11095-43-5Relevant articles and documents
A novel synthesis of benzo[b]thiophene
Liao, Zutai,Lv, Xuehao,Tao, Ming
, p. 4021 - 4024 (2013)
We report a convenient method of preparation of benzo[b]thiophene, using 2-chlorobenzaldehyde and 2-mercaptoacetonitrile as starting materials. The process comprises two steps, neither of which has been reported previously. The reactions in this work are
Charge-Transfer Complexes of Benzo[b]thiophene with σ- And π-Electron Acceptors
Ayad, Mohamad M.
, p. 2369 - 2373 (1997)
The spectrophotometric properties of the charge-transfer (CT) complexes of benzo[6]thiophene with iodine at 24°C in different solvents such as cychlohexane, carbon tetrachloride, chloroform, dichloromethane, and 1,2-dichloroethane are studied. In addition the spectrophotometric and thermodynamic properties of the CT complexes of benzo[b]thiophene with tetracyanoethylene, chloranil, 2,3-dichloro-5,6-dicyano-p-benzoquinone and 7,7,8,8,-tetracyanoquinodimethane are studied. The results show that the equilibrium and the thermodynamic parameters and the wavelengths of the maximum absorption bands (λmax) of the complexes vary markedly with the solvent. The ionization potential and the donor sites of benzo[b]thiophene are also determined and discussed.
A convenient one-pot preparation of benzo[b] -tellurophenes, - selenophenes, and -thiophenes from o- bromoethynylben zenes
Sashida, Haruki,Sadamori, Kunio,Tsuchiya, Takashi
, p. 713 - 727 (1998)
2-Substituted and unsubstituted benzo[b]tellurophenes (3Aa-e) were synthesized in one-pot from o-bromoethynylbenzenes (2) via three steps in good yields. Similarly, benzo[b]-selenophenes (3Ba-e) and -thiophenes (3Ca- e) were also obtained.
Synthesis and reactivities of a highly strained thiophene with two fused four-membered rings, 1,2,4,5-tetahydrodicyclobuta[b,d] thiophene
Nakayama, Juzo,Kuroda, Koichiro
, p. 4612 - 4617 (1993)
The successful synthesis of 1,2,4,5-tetrahydrodicyclobuta[b,d]thiophene (1) and its ususually enhanced reactivities because of large ring strain are described. Thus, intramolecular pinacol coupling of diketo sulflde 14, obtainable from 2-bromocyclobutanone and sodium sulfide, with a low-valent titanium reagent affords the thiolane3,4-diol 15 in 36% yield based on the bromo ketone. After conversion of 15 to the bis-methanesulfonate 16 in 66% yield, the latter was treated with potassium tert-butoxide to give 1 nearly quantitatively as a rather thermally stable, colorless, highly sublimative, nicely crystalline compound. Bromine rapidly adds to 1 to give the tetrabromide 21, revealing its olefinic character. Furthermore, 1 undergoes Diels-Alder reaction with tetracyanoethylene at room temperature to afford the adduct 22 in 83% yield. The Diels-Alder reaction with maleic anhydride at room temperature gives the adduct 23 in 87% yield in the endo-exo isomer ratio 5:1, whereas the reaction with excess maleic anhydride in refluxing benzene produces the bisadduct 24 in 84% yield with loss of sulfur. Similar behaviors of 1 toward N-phenylmaleimide were also observed. Flash vacuum pyrolysis of 1 gave benzo[b]thiophene in 16% yield but not the expected radialene 11 or its dimer, superthiophenophane. Other attempts to obtain 11 or to trap it with a dienophile were also unsuccessful.
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Wynberg,Bantjes
, p. 1421 (1959)
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The role of neighbouring group participation in TTF-mediated 'radical- polar crossover' reactions: Trapping of aliphatic radicals by TTF+.
Bashir, Nadeem,Murphy, John A.
, p. 627 - 628 (2000)
Trapping of secondary alkyl radicals with tetrathiafulvalenium tetrafluoroborate (TTF+.BF4-) leads to S-alkyltetrathiafulvalenium tetrafluoroborate salts; the solvolysis of such salts is critically dependent on the presence of appropriately sited neighbouring groups.
1,3-Cycloaddition of Benzyne to Thiophenes
Mazza, Dario Del,Reinecke, Manfred G.
, p. 124 - 125 (1981)
Benzyne, generated from diphenyliodonium-2-carboxylate, reacts with various thiophens by addition to the sulphur and β-carbon to give, after loss of an acetylene moiety, benzothiophenes in low but reproducible yields.
Kinetics of bromine-magnesium exchange reactions in heteroaryl bromides
Shi, Lei,Chu, Yuanyuan,Knochel, Paul,Mayr, Herbert
, p. 3502 - 3505 (2009)
Competition experiments are reported which compare the relative reactivities of bromoheteroarenes toward i-PrMgCl.LiCl in THF at 0 °C
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Fields,Meyerson
, p. 708 (1966)
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Synthesis, crystal structure and reactivity of η2-thiophyne Ni complexes
Terada, Misaki,Nishii, Yuji,Miura, Masahiro
, p. 2918 - 2921 (2018)
The first synthesis and crystal structures of five-membered ring aryne complexes, Ni(dcpe)(η2-thiophyne) and Ni(dcpe)(η2-benzo[b]thiophyne), are described. The aryne fragments retain considerable aromatic character and the two coordi
AN UNUSUAL CONVERSION OF 2,2,3,3-TETRAFLUORO-2,3-DIHYDROBENZOTHIOPHENE WITH LITHIUM ALUMINUM HYDRIDE
Maksimov, A. M.,Platonov, V. E.
, p. 1549 (1985)
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Boswell et al.
, p. 5265 (1970)
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The preparation of (Z)-2-lithio-ortho-styryllithium via an ortho-directed lithiation
Ashe, Arthur J.,Savla, Paresh M.
, p. 1 - 4 (1993)
Lithiation of (Z)-2-lithiostyrene with t-butyllithium/TMEDA pentane led directly to (Z)-2-lithio-ortho-styryllithium. subsequent treatment of this dilithio compound with difunctional electrophiles allowed the preparation of a variety of benzoheteroles.
High-temperature synthesis of thiophene from bis(2-chloroethyl) sulfide
Voronkov,Levanova,Sukhomazova,Russavskaya,Deryagina,Korchevin
, p. 891 - 893 (2005)
Gas-phase reaction of bis(2-chloroethyl) sulfide (Yperite) with acetylene at 550-700°C leads to formation of thiophene in 45% yield, the conversion of the initial sulfide being complete. The yield of thiophene reaches 63-68% in the thermolysis of a mixture of acetylene, bis(2-chloroethyl) sulfide, and lower organic disulfides.
Photolysis of β-(o-Methylthiophenyl)vinyl Bromides. A Versatile Synthesis of Benzothiophens
Kitamura, Tsugio,Kobayashi, Shinjiro,Taniguchi, Hiroshi
, p. 1637 - 1638 (1988)
Exclusive cyclization in photolysis of β-(o-methylthiophenyl)vinyl bromides to give benzothiophens is described.
Metal-Free Heterogeneous Semiconductor for Visible-Light Photocatalytic Decarboxylation of Carboxylic Acids
Shi, Jiale,Yuan, Tao,Zheng, Meifang,Wang, Xinchen
, p. 3040 - 3047 (2021/03/09)
A suitable protocol for the photocatalytic decarboxylation of carboxylic acids was developed with metal-free ceramic boron carbon nitrides (BCN). With visible light irradiation, BCN oxidize carboxylic acids to give carbon-centered radicals, which were trapped by hydrogen atom donors or employed in the construction of the carbon-carbon bond. In this system, both (hetero)aromatic and aliphatic acids proceed the decarboxylation smoothly, and C-H, C-D, and C-C bonds are formed in moderate to high yields (35 examples, yield up to 93%). Control experiments support a radical process, and isotopic experiments show that methanol is employed as the hydrogen atom donor. Recycle tests and gram-scale reaction elucidate the practicability of the heterogeneous ceramic BCN photoredox system. It provides an alternative to homogeneous catalysts in the valuable carbon radical intermediates formation. Moreover, the metal-free system is also applicable to late-stage functionalization of anti-inflammatory drugs, such as naproxen and ibuprofen, which enrich the chemical toolbox.
Site-Selective Silver-Catalyzed C-H Bond Deuteration of Five-Membered Aromatic Heterocycles and Pharmaceuticals
Tlahuext-Aca, Adrian,Hartwig, John F.
, p. 1119 - 1127 (2021/02/01)
Catalytic methods for the direct introduction of hydrogen isotopes into organic molecules are essential to the development of improved pharmaceuticals and to the alteration of their absorption, distribution, metabolism, and excretion (ADME) properties. However, the development of homogeneous catalysts for selective incorporation of isotopes in the absence of directing groups under practical conditions remains a long-standing challenge. Here, we show that a phosphine-ligated, silver-carbonate complex catalyzes the site-selective deuteration of C-H bonds in five-membered aromatic heterocycles and active pharmaceutical ingredients that have been resistant to catalytic H/D exchange. The reactions occur with CH3OD as a low-cost source of the isotope. The silver catalysts react with five-membered heteroarenes lacking directing groups, tolerate a wide range of functional groups, and react in both polar and nonpolar solvents. Mechanistic experiments, including deuterium kinetic isotope effects, determination of kinetic orders, and identification of the catalyst resting state, support C-H bond cleavage from a phosphine-ligated, silver-carbonate intermediate as the rate-determining step of the catalytic cycle.