- A Ratiometric Near-Infrared Fluorogen for the Real Time Visualization of Intracellular Redox Status during Apoptosis
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Direct monitoring of apoptotic progression is a major step forward for the early assessment of therapeutic efficacy of certain treatments and the accurate evaluation of the spread of a disease. Here, the regulatory role of glutathione (GSH) is explored as a potential biomarker for tracking apoptosis. For this purpose, a near- infrared (NIR) squaraine dye is introduced that is capable of sensing GSH in a ratiometric manner by switching its emission from NIR (690 nm) to visible region (560 nm). The favorable biocompatible attributes of the probe facilitated the real-time monitoring of apoptotic process in line with the conventional apoptotic assay. Furthermore, the robust nature of the probe was utilized for the quantitative estimation of GSH during different stages of apoptosis. Through this study, an easy and reliable method of assaying apoptosis is demonstrated, which can provide valuable insights in translational clinical research.
- Saranya, Giridharan,Anees, Palapuravan,Joseph, Manu M.,Maiti, Kaustabh K.,Ajayaghosh, Ayyappanpillai
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Read Online
- Synthesis and Properties of Chromophores with a Pyrroline-Type Acceptor for Electro-Optic Polymers
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We synthesized four electro-optic (EO) chromophores, which contained an aniline donor and an acceptor of 4-cyano-5-dicyanomethylene-2-oxo-3-pyrroline (CDCOP) with alkyl groups and/or oxyethylene chains terminated by an acrylate group as the three substituents. Photopolymerization of the mixture composed of the CDCOP derivatives, a liquid acrylate monomer and a radical photoinitiator was performed, and the chromophore fixation by crosslinking was achieved although about 30% of the chromophores were degraded by the radical attacks during crosslinking. Corona poling of these CDCOP derivatives in PMMA as a matrix polymer was successful regardless of the substituents. However, poling of the CDCOP derivatives in the liquid acrylate monomer matrix during photocrosslinking was difficult, and the poling conditions should be optimized.
- Sato, Yukichi,Inada, Shunsuke,Araki, Tatsunori,Tatewaki, Yoko,Okada, Shuji
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Read Online
- Product selective reaction controlled by the combination of palladium nanoparticles, continuous microwave irradiation, and a co-existing solid; ligand-free Buchwald-Hartwig aminationvs.aryne amination
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We have developed a continuous microwave irradiation-assisted Buchwald-Hartwig amination using our original Pd nanoparticle catalyst with a copper plate as a co-existing metal solid. In this methodology, a microwave-controlled product selectivity was achieved between Buchwald-Hartwig amination and aryne amination performed under strongly basic conditions and at a high reaction temperature, because a polar chemical species such as Ar-Pd-halogen might be activated selectively by microwave radiation. Moreover, our catalyst could be used repeatedly over 10 times, and the amount of Pd leaching could be suppressed to a low level.
- Akiyama, Toshiki,Arai, Masayoshi,Arisawa, Mitsuhiro,Haneoka, Hitoshi,Harada, Kazuo,Murai, Kenichi,Murakami, Yosuke,Ohki, Yuuta,Ohta, Ryousuke,Sako, Makoto,Sirimangkalakitti, Natchanun,Suzuki, Takeyuki,Takahashi, Naoyuki,Takehara, Tsunayoshi,Yamada, Makito
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supporting information
p. 8131 - 8137
(2021/10/29)
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- Reduced Phenalenyl in Catalytic Dehalogenative Deuteration and Hydrodehalogenation of Aryl Halides
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Dehalogenative deuteration reactions are generally performed through metal-mediated processes. This report demonstrates a mild protocol for hydrodehalogenation and dehalogenative deuteration of aryl/heteroaryl halides (39 examples) using a reduced odd alternant hydrocarbon phenalenyl under transition metal-free conditions and has been employed successfully for the incorporation of deuterium in various biologically active compounds. The combined approach of experimental and theoretical studies revealed a single electron transfer-based mechanism.
- Singh, Bhagat,Ahmed, Jasimuddin,Biswas, Amit,Paira, Rupankar,Mandal, Swadhin K.
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p. 7242 - 7255
(2021/05/29)
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- Heterogeneous Ru/TiO2for hydroaminomethylation of olefins: multicomponent synthesis of amines
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Synthesizing aminesviathe hydroaminomethylation (HAM) reaction of olefins, a multicomponent reaction, has been regarded as one of the most attractive methods compared with the traditional methods considering the atom economy and environmental friendliness. However, the use of homogeneous catalysts, complex ligands containing diphosphine or nitrogen, and base or acid additives has severely hampered the utilization of these methods. Herein, an efficient heterogeneous Ru/TiO2-catalyzed HAM reaction of olefins is developed without any additives. Various amines, including secondary and tertiary amines, can be successfully obtained from olefins including aromatic and aliphatic olefins. Systematic studies demonstrate the lower electron density of Ruδ+and the higher number of acid sites of Ru/TiO2, leading to the high HAM reaction activity of olefins. Most importantly, nitrobenzene derivatives can also be transformed to the corresponding products over Ru/TiO2in excellent yields.
- An, Jinghua,Gao, Zhuyan,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Li, Lu,Tang, Bo,Wang, Feng
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supporting information
p. 2722 - 2728
(2021/04/21)
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- Synthesis ofN-aryl amines enabled by photocatalytic dehydrogenation
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Catalytic dehydrogenation (CD)viavisible-light photoredox catalysis provides an efficient route for the synthesis of aromatic compounds. However, access toN-aryl amines, which are widely utilized synthetic moieties,viavisible-light-induced CD remains a significant challenge, because of the difficulty in controlling the reactivity of amines under photocatalytic conditions. Here, the visible-light-induced photocatalytic synthesis ofN-aryl amines was achieved by the CD of allylic amines. The unusual strategy using C6F5I as an hydrogen-atom acceptor enables the mild and controlled CD of amines bearing various functional groups and activated C-H bonds, suppressing side-reaction of the reactiveN-aryl amine products. Thorough mechanistic studies suggest the involvement of single-electron and hydrogen-atom transfers in a well-defined order to provide a synergistic effect in the control of the reactivity. Notably, the back-electron transfer process prevents the desired product from further reacting under oxidative conditions.
- Kim, Jungwon,Kim, Siin,Choi, Geunho,Lee, Geun Seok,Kim, Donghyeok,Choi, Jungkweon,Ihee, Hyotcherl,Hong, Soon Hyeok
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p. 1915 - 1923
(2021/02/22)
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- Preparation method of N-alkylated derivative of primary amine compound
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The invention relates to a preparation method of an N-alkylated derivative of a primary amine compound. The method comprises the following steps: uniformly mixing a primary amine compound, an alcohol compound and a catalyst in a reactor, and heating to react for a period of time to generate an N-alkylated substituted tertiary amine compound; wherein the catalyst is a copper-cobalt bimetallic catalyst, and the carrier of the catalyst is Al2O3. According to the method, alcohol is adopted as an alkylating reagent and is low in price and easy to obtain, a byproduct is water, no pollution is caused to the environment, and the overall reaction atom economy is high; the catalyst is simple in preparation method, low in cost, high in reaction activity and good in structural stability; meanwhile, by using the copper-cobalt bimetallic catalyst, the use of strong base additives can be avoided, and the requirement on reaction equipment is low; and the reaction post-treatment is convenient, and the catalyst can be recycled and is environment-friendly.
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Paragraph 0021; 0056
(2021/07/09)
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- Novel yellow- to red-emitting fluorophores: Facile synthesis, aggregation-induced emission, two-photon absorption properties, and application in living cell imaging
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Four novel yellow-to red-emitting fluorophores with a 1-(2-hydroxyethyl) pyridinium core and different electron-donating terminal moieties (N-methylcarbazole, N,N-dibutylbenzenamine, N-methylpyrrole, and 2-methylfuran) were designed and facilely synthesized via the one-step Knoevenagel condensation. All these compounds (HPs) were characterized by 1H NMR, 13C NMR, and HRMS. Their photophysical properties including linear absorption, one-photon excited fluorescence, two-photon absorption, and two-photon excited fluorescence, were systematically investigated in various solvents. And the density functional theory calculations were conducted to analyze the electronic structures of HPs. The two-photon absorption cross-sections (δ) values of HPs measured by the Z-scan technique were determined to be as large as 1354 (1HP-CZ), 4462 (2HP-BA), 836 (3HP-PR), and 2944 GM (4HP-FU) in DMSO. The two-photon action cross-sections (Φ × δ) values of 1HP-CZ and 2HP-BA in H2O measured by the two-photon induced fluorescence method were about 50 GM. 1HP-CZ, 3HP-PR, and 4HP-FU also exhibited good water solubility. Meanwhile, it was found that 2HP-BA exhibited notable aggregation-induced emission characteristic in DMSO/H2O mixture. The aggregate particle size distribution of 2HP-BA was measured by the dynamic light scattering method, and the aggregation characteristic of 2HP-BA was observed by the transmission electron microscopy. Besides, 2HP-BA also exhibited red emission. Then, HPs with relatively low cytotoxicity were used for one- and two-photon excited fluorescence imaging in living HepG2 cells. The results indicate that HPs are potential candidates in the bioimaging field due to their photophysical properties and biocompatibility.
- Dong, Qi-Ji,Cai, Zhi-Bin,Ding, Ling,Luo, Pei-Hua,He, Qiao-Jun,Li, Sheng-Li,Chen, Li-Jun,Ye, Qing,Tian, Yu-Peng
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- N -Arylation of (hetero)arylamines using aryl sulfamates and carbamates via C-O bond activation enabled by a reusable and durable nickel(0) catalyst
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An effective and general aryl amination protocol has been developed using a magnetically recoverable Ni(0) based nanocatalyst. This new stable catalyst was prepared on Fe3O4@SiO2 modified by EDTA and investigated by FT-IR, EDX, TEM, XRD, DLS, FE-SEM, XPS, NMR, TGA, VSM, ICP and elemental analysis techniques. The reaction proceeded via carbon-oxygen bond cleavage of (hetero)aryl carbamates and sulfamates under simple and mild conditions without the use of any external ligands. This method demonstrated functional group tolerance in the N-arylation of various nitrogen-containing compounds as well as aliphatic amines, anilines, pyrroles, pyrazoles, imidazoles, indoles, and indazoles with good to excellent yields. Furthermore, the catalyst could be easily recovered by using an external magnetic field and directly reused at least six times without notable reduction in its activity. This journal is
- Dindarloo Inaloo, Iman,Majnooni, Sahar,Eslahi, Hassan,Esmaeilpour, Mohsen
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p. 13266 - 13278
(2020/10/07)
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- C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
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Abstract: An approach to C–N cross-coupling reactions of aryl halides with amines in the presence of an amide-based pincer nickel(II) catalyst (2) is described. For 3?h reactions at 110?°C with 0.2?mol% catalyst, aryl bromides gave higher turnover numbers (TON) than the corresponding chlorides or iodides. Both primary and secondary amines could be used with the former giving higher TON. However, sterically hindered amines showed lower TON. In elucidating the mechanism of this nickel complex-catalyzed C–N cross coupling reaction it was found that the rate of reaction was unchanged in the presence of radical quenchers and a plausible Ni(I)–Ni(III) pathway is proposed. Graphic Abstract: [Figure not available: see fulltext.]Nickel pincer catalyst proved to be excellent catalyst for the C-N cross-coupling reaction with the high turnover number (TON) for 1° and 2° amines and different nonactivated aryl halides under optimum conditions.
- Albkuri, Yahya M.,RanguMagar, Ambar B.,Brandt, Andrew,Wayland, Hunter A.,Chhetri, Bijay P.,Parnell, Charlette M.,Szwedo, Peter,Parameswaran-Thankam, Anil,Ghosh, Anindya
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p. 1669 - 1678
(2019/12/27)
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- Plasma-Made (Ni0.5Cu0.5)Fe2O4 Nanoparticles for Alcohol Amination under Microwave Heating
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Amine N-alkylation is a process involved in the production of a wide range of chemicals. Here we describe the synthesis of well-defined (Ni0.5Cu0.5)Fe2O4 magnetic nanoparticles by plasma induction, and their successful application to amine N-alkylation using alcohols as coupling agents through a borrowing hydrogen pathway. Plasma induction allows precise morphology and size control over nanoparticle synthesis, while allowing the one-pot production of decagram quantities of material. Up to date, such nanoparticles have never been applied for organic reactions. By coupling high-end characterization techniques with catalytic optimization, we showed that small Cu(0) satellite nanoparticles played an essential role in alcohol oxidation, whereas both Ni and Cu were required for the last step of the reaction. Using elemental mapping, we demonstrated that catalyst deactivation occurred through a leaching/re-deposition mechanism of Cu and Ni. The reactions were conducted under microwave conditions, which exerted a positive effect on catalytic activity. Finally, the catalyst was active at low metal loadings (2 mol%) even on the gram-scale, and affording unprecedented TON for this reaction catalyzed by Ni/Cu bimetallic systems (19).
- Li, Alain You,Dumaresq, Nicolas,Segalla, Andréanne,Braidy, Nadi,Moores, Audrey
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p. 3959 - 3972
(2019/08/12)
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- Practical Catalytic Cleavage of C(sp3)?C(sp3) Bonds in Amines
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The selective cleavage of thermodynamically stable C(sp3)?C(sp3) single bonds is rare compared to their ubiquitous formation. Herein, we describe a general methodology for such transformations using homogeneous copper-based catalysts in the presence of air. The utility of this novel methodology is demonstrated for Cα?Cβ bond scission in >70 amines with excellent functional group tolerance. This transformation establishes tertiary amines as a general synthon for amides and provides valuable possibilities for their scalable functionalization in, for example, natural products and bioactive molecules.
- Li, Wu,Liu, Weiping,Leonard, David K.,Rabeah, Jabor,Junge, Kathrin,Brückner, Angelika,Beller, Matthias
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supporting information
p. 10693 - 10697
(2019/07/09)
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- Iridium-Catalyzed Alkylation of Amine and Nitrobenzene with Alcohol to Tertiary Amine under Base- and Solvent-Free Conditions
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Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.
- Li, Chao,Wan, Ke-Feng,Guo, Fu-Ya,Wu, Qian-Hui,Yuan, Mao-Lin,Li, Rui-Xiang,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua
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p. 2158 - 2168
(2019/05/16)
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- Tertiary amine synthesis method
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The invention relates to the technical field of organic matters, and specifically relates to a tertiary amine synthesis method. Under the action of a catalyst, in the absence of solvent and alkali, primary amine, secondary amine, or a nitro derivative reacts with alcohol to prepare tertiary amine. The provided synthesis method has the advantages that no toxic solvent is used during the preparationprocess, the method is green and environmentally friendly, the atom utilization rate is high, the operation is simple, the application range of the functional groups and substrate is wide, and the yield of tertiary amine is high, in particular reactions between aliphatic amine and alcohol.
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Paragraph 0033-0039
(2019/01/24)
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- Direct Installation of a Silyl Linker on Ready-Made NHC Ligands: Immobilized NHC-Pd Complex for Buchwald-Hartwig Amination
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An immobilized N-heterocyclic carbene (NHC)-Pd complex was prepared via direct silyl linker installation onto the imidazole backbone of commercially available 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) ligand. The IPr backbone was lithiated and treated with Me2SiCl2 to afford ClMe2Si-IPr, which reacted with [Pd(π-allyl)Cl]2 to yield a ClMe2Si-IPr-Pd complex, and this was immobilized on Wang resin. The immobilized NHC-Pd complex facilitated quantitative Buchwald-Hartwig amination of aryl chlorides within 10 min, even at a low Pd loading of 0.2 mol %. The catalyst could be removed from the reaction mixture by simple filtration, and Pd leaching into the reaction medium was suppressed to below 1 ppm.
- Mizusaki, Tomoteru,Matsumoto, Kazuhiro,Takeuchi, Katsuhiko,Fukaya, Norihisa,Takagi, Yukio,Choi, Jun-Chul
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supporting information
p. 1872 - 1876
(2019/05/07)
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- Robust Buchwald-Hartwig amination enabled by ball-milling
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An operationally simple mechanochemical method for the Pd catalysed Buchwald-Hartwig amination of arylhalides with secondary amines has been developed using a Pd PEPPSI catalyst system. The system is demonstrated on 30 substrates and applied in the context of a target synthesis. Furthermore, the performance of the reaction under aerobic conditions has been probed under traditional solution and mechanochemical conditions, the observations are discussed herein.
- Cao, Qun,Nicholson, William I.,Jones, Andrew C.,Browne, Duncan L.
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supporting information
p. 1722 - 1726
(2019/02/20)
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- [Pd(4-R3Si-IPr)(allyl)Cl], a Family of Silyl-Substituted Pd-NHC Complexes: Catalytic Systems for the Buchwald-Hartwig Amination
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A family of Pd-IPr complexes (1Pd-6Pd) featuring electropositive and bulky R3Si substituents at the 4-position of the NHC ring was prepared and fully characterized. The catalytic performance of 1Pd (R3Si = SiMe3) and 3Pd (R3Si = Si(allyl)Me2) in the Buchwald-Hartwig amination was excellent, notably outperforming those of other previously reported catalytic systems by requiring shorter reaction times, lower catalyst loadings, and milder reaction conditions. Furthermore, a systematic evaluation of both the electronic and steric influences of the 4-R3Si-IPr ligand on the overall catalytic performance of 1Pd-6Pd revealed that electronic rather than steric factors play a dominant role.
- Fukaya, Norihisa,Mizusaki, Tomoteru,Hatakeyama, Kouhei,Seo, Yuto,Inaba, Yuuya,Matsumoto, Kazuhiro,Lee, Vladimir Ya.,Takagi, Yukio,Kuwabara, Junpei,Kanbara, Takaki,Choe, Yoong-Kee,Choi, Jun-Chul
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p. 375 - 384
(2019/01/11)
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- 3-hydroxy flavone compound and application thereof
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The invention belongs to the technical field of biological fluorescence analysis, and particularly relates to a 3-hydroxy flavone compound and an application thereof. The compound is particularly a 4-n,n-dialkylamino-3-hydroxy flavone compound, and when the compound is used as a fluorescent dye, the lipid droplet targeting property is better, and a cytoskeleton is hardly colored. When conjugated structures such as a benzene ring and the like are added to the left side of a molecule of the compound, the emission wavelength of the molecule can be greatly prolonged, and fluorescence crossing of the molecule from yellow to red is realized. The compound can be applied to the aspects of dynamic lipid droplet imaging in cells, lipid droplet growth process imaging, adipose tissue imaging, even simultaneous imaging of intramuscular fat and intermuscular fat in skeletal muscle tissues, and the like, and has important application values in the fields of fluorescent dyes, biological fluorescent labels and the like.
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Paragraph 0043; 0047-0053; 0054
(2019/11/28)
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- N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds
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N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.
- Bayguzina,Musina, Ch. F.,Khusnutdinov
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p. 1652 - 1659
(2019/02/12)
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- Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts
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With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.
- Zhang, Zhiang,Wu, Xunshen,Han, Jianwei,Wu, Wenjun,Wang, Limin
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supporting information
p. 1737 - 1741
(2018/04/02)
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- An Effective Heterogeneous Copper Catalyst System for C-N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)
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A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N (-(4-(aminomethyl)naphthalen-1-yl)- N (-phenyl-1 H -pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C-N coupling based on the homogeneous catalyst system N ′, N ′-diphenyl-1 H -pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.
- Yi, Zhou,Huang, Manna,Wan, Yiqian,Zhu, Xinhai
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p. 3911 - 3920
(2018/09/29)
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- n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature
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A simple and facile method for the synthesis of aromatic tertiary amines by amination of fluoroarenes with secondary amines in the presence of n-butyllithium at room temperature was reported.
- Lin, Yingyin,Li, Meng,Ji, Xinfei,Wu, Jingjing,Cao, Song
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p. 1466 - 1472
(2017/02/18)
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- Sulfonato-imino copper(II) complexes: Fast and general Chan-Evans-Lam coupling of amines and anilines
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Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.
- Hardouin Duparc,Schaper
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supporting information
p. 12766 - 12770
(2017/10/11)
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- Sulfonato-diketimine Copper(II) Complexes: Synthesis and Application as Catalysts in Chan-Evans-Lam Couplings
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Copper complexes bearing a diketimino-sulfonate ligand, LCu(NO3)(NCMe), were prepared and proved to be stable to water for several hours in solution. Prolonged standing in the presence of water or strong bases led to desulfonation of the ligand. LCu(NO3) was inactive in the polymerization of lactide (in the presence of benzyl alcohol), but showed high activity for the Chan-Evans-Lam coupling of a variety of amines and anilines. Couplings do not require addition of base, ligand, or molecular sieves. Mechanistic investigations indicate a catalytic cycle involving dioxygen as the required oxidant, precoordination of boronic acid to the sulfonate group, and transmetalation occurring prior to reaction with the nucleophile.
- Hardouin Duparc, Valérie,Schaper, Frank
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supporting information
p. 3053 - 3060
(2017/09/05)
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- Room-Temperature CuI-Catalyzed Amination of Aryl Iodides and Aryl Bromides
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A general and effective CuI/N′,N′-diaryl-1H-pyrrole-2-carbohydrazide catalyst system was developed for the amination of aryl iodides and bromides at room temperature with good chemoselectivity between -OH and -NH2 groups. Only 5 mol % of CuI and ligands was needed in this protocol to effect the amination of various aryl bromides and aryl iodides with a wide range of aliphatic and aryl amines (1.3 equiv).
- Ding, Xiaomei,Huang, Manna,Yi, Zhou,Du, Dongchen,Zhu, Xinhai,Wan, Yiqian
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p. 5416 - 5423
(2017/05/25)
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- An Unsymmetrical Squaraine-Dye-Based Chemical Platform for Multiple Analyte Recognition
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The design of fluorescent molecular platforms capable of responding to multiple analytes is a topic of great interest. Herein, the use of a Zn2+-complexed unsymmetrical squaraine dye, Sq–Zn2+, as a chemical platform for recognizing structurally distinct analytes is reported. The squaraine ring is substituted on one side with a dipicolylamine unit, which acts as the metal ion receptor, whereas the other part of the molecule carries a dibutylaniline moiety, which is an electron donor. The molecular system is unique because it can respond specifically to different types of analytes, namely, atmospheric carbon dioxide, cyclic phosphates, and picric acid. Moreover, the interaction of these analytes can be monitored colorimetrically and fluorimetrically, which favors both qualitative and quantitative analyses. The distinct response towards cyclic and linear phosphates, as well as the selective response towards picric acid, among the various nitroaromatic compounds was achieved with sensitivity at the ppm level. The flexible coordination offered by Zn2+ plays a significant role in the discrimination of these analytes with high specificity. Dye Sq–Zn2+ introduced herein is a single-molecule construct that can be used for the selective and sensitive response towards analytes of environmental and biological relevance.
- Philips, Divya S.,Ghosh, Samrat,Sudheesh, Karivachery V.,Suresh, Cherumuttathu H.,Ajayaghosh, Ayyappanpillai
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supporting information
p. 17973 - 17980
(2017/12/04)
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- With near-infrared absorbing organic small molecule semiconductor material and its preparation and use
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The present invention relates to a 2,2'-(2,8-bis(dialkyl amine)-indeno [1,2-b] fluorenes-6,12-diylidene)-dimalononitrile derivative as shown in a formula I, and a preparation method and use. The compound provided by the present invention as shown in the specification is a near-infrared absorbing organic small molecule semiconductor material, which can be used as an active layer of a bipolar organic field effect transistor, an active layer of a near-infrared light detector and other optoelectronic devices.
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Paragraph 0033; 0034; 0035
(2017/08/24)
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- Palladium-Catalyzed N-Arylation of Amines and Amides with Aryltrimethylgermanes
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Described herein is a novel palladium-catalyzed C-N bond-formation reaction employing aryltrimethylgermanes as the new arylating reagents. Primary/secondary amines or even amides could be smoothly arylated to provide the corresponding N-arylation products in moderate to excellent yields.
- Zhang, Qiang,Liu, Cunfang,Shi, Juan,Xu, Qiong,Jin, Lingxia,Zhao, Chaibin,Zhang, Tianlei
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supporting information
p. 1945 - 1948
(2016/08/09)
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- The Use of Ureates as Activators for Samarium Diiodide
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A novel mode of SmI2 activation has been developed using ureates as reaction promoters. Several ureates formed by treatment of the corresponding ureas with n-BuLi have been shown to activate SmI2 to a substantial extent toward the reduction of 1-chlorodecane. Complexes formed from SmI2 and various ureates have been shown to be useful for the reduction of a variety of organohalides, including substrates of low reactivity such as aryl fluorides. Because of ease of synthesis and low molecular weight, the conjugate base of triethylurea (TEU-) was of primary focus. Visible spectroscopy and reactivity data are consistent with the hypothesis that the same complex is being formed when SmI2 is combined with either 2 or 4 equiv of TEU-, in spite of the greater reactivity of SmI2/4 TEU- with some alkyl halides. We propose that the active reductant is an N,O chelate formed between SmI2 and 2 equiv of TEU-.
- McDonald, Chriss E.,Ramsey, Jeremy D.,McAtee, Christopher C.,Mauck, Joseph R.,Hale, Erin M.,Cumens, Justin A.
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p. 5903 - 5914
(2016/07/23)
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- Cs2CO3-Promoted Direct N-Alkylation: Highly Chemoselective Synthesis of N-Alkylated Benzylamines and Anilines
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Herein is described an efficient and chemoselective method for the synthesis of diversely substituted secondary amines in yields up to 98 %. Direct mono-N-alkylation of primary benzylamines and anilines with a wide range of alkyl halides is promoted by a cesium base in the absence of any additive or catalyst. The basicity and solubility of cesium carbonate in anhydrous N,N-dimethylformamide not only enables mono-N-alkylation of primary amines but also suppresses undesired dialkylation of the desired amines.
- Castillo, Juan-Carlos,Orrego-Hernández, Jessica,Portilla, Jaime
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p. 3824 - 3835
(2016/08/20)
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- Chan-Evans-Lam Amination of Boronic Acid Pinacol (BPin) Esters: Overcoming the Aryl Amine Problem
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The Chan-Evans-Lam reaction is a valuable C-N bond forming process. However, aryl boronic acid pinacol (BPin) ester reagents can be difficult coupling partners that often deliver low yields, in particular in reactions with aryl amines. Herein, we report effective reaction conditions for the Chan-Evans-Lam amination of aryl BPin with alkyl and aryl amines. A mixed MeCN/EtOH solvent system was found to enable effective C-N bond formation using aryl amines while EtOH is not required for the coupling of alkyl amines.
- Vantourout, Julien C.,Law, Robert P.,Isidro-Llobet, Albert,Atkinson, Stephen J.,Watson, Allan J. B.
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p. 3942 - 3950
(2016/05/24)
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- 1,4-Dihydroxyanthraquinone-copper(II) supported on superparamagnetic Fe3O4@SiO2: An efficient catalyst for N -arylation of nitrogen heterocycles and alkylamines with aryl halides and click synthesis of 1-aryl-1,2,3-triazole derivatives
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1,4-Dihydroxyanthraquinone-copper(ii) supported on a superparamagnetic Fe3O4@SiO2 catalyst was employed for the N-arylation of nitrogen heterocycles and alkylamines with aryl halides to afford the corresponding coupled products in good to excellent yields without using external ligands or additives as promoters. Also, we have reported this recyclable catalytic system for efficient synthesis of 1-aryl-1,2,3-triazole derivatives in excellent yields. The desired triazoles were obtained from the reaction of the corresponding aryl boronic acid derivatives, alkyne, NaN3, and 0.5 mol% catalyst in water/acetonitrile as the solvent at room temperature without the additional use of an external reducing agent. These methods show notable advantages such as the heterogeneous nature of the catalyst, low catalyst loading, easy preparation, excellent yields, short reaction times and simplicity of operation. Also, the catalyst can be separated from the reaction mixture by applying a permanent magnet externally and can be reused in six consecutive reaction cycles without significant loss of activity.
- Zahmatkesh, Saeed,Esmaeilpour, Mohsen,Javidi, Jaber
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p. 90154 - 90164
(2016/10/09)
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- COMPOUND FOR GENERATING SECOND HARMONIC OF LIGHT, DYE COMPOSITION FOR GENERATING SECOND HARMONIC OF LIGHT, AND CELL EXAMINATION METHOD
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Provided are a compound that generates an SHG signal but has suppressed generation of a TPF signal. Also provided is a cell examination method using the same. A compound for generating a second harmonic of light, the compound being an azobenzene derivative of formula (1), or a salt thereof. (R1 and R2 independently represent alkyl groups having 6-12 carbon atoms, and R3 to R18 independently represent substituents selected from hydrogen, halogens, alkyl groups, alkoxy groups, aryl groups, amino groups, hydroxyl groups, nitro groups, and cyano groups, but R5 and R6, R9 and R10, R13 and R14, and R17 and R18 may combine together and form a ring structure having 5-7 carbon atoms. X represents —N+R19R20R21, a sulfonyl group, a carboxyl group, or an —OR group. Here, R19, R20, and R21 independently represent straight-chain or branched alkyl groups having 1-5 carbon atoms, and —OR represents a monovalent polyalkylene oxide group terminated by an alkoxy group. a is 0 or 1, b is 0 or 1, and n is an integer of 1-10.)
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Paragraph 0064; 0065; 0066
(2016/05/19)
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- Substituent modification of electro-optic chromophores with 4-cyano-5-dicyanomethylene-2,5-dihydro-1H-pyrrol-2-one as an acceptor
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Electro-optic chromophores with 4-cyano-5-dicyanomethylene-2,5-dihydro-1H-pyrrol-2-one (CDCOP) and aniline moieties as an acceptor and a donor, respectively, were synthesized with modification of three substituents, among which two were attached to the aniline moiety (R) and one was introduced to the CDCOP ring (R′). Butyl and hexyl groups were introduced as R and R′, and higher melting points were observed when R and R′ were the same. For the chromophore fixation, thermal crosslinking based on cyanate trimerization was performed. The chromophore with cyanate moiety in R′ was combined with bisphenol A dicyanate, and the thermal chromophore fixation was confirmed with almost no chromophore degradation.
- Inada, Shunsuke,Araki, Tatsunori,Sato, Yukichi,Tatewaki, Yoko,Okada, Shuji
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- Nano PdAu Bimetallic Alloy as an Effective Catalyst for the Buchwald-Hartwig Reaction
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It is highly challenging but desirable to develop efficient heterogeneous catalysts for C-Cl bond activation in coupling reactions. Here, we succeeded in synthesizing bimetallic Pd-Au nanoparticles through a convenient one-pot wet chemical route. The composition and alloyed structure of the as-prepared nanoparticles were fully characterized. We have evaluated the catalytic activity of these Pd-Au alloy catalysts in Buchwald-Hartwig reactions of aryl chlorides. The excellent catalytic activity of the as-obtained Pd-Au nanoparticles indicates that exploiting the catalytic power of nano-alloy catalysts could enable effective C-Cl bond activation suitable for cross-coupling reactions.
- Chen, Zheng,Wang, Shuo,Lian, Chao,Liu, Yuxi,Wang, Dingsheng,Chen, Chen,Peng, Qing,Li, Yadong
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p. 351 - 355
(2016/05/19)
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- Preparation method of novel bidentate phosphite ligand and application thereof in Buchwald-Hartwig reaction
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The invention discloses a preparation method of novel bidentate phosphite ligands and application thereof in Buchwald-Hartwig reaction and belongs to the field of organic synthetic chemistry. A series of novel bidentate phosphite ligands are synthesized by using 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxyl diphenyl and glycols with different structures as raw materials through a two-step one-pot method, are compounds very wide in application range and have the following structures. The novel preparation method has the advantages of being stable in structure, simple and convenient to synthesize, high in yield and easy to prepare in a large-scale mode. The ligands have higher reaction activity and substrate universality in the Pd catalyzed Buchwald-Hartwig reaction.
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Paragraph 0050; 0051; 0052; 0053; 0054; 0057; 0058; 0060-67
(2016/10/09)
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- Aminostyrylpyridinium-salt fluorescent monomer and preparing and application of polymer of aminostyrylpyridinium-salt fluorescent monomer
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The invention relates to an aminostyrylpyridinium-salt fluorescent monomer, a synthesis method of a polymer of the aminostyrylpyridinium-salt fluorescent monomer and application prospects of the water-soluble fluorescent polymer in the field of oil fields. The fluorescent monomer structure is shown as the formula (I) (please see the specification). The synthesis method includes the steps that 4-methylpyridine and alkyl halide are subjected to an alkylation reaction to generate 4-methylpyridine salt, aniline is subjected to a N-alkylation reaction or an acylation reaction and then subjected to a Vilsmeier reaction, an aldehyde group is led in a para-position mode, and finally, the aldehyde group and methyl of the 4-methylpyridine salt are condensated to generate the aminostyrylpyridinium-salt fluorescent monomer. The fluorescent monomer and water-soluble monomers such as acrylamide, acrylic acid, methacrylamide, methylpropanesulfonic acid, N,N-dimethylacrylamide and N,N-diethylacrylamide are subjected to binary polymerization or terpoly polymerization, and a water-soluble fluorescent tracing polymer is prepared. The fluorescent tracing polymer can be applied to concentration detection of the polymer through polymer flooding.
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Paragraph 0041; 0043; 0044; 0046
(2017/07/21)
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- Unsymmetrical squaraines with new linkage manner for high-performance solution-processed small-molecule organic photovoltaic cells
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Squaraines are promising donor materials because of their strong and broad absorption band in the visible and near infrared regions which is suitable for application in organic photovoltaic (OPV) cells. Two unsymmetrical squaraines (USQs), namely BIBISQ and TIBISQ, with two electron-donating aryls directly linked to the electron-withdrawing squaric acid core (Y-manner) can act as high performance donor materials for solution-processed bulk-heterojunction (BHJ) OPV cells. Both USQs show ideal low bandgaps (1.47 eV for BIBISQ and 1.39 eV for TIBISQ) with an intense and broad absorption band in the range of 500-900 nm, and relatively low HOMO levels of ~-5.10 eV. The BHJ-OPV device based on both of them simultaneously showed excellent short current density (Jsc) (over 13 mA cm-2), open circuit voltage (Voc) (0.84 V), fill factor (FF) (0.49) and power conversion efficiency (PCE) of over 5% under a blend ratio of USQs:PC71BM = 1:3. These results indicate that the two USQs are quite promising candidates for small molecular (SM) OPV cells and the Y-manner should be a quite successful linking method for USQs.
- Yang, Lin,Yang, Daobin,Chen, Yao,Luo, Qian,Zhang, Mangang,Huang, Yan,Lu, Zhiyun,Sasabe, Hisahiro,Kido, Junji
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p. 1877 - 1884
(2016/01/20)
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- Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen
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A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.
- Sorribes, Iván,Cabrero-Antonino, Jose R.,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
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p. 13580 - 13587
(2015/11/10)
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- Transition-Metal-Free, Potassium tert -Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides
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A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.
- Huang, Pei,He, Bang-Yue,Wang, Hui-Min,Lu, Jian-Mei
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p. 221 - 227
(2015/08/25)
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- Transition-Metal-Free, Potassium tert -Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides
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A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.
- Huang, Pei,He, Bang-Yue,Wang, Hui-Min,Lu, Jian-Mei
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p. 221 - 227
(2015/08/25)
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- Modular Synthesis of Biaryl-Substituted Phosphine Ligands: Application in Microwave-Assisted Palladium-Catalyzed C-N Cross-Coupling Reactions
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Biaryl-substituted monophosphine-based ligands have been synthesized by transition-metal-free "ARYNE" cross-coupling reaction of aryllithiums with 1,2-dibromobenzene and subsequent regioselective functionalization through bromine-lithium interconversion. These ligands were employed in palladium-catalyzed C-N bond-forming reactions. The reaction was found to be general with wide substrate applicability. A wide variety of both primary and secondary amines were successfully coupled with an array of differently substituted halobenzenes under microwave irradiation to give the expected products in good to excellent yields. A number of biaryl-substituted phosphine ligands screened for the coupling reaction showed that steric bulk and the electronic properties of substituents on phosphorus play a crucial role in governing the catalytic activity of C-N cross-coupling reactions. Biaryl-substituted monophosphines have been synthesized by transition metal free ARYNE cross-coupling reactions and subsequent regioselective functionalization through bromine-lithium interconversion. These ligands were employed in palladium-catalyzed C-N bond-forming reactions.
- Singh, Chandani,Rathod, Jayant,Jha, Vishwajeet,Panossian, Armen,Kumar, Pradeep,Leroux, Frédéric R.
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p. 6515 - 6525
(2015/10/19)
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- 2-Phenyl-2-(4-phenyl-1 H-1,2,3-triazol-1-yl)ethanol as an efficient and versatile auxiliary ligand in copper(II)-catalyzed Buchwald-Hartwig and Sharpless-Meldal C-N bond-forming reactions
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A highly active, air-stable, and versatile procedure for Buchwald-Hartwig and Sharpless-Meldal C-N bond formation is reported. Under nearly solvent-free conditions using copper(II) acetate and 2-phenyl-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanol, a variety of N-heterocycles and various cyclic and noncyclic secondary amines were arylated to form N-aryl compounds in moderate to excellent yields. This methodology also provides rapid access to diverse 1,4-disubstituted 1,2,3-triazoles in good to excellent yields. All reactions are performed in short times under air.
- Sharghi, Hashem,Shiri, Pezhman
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p. 1131 - 1146
(2015/04/14)
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- Efficient and versatile buchwald-hartwig amination of (hetero)aryl chlorides using the Pd-PEPPSI-IPr(NMe2)2 precatalyst in the presence of carbonate base
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The precatalyst Pd-PEPPSI-IPr(NMe2)2, in which the IPr ligand was modified by attachment of two dimethylamino groups on to the 4- and 5-positions of the imidazolyl heterocycle, was found to show high catalytic efficiency in the Buchwald-Hartwig amination under mild conditions using Cs2CO3 as a weak base, using a low catalyst loading of 1 mol-%. The protocol is applicable to aryl chlorides bearing base-sensitive substituents, as exemplified by the coupling of 4-chloroacetophenone with aniline. It can also be used with an unprecedentedly wide range of amines, including strongly basic secondary alkylamines, primary arylamines, and primary alkylamines. The Palladium precatalyst Pd-PEPPSI-IPr(NMe2)2, whose supporting N-heterocyclic carbene ligand was decorated with two dimethylamino groups, was found to catalyse the Buchwald-Hartwig amination of aryl halides with a wide range of amines under mild conditions using cesium carbonate as base.
- Zhang, Yin,César, Vincent,Lavigne, Guy
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p. 2042 - 2050
(2015/03/18)
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- Asymmetrically Substituted and π-Conjugated 2,2′-Bipyridine Derivatives: Synthesis, Spectroscopy, Computation, and Crystallography
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A new series of monosubstituted styryl- and bistyryl-2,2′-bipyridine luminophores (compounds 16-23) have been synthesized via Horner-Wadsworth-Emmons reaction involving a monophosphonate and donor aromatic aldehydes. In the title chromophores, the amino donors are varied between acyclic and cyclic while the alkoxy donors are varied in terms of their number and position. The absorption maxima of these chromophores shift predominantly due to intramolecular charge transfer (ICT) between different donor and acceptor moieties. The title donor-acceptor molecules exhibit intense fluorescence in solution at room temperature, and their emissive behavior has been found to be highly sensitive to solvent polarity. The fluorescence spectra and quantum yields of all the chromophores were recorded in four different solvent media, and the chromophores 16, 17, 19, and 21 exhibit fluorescence in the solid state too. The influence of the nature and position of the donor functionalities in the conjugated backbone of the bipyridine moiety on the electronic absorption properties of the title chromophores (16-23) has been demonstrated, which has further been corroborated by DFT and TD-DFT computation both in gas phase and in solution phase. The crystal structure of compound 18 has been described as a representative member of the family (16-23).
- Bodapati, Ramakrishna,Sarma, Monima,Kanakati, Arunkumar,Das, Samar K.
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supporting information
p. 12482 - 12491
(2016/01/09)
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- Monocarboxylate transporter 1 inhibitors as potential anticancer agents
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Potent monocarboxylate transporter 1 inhibitors (MCT1) have been developed based on α-cyano-4-hydroxycinnamic acid template. Structure-activity relationship studies demonstrate that the introduction of p-N, N-dialkyl/diaryl, and o-methoxy groups into cyanocinnamic acid has maximal MCT1 inhibitory activity. Systemic toxicity studies in healthy ICR mice with few potent MCT1 inhibitors indicate normal body weight gains in treated animals. In vivo tumor growth inhibition studies in colorectal adenocarcinoma (WiDr cell line) in nude mice xenograft models establish that compound 27 exhibits single agent activity in inhibiting the tumor growth.
- Gurrapu, Shirisha,Jonnalagadda, Sravan K.,Alam, Mohammad A.,Nelson, Grady L.,Sneve, Mary G.,Drewes, Lester R.,Mereddy, Venkatram R.
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supporting information
p. 558 - 561
(2015/05/27)
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- Functionalized ionic liquids based on imidazolium cation: Synthesis, characterization and catalytic activity for N-alkylation reaction
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The novel functionalized ionic liquids based on imidazolium cation are synthesized and characterized by studying its 1H, 13C, and 31P NMR and elemental analysis. These ionic liquids have been reported as a highly efficient catalyst for N-alkylation reaction of aniline with butyl chloride. The reaction was efficiently performed in ionic liquid as an environmentally benign solvent with good yields without transition metal.
- Demir, Serpil,Damarhan, Yunus,?zdemir, Ismail
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p. 210 - 215
(2015/03/05)
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- Coupling of boronic acids with amines in the presence of a supported copper catalyst
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An efficient heterogeneous catalytic method was developed for Chan-Lam reaction, coupling of amines and boronic acid. Copper on 4 A molecular sieve provided yields comparable to the methods published. The method provides the main advantages of a heterogeneous catalytic procedure, the preparation of the catalyst is easy, the workup of the reaction mixture is simple. Graphical abstract: [Figure not available: see fulltext.]
- Debreczeni, Nora,Fodor, Anna,Hell, Zoltan
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p. 1547 - 1551,5
(2014/11/12)
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- Selective N-alkylation of primary amines with R-NH2·HBr and alkyl bromides using a competitive deprotonation/protonation strategy
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Monoalkylation of primary amines using amine hydrobromides and alkyl bromides has been carried out. Under controlled reaction conditions the reactant primary amine was selectively deprotonated and made available for reaction, while the newly generated secondary amine remained protonated, and did not participate in alkylation further. Reaction was carried out under mild reaction conditions and was applicable to a wide range of primary amines and alkyl bromides.
- Bhattacharyya, Shubhankar,Pathak, Uma,Mathur, Sweta,Vishnoi, Subodh,Jain, Rajeev
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p. 18229 - 18233
(2014/05/20)
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- Ligand-free copper(i) oxide nanoparticle-catalysed amination of aryl halides in ionic liquids
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In the following, we present a simple and feasible methodology for a C-N coupling reaction using nanoscale Cu2O catalysts incorporated in n-Bu4POAc ionic liquid media. It is shown that a wide range of amines and aryl halides can be coupled selectively in high yields, without the use of ligands or additives (bases) and without precautions against water or air. All catalyses can be carried out with a nanoparticle catalyst loading as low as 5 mol%, based on the used precursor.
- Kessler, Michael T.,Robke, Silas,Sahler, Sebastian,Prechtl, Martin H. G.
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p. 102 - 108
(2014/01/06)
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