1483-82-5Relevant articles and documents
Analysis of substituent effects on C-13 NMR parameters of substituted arylacetylene derivatives. Linear free energy relationships and PM3 semiempirical calculations
Lin, Shaw-Tao,Lee, Chuan-Chen,Liang, David W.
, p. 9619 - 9623 (2000)
The substituent-induced chemical shifts (SCS) of C(α,β) on the 13C NMR spectra of arylalkynes (i.e. containing H, CH3, Cl and Br) were studied. The correlation between SCS and Hammett constants shows that the tendency of the effect by the substituents on the phenyl ring is Br (ρ=8.15)>Cl (ρ=7.27)>CH3 (ρ=6.79)>H (ρ=5.78). This order can be rationalized as due to the ability of the group on the alkyne to stabilize the partial positive charge on C(β) resulting from polarization with π electron transfer from C(β) to the phenyl ring. The SCS values are also well correlated with the electron densities obtained from PM3 calculations. The solvent effect on the 13C chemical shifts of phenylalkynyl bromide demonstrates a strong dependence on the relative permittivity as well as the shielding character of the solvents. (C) 2000 Elsevier Science Ltd.
Synthesis of new halo-containing acetylenes and their application to the synthesis of azoles
Martins, Marcos A.P.,Emmerich, Daniel J.,Pereira, Claudio M.P.,Cunico, Wilson,Rossato, Marcelo,Zanatta, Nilo,Bonacorso, Helio G.
, p. 4935 - 4938 (2004)
The convenient synthesis of ten halo- and an isoxazole-containing acetylenes from the reaction of acetylenes with n-butyl lithium and subsequent reaction with an electrophile agent (ethyl trichloroacetate, ethyl dichloroacetate, trifluoroacetic anhydride,
Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene. Generation and experimental discrimination of hypotheses
Bruk,Gorodskii,Zeigarnik,Valdes-Perez,Temkin
, p. 873 - 880 (1999)
Formal and informal methods for advancing hypotheses on mechanisms were used in a study of the oxidative carbonylation of phenylacetytene to methyl phenylpropiolate catalyzed by the PdCl2-CuCl-CuCl2 system. The hypotheses remaining a
Synthesis of 1-chloroalkynes from alkynylsilanes using trichloroisocyanuric acid as chlorinating agent
Vilhelmsen, Mie Hojer,Andersson, Asbjorn Sune,Nielsen, Mogens Brondsted
, p. 1469 - 1472 (2009)
A new method is reported for preparing 1-chloroalkynes from alkynylsilanes using trichloroisocyanuric acid (TCCA) as chlorinating agent and AgNO 3 for in situ desilylation. The method is selective for trimethylsilyl-protected alkynes relative t
Straightforward Synthesis of α-Chloromethylketimines Catalyzed by Gold(I). A Clean Way to Building Blocks
Asensio, Gregorio,Cárcel, María,Olmos, Andrea,Ramírez De Arellano, Carmen,Sarmiento, Jeymy T.,Varea, Teresa
supporting information, p. 3114 - 3122 (2022/03/14)
α-Chloromethylketimines have been obtained through a gold-catalyzed hydroamination of aromatic and aliphatic 1-chloroalkynes with aromatic amines by using equimolar amounts of both reagents. This procedure has allowed the preparation and spectroscopic characterization of α-chloromethylketimines for the first time with a high degree of purity, complete conversion, and atom economy. The synthetic usefulness of the methodology has been demonstrated with the preparation of β-chloroamines and indoles.
Method for preparing 1-halogenated alkyne under catalysis of heterogeneous Ag catalyst at room temperature
-
Paragraph 0023-0036, (2021/05/12)
The invention discloses a novel method for preparing 1-halogenated alkyne under the catalysis of a heterogeneous Ag catalyst at room temperature. The method comprises the steps of mixing terminal alkyne compounds containing different substituent groups, N
Nickel-Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N -Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes
Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Krishna, Gamidi Rama,Reddy, Raju Jannapu
supporting information, p. 2850 - 2864 (2021/05/18)
An efficient nickel-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1-bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal -dithiolation of alkynyl bromides with N -arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thio-sulfonylation.
Selective Synthesis of Non-Aromatic Five-Membered Sulfur Heterocycles from Alkynes by using a Proton Acid/N-Chlorophthalimide System
Yu, Wentao,Zhu, Baiyao,Shi, Fuxing,Zhou, Peiqi,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 1313 - 1322 (2020/12/01)
A multicomponent strategy to achieve two different regioselectivities from alkynes, isothiocyanates and H2O with a proton acid/N-chlorophthalimide (NCPI) system is described to selectively obtain non-aromatic five-membered sulfur heterocycles (1,3-oxathiol-2-imines/thiazol-2(3H)-one derivatives) through multiple bond formations. The process features readily available starting materials, mild reaction conditions, broad substrate scope, good functional-group tolerance, high regio- and chemo- selectivities, gram-scale synthesis and late-stage modifications. Mechanistic studies support the proposal that the transformation process includes a combination of H2O and isothiocyanate, free-radical formation, carbonation and intramolecular cyclization to give the products. Furthermore, the 1,3-oxathiol-2-imine derivatives possess unique fluorescence characteristics and can be used as Pd2+ sensors with a “turn-off” response, demonstrating potential applications in environmental and biological fields.
Decatungstate as Direct Hydrogen Atom Transfer Photocatalyst for SOMOphilic Alkynylation
Capaldo, Luca,Ravelli, Davide
supporting information, p. 2243 - 2247 (2021/04/05)
A versatile approach for the alkynylation of a variety of aliphatic hydrogen donors, including alkanes, is reported. We used tetrabutylammonium decatungstate as photocatalyst to generate organoradicals from C-H/Si-H bonds via hydrogen atom transfer. The l
Access to (Z)-1,2-Endiamides and 1,1-Endiamides via a Base-Promoted Tandem Reaction
Zhang, Zhenming,Fu, Bei,Wang, Hui,Chen, Han,Tu, Yongliang,Zhao, Junfeng
, p. 5245 - 5254 (2020/05/18)
An efficient base-promoted tandem reaction between vinyl 1,1-dichlorides and secondary sulfonamides with ynamide as the key intermediate is described. This method provides a facile approach to (Z)-1,2-endiamide and aryl 1,1-endiamide derivatives via the β-hydroamidation of terminal ynamides and the α-hydroamidation of internal ynamides, respectively. This reaction proceeded through double elimination of vinyl chlorides and double addition of nucleophiles to alkynes. In addition, it features readily available starting materials, mild reaction conditions, a broad substrate scope, a wide functional group tolerance, and an operational convenience.
