- Rapid and Simple Access to α-(Hetero)arylacetonitriles from Gem-Difluoroalkenes
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A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reacti
- Hu, Dandan,Liu, Jiayue,Ren, Hongjun,Song, Jinyu,Zhang, Jun-Qi,Zhu, Guorong
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supporting information
p. 786 - 790
(2022/01/28)
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- Flash vacuum pyrolysis of 2-acetyl-3-azido[1]benzothiophene
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Flash vacuum pyrolysis (FVP) of 2-acetyl-3-azido[1]benzothiophene at 300 °C provides 3-methyl [1]benzothieno[3,2-c]isoxazole (72%). At higher temperatures, the heteroindoxyl 1,2-dihydro[1]benzo-thieno[3,2-b]pyrrol-3-one was obtained in low yield (ca. 10%). The heteroindoxyl exists as a mixture of keto and enol forms in DMSO solution. Because of the easy oxidative dimerisation of these products to indigotin (and its heteroanalogues), such reactions are excellent examples of the synthetic advantages of FVP with the monomeric products conveniently generated under vacuum in a solvent-free, air-free environment.
- Gaywood, Alexander P.,McNab, Hamish,McNab, Lilian
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p. 228 - 237
(2020/09/09)
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- Photoinduced Copper(I)-Catalyzed Cyanation of Aromatic Halides at Room Temperature
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The first photoinduced copper(I)-catalyzed cyanation of aromatic halides at room temperature has been developed. The sp2 cyanation reaction exhibits outstanding tolerance to functional groups including primary amines and carboxylic acids, and chemoselectivity to SN2-reactive alkyl chlorides. Mechanistic investigations indicate that the reaction occurs via a single-electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate. (Figure presented.).
- Kim, Kicheol,Hong, Soon Hyeok
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supporting information
p. 2345 - 2351
(2017/07/22)
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- Synthesis, optical and nonlinear optical properties of new pyrazoline derivatives
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We report on synthesis and optical properties of new organic compounds based on substituted pyrazole ring. The investigated pyrazoline derivatives (PRDs) exhibit efficient broadband photoluminescence which covers nearly whole visible spectrum. The experimental results are compared to quantum chemical calculations. Amplified spontaneous emission and photodegradation measurements were performed for hybrid systems based on selected PRDs doped into poly(methyl methacrylate) matrix proving the potential utility of such systems in lasing applications. Two-photon absorption (TPA) properties were characterized by the femtosecond Z-scan technique.
- Mysliwiec,Szukalski,Sznitko,Miniewicz,Haupa,Zygadlo,Matczyszyn,Olesiak-Banska,Samoc
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- A heterogeneous palladium catalyst hybridised with a titanium dioxide photocatalyst for direct C-C bond formation between an aromatic ring and acetonitrile
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A palladium catalyst hybridised with a titanium dioxide photocatalyst can promote cyanomethylation of an aromatic ring by using acetonitrile, where the photocatalyst activates acetonitrile to form a cyanomethyl radical before the C-C bond formation using the palladium catalyst.
- Yoshida, Hisao,Fujimura, Yuki,Yuzawa, Hayato,Kumagai, Jun,Yoshida, Tomoko
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supporting information
p. 3793 - 3795
(2013/05/22)
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- 3-Hydroxypyrrolo[2,3-b]pyridine and related compounds - Indoxyl analogues with fused electron deficient rings
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Flash vacuum pyrolysis (FVP) of 4-acetyltetrazolo[1,5-a]pyridine 5 at 400 °C provides 3-methyl isoxazolo[3,4-b]pyridine 6 whose structure was confirmed by X-ray crystallography. At higher pyrolysis temperatures, the unstable heteroindoxyl 8 was obtained, which exists as the keto form (1,2-dihydropyrrolo[2,3-b]pyridin-3-one) 8K in CDCl3 solution and the enol tautomer (3-hydroxypyrrolo[2,3-b]pyridine) 8E in DMSO. The heteroindoxyl 8 oxidatively dimerises to the heteroindigotin 9, undergoes condensation reactions at the 2-position and reacts with methoxymethylene Meldrum's acid at the 1-position. FVP of the corresponding acetyltetrazolo[1,5-a]quinoline 19 was much more complex, with 2-(cyanophenyl)acetonitrile 30 (rather than a heteroindoxyl) the major product at 750 °C. FVP of 3-acetyl-4-azidoquinoline 24 at 400 °C gave 3-methylisoxazolo[4,3-c]quinoline 33, but rearrangement to the heteroindoxyl was not observed at higher temperatures.
- Gaywood, Alexander P.,McNab, Hamish
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supporting information; experimental part
p. 5166 - 5173
(2010/12/25)
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- Efficient methods for the synthesis of arylacetonitriles
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Various approaches to [2-fluoro-4-(trifluoromethyl)phenyl]acetonitrile were investigated. Two of these methods were selected and applied to a variety of electron-deficient substrates, thereby expanding the scopes of the procedures.
- Stazi, Federica,Maton, William,Castoldi, Damiano,Westerduin, Pieter,Curcuruto, Ornella,Bacchi, Sergio
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experimental part
p. 3332 - 3338
(2010/11/20)
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- Straightforward construction of diarylmethane skeletons via aryne insertion into carbon-carbon σ-bonds
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Two molar amounts of arynes were found to couple with nitriles via carbon-carbon σ-bond cleavage, assembling diverse diarylmethane skeletons in a straightforward manner. The Royal Society of Chemistry.
- Yoshida, Hiroto,Watanabe, Masahiko,Morishita, Takami,Ohshita, Joji,Kunai, Atsutaka
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p. 1505 - 1507
(2008/02/02)
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- In vitro, and in vivo, evaluation of dihydropyrimidinone C-5 amides as potent and selective α(1A) receptor antagonists for the treatment of benign prostatic hyperplasia
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α1 Adrenergic receptors mediate both vascular and lower urinary tract tone, and α1 receptor antagonists such as terazosin (1b) are used to treat both hypertension and benign prostatic hyperplasia (BPH). Recently, three different subtypes of this receptor have been identified, with the α(1A) receptor being most prevalent in lower urinary tract tissue. This paper explores 4-aryldihydropyrimidinones attached to an aminopropyl-4- arylpiperidine via a C-5 amide as selective α(1A) receptor subtype antagonists. In receptor binding assays, these types of compounds generally display K(i) values for the α(1a) receptor subtype 20%) and half-life (>6 h) in both rats and dogs. Due to its selectivity for the α(1a) over the α(1b) and α(1d) receptors as well as its favorable pharmacokinetic profile, 48 has the potential to relieve the symptoms of BPH without eliciting effects on the cardiovascular system.
- Barrow, James C.,Nantermet, Philippe G.,Selnick, Harold G.,Glass, Kristen L.,Rittle, Kenneth E.,Gilbert, Kevin F.,Steele, Thomas G.,Homnick, Carl F.,Freidinger, Roger M.,Ransom, Rick W.,Kling, Paul,Reiss, Duane,Broten, Theodore P.,Schorn, Terry W.,Chang, Raymond S. L.,O'Malley, Stacey S.,Olah, Timothy V.,Ellis, Joan D.,Barrish, Andrea,Kassahun, Kelem,Leppert, Paula,Nagarathnam, Dhanapalan,Forray, Carlos
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p. 2703 - 2718
(2007/10/03)
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- Carboanion Reactivity: Kinetics of the Reactions of Benzyl Cyanide Anions with Aromatic Nitro-compounds
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Rate and equilibrium measurements are reported for the reactions in methanol of carbanions derived from 12 ring-substituted benzyl cyanides with 1,3,5-trinitrobenzene to give ?-adducts.Some data for reaction of the carbanions with 4-nitrobenzofuroxan were also measured.With increasing carbanion reactivity, rate constants approach a limit of just below 109 dm3 mol-1 s-1.Intrinsic reactivities of carbanions in ?-adduct forming reactions and in proton transfer reactions are compared.
- Atherton, John H.,Crampton, Michael R.,Duffield, Gaynor L.,Stevens, J. Andrew
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p. 443 - 448
(2007/10/02)
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- Intrinsic Reactivities of Some Carbanions in ?-Adduct Forming Reactions
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Kinetic and equilibrium data are reported for nucleophilic attack in methanol at unsubstituted ringpositions of 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene and 1-chloro-2,4,6-trinitrobenzene by carbanions derived from dimethyl malonate, ethyl cyanoacetate and 4-nitro-, 4-cyano- and 2-cyanobenzyl cyanides.The results are used to determine intrinsic reactivities for the carbanions in these ?-adduct forming reactions and are discussed in terms of the electronic and solvent reorganisation occurring during reaction.
- Crampton, Michael R.,Stevens, Andrew J.
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p. 1715 - 1720
(2007/10/02)
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- Heterocyclic Imines and Amines. Part 19. Isoquinoline and Other Products from α,o-Dicyanostilbene and Basic Reagents
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α,o-Dicyanostilbene (1) was cleaved by hydrazine or hydroxylamine under mildly acid conditions to o-cyanobenzyl cyanide (2) and benzaldehyde, isolated as derivatives.Sodamide with compound (1) gave 1-amino-4-cyano-3-phenylisoquinoline: alkoxides similarly gave the 1-alkoxy compounds, the presumed intermediate 3,4-dihydroisoquinoline from the methoxide reaction being isolated and separately dehydrogenated.Acid hydrolysis of the 1-ethoxy compound gave the known 4-cyano-3-phenylisoquinolin-1(2H)-one.With the anion of o-cyanobenzyl cyanide, compound (1) gave a 1-amino-4-cyano-3-(2-substituted phenyl)isoquinoline, which was oxidised to 1-amino-4-cyano-3-(2-carboxyphenyl)isoquinoline.The latter lost water at 210 deg C to give yellow 12-cyano-5-iminoisoindoloisoquinolin-7(5H)-one, closely related to known compounds.
- Barnard, Ian F.,Elvidge, John A.
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p. 1813 - 1818
(2007/10/02)
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