyanate. These results suggest that thiocyanate is more reactive than nitrile moiety in such (3+2)-cycloaddition reactions.
- Ali, Shamsad,Goswami, Avijit,Kalaramna, Pratibha,Singh, Prasoon Raj
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supporting information
p. 4683 - 4689
(2021/09/10)
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- Selectfluor-initiated cyanation of disulfides to thiocyanates
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A Selectfluor-initiated cyanation of disulfides to thiocyanates has been developed. In this process, Selectfluor was employed as the oxidant and trimethylsilyl cyanide was used as the cyanation reagent. It provides an eco-friendly and simple way to synthesize the thiocyanates.
- Zhou, Pengpeng,Chen, Chuan,Li, Shubai
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p. 376 - 380
(2020/02/13)
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- Two-Phase Electrochemical Generation of Aryldiazonium Salts: Application in Electrogenerated Copper-Catalyzed Sandmeyer Reactions
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The electrochemical generation of aryldiazonium salts from nitroarenes in a two-phase system (ethyl acetate/water) was reported for the first time. Some compounds including azo, azosulfone, and arylazides were prepared in good yields with good purity. Cathodically generated aryldiazoniums and anodically produced copper(Ι) ions were used to perform Sandmeyer reactions. To improve the method, an H-type self-driving cell equipped with a Zn rod as an anode was introduced and used for two-phase aryldiazonium production.
- Goljani, Hamed,Tavakkoli, Zahra,Sadatnabi, Ali,Nematollahi, Davood
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supporting information
p. 5920 - 5924
(2020/08/12)
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- Fluorium-Initiated Dealkylative Cyanation of Thioethers to Thiocyanates
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Thioethers are converted to thiocyanates via fluorium-initiated dealkylative cyanation. Selectfluor is used as the oxidant, and trimethylsilyl cyanide is used as the cyanation reagent. The well-streamlined procedure is user-friendly, operationally simple, and step-economical. The current mechanistic studies show that the sulfur radical cation and cyano radical are both involved. They combine to deliver cyanosulfonium, an intermediate toward thiocyanate after dealkylation. Alternatively, a nucleophilic mechanism is also possible. Our dealkyaltive cyanation is also efficient in synthesizing thiocyanates with strongly electrophilic functionalities.
- Chen, Yang,Qi, Hongyi,Chen, Ning,Ren, Demin,Xu, Jiaxi,Yang, Zhanhui
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p. 9044 - 9050
(2019/08/12)
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- Direct Photocatalytic S-H Bond Cyanation with Green cN Source
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Herein we report a novel C-S bond cleavage and reconstruction strategy for the synthesis of thiocyanates through direct photocatalytic S-H bond cyanation from thiols and inorganic thiocyanate salts. In our strategy, the unprecedented example of cutting off C-S bond of SCN- to deliver the green CN sources is demonstrated. This transformation features nontoxic and inexpensive CN sources, available starting materials, metal-/base-/ligand-/peroxide-free, high step economy and mild conditions. It leads to the construction of various thiocyanates and some medicinally and biologically active thiocyanate-containing molecules.
- Guo, Wei,Tan, Wen,Zhao, Mingming,Zheng, Lvyin,Tao, Kailiang,Chen, Deliang,Fan, Xiaolin
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supporting information
p. 6580 - 6588
(2018/05/29)
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- Preparation method for thiocyanide compound
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The invention discloses a preparation method for a thiocyanide compound. The preparation method comprises the following steps: taking a sulfhydryl compound, thiocyanate as raw materials, taking rose-bengal, eosine Y or eosin B as a catalyst, performing illumination, generating a thiocyanide compound after the illumination reaction. According to the preparation method provided by the invention, thiocyanide is decomposed into thiocyanate ions; the sulfhydryl compound generates sulfhydryl radical under the action of light and the catalyst, and the sulfhydryl radical is used for attacking carbon atoms in thiocyanate ions to obtain a intermediate; sulfide is removed from the intermediate to obtain the thiocyanide compound. The rose-bengal, the eosine Y or the eosin B used by the method containno heavy metal ion, and the adverse effect on the performance of the thiocyanide compound by the heavy metal ion residue is avoided; in addition, the catalyst is easily removed, so that a favorable condition is provided for the preparation of the thiocyanide compound with higher purity.
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Paragraph 0106; 0107; 0112; 0113
(2018/06/16)
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- Synthesis of perfluoroalkyl thioethers from aromatic thiocyanates by iron-catalysed decarboxylative perfluoroalkylation
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Easily available aryl and heteroaryl thiocyanates were converted into the corresponding perfluoroalkyl thioethers via decarboxylation of potassium perfluoroalkylcarboxylates, catalysed by the inexpensive and environmentally benign iron(III) chloride.
- Exner, Benjamin,Bayarmagnai, Bilguun,Matheis, Christian,Goossen, Lukas J.
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supporting information
p. 89 - 93
(2017/06/23)
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- SUBSTITUTED IMIDAZOLIUM SULFURANES AND THEIR USE
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The present invention refers to substituted imidazolium sulfuranes, the use thereof for the transfer of a -CN group or an alkyne group.
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Page/Page column 13; 14; 15
(2017/01/26)
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- One-pot synthesis of (ethoxycarbonyl)difluoromethylthioethers from thiocyanate sodium and ethyl 2-(trimethylsilyl)-2,2-difluoroacetate (TMS-CF2CO2Et)
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An efficient one-pot cascade methodology for the synthesis of (ethoxycarbonyl)difluoromethyl thioethers is described. Benzyl, allyl, alkyl halides or diazonium salts as the starting materials together with thiocyanate sodium and TMS-CF2CO2Et in the presence of CsF or NaOAc afford a variety of the fluoroalkylthiolated products in moderate to good yields.
- Xu, Lijun,Wang, Hongyu,Zheng, Changwu,Zhao, Gang
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p. 6057 - 6066
(2017/09/23)
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- Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
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Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
- Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
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supporting information
p. 17220 - 17223
(2016/01/25)
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- Nitromethane as a cyanating reagent for the synthesis of thiocyanates
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Nitromethane has been developed to be an effective cyanating reagent for the synthesis of thiocyanates. In the presence of iodine and base, a wide range of disulfides were reacted with nitromethane smoothly to give diverse thiocyanates in moderate to good yields.
- Wang, Zuo-Hui,Ji, Xiao-Ming,Hu, Mao-Lin,Tang, Ri-Yuan
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supporting information
p. 5067 - 5070
(2015/08/06)
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- Dihalo(imidazolium)sulfuranes: A Versatile Platform for the Synthesis of New Electrophilic Group-Transfer Reagents
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The syntheses of imidazolium thiocyanates and imidazolium thioalkynes from dihalo(imidazolium) sulfuranes are reported and their reactivities as CN+ and R-CC+ synthons evaluated, respectively. The easy and scalable preparation of these electrophilic reagents, their operationally simple handling, broad substrate scope, and functional group tolerance clearly illustrate the potential of these species to become a reference for the direct electrophilic cyanation and alkynylation of organic substrates.
- Talavera, Garazi,Pe?a, Javier,Alcarazo, Manuel
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supporting information
p. 8704 - 8707
(2015/07/27)
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- Synthesis of difluoromethyl thioethers from difluoromethyl trimethylsilane and organothiocyanates generated in situ
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A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts. This strategy enables the introduction of difluoromethylthio groups - a largely unexplored substituent with highly promising properties - into drug-like molecules. A copper-CF2H complex generated in situ from copper thiocyanate and TMS-CF2H smoothly converts organothiocyanates into valuable difluoromethyl thioethers. This reaction step can be combined with several thiocyanation methods to one-pot protocols, allowing late-stage difluoromethylthiolations of widely available alkyl halides and arenediazonium salts.
- Bayarmagnai, Bilguun,Matheis, Christian,Jouvin, Kvin,Goossen, Lukas J.
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p. 5753 - 5756
(2015/06/10)
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- Transition-metal-free cross-coupling of thioethers with aryl(cyano)iodonium triflates: A facile and efficient method for the one-pot synthesis of thiocyanates
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A novel transition-metal-free cross-coupling method for the one-step synthesis of thiocyanates via the C-S bond cleavage of readily available thioethers with aryl(cyano)-iodonium triflates as the cyanating agent is developed. This process features relatively broad substrate scopes, less-toxic hypervalent iodine reagents, mild operating conditions, excellent functional group compatibilities, and affords various thiocyanates in moderate to good yields. This journal is
- Zhu, Dan,Chang, Denghu,Shi, Lei
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supporting information
p. 7180 - 7183
(2015/04/27)
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- General and practical formation of thiocyanates from thiols
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A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.
- Frei, Reto,Courant, Thibaut,Wodrich, Matthew D.,Waser, Jerome
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supporting information
p. 2662 - 2668
(2015/02/05)
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- A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS
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A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups.
- Sun, Nan,Che, Liusheng,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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supporting information
p. 691 - 696
(2015/02/19)
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- Copper-catalyzed cyanation of disulfides by azobisisobutyronitrile leading to thiocyanates
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The copper-catalyzed cyanation of disulfides by azobisisobutyronitrile (AIBN) was developed, leading to thiocyanates in moderate to good yields. This procedure tolerates a series of functional groups, such as chloro, nitro, methyl and methoxycarbonyl in the phenyl ring of disulfides. Notably, it enables the use of two ArS units in (ArS)2. CuI was found to be essential for the in situ formation of cyanide anions. This journal is
- Teng, Fan,Yu, Jin-Tao,Yang, Haitao,Jiang, Yan,Cheng, Jiang
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supporting information
p. 12139 - 12141
(2014/12/11)
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- Synthesis of aryl thiocyanates via copper-catalyzed aerobic oxidative cross-coupling between arylboronic acids and KSCN
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A new protocol for the preparation of aryl thiocyanates by the cross-coupling reaction of arylboronic acids with KSCN salt is described. The coupling reaction was catalyzed by 20 mol% of copper acetate in the presence of 2.0 equivalents 4-methylpyridine serving both as ligand and base under 0.2 MPa of molecular oxygen. A variety of arylboronic acids, including those with substituents at ortho position, were suitable under the reaction conditions. Georg Thieme Verlag Stuttgart · New York.
- Sun, Nan,Zhang, Han,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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supporting information
p. 1443 - 1447
(2013/07/26)
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- Catalytic thiocyanation of aryldiazonium salts in the presence of copper salts
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Aryldiazonium fluoroborates readily react with potassium thiocyanate in the presence of the CuI/CuII/Phen catalytic system to give arylthiocyanates in high yields.
- Beletskaya, Irina P.,Sigeev, Alexander S.,Peregudov, Alexander S.,Petrovskii, Pavel V.
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p. 250 - 251
(2007/10/03)
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- Improved procedure to aryl thiocyanates: A new synthetic application of dry arenediazonium o-benzenedisulfonimides
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Aryl thiocyanates 3 (22 examples) were easily prepared by reaction of dry arenediazonium o-benzenedisulfonimides 1 and sodium thiocyanate (2) in anhydrous acetonitrile at room temperature (20-25 °C) in the presence of copper powder (Procedure A) and at 50 °C or room temperature without the metal catalyst (Procedure B). The yields were from very good to excellent in Procedure A (average yield = 83%), and from modest to excellent in Procedure B (average yield = 63%). In comparison with the thiocyanod-ediazoniation carried out under traditional Sandmeyer-type conditions, the yields of 3 were higher and the isothiocyanate isomers were formed only in traces. Moreover, the results obtained in the absence of copper confirm the role of the anion of salts 1 as an electron transfer agent.
- Barbero,Degani,Diulgheroff,Dughera,Fochi
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p. 585 - 590
(2007/10/03)
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- Pyridine N-Sulphides. Some Simple N-Arylthiopyridinium Salts and a Possible Source of Arylsulphenium Ions
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N,N'-Dipyridinium disulphide dichloride (1) and 1-(4-nitrophenylthio)pyridinium chloride (5) and its 4-NMe2 derivative (2) have been synthesized and their structures established unambiguously; they undergo nucleophilic attack at sulphur rather than in the
- Abramovitch, Rudolph A.,Miller, Adrian L.,Pilski, Jacek
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p. 703 - 704
(2007/10/02)
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- Effect of Solvation on the Nucleophilic Reaction of Stable Carbanions with Diaryl Disulfides
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Stable carbanions react with diaryl disulfides in aqueous solution by direct displacement (SN2) reaction to yield an arylthiol anion and the corresponding sulfide as products.The reaction of 1,3-dicarbonyl carbanions with 5,5'-dithiobis(2-nitrobenzoic acid) is characterized by Broensted βC value of 0.5.Nitroalkane carbanions react 102-104 slower than 1,3-dicarbonyl carbanions of the same pK and are correlated by a Broensted βC of 0.95.The second-order rate constants for the reaction of nitroalkane carbanions increase by factors of 104-106 as the solvent is changed from water to dimethyl sulfoxide.Smaller increases are observed in the rate constants for reaction of 2,4-pentadienone carbanion (102) and malonitrile carbanion (100.6) with the same sulfide.A linear correlation is found between log (kMe2SO4/kHOH) and the increase in pK for the carbon acid ionization on changing the solvent from water to dimethyl sulfoxide.The effect is attributed to large differences in ground-state carbanion solvation which are reduced or absent in the transition state.Parallels are drawn between the nucleophilic reaction of stable carbanions with diaryl disulfides and proton-transfer reactions of the same carbanions.
- Gilbert, H. F.
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p. 7059 - 7065
(2007/10/02)
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