- Method for synthesizing asymmetric sulfide from molecular oxygen oxidation water phase under catalysis of water-soluble transition metal compound
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Aiming at problems that in the prior art organic solvent pollution can be caused and a great number of reaction byproducts are generated when asymmetric sulfides are prepared, the invention disclosesa method for synthesizing an asymmetric sulfide from a molecular oxygen oxidation water phase under catalysis of a water-soluble transition metal compound. The method comprises the following steps: dispersing a sulfydryl compound and a hydrazine compound as substrates in a mole ratio of 1:1 into an alkali solution, and at 40-100 DEG C, in the presence of oxygen, and with a water-soluble transitionmetal compound as a catalyst, stirring to carry out reactions, thereby obtaining the asymmetric sulfide. By adopting the method, molecular oxygen is adopted as an oxidant, and water is adopted as a solvent, so that an organic solvent is avoided, a high yield can be achieved, and the problem of byproducts can be generally avoided.
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Paragraph 0061-0064
(2019/07/29)
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- Surfactant-Type Catalyst for Aerobic Oxidative Coupling of Hydrazine with Thiol in Water
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A series of PEG-functionalized nitrogen ligands were developed to conduct an aerobic oxidative cross-coupling reaction between alkyl- or aryl-hydrazines with thiols in water. This surfactant-type catalyst enables high efficiencies and selectivities, while tolerating a large variety of functional groups. The mother liquor is still catalytically active after five runs.
- Ren, Xuanhe,Tang, Shanyu,Li, Longjia,Li, Jiao,Liang, Helong,Li, Ganzhong,Yang, Guanyu,Li, Heng,Yuan, Bingxin
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p. 8683 - 8690
(2019/07/08)
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- Aerobic copper-catalyzed decarboxylative thiolation
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Copper-catalyzed decarboxylative thiolation using molecular oxygen as the sole oxidant was developed. A variety of aromatic carboxylic acids including 2-nitrobenzoic acids, pentafluorobenzoic acid and several heteroaromatic carboxylic acids undergo efficient thiolation to furnish the aryl sulfides in moderate to excellent yields.
- Li, Minghao,Hoover, Jessica M.
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supporting information
p. 8733 - 8736
(2016/07/15)
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- Iridium and phosphine promoted C-F bond activation: The C-S cross-coupling of aryl fluorides with diaryl disulfides to synthesize thioethers
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Carbon-fluorine bond is the strongest known single bond to carbon and proved very difficult to cleave. An iridium and phosphine promoted C-F bond activation was developed, for the first time achieving the C-S cross-coupling reaction of disulfides with aryl fluorides using iridium complex. The corresponding monoarylthiolation products were obtained at moderate to good yields. Thus, it represents a new method for the synthesis of aryl sulfides through C-F bond activation.
- Li, Liang,Miao, Hongyan,Ding, Yuqiang
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supporting information
p. 6405 - 6408
(2015/11/16)
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- Bis(2-pyridyl)diselenoethers as versatile ligands for copper-catalyzed C-S bond formation in glycerol
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In this Letter, we describe a simple and efficient general methodology for CuI/bis(2-pyridyl)diselenoether-catalyzed C-S coupling reactions of aryl halides with thiols using glycerol as an environmentally friendly solvent. The products were obtained in moderate to excellent yields. The performance of CuI/L3-catalyzed C-S coupling reactions in glycerol is comparable to the related cross-coupling reactions in common organic solvents using transition-metal salts as catalyst. The use of the system CuI/L3/glycerol related in this work offers the possibility of performing the reaction in the absence of toxic organic solvents, expensive metals and using ultrasound as an alternative energy source.
- Cargnelutti, Roberta,Lang, Ernesto S.,Schumacher, Ricardo F.
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supporting information
p. 5218 - 5222
(2015/08/19)
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- Synthesis and biological evaluation of optimized inhibitors of the mitotic kinesin Kif18A
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The mitotic spindle, a highly dynamic structure composed of microtubules, mediates the segregation of the previously duplicated genome into the two nascent daughter cells. Errors in this process contribute to pathology including tumor formation. Key for the shape and function of the mitotic spindle are kinesins, molecular motor proteins that convert chemical energy into mechanical work. Due to their fast mode of action, small molecules are valuable tools to dissect the dynamic functions of kinesins during mitosis. In this study, we report the identification of optimized small molecule inhibitors of the mitotic kinesin Kif18A. Using BTB-1, the first identified Kif18A inhibitor, as a lead compound, we synthesized a collection of derivatives. We demonstrate that some of the synthesized derivatives potently inhibited the ATPase activity of Kif18A with a half maximal inhibitory concentration (IC50) value in the low micromolar range. In vitro analysis of a panel of Kif18A-related kinesins revealed that the two most potent compounds show improved selectivity compared to BTB-1. Structure-activity relationship studies identified substituents mediating undesired inhibitory effects on microtubule polymerization. In summary, our study provides key insights into the mechanism of action of BTB-1 and its analogs, which will have a great impact on the further development of highly selective and bioactive Kif18A inhibitors. Since Kif18A is frequently overexpressed in solid tumors, such compounds are not only of great interest for basic research but also have the potential to open up new strategies for the treatment of human diseases.
- Braun, Joachim,M?ckel, Martin M.,Strittmatter, Tobias,Marx, Andreas,Groth, Ulrich,Mayer, Thomas U.
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p. 554 - 560
(2015/04/21)
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- Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides
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Potassium tert-butoxide mediated carbon-chalcogen C-E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.
- Kumar, Amit,Bhakuni, Bhagat Singh,Prasad, Ch. Durga,Kumar, Shailesh,Kumar, Sangit
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p. 5383 - 5392
(2013/07/04)
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- KF/clinoptilolite: An efficient promoter for the synthesis of thioethers
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Potassium fluoride impregnated on natural zeolite as a new solid base system effectively catalyzes the coupling of thiophenols with electron-deficient fluoro-, chloro- and bromo-arenes in DMSO. This versatile and efficient solid base has been demonstrated to afford the corresponding desired products in good to excellent yields. This procedure provides a convenient, efficient and practical method for the preparation of diaryl thioethers.
- Salmanpour, Sadegh,Khalilzadeh, Mohammad A.,Hosseini, Abolfazl
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p. 339 - 344
(2013/07/28)
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- Microwave-assisted cross-coupling for the construction of diaryl sulfides
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The construction of diaryl sulfides through the cross-coupling of aryl iodides and thiols in microwave heating is described. By using this method, a variety of diaryl sulfides can be prepared in a mild condition and in high yields. Deactivated 4-nitrothiophenol was effective to afford the product in 94% yield. Sterically hindered ortho-substituted aryl iodides or thiophenols provided diaryl sulfides effectively by this microwave-assisted coupling reaction.
- Tan, Chen-Ming,Chen, Grace Shiahuy,Chena, Chien-Shu,Chern, Ji-Wang
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experimental part
p. 94 - 100
(2011/11/06)
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- Synthesis of aryl sulfides by decarboxylative C-S cross-couplings
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A study was conducted to demonstrate the transition-metal-catalyzed synthesis of aryl sulfides by decarboxylative C-S cross-couplings. Coupling reaction of 2-nitrobenzoic acid with 1-octanethiol were carried in the presence of different combinations of tr
- Duan, Zhongyu,Ranjit, Sadananda,Zhang, Pengfei,Liu, Xiaogang
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supporting information; experimental part
p. 3666 - 3669
(2009/12/07)
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- Rhodium-catalyzed substitution reaction of aryl fluorides with disulfides: P-orientation in the polyarylthiolation of polyfluorobenzenes
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In the presence of a catalytic amount of RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene, an aromatic fluoride, an organic disulfide (0.5 equiv), and triphenylphosphine (0.5 equiv) reacted in refluxing chlorobenzene to give an aryl sulfide in high yield. Since triphenylphosphine trapped fluoride atoms forming phosphine difluoride, both organothio groups of the disulfide reacted effectively, and the fluoride substituent reacted more readily than the chloride and bromide. The reaction of hexafluorobenzene and a diaryl disulfide gave 1,4-diarylthio-2,3,5,6-tetrafluorobenzene, 1,2,4,5-tetraarylthio-3,6-difluorobenzene, and hexaarylthiobenzene in a stepwise manner; pentafluorobenzene gave 1-arylthio-2,3,5,6-tetrafluorobenzene; 1,2,3,4-tetrafluorobenzene gave 1,2-diarylthio-3,6-difluorobenzene; and 1,2,4,5-tetrafluorobenzene gave 1,4-diarylthio-2-5-difluorobenzene. The polyarylthiolation reaction of polyfluorobenzenes exhibited a strong tendency to form 1,4-difluorobenzenes. Copyright
- Arisawa, Mieko,Suzuki, Takaaki,Ishikawa, Tomofumi,Yamaguchi, Masahiko
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supporting information; scheme or table
p. 12214 - 12215
(2009/02/04)
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- Discovery and SAR development of 2-(phenylamino) imidazolines as postacyclin receptor antagonists
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On the basis of screening hits (1a,b), a series of selective, high affinity prostacyclin receptor antagonists was developed. The optimized lead compound 25d [(4,5-dihydro-1H-imidazol-2-yl)-[4-(4-isopropoxybenzyl)phenyl] amine] had analgesic activity in the rat.
- Clark, Robin D.,Jahangir, Alam,Severance, Daniel,Salazar, Rick,Chang, Thomas,Chang, David,Jett, Mary Frances,Smith, Steven,Bley, Keith
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p. 1053 - 1056
(2007/10/03)
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- Nitrophenyl derivatives as aldose reductase inhibitors
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Nitrophenyl derivatives were recently discovered as a new class of ALR2 inhibitors by means of docking and database screening of the National Cancer Institute database of organic molecules. The nitro group was predicted to bind to the Tyr48 and His110 act
- Costantino, Luca,Ferrari, Anna Maria,Gamberini, Maria Cristina,Rastelli, Giulio
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p. 3923 - 3931
(2007/10/03)
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- Synthesis of diaryl ethers, diaryl thioethers, and diarylamines mediated by potassium fluoride-alumina and 18-crown-6: Expansion of scope and utility
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An efficient alternative to the Ullmann ether synthesis of diaryl ethers, diaryl thioethers, and diarylamines involving the S(N)Ar addition of a phenol, thiophenol, or aniline to an appropriate aryl halide, mediated by potassium-fluoride alumina and 18-crown-6 in acetonitrile or DMSO, is described. Expansion of the reaction conditions to include DMSO as solvent has resulted in a far greater range of substitution patterns permitted on the electrophile. For example, it was found that electronically unfavorable 3- chlorobenzonitrile could be condensed with 3-methoxyphenol to form the corresponding diaryl ether in 66% yield, a combination not normally amenable to Ullmann coupling. Electron-withdrawing groups present on the electrophile may be as diverse as nitro, cyano, formyl, acetyl, ester, amide, and even aryl. The method features a simple reaction procedure that provides products in generally good to excellent purified yields.
- Sawyer, J. Scott,Schmittling, Elisabeth A.,Palkowitz, Jayne A.,Smith III, William J.
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p. 6338 - 6343
(2007/10/03)
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- Syntheses and photophysical properties of fluorescent dibenzofurans, a dibenzothiophene, and carbazoles substituted with bensoxazole and hydroxyl groups to produce excited state intramolecular proton-transfer
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Dibenzofurans, a dibenzothiophene, and carbazoles, each substituted with a 2-benzoxazolyl group as well as an ortho-hydroxyl group, were synthesized to produce fluors with fluorescence due to excited-state intramolecular proton-transfer. The orientations for Friedel-Crafts acylation of 3-methoxydibenzothiophene and of the analogous carbazole were determined. The fluors displayed absorption peaks in the 330-385 nm region with molar extinction coefficients up to 57,000. Fluorescence quantum efficiencies of 0.17-0.44 were obtained at wavelengths that had peak values from 540-600 nm. The fluors are of potential use as wavelength shifters in scintillating polystyrene fibers.
- Kauffman,Litak,Boyko
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p. 1541 - 1555
(2007/10/03)
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- MOLECULAR POLARIZABILITY OF ORGANIC COMPOUNDS AND THEIR COMPLEXES. XLIV. CONFORMATIONS OF DIARYL SULFONES IN DIOXANE
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We determined molar Kerr constants and dipole moments in dioxane solutions for a number of diaryl sulfones with various substituents in the aromatic nuclei.The data obtained were analyzed to establish the preferential molecular conformations.It was shown that diaryl sulfones occur in solution mainly in the form of orthogonal or planar-orthogonal conformers, or as an equilibrium between these two.In the orthogonal conformer both aromatic rings are perpendicular to the plane of the CArSCAr bonds, whereas in the planar-orthogonal conformer one ring is coplanar and the other orthogonal to this plane.The orthogonal orientation of aromatic rings relative to the CArSCAr plane originates from the ?-conjugation of the nuclei and the sulfonyl gruop of the sulfone molecules.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Filippov, S. E.,Finocchiaro, P.,Failla, S.
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p. 379 - 387
(2007/10/02)
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- Conformational investigation of diarylsulphides by Kerr effect and dipole moment methods
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Molar Kerr constants and electric dipole moments are reported for (4-NO2C6H4)2S, (4-MeOC6H4)2S, (4-MeOC6H4)(4'-NO2C6H4)S, (2-MeOC6H4)(4'-NO2C6H4)S, (4-MeOC6H4)(2'-NO2C6H4)S, (2-MeOC6H4)(2'-NO2C6H4)S and (4-ClC6H4)2SO as solutes in dioxane at 298 K.The data are analysed in terms of the preferred conformations adopted in solution.In most cases these data are consistent with the presence, in dioxane, of helical conformers, where both aromatic rings are twisted in the same direction with respect to the CAr-S-CAr molecular reference plane.The (4-ClC6H4)2SO molecule adopts an orthogonal conformation where both aryl rings are approximately perpendicular to the CAr-S-CAr molecular reference plane.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Finocchiaro, P.,Failla, S.
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p. 207 - 222
(2007/10/02)
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- Conformational investigation of diarylsulphones by Kerr effect and dipole moment methods
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Molar Kerr constants and electric dipole moments are reported for (C6H5)2SO2, (4Cl-C6H4)(C6H5)SO2, (2,4,6-Me3C6H2)(4'-Br-C6H4)SO2, (4-NO2C6H4)2SO2, (4-MeOC6H4)(4'-NO2C6H4)SO2, (2-MeOC6H4)(4'-NO2C6H4)SO2, (2-NO2C6H4)(4'-MeOC6H4)SO2 and (2-MeOC6H4)(2'-NO2C6H4)SO2 as solutes in dioxane solution at 298 K.The data are analysed in terms of the preferred conformations adopted in solution.In most cases these data are consistent with the presence, in dioxane, of orthogonal or planar-orthogonal conformers, or of a mixture of them.In the orthogonal rotamer both aromatic rings are approximately perpendicular to the CAr-S-CAr molecular reference plane whereas in the planar-orthogonal conformer one ring is coplanar and the other is orthogonal to the reference CAr-S-CAr plane.
- Bulgarevich, S. B.,Movshovich, D. Ya.,Ivanova, N. A.,Filippov, S. E.,Finocchiario, P.,Failla, S.
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p. 365 - 376
(2007/10/02)
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- Diphenyl ethers for tobacco sucker control
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Diphenyl ethers having the formula STR1 WHERE Y and Z are halogen, alkyl, trifluoromethyl, alkoxy, hydroxy, nitro, cyano, carboxy, carbalkoxy, carbamoyl, or alkylthio, and m and n are 0, 1, 2, or 3, Are useful in controlling undesirable secondary growth in plants, particularly sucker growth in tobacco.
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