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Dehydroxylative Trifluoromethylthiolation, Trifluoromethylation, and Difluoromethylation of Alcohols

CF3S, CF3 and HCF2 groups have been identified as valuable functionalities for drug development. Despite significant accomplishments in the trifluoromethylthiolation, trifluoromethylation and difluoromethylation reactions, directly converting common functional groups into CF3S, CF3 or HCF2 groups is still highly desirable. Described here is the dehydroxylative trifluoromethylthiolation, trifluoromethylation and difluoromethylation of alcohols promoted by a R3P/ICH2CH2I system. All of these dehydroxylative reactions were achieved under mild conditions via the activation of the hydroxyl group by the R3P/ICH2CH2I system. A wide substrate scope and good functional group tolerance were observed.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Ligand-controlled mixed-valence copper rectangular grid-type coordination polymers based on pyridylterpyridine

Six mixed-valence CuICuII compounds containing 4?-(4-pyridyl)-2,2?:6?,2?-terpyridine (L1) or 4?-(2-pyridyl)-2,2?:6?,2?-terpyridine (L2) were prepared under the hydrothermal and ambient conditions, and their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl 2¡¤2H2O or Cu(CH3COO)2¡¤ H2O with the L1 ligand and NH4SCN, KI, or KBr under hydrothermal conditions afforded 1-dimensional mixed-valence Cu ICuII compounds [Cu2(L1)(mu-1,1-SCN)(mu-Cl) Cl]n (1), [Cu2(L1)(mu-l)2Cl]n (2), [Cu2(L1)(mu-Br)2Br]n (3), and [Cu 2(L1)(mu-1,3-SCN)2(SCN)]n (4), respectively. Compound 5, prepared by layering with CuSCN and L1, is a 2-dimensional bilayer structure. In compounds 1-5, the L1 ligand and X (X = Cl, Br, I, SCN) linked between monovalent and divalent copper atoms resulting in the formation of mixed-valence rectangular grid-type M4L4 or M 6L6 building blocks, which were further linked by X (X = Cl, Br, I, SCN) to form 1- or 2-dimensional polymers. The sizes of M 4L4 units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH3COO)2¡¤H2O with L2 and NH4SCN under hydrothermal conditions gave mixed-valence CuICuII compound [Cu2(L2)(mu-1,3-SCN) 3]n (6). Unlike those in 1-5, the structure of 6 was constructed from thiocyanate groups and the pendant pyridine of L2 left uncoordinated. The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence electronic structure.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Top Picks: new discover of Cuprous thiocyanate

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Palladium-catalyzed cyanation of aryl halides with CuSCN

A palladium-catalyzed cyanation of aryl halides and borons has been developed by employing cuprous thiocyanate as a safe cyanide source. This protocol avoids the use of a highly toxic cyanide source, providing aromatic nitriles in moderate to good yields with good functional tolerance.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Some scientific research about Cuprous thiocyanate

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Related Products of 1111-67-7, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.1111-67-7, Name is Cuprous thiocyanate, molecular formula is CCuNS. In a Article£¬once mentioned of 1111-67-7

Nanostructured Silicon-Based Heterojunction Solar Cells with Double Hole-Transporting Layers

Hybrid nanostructured silicon?organic solar cells have been pursued as a low-cost solution for silicon photovoltaic devices. However, it is difficult for the organic semiconductor, typically poly(3,4-ethylenedioxythiophene):polystyrene (PEDOT:PSS), to fully cover the nanostructured silicon surface due to the high surface tension of the polymer solution and the small size of the cavities in nanostructured silicon. As a result, the performance of the hybrid solar cells is limited by the defect-induced surface recombination and poor hole extraction. In this work, an inorganic hole-transporting layer, copper(I) thiocyanate (CuSCN), is introduced between silicon nanowire (SiNW) and PEDOT:PSS to improve the junction quality. The effect of CuSCN on as-fabricated SiNW and tetramethylammonium hydroxide (TMAH)-treated SiNW structures is examined, and it is shown that in both cases CuSCN can well cover the SiNW surface due to the easy penetration of its solution into the silicon nanostructure. As a result, the power conversion efficiency of the solar cells has been dramatically improved from 7.68% to 10.5% for as-fabricated SiNW-based-hybrid cells, and from 10.75% to 12.24% for TMAH-passivated SiNW-based-hybrid cells, suggesting that the double hole-transporting layer approach can effectively improve the junction quality in hybrid organic-nanostructured silicon-based devices.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Investigation of structure-directing interactions within copper(i) thiocyanate complexes through X-ray analyses and non-covalent interaction (NCI) theoretical approach

Herein, we reported the synthesis of copper(i) thiocyanate complexes with ortho-pyridinyl carbohydrazones containing a thiophene (L1) or a furyl ring (L2) as a mixture of two different crystals for each compound, linkage isomers of C1N, [Cu(NCS)(L1)PPh3] and C1S, [Cu(SCN)(L1)PPh3], for L1, whereas monomeric and polymeric structures C2N, [Cu(NCS)(L2)PPh3], and C2P, [-(NCS)Cu(L2)-]n, for L2. Crystallographic information and theoretical calculations, mainly noncovalent interaction reduced density gradient (NCI-RDG) analyses, were pursued to generate a profound understanding of the structure-directing interactions in these complexes. The supramolecular assemblies are first driven by cooperative pi?pi interactions and hydrogen bonds followed by CH?pi, S?S and S?pi linkages. In the case of the linkage isomers, intermolecular interactions may have a significant role in the formation of the less stable S-bound isomer C1S.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Some scientific research about Cuprous thiocyanate

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Synthesis, Crystal Structures and Thermal Properties of the New Copper(I) Pseudohalide Coordination Polymers Catena[(mu2-thiocyanato-N,S)-(1- ethyl-2-methylpyrazine-N)]copper(I) and Poly[(di-mu2-tniocyanato-N, S)-(mu2-1-ethyl-2-methylpyrazine-N,N?)]dicopper(I)

Reaction of copper(I) thiocyanate with 1-ethyl-2-methyl-pyrazine in acetonitrile yields the two new coordination polymers catena[(mu 2-thiocyanato-N,S)-(1-ethyl-2-methylpyrazine-N)] copper(I)(I) and poly[(di-mu2-thiocyanato-N,S)-(mu2-1-ethyl-2-methyl- pyrazine-N,N?)] di-copper(I) (II). The crystal structure of I is composed of CuSCN double chains in which each copper atom is connected to two thiocyanate anions and two 1-ethyl-2-methyl-pyrazine ligands. In this compound only one nitrogen atom of the 1-ethyl-2-methyl-pyrazine ligand is involved in copper coordination. The crystal structure of II is composed of CuSCN layers that are connected by the N-donor ligands via mu-N,N? coordination into a three-dimensional coordination network. On heating the amine rich compound I loses half of the ligands and transforms into the amine-poorer compound II which occurs as an intermediate. Compound II decomposes on further heating to CuSCN. This reaction was investigated using simultaneous differential thermoanalysis and thermogravimetry coupled with mass spectroscopy and temperature dependent X-ray powder diffraction.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1111-67-7, and how the biochemistry of the body works.Electric Literature of 1111-67-7

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Doping CuSCN films for enhancement of conductivity: Application in dye-sensitized solid-state solar cells

Construction of dye-sensitized solid-state solar cells requires high band-gap (therefore, transparent) hole collectors which can be deposited on a dye-coated nanocrystalline semiconductor surface without denaturing the dye. Copper (I) thiocyanate (CuSCN) is an important p-type semiconductor satisfying the above requirements. However, the conductivity of this material, which depends on excess SCN, is not sufficiently high and polymerization of SCN prevents incorporation of sufficient amount of excess SCN during the process of synthesis of CuSCN. We have found that the conductivity of solid CuSCN can be increased by exposure to halogen gases which generate SCN or to a solution of (SCN)2 in CCl4. The latter method is suitable for doping of CuSCN films in dye-sensitized solid-state solar cells.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

Properties and Exciting Facts About Cuprous thiocyanate

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Dependence of Tc on hydrostatic pressure in beta?-(ET)2SF5CH2CF2SO 3 and kappa-(ET)2Cu(NCS)2

The dependence of Tc on hydrostatic (He-gas) pressure is determined for the recently discovered organic superconductor beta?-(ET)2SF5CH2CF2SO 3 [ET = bis(ethylenedithio)-tetrathiafulvalene] with Tc(0) ? 5 K, yielding the pressure derivative dTc/dP ? -1.34 K kbar-1. The present experiments also included kappa-(ET)2Cu(NCS)2 where we find the extremely large value dTc/dP ? -3.84 K kbar-1, in agreement with earlier studies. For both samples the pressure dependence Tc(P) does not depend on the temperature at which the pressure is changed.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Application of 1111-67-7, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1111-67-7, molcular formula is CCuNS, introducing its new discovery.

Syntheses of 1,5-Benzothiazepines: Part III – Syntheses of 4-(p-Chlorophenyl)-2-(p-methoxyphenyl)-8-substituted-2,3-dihydro-1,5-benzothiazepines

4-Methoxy-4′-chlorobenzalacetophenone (IV) on reaction with 5-substituted 2-aminothiophenols (IIIa-f) in toluene gives 4-(p-chlorophenyl)-2-(p-methoxyphenyl)-8-substituted-2,3-dihydro-1,5-benzothiazepines (Va-f).Their structures have been established by IR, PMR and mass spectral data.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

A new application about Cuprous thiocyanate

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Electric Literature of 1111-67-7. In my other articles, you can also check out more blogs about 1111-67-7

Electric Literature of 1111-67-7, A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1111-67-7, Name is Cuprous thiocyanate, molecular formula is CCuNS. In a Article£¬once mentioned of 1111-67-7

Synthesis, crystal structure, and characterization of a novel supramolecular coordination polymer [Cu(Pcba)3]n

The authors present a novel compound [Cu(Pcba)2]n synthesized from the reaction between copper(I) thiocyanate and the ligand Pcba (Pcba = 2-pyrazine carboxylic acid), which exhibits a one-dimensional structure and has been characterized by Xray crystallography. In the process of synthesis, copper(I) ion has been oxidized into copper(II). This compound crystallizes in monoclinic, space group P2 (1)/c with cell parameters of a = 5.0387(4) A, b = 15.3317(13) A, c = 7.0720(6) A, beta = 106.63(0). The central ion Cu(II) is six-coordinated in a typical hexahedral geometry by four oxygen atoms and two nitrogen atoms in Pcba. Except chelating with two Pcbas, each central ion Cu(II) is extended to form one-dimensional linear structure through Pcba as the bridge. This compound was further characterized with IR spectra, fluorescence properties, UV-vis properties, and thermal analysis. Copyright Taylor & Francis Group, LLC 2013.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Electric Literature of 1111-67-7. In my other articles, you can also check out more blogs about 1111-67-7

Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”