- Diaza-analogs of benzopyrene and perylene containing thienyl and 4-(phenylamino)phenyl groups: Synthesis, characterization, optical and electrochemical properties
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Series of 1,8-diazabenzopyrenes and 1,7-diazaperylenes with thienyl or 4-(phenylamino)phenyl groups were designed and synthesized by a one-pot process from the functionalized terminal alkynes and either 1,4- or 1,5-diiodoanthraquinones in order to investigate the effect of extending π-conjugation at the 2,7- and 2,8-positions on the optical and electrochemical properties. The substances synthesized were characterized by X-ray analysis, cyclic voltammetry, UV–vis and luminescence spectroscopy. Energies and spin-densities of frontier molecular orbitals were calculated by DFT. Practically planar crystal structures of 1,8-diazabenzopyrene and 1,7-diazaperylene with thienyl groups were confirmed by X-ray diffraction data. Solid-state luminescence was obtained for the synthesized substances in drop-casted films and in 1,4-dioxane/water mixtures.
- Baranov, Denis S.,Uvarov, Mikhail N.,Kazantsev, Maxim S.,Mostovich, Evgeny A.,Glebov, Evgeni M.,Gatilov, Yurii V.,Kulik, Leonid V.
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- Palladium-catalyzed amination of aryl sulfides with aliphatic amines
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Conditions for the palladium-NHC-catalyzed amination of aryl sulfides with aliphatic as well as aromatic amines were established. The KHMDS-mediated amination of heteroaryl sulfides could proceed without palladium. Based on the distinct difference in reactivity of C-Br and C-S bonds, a sequential amination of bromothioanisole can take place to install two different alkylamino groups onto the aromatic ring in one pot. A palladium-NHC precatalyst shows high efficiency for C-S bond cleavage for the amination of aryl sulfides with aliphatic amines or aromatic amines.
- Gao, Ke,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 2678 - 2682
(2015/04/27)
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- N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole complexes: Synthesis and catalytic activity toward amination of aryl chlorides
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A series of novel N-heterocyclic carbene-palladium(II)-4,5-dihydrooxazole (NHC-PdII-Ox) complexes 3 were successfully synthesized from commercially available imidazolium salts 1, PdCl2, and 4,5-dihydrooxazoles 2 in a one-step process, and these complexes showed efficient catalytic activity toward the amination of aryl chlorides. Both secondary and primary amines were tolerated under the same reaction conditions. Under the optimal reaction conditions, the expected coupling products were obtained in moderate to high yields.
- Huang, Pei,Wang, Yi-Xiang,Yu, Hong-Fei,Lu, Jian-Mei
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supporting information
p. 1587 - 1593
(2014/05/06)
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- Probing the utility of palladium complexes supported by morpholine-functionalized N -heterocyclic carbene ligands in Buchwald-Hartwig amination
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Convenient and high-yielding syntheses of two new morpholine-substituted N-heterocyclic carbene ligands, 1-Ar-3-{2-(4-morpholinyl)phenyl}imidazolidin-2- ylidene (Ar = Dipp, Mes), are described. An investigation of corresponding palladium complexes reveals hemilability, and examples of both monodentate and bidentate coordination are observed. A preliminary investigation of the activity of these palladium complexes for Buchwald-Hartwig amination catalysis is presented.
- Wheaton, Craig A.,Stradiotto, Mark
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p. 755 - 762
(2013/08/23)
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- Well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides
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We report herein a well-defined NHC-Pd(II)-Im (NHC=N-heterocyclic carbene; Im=1-methylimidazole) complex catalyzed C-N coupling of primary amines with aryl chlorides. Under the optimal reaction conditions, a variety of primary amines can be coupled with aryl chlorides to give the amination products in good to high yields within 4 h. It is worthy of noting here that the NHC-Pd(II)-Im complex showed especially high catalytic activity toward challenging sterically hindered substrates including both of aryl amines and aryl chlorides. In addition, alkyl amines were also proved to be suitable reaction partners to give the corresponding amination products in good to high yields.
- Zhu, Lei,Ye, Yue-Mei,Shao, Li-Xiong
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experimental part
p. 2414 - 2420
(2012/04/10)
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- Structrure and Reactivity of Lithium Amides. Role of Aggregates, Mixed Aggregates, Monomers, and Free Ions on the Rates and Selectivities of N-Alkylation and E2 Elimination
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Rate studies of the N-alkylation of lithium diphenylamide with n-butyl bromide in THF/hydrocarbon mixtures (THF=tetrahydrofuran) are described.Dramatic induction periods observed for the N-alkylation at low THF concentrations are described to the intervention of reactive mixed dimers of lithium diphenylamide and lithium bromide.In the presence of 1.0 equiv. of added lithium bromide, the alkylation rate exhibits a first-order dependence on both the mixed aggregate and n-butyl bromide concentration, indicating the contribution of an additional, highly solvent dependentalkylation pathway.This latter pathway exhibits fractional-order dependence on the amide concentration, approximate first order dependence on the n-butyl bromide concentration, and a seventh-order dependence on the THF concentration.Common ion rate inhibitions by lithium perchlorate and lithium tetraphenylborate, a significant dependence on dielectric effects, and the observed reaction orders implicate a mechanism involving predissociation of free lithium ions.The appearence of competitive eliminations of n-alkyl bromides to form 1-alkenes coincides with the appearence of the free ion alkylation pathway.
- DePue, Jeffrey S.,Collum, David B.
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p. 5524 - 5533
(2007/10/02)
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- Chromogenic fluoran derivatives and the preparation and use thereof
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Certain 3-substituted amino-7-substituted fluoran derivatives useful as color recording materials.
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