- CONFORMATIONAL CONSEQUENCES OF INTRAMOLECULAR HYDROGEN BONDING BY OH TO THE DIRECTIONAL LONE-PAIR OF SULFUR IN DERIVATIVES OF METHYL PHENYL SULFIDE, DIPHENYL SULFIDE, AND DIPHENYL DISULFIDE
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Complete spectral parameters for the 1H nmr spectra of 2-hydroxyphenyl methyl sulfide, 2, 2-hydroxyphenyl phenyl sulfide, 3, bis(2-hydroxy-3-tert-butyl-5-methylphenyl) sulfide, 4, and bis(2-hydroxyphenyl)disulfide, 5, are reported for CCl4 solu
- Schaefer, Ted,Salman, Salman R.,Wildman, Timothy A.,Clark, Peter D.
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- Regioselective Ortho‐C–H sulfenylation of free phenols catalyzed by Co(II)-immobilized on silica-coated magnetic nanoparticles
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Fe3O4?SiO2-UT?CoII is prepared by the silica-coated magnetic nanoparticles, urea-triazole, and CoCl2. This organic-inorganic hybride composite showed a good to excellent catalytic activity toward regioselective ortho-sulfenylation of free phenols and naphthols using pivalic anhydride as a directing group, also K2S2O8 and PPh3 were employed as oxidant and additive respectively. The newly synthesized catalyst was fully characterized by using different techniques such as FT-IR, TGA, DTG, TEM, SEM, EDS, ICP and VSM analyses. The competitive price, accessibility and lower toxicity of cobalt compared to expensive transition metals using for C–H bond activation and functionalization constitute precious advantages for this method. Moreover, this heterogeneous catalyst could be magnetically recovered and reused without significant loss of its catalytic activity after five cycles.
- Khaef, Sepideh,Rostami, Abed,Khakyzadeh, Vahid,Zolfigol, Mohammad Ali,Taherpour, Avat Arman,Yarie, Meysam
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- Achieving Nickel Catalyzed C-S Cross-Coupling under Mild Conditions Using Metal-Ligand Cooperativity
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A simple and efficient approach of C-S cross-coupling of a wide variety of (hetero)aryl thiols and (hetero)aryl halides under mild conditions, mostly at room temperature, catalyzed by well-defined singlet diradical Ni(II) catalysts bearing redox noninnocent ligands is reported. Taking advantage of ligand centered redox events, the high-energetic Ni(0)/Ni(II) or Ni(I)/Ni(III) redox steps were avoided in the catalytic cycle. The cooperative participation of both nickel and the coordinated ligands during oxidative addition/reductive elimination steps allowed us to perform the catalytic reactions under mild conditions.
- Sikari, Rina,Sinha, Suman,Das, Siuli,Saha, Anannya,Chakraborty, Gargi,Mondal, Rakesh,Paul, Nanda D.
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p. 4072 - 4085
(2019/04/01)
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- Phenyldithiocarbamates: Efficient Sulfuration Reagents in the Chan–Lam Coupling Reaction
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The Chan–Lam coupling reaction starting from phenyldithiocarbamates and phenylboronic acids is reported. To avoid using the volatile, hazardous, and foul-smelling thiols, which are sometimes expensive and not sufficiently available, phenyldithiocarbamates can be employed. They are demonstrated to be good sulfuration reagents in the Chan–Lam coupling to prepare biaryl sulfides. By using this protocol, dithiocarbamate substrates with a wide range of functional groups including electron-rich and electron-deficient ones are explored to obtain the desired substituted biaryl sulfides smoothly. This method is ligand-free, has a broad substrate scope, enables good yields, and is easy to perform. It provides a facile and convenient preparation of biaryl sulfides.
- Cheng, Yu,Liu, Xing,Dong, Zhi-Bing
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p. 815 - 820
(2018/02/21)
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- SULFONIUM COMPOUND, RESIST COMPOSITION, AND PATTERN FORMING PROCESS
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A sulfonium compound having formula (1) is provided wherein R1, R2 and R3 are a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, p=0-5, q=0-5, and r=0-4. A resist composition comprising the sulfonium compound is processed by lithography to form a resist pattern with improved LWR and pattern collapse.
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Paragraph 0172-0173
(2018/04/20)
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- SINGLE-STEP SYNTHESIS METHOD OF ARYL THIOL AND APPLICATION THEREOF
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The present invention relates to a single-step synthesis method of aryl thiol, and more specifically, to a method of synthesizing aryl thiol in a single-step by making aryl halide react with alkane dithiol in the presence of a transition metal catalyst. According to the present invention, a single-step synthesis method using the transition metal catalyst, the synthesis method which is capable of synthesizing aryl thiol from aryl halide at a high yield, can be provided. Various aryl halides may be applied to the synthesis method. Further, the synthesis method has advantages that an easily usable reagent may be used, operations are simple, and reactions can be performed under mild conditions. In addition, the synthesized aryl thiol may be used in the synthesis of advanced molecules such as diaryl sulfides and benzothiophenes.COPYRIGHT KIPO 2017
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Paragraph 0038; 0039; 0083; 0087; 0089; 0091
(2017/09/02)
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- Nickel-Catalyzed C–S Coupling: Synthesis of Diaryl Sulfides Starting from Phenyldithiocarbamates and Iodobenzenes
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A nickel-catalyzed C–S bond-formation protocol for the synthesis of diaryl sulfides is described. In a reaction catalyzed by NiCl2, phenyldithiocarbamates react with iodobenzenes to give diaryl sulfides smoothly in good to excellent yields (66–93 %). The catalyst is cheap, the reaction is easy to carry out, the substrate scope is broad, and the yields are good. Thus, this gives an alternative way to prepare diaryl sulfides.
- Liu, Xing,Cao, Qiang,Xu, Wan,Zeng, Meng-Tian,Dong, Zhi-Bing
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p. 5795 - 5799
(2017/10/23)
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- Reaction of Arynes with Vinyl Sulfoxides: Highly Stereospecific Synthesis of ortho-Sulfinylaryl Vinyl Ethers
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The reaction of in situ generated arynes with aryl vinyl sulfoxides provides ortho-arylsulfinylaryl vinyl ethers via aryne σ-bond insertion into the S-O-bond and concomitant stereospecific S-O-vinyl migration. The cascade allows preparing di- or trisubsti
- Li, Yuanming,Studer, Armido
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p. 666 - 669
(2017/02/10)
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- Calix[8]arene nanoreactor for Cu(i)-catalysed C-S coupling
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The catalytic activity of Cu(i) confined within a phenanthroline-containing calix[8]arene derivative was tested in C-S cross-coupling reactions. The substrate selectivity, solvent dependence, and catalyst loading differ significantly from those reported for bimetallic molecular systems. The putative monomeric complex represents the first calix[8]arene functionalised for endo-oriented metal chelation used as a nanoreactor.
- Guzmán-Percástegui, Edmundo,Hernández, David J.,Castillo, Ivan
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supporting information
p. 3111 - 3114
(2016/02/23)
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- Copper-Catalyzed Reaction Cascade of Thiophenol Hydroxylation and S-Arylation through Disulfide-Directed C-H Activation
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Copper-catalyzed thiophenol C-H activation is described. Through an initial attempt to conduct C-arylation with arylboronic acid, a rather surprising sequential C-H activation and S-arylation was discovered. Mechanistic investigation revealed the disulfide intermediate as the key component in directing C-H oxidation. The overall reaction proceeded under mild conditions with molecular oxygen as the oxidant. Discovery of disulfide as the directing group provides a potential new direction for catalytic C-H functionalization under mild conditions.
- Wang, Dawei,Yu, Xin,Yao, Wei,Hu, Wenkang,Ge, Chenyang,Shi, Xiaodong
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supporting information
p. 5543 - 5546
(2016/04/20)
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- Efficient method for selectively synthesizing 2-hydroxybenzene sulfur ether compound
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The invention provides an efficient method for selectively synthesizing a 2-hydroxybenzene sulfur ether compound. The method includes the steps of making a thiophenol compound shown in the formula (I) and an aryl halide compound shown in the formula (II) sufficiently react in a reaction medium with dimethyl sulfoxide as solvent under the effects of a catalyst, ligand and alkali carbonate to prepare a reagent, and conducting postprocessing on the reagent to prepare the 2-hydroxybenzene sulfur ether compound, wherein cuprous iodide serves as the catalyst, enaminone serves as the ligand, and cesium carbonate serves as the alkali carbonate. R1 in the formula (I) or the formula (II) is selected from one of alkyl and halogen. R2 in the formula (II) or the formula (III) is selected from one of methoxyl, halogen and trifluoromethyl. Raw materials can be easily obtained, the synthesis condition is gentle, the chemical selectivity is high and controllable, cost is saved, the requirements for devices are low, solvent and water can dissolve each other, postprocessing is convenient, the catalytic system is wide in adaptability, and the method is suitable for large-scale industrialized production.
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Paragraph 0017; 0018
(2016/10/08)
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- The convenient synthesis and reaction of 2-(arylthio)phenols under ligand-free conditions: arylthioquinone preparation through cascade C–H functionalization and oxidation from arylthiols and aryl iodides
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A convenient and simple method for copper-catalyzed synthesis of 2-(arylthio)phenols through C–H functionalization of arylthiols and aryl iodides was developed under ligand-free conditions without nitrogen protection. In addition, arylthioquinone derivatives were very easily prepared for one more step of oxidation with moderate to good yields. This provide an alternative and efficient way to 2-(arylthio)phenols and arylthioquinone derivatives smoothly without using ligands and nitrogen protection or expensive arylboronic acids.
- Wang, Dawei,Yu, Xiaoli,Wang, Likui,Yao, Wei,Xu, Zhaojun,Wan, Huida
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p. 5211 - 5214
(2016/11/13)
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- Copper(II)-Catalyzed Single-Step Synthesis of Aryl Thiols from Aryl Halides and 1,2-Ethanedithiol
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A highly efficient transition metal-catalyzed single-step synthesis of aryl thiols from aryl halides has been developed employing copper(II) catalyst and 1,2-ethanedithiol. The key features are use of readily available reagents, a simple operation, and relatively mild reaction conditions. This new protocol shows a broad substrate scope with excellent functional group compatibility. A variety of aryl thiols are directly prepared from aryl halides in high yields. Furthermore, the aryl thiols are used in situ for the synthesis of more advanced molecules such as diaryl sulfides and benzothiophenes.
- Liu, Yajun,Kim, Jihye,Seo, Heesun,Park, Sunghyouk,Chae, Junghyun
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supporting information
p. 2205 - 2212
(2015/07/27)
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- Iodine-promoted 2-arylsulfanylphenol formation using cyclohexanones as phenol source
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A novel method for the formation of 2-arylsulfanylphenols using cyclohexanones as phenol source via dehydrogenation is described. Various aromatic sodium sulfinates and sulfonyl chlorides acted as efficient coupling partners to construct new C-S bonds in the presence of an iodine promoter.
- Chen, Ya,Xiao, Fuhong,Chen, Hui,Liu, Saiwen,Deng, Guo-Jun
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p. 44621 - 44628
(2014/12/10)
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- Continuous-flow synthesis of functionalized phenols by aerobic oxidation of grignard reagents
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Phenols are important compounds in chemical industry. An economical and green approach to phenol preparation by the direct oxidation of aryl Grignard reagents using compressed air in continuous gas-liquid segmented flow systems is described. The process tolerates a broad range of functional groups, including oxidation-sensitive functionalities such as alkenes, amines, and thioethers. By integrating a benzyne-mediated in-line generation of arylmagnesium intermediates with the aerobic oxidation, a facile three-step, one-flow process, capable of preparing 2-functionalized phenols in a modular fashion, is established. Putting on airs: Aerobic oxidation of (hetero)aryl Grignard reagents using compressed air proceeds with a gas-liquid continuous-flow system, thus enabling preparation of fucntionalized phenols. By integrating an in-line generation of ArMgBr intermediates with the aerobic oxidation, ortho-functionalized phenols can be assembled. The method demonstrates good functional-group (FG) compatibility, mild reaction conditions, and short reaction times.
- He, Zhi,Jamison, Timothy F.
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supporting information
p. 3353 - 3357
(2014/04/03)
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- Iodine-catalyzed selective synthesis of 2-sulfanylphenols via oxidative aromatization of cyclohexanones and disulfides
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Iodine-catalyzed intermolecular dehydrogenative aromatizations of six-membered cyclohexanones for the selective synthesis of 2-sulfanylphenols have been developed. Both aryl and alkyl disulfides can be used as sulfanylation reagents to give the desired pr
- Ge, Wenlei,Zhu, Xun,Wei, Yunyang
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p. 3014 - 3021
(2014/03/21)
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- Transition-metal-free synthesis of unsymmetrical diaryl chalcogenides from arenes and diaryl dichalcogenides
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A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioanisole, diphenyl ether, phenol, naphthol, di- and trimethoxy benzenes, xylene, mesitylene, N,N-dimethylaniline, bromine-substituted arenes, naphthalene, and diaryl dichalcogenides underwent carbon-chalcogen bond-forming reaction to give unsymmetrical diaryl chalcogenides in trifluoroacetic acid. To understand the mechanistic part of the reaction, a detailed in situ characterization of the intermediates has been carried out by 77Se NMR spectroscopy by using diphenyl diselenide as the substrate. 77Se NMR study suggests that electrophilic species ArE+ is generated by the reaction of diaryl dichalcogenide with persulfate in trifluoroacetic acid. The electrophilic attack of arylchalcogenium ion on the arene may be responsible for the formation of the aryl-chalcogen bond.
- Prasad, Ch Durga,Balkrishna, Shah Jaimin,Kumar, Amit,Bhakuni, Bhagat Singh,Shrimali, Kaustubh,Biswas, Soumava,Kumar, Sangit
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p. 1434 - 1443
(2013/03/29)
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- Nickel-mediated inter- and intramolecular C-S coupling of thiols and thioacetates with aryl iodides at room temperature
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A Ni(0)-catalyzed intermolecular cross-coupling of various functionalized thiols and aryl iodides has been developed and successfully extended to less explored intramolecular versions, where thioacetates could also be utilized as the strategic surrogate. Air-stable precatalysts, very mild conditions, and an easy protocol allow rapid access to medicinally useful aryl thioethers, as demonstrated in the facile synthesis of (±)-chuangxinmycin as a key step.
- Xu, Xiao-Bo,Liu, Jian,Zhang, Jian-Jian,Wang, Ya-Wen,Peng, Yu
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supporting information
p. 550 - 553
(2013/04/11)
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- Nano-CuFe2O4 as a magnetically separable and reusable catalyst for the synthesis of diaryl/aryl alkyl sulfides via cross-coupling process under ligand-free conditions
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An efficient protocol was developed for the CuFe2O4 nanopowder-catalyzed aryl-sulfur bond formation between aryl halide and thiol/disulfide. A variety of aryl sulfides were synthesized in impressive yields with good chemoselectivity and functional group tolerance in the presence of a catalytic amount of CuFe2O4, Cs2CO 3 as base, in nitrogen atmosphere, under ligand-free conditions, in DMSO as solvent at 100 °C. The catalyst is air-stable, inexpensive, magnetically separable and recyclable up to four cycles.
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Jyothi, Mocharla Tarani,Nageswar, Yadavalli Venkata Durga
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experimental part
p. 5989 - 5996
(2011/10/08)
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- Facile synthesis of 2-(phenylthio)phenols by copper(I)-catalyzed tandem transformation of C-S coupling/C-H functionalization
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2-(Phenylthio)phenols were successfully synthesized from simple phenols and aromatic halides by using dimethyl sulfoxide as the oxidant. The transformation was accomplished via tandem copper(I)-catalyzed C-S coupling/C-H functionalization employing the CuI/L [L = (E)-3-(dimethylamino)-1-(2- hydroxyphenyl)prop-2-en-1-one] catalyst system. The mechanism of the reaction was elucidated based on an isotope labeling strategy.
- Xu, Runsheng,Wan, Jie-Ping,Mao, Hui,Pan, Yuanjiang
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supporting information; experimental part
p. 15531 - 15533
(2011/02/28)
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- A highly efficient and widely functional-group-tolerant catalyst system for copper(I)-catalyzed S-arylation of thiols with aryl halides
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A mild, general, and efficient copper-catalyzed system for C-S bond formation with high chemoselectivity and wide functional group tolerance is developed. With CuBr as catalyst and 1,2,3,4-tetrahydro-8-hydroxy-quinoline as ligand, the S-arylation of thiols with aryl halides performed well, the activated aryl iodides could take place even at room temperature, and the activated aryl bromides and chlorides give the corresponding products with good to excellent yields as well.
- Feng, Yang,Wang, Huifeng,Sun, Fangfang,Li, Yaming,Fu, Xinmei,Jin, Kun
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supporting information; experimental part
p. 9737 - 9741
(2010/02/27)
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- Methods for formation of aryl-sulfur and aryl-selenium compounds using copper(I) catalysts
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A mild, palladium-free synthetic protocol for the cross-coupling reaction of vinyl or aryl iodides and thiols or selenols using, in certain embodiments, 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 ° C. A variety of vinyl/aryl sulfides and vinyl/aryl selenides can be synthesized in excellent yields from readily available iodides and thiols or selenols.
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Page/Page column 7-8; 23-24
(2008/06/13)
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- A general method for the formation of aryl-sulfur bonds using copper(I) catalysts.
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[reaction: see text] We report a mild, palladium-free synthetic protocol for the cross-coupling reaction of aryl iodides and thiols using 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 degrees C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available iodides and thiols.
- Bates, Craig G,Gujadhur, Rattan K,Venkataraman
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p. 2803 - 2806
(2007/10/03)
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- Novel reaction: Brominative aromatization of 2-alkyl(aryl)thio cyclohexanones
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2-Alkyl(aryl)thio cyclohexanones are transformed into o-alkyl(aryl)thio phenols by treatment with bromine or N-bromosuccinimide.
- Samoshin, Vyacheslav V.,Kudryavtsev, Konstantin V.
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p. 7413 - 7414
(2007/10/02)
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- AROMATIZATION OF 2-ALKYLTHIO(ARYLTHIO)-CYCLOHEXANONES DURING BROMINATION
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When treated with bromine or N-bromosuccinimide under mild conditions, 2-alkylthio- and 2-arylthiocyclohexanones are converted into the corresponding o-alkylthio- and o-arylthiophenols.
- Kudryavtsev, K. V.,Lonina, N. N.,Samoshin, V. A.
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p. 1425 - 1431
(2007/10/03)
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- Acid-catalysed Aromatisation of Benzene cis-1,2-dihydrodiols: a Carbocation Transition State poorly stabilised by Resonance
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Acid-catalysed dehydration of 3-substituted benzene cis-1,2-dihydrodiols exhibits a Hammett plot with ρ=-8.2, consistent with reaction via a benzenonium ion-like intermediate; however, correlation of +M resonance substituents such as Me and MeO by ?p rather than ?+ constants indicates a marked imbalance between resonance and inductive stabilisation of the transition state.
- Boyd, Derek R.,Blacker, John,Byrne, Briege,Dalton, Howard,Hand, Mark V.,et al.
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p. 313 - 314
(2007/10/02)
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- HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXXIII. REACTIONS OF ARYL HALIDES WITH DIPHENYL DISULFIDE IN HYDROGEN SULFIDE
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When heated at 125-240 deg C, 2- and 4-bromophenol, 4-bromophenetole, 1-bromonaphthalene, 1-bromo-2-naphthol, and 4-bromobenzonitrile react effectively with diphenyl disulfide in hydrogen sulfide with the formation of the corresponding phenyl aryl sulfides with yields of 49-84percent.The thiylation temperature is reduced if a ?-donating substituent is introduced into the benzene ring.
- Papernaya, L. K.,Deryagina, E. N.,Voronkov, M. G.
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p. 125 - 128
(2007/10/02)
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- HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXVIII. LIQUID-PHASE REACTIONS OF THIOLS WITH AROMATIC BROMINE COMPOUNDS
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In the liquid phase at 125-215 deg C thiophenol only reacts effectively with 2- and 4-bromophenol, 1-bromo-2-napthol, 1-bromonapthalene, and 9-bromoanthracene, forming the corresponding phenyl aryl sulfides. 2-Thiophenethiol and 1-thionapthol reduce the same bromine derivatives to the corresponding arenes.The disulfides formed here undergo secondary transformations.The reactions of thiophenol with 2- and 4-bromophenol and 1-bromo-2-napthol are convenient preparative methods for the synthesis of the previously difficulty obtainable phenyl hydroxyaryl sulfides.
- Papernaya, L. K.,Panova, G. M.,Deryagina, E. N.,Voronkov, M. G.
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p. 1774 - 1777
(2007/10/02)
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