188290-36-0Relevant articles and documents
The photoinduced reaction of 2-iodothiophene in solutions of n-heptane, dichloromethane and methanol
Herrera,Nieto,Olleta,Lane
, p. 398 - 406 (2011)
The photoinduced reaction of 2-iodothiophene in n-heptane, dichloromethane and methanol was studied at room temperature from experiments carried out with degassed solutions. The photoproducts of the reaction were mainly thiophene and small amounts of iodine in all three solvents used. The concentration of 2-iodothiophene decreases throughout photolysis, following a first-order rate law and the pseudo-first-order rate constants were determined in the three solvents used. The photochemistry of the system was quantified determining the quantum yields of 2-iodothiophene consumption and thiophene formation in n-heptane solutions. The results show that under the experimental conditions of this research, products deriving only from the reaction of the thienyl radical were observed. To support the experimental results, calculations were performed of the ionization potential of the thienyl radical, electron affinity of the iodine atom and free energy of solvation of the corresponding iodide and carbocation in the different solvents used. Copyright
UNEXPECTED FORMATION OF 2-ETHYLTHIOPHENE BY THERMOLYSIS OF 1,1-DIPROPENYLSULFIDE
Korchevin, N. A.,Ostroukhova, L. A.,Musorin, G. K.,Nosyreva, V. V.,Amosova, S. V.,et al.
, p. 466 (1988)
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Ryashentseva et al.
, (1972)
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High-Temperature Synthesis of 1,2-Dithiol-3-One
Ostroukhova, L. A.,Turchaninova, L. P.,Korchevin, N. A.,Deryagina, E. N.,Voronkov, M. G.
, p. 824 (1988)
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Competitive carbon-sulfur vs carbon-carbon bond activation of 2-cyanothiophene with [Ni(dippe)H]2
Grochowski, Matthew R.,Li, Ting,Brennessel, William W.,Jones, William D.
, p. 12412 - 12421 (2010)
The processes of C-C and C-S bond cleavage have been studied with the homogeneous organometallic compound [Ni(dippe)H]2 (1). When 1 is reacted with 2-cyanothiophene at room temperature, cleavage of the nitrile-substituted C-S bond occurs, forming the Ni-metallacycle complex (dippe)Ni(κ2-S,C-SCH=CHCH=C(CN)) (2a), which has been fully characterized by NMR spectroscopy and X-ray diffraction. 2a was converted to the C-CN cleavage product (dippe)Ni(CN)(2-thiophenyl) (3) when heated in solution. On closer inspection, four other intermediates were observed by 31P NMR spectroscopy at low temperature. Structures for the intermediates were elucidated through a combination of independent synthesis, theoretical calculations, chemical characterization, and experimental precedent. A kinetic product (dippe)Ni(κ2-S,C-SC(CN)=CHCH=CH) (2b) was formed from cleavage of the nonsubstituted C-S bond, as well as a Ni(0) η2- nitrile intermediate, (dippe)Ni(η2-C,N-2-cyanothiophene) (4), and a dinuclear mixed Ni(0)-Ni(II) product (6b). A complete DFT analysis of this system has been carried out to reveal comparative details about the two bond cleavage transition states.
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Deryagin et al.
, (1979)
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CHROMIUM OXIDE CATALYSTS WITH LOW VALENCE STATE IONS FOR HETEROCYCLIC RING ROFMATION
Ryashentseva, M. A.,Belanova, E. P.,Slovetskaya, K. I.,Aleshin, E. G.
, p. 710 - 712 (1986)
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NEW METHOD FOR THE PREPARATION OF THIOPHENE
Voronkov, M. G.,Trofimov, B. A.,Kryuchkov, V. V.,Amosova, S. V.,Skvortsov, Yu. M.,et al.
, p. 1249 (1981)
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Tomkinson, M. G.
, p. 2264 - 2266 (1924)
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Radical Hydrodehalogenation of Aryl Halides with H2 Catalyzed by a Phenanthroline-Based PNNP Cobalt(I) Complex
Jheng, Nai-Yuan,Ishizaka, Yusuke,Naganawa, Yuki,Minami, Yasunori,Sekiguchi, Akira,Iizuka, Kosuke,Nakajima, Yumiko
, p. 2320 - 2329 (2022/02/16)
Radical hydrodehalogenation of aryl halides (Ar-X; X = Cl, Br, I) is achieved in the presence of atmospheric pressure H2 as a H-atom donor using a Co(I) catalyst bearing a phenanthroline-based PNNP ligand (2,9-bis((diphenylphosphanyl)methyl)-1,10-phenanthroline). The reaction proceeds under mild conditions (1 atm H2) and is applicable to aryl bromides and aryl chlorides with various functional groups. A mechanistic study revealed that the PNNP-Co complex underwent facile H-H cleavage and facilitated a H-atom transfer. This process is mediated by a long-range metal-ligand cooperation of the PNNP-Co system, which includes the dearomatization/aromatization sequence of the phenanthroline ligand backbone. A radical clock experiment demonstrated the Ar-X bond cleavage via a radical mechanism. Further kinetic study supported that the rate-determining step includes electron transfer from the Co center to the substrate, affording a radical pair ArX?- and an odd-electron metal-halide complex [Co(II) + ArX?-]? as a transition state.
Exploiting a silver-bismuth hybrid material as heterogeneous noble metal catalyst for decarboxylations and decarboxylative deuterations of carboxylic acids under batch and continuous flow conditions
?tv?s, Sándor B.,Fül?p, Ferenc,Kónya, Zoltán,Kukovecz, ákos,Márton, András,Mészáros, Rebeka,Pálinkó, István,Szabados, Márton,Varga, Gábor
, p. 4685 - 4696 (2021/07/12)
Herein, we report novel catalytic methodologies for protodecarboxylations and decarboxylative deuterations of carboxylic acids utilizing a silver-containing hybrid material as a heterogeneous noble metal catalyst. After an initial batch method development, a chemically intensified continuous flow process was established in a simple packed-bed system which enabled gram-scale protodecarboxlyations without detectable structural degradation of the catalyst. The scope and applicability of the batch and flow processes were demonstrated through decarboxylations of a diverse set of aromatic carboxylic acids. Catalytic decarboxylative deuterations were achieved on the basis of the reaction conditions developed for the protodecarboxylations using D2O as a readily available deuterium source.
Nucleophilic C-H Etherification of Heteroarenes Enabled by Base-Catalyzed Halogen Transfer
Bandar, Jeffrey S.,Klaus, Danielle R.,Puleo, Thomas R.
supporting information, p. 12480 - 12486 (2021/08/24)
We report a general protocol for the direct C-H etherification of N-heteroarenes. Potassium tert-butoxide catalyzes halogen transfer from 2-halothiophenes to N-heteroarenes to form N-heteroaryl halide intermediates that undergo tandem base-promoted alcohol substitution. Thus, the simple inclusion of inexpensive 2-halothiophenes enables regioselective oxidative coupling of alcohols with 1,3-azoles, pyridines, diazines, and polyazines under basic reaction conditions.
