- Ruthenium-Catalyzed meta-CAr–H Bond Difluoroalkylation of 2-Phenoxypyridines
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A ruthenium-catalyzed meta-selective CAr–H bond difluoroalkylation of 2-phenoxypyridine using 2-bromo-2,2-difluoroacetate has been developed. Mechanistic studies indicated that this difluoroalkylation might involve a radical process. Furthermore, a new method is reported for the synthesis of 2-(meta-difluoroalkylphenoxy)pyridine derivatives, which are present in many pharmaceuticals and other functional compounds.
- Jia, Chunqi,Wang, Shichong,Lv, Xulu,Li, Gang,Zhong, Lei,Zou, Lei,Cui, Xiuling
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supporting information
p. 1992 - 1995
(2020/03/23)
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- A directing group-assisted ruthenium-catalyzed approach to access: Meta -nitrated phenols
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meta-Selective C-H nitration of phenol derivatives was developed using a Ru-catalyzed σ-activation strategy. Cu(NO3)2·3H2O was employed as the nitrating source, whereas Ru3(CO)12 was found to be the most suitable metal catalyst for the protocol. Mechanistic studies suggested involvement of an ortho-CAr-H metal intermediate, which promoted meta-electrophilic aromatic substitution and silver-assisted free-radical pathway.
- Sasmal, Sheuli,Sinha, Soumya Kumar,Lahiri, Goutam Kumar,Maiti, Debabrata
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supporting information
p. 7100 - 7103
(2020/07/14)
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- Transition-Metal-Catalyzed Transformation of Sulfonates via S-O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether
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The catalytic conversion of sulfonates, a versatile class of pharmaceutical intermediates, is usually based on C-O bond cleavage. In this paper, however, we discover a rare transformation of sulfonates via S-O bond cleavage catalyzed by transition metal, through which alkyl sulfonates could undergo an intramolecular desulfitative C-O coupling to form aryl alkyl ethers in the presence of a nickel catalyst. Meanwhile, aryl sulfonates perform similarly to give diaryl ethers catalyzed by a palladium complex. This transformation could tolerate a wide range of functionalities. Controlled experiments reveal that the 2-pyridyl group is necessary to promote the reaction as designed. Crossover experiments proved that this transformation might proceed partly in an intermolecular pathway.
- Chen, Xuemeng,Xiao, Xue,Sun, Haotian,Li, Yue,Cao, Haolin,Zhang, Xuemei,Yang, Shengyong,Lian, Zhong
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supporting information
p. 8879 - 8883
(2019/11/14)
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- Identification of an Oxalamide Ligand for Copper-Catalyzed C?O Couplings from a Pharmaceutical Compound Library
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A typical pharmaceutical compound library is stocked with molecular diversity and could provide a platform for the discovery of new ligand structures. Herein, we describe the use of this approach in combination with high throughput screening to identify N,N’-bis(thiophene-2-ylmethyl)oxalamide as a ligand that is generally effective for copper-catalyzed C?O cross-couplings to prepare both biarylethers as well as phenols under mild conditions.
- Chan, Vincent S.,Krabbe, Scott W.,Li, Changfeng,Sun, Lijie,Liu, Yue,Nett, Alex J.
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- Chromium-Catalyzed Regioselective Kumada Arylative Cross-Coupling of C(aryl)-O Bonds with a Traceless Activation Strategy
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We report here the chromium-catalyzed regioselective Kumada arylative cross-coupling of C(aryl)-O bonds at ambient temperature. By using a simple and low-cost chromium(II) chloride salt as a precatalyst, accompanied by a 2-pyridyl ligation, the catalytic cleavage and arylative coupling of C(aryl)-O bonds were achieved with a traceless activation strategy, overcoming the regioselectivity obstacle when several C-O bonds coexist in the Kumada coupling system.
- Fan, Fei,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
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p. 13549 - 13559
(2018/10/31)
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- Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative C-H/C-H Coupling of Phenols with Aromatic Amides Using Air as Oxidant: Scope, Synthetic Applications, and Mechanistic Insights
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We herein illustrate the dual chelation-assisted strategy for a Ru(II)-catalyzed oxidative ortho-C-H/C-H cross-coupling of phenols with (hetero)aromatic amides with the aid of Zn(OTf)2, which enables to rapidly assemble a rich library of 2′-hyd
- Zhang, Luoqiang,Zhu, Lei,Zhang, Yuming,Yang, Yudong,Wu, Yimin,Ma, Weixin,Lan, Yu,You, Jingsong
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p. 8324 - 8335
(2018/09/06)
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- Decarbonylative Diaryl Ether Synthesis by Pd and Ni Catalysis
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Because diaryl ethers are present as an important motif in pharmaceuticals and natural products, extensive studies for the development of novel methods have been conducted. A conventional method for the construction of the diaryl ether moiety is the intermolecular cross-coupling reaction of aryl halides and phenols with a copper or palladium catalyst. We developed a catalytic decarbonylative etherification of aromatic esters using a palladium or nickel catalyst with our enabling diphosphine ligand to give the corresponding diaryl ethers. The present reaction can be conducted on gram scale in excellent yield. This reaction not only functions in an intramolecular setting but also allows for a cross-etherification using other phenols.
- Takise, Ryosuke,Isshiki, Ryota,Muto, Kei,Itami, Kenichiro,Yamaguchi, Junichiro
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supporting information
p. 3340 - 3343
(2017/03/15)
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- Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives
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The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed CAr-H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-CAr-H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.
- Li, Gang,Gao, Panpan,Lv, Xulu,Qu, Chen,Yan, Qingkai,Wang, Ya,Yang, Suling,Wang, Junjie
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supporting information
p. 2682 - 2685
(2017/05/24)
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- PRODUCTION METHOD FOR BI(HETERO)ARYL(THIO)ETHER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for synthesizing a bi(hetero)aryl(thio)ether compound at low cost without discharging halogen-derived waste. SOLUTION: The production method includes, for example as shown in the following formula, reacting a (thio)ester compound represented by formula (1) in the presence of a nickel catalyst (or a palladium catalyst) as well as a ligand compound to produce bi(hetero)aryl(thio)ether compound represented by formula (2). [Ar and Ar' are each independently a substituted/unsubstituted aryl group or heteroaryl group; Y is O or S.]. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0111-0115; 0117
(2017/10/31)
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- Synthesis of 2 - fluoro phenol compounds
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The present invention provides a method for synthetizing a 2-fluoro phenol compound shown in a formula IV. The phenol compound shown in the formula I is prepared into a 2-pyridine oxygroup arene compound shown in a formula II through an Ullmann reaction, the 2-pyridine oxygroup arene compound shown in the formula II is mixed with a palladium catalyst, a fluorinating reagent, an additive and an organic solvent, the mixture is stirred under the temperature of 30-160 DEG C to perform a fluorination reaction to obtain an ortho-position fluoridated 2-pyridine oxygroup arene compound shown in a formula III, and the ortho-position fluoridated 2-pyridine oxygroup arene compound shown in the formula III is prepared into the 2-fluoro phenol compound shown in the formula IV through the action of alkali. The method provided by the present invention has the advantages of mild reaction conditions, simplicity in operations, good substrate adaptability, high fluorination selectivity and the like. The 2-fluoro phenol compound is shown in the figure below.
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Paragraph 0064; 0066
(2017/04/21)
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- Para-Selective Cu-Catalyzed C-H Aryloxylation of Electron-Rich Arenes and Heteroarenes
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Cu-catalyzed reaction of phenols with electron-rich arene or heteroarene ligands of unsymmetrical diaryl-λ3-iodanes is a key step in the developed one-pot two-step method for intermolecular para-selective C-H aryloxylation of heteroarenes and arenes.
- Sokolovs, Igors,Suna, Edgars
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p. 371 - 379
(2016/01/25)
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- Rhodium-catalyzed borylation of aryl 2-pyridyl ethers through cleavage of the carbon-oxygen bond: Borylative removal of the directing group
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The rhodium-catalyzed reaction of aryl 2-pyridyl ethers with a diboron reagent results in the formation of arylboronic acid derivatives via activation of the C(aryl)-O bonds. The straightforward synthesis of 1,2-disubstituted arenes was enabled through catalytic ortho C-H bond functionalization directed by the 2-pyridyloxy group followed by substitution of this group with a boryl group. Several control experiments revealed that the presence of a sp2 nitrogen atom at the 2-position of the substrate and the use of a boron-based reagent were crucial for the activation of the relatively inert C(aryl)-O bond of aryl 2-pyridyl ethers.
- Kinuta, Hirotaka,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1593 - 1600
(2015/03/05)
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- Palladium-catalyzed oxidative olefination of phenols bearing removable directing groups under molecular oxygen
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An efficient Pd(II)-catalyzed oxidative olefination of phenols bearing removable directing groups with molecular oxygen as the sole oxidant has been developed. This reaction protocol provides an efficient and robust synthetic tool for the synthesis of o-alkenyl phenols under mild conditions.
- Liu, Bin,Jiang, Huai-Zhi,Shi, Bing-Feng
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supporting information
p. 1521 - 1526
(2014/03/21)
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- Pd(ii)-catalyzed oxidative alkoxycarbonylation of 2-phenoxypyridine derivatives with CO and alcohols
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A Pd(ii)-catalyzed oxidative alkoxycarbonylation of phenol derivatives with atmospheric pressure of CO-O2 and alcohols has been achieved. The reaction provides an efficient strategy for the synthesis of carboxylic esters and can be applied to the late-stage modification of complex molecules. This journal is the Partner Organisations 2014.
- Liu, Bin,Jiang, Huai-Zhi,Shi, Bing-Feng
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supporting information
p. 2538 - 2542
(2014/04/17)
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- Palladium-catalyzed decarboxylative coupling of α-oxocarboxylic acids with C(sp2)-H of 2-aryloxypyridines
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An efficient palladium-catalyzed decarboxylative ortho-acylation of 2-aryloxypyridines with α-oxocarboxylic acids is described. In this new transformation, the aromatic C(sp2)-H bond was successfully acylated to give diverse aromatic ketones regioselectively in moderate to good yields. The pyridine group can be removed easily after the acylation to give the corresponding 2-hydroxy aromatic ketones. Copyright
- Yao, Jinzhong,Feng, Ruokun,Wu, Zaihong,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 1517 - 1522
(2013/06/27)
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- Pd-catalyzed oxidative acylation of 2-phenoxypyridines with alcohols via C-H bond activation
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A palladium-catalyzed oxidative acylation of 2-phenoxypyridines with benzylic and aliphatic alcohols via C-H bond activation is described. This protocol represents direct access to biologically active ortho-acylphenol derivatives, and provides new opportunities to use readily available alcohols as starting materials for catalytic acylation reactions.
- Kim, Minyoung,Sharma, Satyasheel,Park, Jihye,Kim, Mirim,Choi, Yeonhee,Jeon, Yukyoung,Kwak, Jong Hwan,Kim, In Su
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p. 6552 - 6559
(2013/07/25)
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- Metal- and ligand-free Ullmann-type C-O and C-N coupling reactions promoted by potassium tert-butoxide
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A simple, metal- and ligand-free procedure for the Ullmann-type C-O coupling reactions has been achieved by allowing aryl bromides to react with a variety of phenols in the presence of t-BuOK. Moderate to excellent yields of O-arylation products are obtained under mild conditions in a short time. In addition, two examples of C-N coupling reactions are also reported. A benzyne mechanism is proposed according to the experiment data.
- Yang, Shuliang,Wu, Cunqi,Ruan, Mingbo,Yang, Yanqin,Zhao, Yongxia,Niu, Jiajia,Yang, Wei,Xu, Jingwei
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supporting information; experimental part
p. 4288 - 4292
(2012/09/22)
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- Mild addition of nucleophiles to pyridine-N-oxides
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A general and facile one-pot procedure for the synthesis of 2-substituted pyridines from the corresponding pyridine-N-oxides and nucleophiles is presented as a mild alternative to SNAr chemistry. A variety of nucleophiles and heterocyclic-N-oxi
- Londregan, Allyn T.,Jennings, Sandra,Wei, Liuqing
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supporting information; experimental part
p. 1840 - 1843
(2011/05/15)
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- Efficient iron/copper-cocatalyzed o-arylation of phenols with bromoarenes
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Low catalytic amount CuI and Fe(acac)3 were found to effectively promote the C-O cross-coupling reaction in the presence of K2CO 3 as the base. A serious of diaryl ethers with different substitutents can be synthesized in good to excellent yields. This efficient and economic method is attractive for applications on an industrial scale. Georg Thieme Verlag Stuttgart New York.
- Liu, Xiaoyan,Zhang, Songlin
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supporting information; experimental part
p. 268 - 272
(2011/03/20)
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- Discovery of dual target inhibitors against cyclooxygenases and leukotriene A4 hydrolyase
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Dual target inhibitors against COX-2 and LTA4H were designed by adding functional groups from a marketed COX-2 inhibitor, Nimesulide, to an existing LTA4H inhibitor 1-(2-(4-phenoxyphenoxy) ethyl) pyrrolidine. A series of phenoxyphenyl pyrrolidine compounds were synthesized and tested for their inhibition activities using enzyme assays and human whole blood assay. Introduction of small electron withdrawing groups like NO2 and CF3 in the ortho-position of the terminal phenyl ring was found to change the original single target LTA4H inhibitor to dual target LTA4H and COX-2 inhibitors. Compound 5a and 5m showed dual LTA 4H and COX-2 inhibition activities in the enzyme assays and the HWB assay with IC50 values in the micromolar to submicromolar range. As their activities in HWB assay were comparable to the two starting single target inhibitors, the two compounds are promising for further studies. The strategy used in the current study may be generally applicable to other dual target drug designs.
- Chen, Zheng,Wu, Yiran,Liu, Ying,Yang, Suijia,Chen, Yunjie,Lai, Luhua
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experimental part
p. 3650 - 3660
(2011/07/08)
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- Palladium(II)-catalyzed ortho arylation of 2-phenoxypyridines with potassium aryltrifluoroborates via C-H functionalization
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An efficient synthesis of ortho-arylated 2-phenoxypyridines catalyzed by palladium acetate is described. Treatment of 2-phenoxypyridines with two and a half equivalents of potassium aryltrifluoroborate and 10 mol % of Pd(OAc) 2 in the presence of two equivalents of Ag2CO3, one equivalent of p-benzoquinone (BQ), and four equivalents of DMSO with (or without) H2O at 130-140 °C for 48 h in dried CH 2Cl2 gave the ortho-arylated 2-phenoxypyridines in modest to excellent yields. p-Benzoquinone is found to be an important ligand and co-oxidant for the transmetalation reductive elimination step in the catalytic reaction. The investigation of kinetic isotope effect (kH/k D) is determined to be 5.25, which indicates that C-H bond cleavage occurs in the rate-determining step. One of the arylated compounds, 2-(4′-nitrobiphenyl-2-yloxy)pyridine, was treated with methyl trifluoromethanesulfonate and subsequently sodium methoxide to give the 2-(4-nitrophenyl)phenol in 79% yield, demonstrating that pyridine is a removable directing group.
- Chu, Jean-Ho,Lin, Pi-Shan,Wu, Ming-Jung
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experimental part
p. 4058 - 4065
(2011/01/03)
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- Highly efficient copper-catalyzed O-arylation using readily available (S)-N-methylpyrrolidine-2-carboxamide as the ligand
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A highly efficient and readily available catalyst system for O-arylation of various phenols using CuI and (S)-N-methylpyrrolidine-2-carboxamide (Pro-NHMe) was developed. The reaction is widely applicable to the synthesis of diaryl ethers. Georg Thieme Verlag Stuttgart.
- Liu, Xianghao,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 221 - 224
(2008/09/21)
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- A versatile and efficient ligand for copper-catalyzed formation of C-N, C-O, and P-C bonds: Pyrrolidine-2-phosphonic acid phenyl monoester
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A new and readily available bidentate ligand, namely, pyrrolidine-2- phosphonic acid phenyl monoester (PPAPM), has been developed for the copper-catalyzed formation of C-N, C-O, and P-C bonds, and various N-, O-, and P-arylation products were synthesized in good to excellent yields by using the CuI/PPAPM catalyst system. Addition of the PPAPM ligand greatly increases the reactivity of the copper catalyst, and the resulting versatile and efficient catalyst system is of widespread and practical application in cross-coupling reactions.
- Rao, Honghua,Jin, Ying,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 3636 - 3646
(2008/02/03)
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- Dimethylaminomethylphosphonic acid derivatives-promoted CuI-catalyzed synthesis of aryl ethers
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An inexpensive and efficient catalyst system for synthesis of aryl ethers has been developed by using 20 mol% CuI as the catalyst, 30 mol% dimethylaminomethylphosphonic acid derivatives as the new ligands, K 2CO3 as the base and toluene as the solvent. This is the first example using aminophosphonates as the ligands for Ullmann ether coupling reaction. Georg Thieme Verlag Stuttgart.
- Jin, Ying,Liu, Jinyong,Yin, Yingwu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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p. 1564 - 1568
(2007/10/03)
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- THE REACTION OF 2,2'-DIPYRIDYL SULFIDE WITH PHENOL
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The reaction of 2,2'-dipyridyl sulfide with phenol affords 2-pyridinethiol and phenyl 2-pyridyl ether, which is the aromatic ipso substitution in 2,2'-dipyridyl sulfide by the phenoxy group.On the other hand, pyridyl tolyl sulfide is formed by the reaction of phenyl pyridyl ether with toluenethiol.
- Inoue, Shordoh
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p. 141 - 144
(2007/10/02)
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