- Revealing resonance effects and intramolecular dipole interactions in the positional isomers of benzonitrile-core thermally activated delayed fluorescence materials
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We report on the properties of the three positional isomers of (2,7-di-tert-butyl-9,9-dimethylacridin-10(9H)-yl)benzonitrile, which are found to have comparable donor steric environments and donor-acceptor dihedral angles. An unexpected intramolecular dip
- Kukhta, Nadzeya A.,Higginbotham, Heather F.,Matulaitis, Tomas,Danos, Andrew,Bismillah, Aisha N.,Haase, Nils,Etherington, Marc K.,Yufit, Dmitry S.,McGonigal, Paul R.,Gra?ulevi?ius, Juozas Vidas,Monkman, Andrew P.
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supporting information
p. 9184 - 9194
(2019/08/08)
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- Salicylic Acid-Catalyzed One-Pot Hydrodeamination of Aromatic Amines by tert-Butyl Nitrite in Tetrahydrofuran
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A significant acceleration in the hydrodeamination of in situ formed diazonium salts (from aromatic amines) has been observed in the presence of 10-mol% salicylic acid, using tetrahydrofuran as the hydrogen donor. The reaction proceeds efficiently at 20 °C for a wide range of substituted anilines, even at 10-mmol scale, without any other additive. The same protocol has been adapted to the selective deuterodeamination of some aromatic amines. Control experiments clearly show that aryl radicals are involved in the reaction mechanism. (Figure presented.).
- Felipe-Blanco, Diego,Alonso, Francisco,Gonzalez-Gomez, Jose C.
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supporting information
p. 2857 - 2863
(2017/08/23)
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- One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides
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A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.
- Leas, Derek A.,Dong, Yuxiang,Vennerstrom, Jonathan L.,Stack, Douglas E.
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supporting information
p. 2518 - 2521
(2017/05/24)
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- Photo-induced Metal-Catalyst-Free Aromatic Finkelstein Reaction
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The facile iodination of aromatic compounds under mild conditions is a great challenge for both organic and medicinal chemistry. Particularly, the synthesis of functionalized aryl iodides by light has long been considered impossible due to their photo-lability, which actually makes aryl iodides popular starting materials in many photo-substitution reactions. Herein, a photo-induced halogen exchange in aryl or vinyl halides has been discovered for the first time. A broad scope of aryl iodides can be prepared in high yields at room temperature under exceptionally mild conditions without any metal or photo-redox catalysts. The presence of a catalytic amount of elemental iodine could promote the reaction significantly.
- Li, Lu,Liu, Wenbo,Zeng, Huiying,Mu, Xiaoyue,Cosa, Gonzalo,Mi, Zetian,Li, Chao-Jun
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supporting information
p. 8328 - 8331
(2015/07/15)
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- Rapid and efficient copper-catalyzed finkelstein reaction of (hetero)aromatics under continuous-flow conditions
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A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method.
- Chen, Mao,Ichikawa, Saki,Buchwald, Stephen L.
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supporting information
p. 263 - 266
(2015/02/05)
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- Cu/nitroxyl-catalyzed aerobic oxidation of primary amines into nitriles at room temperature
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An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4′-tBu 2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one-N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope and are effective with benzylic, allylic, and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction.
- Kim, Jinho,Stahl, Shannon S.
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p. 1652 - 1656
(2013/07/26)
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- A safe and reliable procedure for the iododeamination of aromatic and heteroaromatic amines in a continuous flow reactor
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A method for the safe and reliable iododeamination of aromatic and heteroaromatic amines under copper-free conditions is described and its scope is evaluated.
- Malet-Sanz, Laia,Madrzak, Julia,Holvey, Rhian S.,Underwood, Toby
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experimental part
p. 7263 - 7267
(2010/03/03)
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- Iodination of aryl amines in a water-paste form via stable aryl diazonium tosylates
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The diazotization of aryl amines at room temperature in paste form with NaNO2, p-TsOH and a small amount of water, followed by treatment with KI provides a new, simple, and effective route for the preparation of various aryl iodides. The water-paste and strong acid-free reaction conditions are environmentally friendly and compatible with acid-sensitive functional groups.
- Gorlushko, Dmitry A.,Filimonov, Victor D.,Krasnokutskaya, Elena A.,Semenischeva, Nadya I.,Go, Bong Seong,Hwang, Ho Yun,Cha, Eun Hye,Chi, Ki-Whan
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p. 1080 - 1082
(2008/09/18)
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- A Novel Aromatic Iodination Method Using F2
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A new method for direct aromatic iodination with IF, made in situ from the corresponding elements, is described.Depending on the reaction time and temperature, mono- or polyiodination can be achieved.Even deactivated aromatic rings can be directly iodinated without the presence of any Friedel-Crafts catalyst.Sensitive groups such as aromatic aldehydes are not affected by the reagent.
- Rozen, Shlomo,Zamir, Dov
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p. 3552 - 3555
(2007/10/02)
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- HALOGEN EXCHANGE REACTIONS OF ARYL HALIDES USING SUPPORTED COPPER(I)
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Halogen exchange reactions of unactivated and some activated aryl halides can be achieved using supported copper(I) in non-polar solvents.The complex supported reagent KI-CuI-alumina has been found to be especially effective for the normally unfavourable conversion of bromoaryls to iodoaryls.Negative ion FABMS has revealed the existence of CuX2(-) species on the support surface of most reagents but notably not on that of the complex KI-CuI-alumina reagent.
- Clark, James H.,Jones, Craig W.,Duke, Catherine V. A.,Miller, Jack M.
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p. 1745 - 1758
(2007/10/02)
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- Vapour-phase Chemistry of Arenes. Part 13. Reactivity and Selectivity in the Gas-phase Reactions of Hydroxyl Radicals with Monosubstituted Benzenes at 563 K
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The reactions of hydroxyl radicals with benzene derivates C6H5Z (Z = H, Me, F, Cl, Br, I, CF3, or CN) have been studied in a flow reactor at 563 K in nitrogen, using the thermolysis of ButOOH as a source of .OH.Under these conditions there are two product-forming pathways.The major one involves hydrogen abstraction to give aryl radicals ZC6H4. (II) as the first step; depending on Z, its displacement to form phenol may also occur.Relative rates for hydrogen abstraction were determined in competition experiments using side-chain hydrogen abstraction from added toluene as a reference.This resulted in the order (for Z =): 1,8(Me), 1.0(H), 0.47(F), 0.29(Cl), 0.34(CF3), 0.20(CN), consonant with the electrophilic nature of .OH.The site selectivity of hydrogen abstractions was determined by scavenging part of the aryl radicals (II) with iodine.A Hammett plot, using ? constants for meta and para positions, led to ρ -1.0.The features of hydrogen abstraction by .OH are discussed and compared with those for the analogous reaction of Cl.The formation of phenol was found to decrease in importance in the order F, Cl, Br, and I.This result is rationalized on a thermochemical kinetic basis.
- Mulder, Peter,Louw, Robert
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p. 1167 - 1174
(2007/10/02)
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- 5-substituted[1,2,4]triazolo[1,5-c]pyrimidin-2-amines
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This invention is concerned with 5-substituted[1,2,4]triazolo[1,5-c]pyrimidin-2-amines selected from those of Formula I, which are active as antiasthma agents.
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- Polar Radicals. 17. On the Mechanism of Iodine Atom Transfer. A 9-I-2 Intermediate
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The atom-transfer reaction of iodine from an aryl iodide to a phenyl radical has been shown to proceed via a 9-I-2 ntermediate.The relative kinetics of the reactions of the intermediate were investigated by studying its mode of decomposition upon formation from the reduction of a series of unsymmetrically substituted diaryliodonium salts.The iodonium salts were reduced by the electron-transfer reactions with several reagents: di-tert-butyl nitroxide, sodium 2,6-di-tert-butylphenylate, and sodium phenylate.The reduction by electron transfer of the iodonium salts by the latter reaction gives high yields of diaryl ethers.The mechanism fo ether formation has been shown to proceed by two mechanistic pathways.For the diaryliodonium salts that have a p-cyano or p-nitro substituent, the ether is formed by a nucleophilic aromatic substitution; however, when the substituents were not strongly electron withdrawing, the mechanism resulting in ether formation involved electron transfer from the phenylate anion to the iodonium salt to form the phenoxy radical and a 9-I-2 intermediate.The intermediate decomposes to an aryl radical and an aryl iodide.The ether is formed from the efficient coupling of the aryl radical and the phenoxy radical.
- Tanner, Dennis D.,Reed, Darwin W.,Setiloane, B.P.
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p. 3917 - 3923
(2007/10/02)
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- Electrophilic Aromatic Substitution by Positive Iodine Species. Iodination of Deactivated Aromatic Compounds
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The anodic oxidation of iodine in trifluoroacetic acid containing solvents produces a highly reactive positive iodine species which selectively iodinates even the most highly deactivated monosubstituted benzenes such as nitrobenzene and benzotrifluoride in high yield.The reactivity of the positive iodine species was found to be markedly dependent upon the nature of the solvent.In solvent containing 10percent trifluoroacetic acid, the yield of 3-iodonitrobenzene increased from 0 to 47 to 78percent in the series; acetonitrile, dichloromethane and 1,2-dichloroethane.In the latter solvent the yield of 3-iodonitrobenzene increased from 47 to 78percent upon increasing the trifluoroacetic acid concentration from 1 to 10percent.The mechanism of the reaction involves the direct attack of the positive iodine species on the aromatic compound.
- Lines, Robert,Parker, Vernon D.
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