2754-27-0Relevant articles and documents
Stable -ESiMe3 Complexes of CuI and AgI (E=S, Se) with NHCs: Synthons in Ternary Nanocluster Assembly
Azizpoor Fard, Mahmood,Levchenko, Tetyana I.,Cadogan, Carolyn,Humenny, William J.,Corrigan, John F.
, p. 4543 - 4550 (2016)
As a part of efforts to prepare new "metallachalcogenolate" precursors and develop their chemistry for the formation of ternary mixed-metal chalcogenide nanoclusters, two sets of thermally stable, N-heterocyclic carbene metal-chalcogenolate complexes of the general formula [(IPr)Ag-ESiMe3] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; E=S, 1; Se, 2) and [(iPr2-bimy)Cu-ESiMe3]2 (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene; E=S, 4; Se, 5) are reported. These are prepared from the reaction between the corresponding carbene metal acetate, [(IPr)AgOAc] and [(iPr-bimy)CuOAc] respectively, and E(SiMe3)2 at low temperature. The reaction of [(IPr)Ag-ESiMe3] 1 with mercury(II) acetate affords the heterometallic complex [{(IPr)AgS}2Hg] 3 containing two (IPr)Ag-S- fragments bonded to a central HgII, representing a mixed mercury-silver sulfide complex. The reaction of [(iPr2-bimy)Cu-SSiMe3]2, which contains a smaller N-heterocyclic-carbene, with mercuric(II) acetate affords the high nuclearity cluster, [(iPr2-bimy)6Cu10S8Hg3] 6. The new N-heterocyclic carbene metal-chalcogenolate complexes 1, 2, 4, 5 and the ternary mixed-metal chalcogenolate complex 3 and cluster 6 have been characterized by multinuclear NMR spectroscopy (1H and 13C), elemental analysis and single-crystal X-ray diffraction.
Development of mono- and Di-AcO substituted BODIPYs on the boron center
Jiang, Xin-Dong,Zhang, Jian,Furuyama, Taniyuki,Zhao, Weili
, p. 248 - 251 (2012)
Mono- and di-AcO substituted BODIPYs (1 and 2) were synthesized from TM-BDP. The structures of 1 and 2 were supported by single crystal X-ray analysis. Both 1 and 2 possess a large absorption coefficient, high fluorescence quantum yield, and high light stability. Compound 2 has much improved water solubility which is highly desirable for biological applications. Theoretical calculation supports our observations in X-ray analysis, absorption, and cyclic voltammetry.
A New Entry to p-Allylcobalt Tricarbonyls Using (CH3)3SiCo(CO)4
Chatani, Naoto,Yamasaki, Yasuhiro,Murai, Shinji,Sonoda, Noboru
, p. 5649 - 5652 (1983)
The reactions of (CH3)3SiCo(CO)4 with allyl acetates, enones, and a diene monoepoxide gave corresponding pi-allylcobalt tricarbonyls.
Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf
Aprile, Antonino,Iversen, Kalon J.,Wilson, David J. D.,Dutton, Jason L.
, p. 4934 - 4939 (2015)
We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2]2+. Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought. (Figure Presented).
Production of acyloxysilane
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Paragraph 0059-0064, (2021/10/30)
[A] a method for producing functional chemicals useful as efficient acyloxysilane. The silanol Si-to-OH bond [a], in the presence of a catalyst, comprising the step of reacting a carboxylic acid anhydride, Si-to-OCO bond (OCO is, oxycarbonyl groups (=O) O-a C shown. ) Having an acyloxysilane manufacturing method, wherein the catalyst, or (2) (1) production of acid catalyst selected from the next acyloxysilane. (1) 3 - 15 Of the periodic table of the first group the first group element selected from the perchlorate salt, trifluoromethanesulfonic acid salt, a bis (trifluoromethanesulfonyl imide) salt, lithium hexafluorophosphate salt, chloride, or bromide; inorganic acids; or an organic acid. (2) Inorganic or organic solid acid compounds[Drawing] no
Trimethylsilyl Esters as Novel Dual-Purpose Protecting Reagents
Chen, Jyun-Siao,Huang, Po-Hsun,Hsieh, Ya-Chi,Liu, Jen-Wei,Hsu, Hsiao-Lin,Zhang, Kai-Min,Wu, Ren-Tsung,Chang, Ting-Shuo,Liu, Yu-Hao,Wu, Hsin-Ru,Luo, Shun-Yuan
supporting information, p. 754 - 762 (2021/12/02)
Trimethylsilyl esters, AcOTMS, BzOTMS, TCAOTMS, etc., are inexpensive and chemically stable reagents that pose a negligible environmental hazard. Such compounds prove to serve as efficient dualpurpose reagents to respectively achieve acylation and trimethylsilylation of alcohols under acidic or basic conditions. Herein, a detailed study on protection of various substrates and new methodological investigations is described.
Copper-Catalyzed Radical 1,4-Difunctionalization of 1,3-Enynes with Alkyl Diacyl Peroxides and N-Fluorobenzenesulfonimide
Zhu, Xiaotao,Deng, Weili,Chiou, Mong-Feng,Ye, Changqing,Jian, Wujun,Zeng, Yuehua,Jiao, Yihang,Ge, Liang,Li, Yajun,Zhang, Xinhao,Bao, Hongli
, p. 548 - 559 (2019/01/04)
Many reactions involving allenyl ion species have been studied, but reactions involving allenyl radicals are less well understood, perhaps because of the inconvenience associated with the generation of short-lived allenyl radicals. We describe here a versatile method for the generation of allenyl radicals and their previously unreported applications in the intermolecular 1,4-carbocyanation and 1,4-sulfimidocyanation of 1,3-enynes. With the assistance of the trifunctional reagents, alkyl diacyl peroxides or N-fluorobenzenesulfonimide, a range of synthetically challenging multisubstituted allenes can be prepared with high regioselectivity. These multisubstituted allenes can be easily transformed into synthetically useful structures such as fluorinated vinyl cyanides, lactones, functionalized allenyl amides, 1-aminonaphthalenes, and pyridin-2(1H)-ones, and several novel transformations are reported. The results of radical scavenger and radical clock experiments are consistent with the proposed allenyl radical pathway. Density functional theory (DFT) and IR spectroscopy studies suggest the formation of an isocyanocopper(II) species in the ligand exchange step. On the basis of the results of IR, DFT, and diastereoselectivity studies, an isocyanocopper(II)/copper(I) catalytic cycle is proposed, which differs from the previously considered Cu(III) mechanism in cyanation reactions.
Palladium-Catalyzed Regioselective Synthesis of 1-Benzoazepine Carbonitriles from o-Alkynylanilines via 7-endo-dig Annulation and Cyanation
Dhandabani, Ganesh Kumar,Mutra, Mohana Reddy,Wang, Jeh-Jeng
, p. 4754 - 4763 (2018/11/10)
We herein report a three-component, one-pot cascade reaction involving an imination/annulation/cyanation sequence for the synthesis of 1-benzoazepine carbonitrile derivatives using readily available o-alkynylanilines, cyclic ketones and trimethylsilyl cyanide. This regio- and stereoselective reaction was achieved by combining palladium(II) trifluoroacetate and copper(II) acetate in dimethyl sulfoxide. The important features of this method include a broad substrate scope, the use of trimethylsilyl cyanide as a cyanating agent, the formation of two C?C bonds and one C?N bond, mild reaction conditions and good product yields. (Figure presented.).
Method for Producing Acyloxysilanes, Acyloxysilanes Obtained Thereby, and Use of Same
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Paragraph 0130; 0131, (2018/03/25)
An object of the invention is to provide a method for efficiently producing an acyloxysilane which is useful as a functional chemical, an acyloxysilane obtained thereby, and the use thereof. The present invention provides: a method for producing an acyloxysilane, including a reaction step of reacting an alkoxysilane with a carboxylic anhydride in the presence of a catalyst, wherein the alkoxysilane is a specified alkoxysilane represented by General Formula (I), the carboxylic anhydride is a specified carboxylic acid represented by General Formula (IIA) or (IIB), the catalyst is an acid catalyst, and an acyloxysilane obtained in the reaction step is a specified acyloxysilane represented by General Formula (IIIA) or (IIIB); and the use of the acyloxysilane as a surface treatment agent or the like.
Sysntehsis of trimethylacetoxysilane
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Paragraph 0005; 0006; 0007; 0008; 0009; 0010, (2017/08/28)
The invention relates to synthesis of sysntehsis of trimethylacetoxysilane. Synthesis of the trimethylacetoxysilane includes the steps that 120 g of glacial acetic acid is added into a 500 mL three-mouth bottle equipped with a nitrogen gas inlet, a thermometer and a magnetic stirring and low-temperature condensing pipe (-10 DEG C), and the temperature is raised to 110-130 DEG C; under the conditions of stirring and introduction of nitrogen gas, 217 g of trimethylchlorosilane is dropwise added into a reaction bottle with a constant-pressure funnel after 2-4 hours, and HCl gas discharged through a reaction is absorbed as a NaOH solution; after the trimethylchlorosilane is completely dropwise added, stirring is continued, blowing and washing are performed with the nitrogen gas for one hour; and cooling is performed till the room temperature is reached, then 6 g of potassium acetate is added into the reaction bottle in three separate times, stirring is performed by 1-3 hours, and it is tested that the chlorosilane is completely converted. 222 g of the synthesis of trimethylacetoxysilane is obtained through reaction liquid filtering and filter liquid reduced pressure distillation, and the yield is 84%.
