- A comprehensive spectral, photophysical and electrochemical study of synthetic water-soluble acridones. A new class of pH and polarity sensitive fluorescent probes
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A comprehensive spectroscopic, photophysical and electrochemical investigation of N-alkylacridones, their newly synthesised chlorosulfonyl and water-soluble sulfonic acid derivatives has been undertaken in solution at room temperature. The study includes absorption and emission spectra together with quantitative measurements of the deactivation of the first excited singlet state, from which the rate constants for all the decay processes has been obtained. A comparison on the gradual change of the electronic spectral and photophysical properties with the degree of substitution is considered. In addition the electrochemical behavior of the water-soluble acridones at different pH values was obtained by cyclic and differential pulse voltammetry. The oxidation mechanism of disulfonated acridone is found to occur in one consecutive and irreversible charge transfer pH-dependent reaction. The water-soluble acridones were found to display long lifetime values, dependent on the pH and solvent polarity. This opens a door for its use as selective probes for different cellular environment and targets.
- Pereira, Ricardo C.,Pontinha, Ana Dora R.,Pineiro, Marta,Seixas de Melo, J. Sérgio
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- CHEMILUMINESCENCE OF 9-METHYLENEACRIDANS IN MICELLAR AND MEMBRANOUS SYSTEMS
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Chemiluminescence of a 1,2-dioxetane derived from 9-methylene-10-dodecylacridan was not detected in aqueous solution but was detected in micellar and membranous systems.The quantum yield and the rate of the chemiluminescence decay in the membranous (2C1615G and 2C1630G) system were affected by the chain melting transition.The results indicate that the chemiluminescence is sensitively affected by the microenvironmental effect.
- Shinkai, Seiji,Ishikawa, Yu-ichi,Manabe, Osamu,Kunitake, Toyoki
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- CHEMILUMINESCENCE OF N-METHYL-9-(DICARBOALKOXYMETHYL)ACRIDANES: SUCCESSIVE FORMATION OF TWO 1,2-DIOXETANONE INTERMEDIATES
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N-Methyl-9-(dicarboalkoxymethyl)acridanes (5a-c) which have a similar structural moiety to that of firefly luciferin and give an excellent fluorescent product were found to be chemiluminescent when being oxidized by molecular oxygen in DMSO in the presence of t-BuOK at 70 degC.
- Suzuki, Nobutaka,Tsukamoto, Toshio,Izawa, Yasuji
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- Laser Flash Photolysis and Product Studies of the Photoionization of N-Methylacridan in Aqueous Solution
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Photolysis of N-methylacridan (1) in deaerated aqueous CH3CN solution results in photoionization, to give the N-methylacridan radical cation (1.+) as the first-formed intermediate.Subsequent deprotonation from 1.+ gives N-methylacridyl (1.), which dimerizes to give 9,9'-bis(N-methylacridyl) (2) as the only isolable product.Quantum yields for loss of 1 are 0.085 and 0.022 in 1:1 H2O-CH3CN and 100percent CH3CN, respectively.In the presence of oxygen, 1. is believed to be oxidized further (electron transfer to O2), to give N-methylacridinium ion (4), which was detected by its characteristic UV absorption and fluorescence emission spectra.Laser flash photolysis studies provide direct evidence for photoionization of 1 to give the radical cation 1.+ which subsequently deprotonates to form 1..The combined transient and product studies indicate a monophotonic mechanism from the first excited state.The results demonstrate that photoexcited 1 is an excellent electron donor to bulk solvent.The process does not require externally added electron acceptors for photoredox chemistry.
- Shukla, Deepak,Rege, Francis de,Wan, Peter,Johnston, Linda J.
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- New acridone-and (Thio)xanthone-derived 1,1-donor–acceptor-substituted alkenes: Ph-dependent fluorescence and unusual photooxygenation properties
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A synthetic route to new heterocyclic 1,1-donor–acceptor-substituted alkenes starting with N-methyl-acridone, xanthone, and thioxanthone was investigated, leading to the acridone-and xanthone-derived products methyl 2-methoxy-2-(10-methylacridin-9 (10H)-ylidene)acetate (7) and methyl 2-methoxy-2-(9H-xanthen-9-ylidene)acetate (10) in low yields with the de-methoxylated product methyl 2-(10-methylacridin-9 (10H)-ylidene)acetate (8) and the reduced compound methyl 2-methoxy-2-(9H-xanthen-9-yl)acetate (11) as the major products from N-methyl acridone and xanthone. From thioxanthone, only the rearrangement and reduction products (14) and (15) resulted. The photophysical properties of compounds (7), (8), and (10) were investigated in the presence and absence of the Br?nsted acid TFA by NMR, UV–VIS absorption, and fluorescence spectroscopy. Protonation of the acridone-derived alkenes (7) and (8) led to strong bathochromic and hyperchromic fluorescence shifts and a substantial increase in Stokes shift. The photooxygenation experiments with these substrates showed an unusual reactivity pattern in the singlet oxygen processes: whereas the electron-rich enolether (7) was chemically unreactive, (8) and (10) were oxidatively cleaved, presumably via intermediate 1,2-dioxetanes.
- Griesbeck, Axel,Lippold, Tim,Neud?rfl, J?rg M.
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- Photochemical oxidation of a manganese(III) complex with oxygen and toluene derivatives to form a manganese(V)-Oxo complex
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Visible light photoirradiation of an oxygen-saturated benzonitrile solution of a manganese(III) corrolazine complex [(TBP8Cz)MnIII] (1): [TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato3-] in the presence of toluene derivatives resulted in formation of the manganese(V)-oxo complex [(TBP8Cz)MnV(O)]. The photochemical oxidation of (TBP8Cz)MnIII with O 2 and hexamethylbenzene (HMB) led to the isosbestic conversion of 1 to (TBP8Cz)MnV(O), accompanied by the selective oxidation of HMB to pentamethylbenzyl alcohol (87%). The formation rate of (TBP 8Cz)MnV(O) increased with methyl group substitution, from toluene, p-xylene, mesitylene, durene, pentamethylbenzene, up to hexamethylbenzene. Deuterium kinetic isotope effects (KIEs) were observed for toluene (KIE = 5.4) and mesitylene (KIE = 5.3). Femtosecond laser flash photolysis of (TBP8Cz)MnIII revealed the formation of a tripquintet excited state, which was rapidly converted to a tripseptet excited state. The tripseptet excited state was shown to be the key, activated state that reacts with O2 via a diffusion-limited rate constant. The data allow for a mechanism to be proposed in which the tripseptet excited state reacts with O2 to give the putative (TBP8Cz)Mn IV(O2?-), which then abstracts a hydrogen atom from the toluene derivatives in the rate-determining step. The mechanism of hydrogen abstraction is discussed by comparison of the reactivity with the hydrogen abstraction from the same toluene derivatives by cumylperoxyl radical. Taken together, the data suggest a new catalytic method is accessible for the selective oxidation of C-H bonds with O2 and light, and the first evidence for catalytic oxidation of C-H bonds was obtained with 10-methyl-9,10-dihydroacridine as a substrate.
- Jung, Jieun,Ohkubo, Kei,Prokop-Prigge, Katharine A.,Neu, Heather M.,Goldberg, David P.,Fukuzumi, Shunichi
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- Chemiluminescence in Model Membrane Structures. Chemiluminescence of Lucigenin in the Presence of Mg(OH)2 and Benzyl Alcohol. Temperature Effects
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The quantum yields of the lucigenin light reaction in didodecyldimethylammonium bromide (DDAB) are affected by the presence of Mg(OH)2; a 35percent increase is observed in lamellar and a 65percent increase in vesicular aggregates.The system is insensitive to benzyl alcohol.The quantum yields in DDAB versus those in water, as a function of temperature show a slope change in the region of the phase transition in lamellar aggregates.This effect is far less pronounced in vesicular aggregates.In contrast to the DDAB aggregates, anionic sodium dimethyldidodecylphosphate (SDDP) sonicated aggregates are associated with lower quantum yields and no apparent slope change in the region of the phase transition. - Keywords: Chemiluminescence; Lucigenin; Membranes
- Varveri, Fannie S.,Mantaka-Marketou, Anastasia E.,Vassilopoulos, George,Nikokavouras, John
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- Photocatalytic oxygenation of 10-methyl-9,10-dihydroacridine by O 2 with manganese porphyrins
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Photocatalytic oxygenation of 10-methyl-9,10-dihydroacridine (AcrH 2) by dioxygen (O2) with a manganese porphyrin [(P)Mn III: 5,10,15,20-tetrakis-(2,4,6-trimethylphenyl) porphinatomanganese(III) hydroxide [(TMP)MnIII(OH)] (1) or 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatomanganese(III) acetate [(TPFPP)MnIII(CH3COO)] (2)] occurred to yield 10-methyl-(9,10H)-acridone (Acr -O) in an oxygen-saturated benzonitrile (PhCN) solution under visible light irradiation. The photocatalytic reactivity of (P)MnIII in the presence of O2 is in proportion to concentrations of AcrH2 or O2 with the maximum turnover numbers of 17 and 6 for 1 and 2, respectively. The quantum yield with 1 was determined to be 0.14%. Deuterium kinetic isotope effects (KIEs) were observed with KIE = 22 for 1 and KIE = 6 for 2, indicating that hydrogen-atom transfer from AcrH2 is involved in the rate-determining step of the photocatalytic reaction. Femtosecond transient absorption measurements are consistent with photoexcitation of (P)MnIII, resulting in intersystem crossing from a tripquintet excited state to a tripseptet excited state. A mechanism is proposed where the tripseptet excited state reacts with O 2 to produce a putative (P)MnIV superoxo complex. Hydrogen-atom transfer from AcrH2 to (P)MnIV(O 2?-) generating a hydroperoxo complex (P)Mn IV(OOH) and AcrH? is likely the rate-determining step, in competition with back electron transfer to regenerate the ground state (P)MnIII and O2. The subsequent reductive O-O bond cleavage by AcrH? may occur rapidly inside of the reaction cage to produce (P)MnV(O) and AcrH(OH), followed by the oxidation of AcrH(OH) by (P)MnV(O) to yield Acr -O with regeneration of (P)Mn III.
- Jung, Jieun,Ohkubo, Kei,Goldberg, David P.,Fukuzumi, Shunichi
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- Solvent Effects on Chemiluminescence from the Hydrogen Peroxide-Lucigenin Reaction: Kinetics of Light Emission in Mixed Polar Solvents
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The effect of the reaction media composition on reaction kinetics was studied for the reaction of lucigenin (10,10'-dimethyl-9,9'-biacridinium nitrate) with hydrogen peroxide and alkali.Chemiluminescent emission as well as lucigenin disappearance were recorded in mixtures of water with the co-solvents methanol, ethanol, 1-propanol, dimethylsulfoxide, and dimethylformamide.The kinetic results (base and peroxide concentration influence on the reaction rate and the relative chemiluminescence yield) are very similar in all the reaction media, suggesting that the fundamental step in the disappearance of lucigenin and in light emission decay is HO2- addition to lucigenin.Lucigenin can also disappear through dark reactions with OH- or H2O2.The co-solvent acts as a catalyst for the reaction with HO2- and increases both the initial chemiluminescence intensity and the decay rate constant. Keywords.Chemiluminescence; Lucigenin; Solvent effects.
- Larena, Alicia,Urreaga, Joaquin Martinez
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- Formation of xanthone oxime and related compounds using a combination of tert-butyl nitrite and potassium hexamethyldisilazide
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Synthesis of xanthone oxime and related compounds via nitrosation of the dibenzylic position using a combination of tert-butyl nitrite and potassium hexamethyldisilazide is described. The reaction conditions are effective for the synthesis of xanthone oxime as well as thioxanthone, acridone, and anthrone oximes, which have been difficult to synthesize from the corresponding ketones by conventional dehydrative condensation with hydroxylamine.
- Iwama, Yusuke,Noro, Takahiro,Okano, Kentaro,Cho, Hidetsura,Tokuyama, Hidetoshi
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- Origin of Chemiluminescence Accompanying the Reaction of the 9-Cyano-10-methylacridinium Cation with Hydrogen Peroxide
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The 9-cyano-10-methylacridinium cation possesses an electrophilic center at the carbon atom in position (9) susceptible to the addition of anions. The addition of OOH- to this cation-in weakly acidic, neutral, or alkaline media-initiates processes leading to the formation of electronically excited 10-methyl-9-acridinone, which deactivates by light emission. The effect of changes in reactant concentrations and pH on emission decay with time, as well as other features of the accompanying chemiluminescence, were established. Calculations carried out at the semiempirical and density functional theory level demonstrated that initial addition of OOH- and subsequent processes lead either to the elimination of OCNH (in weakly acidic and neutral media) or OCN- (in alkaline media) and that their exothermicity is sufficiently high to generate electronically excited 10-methyl-9-acridinone. On the other hand, primary addition of OH- to C(9) in alkaline media initiates the conversion of the cation to the nonexcited 10-methyl-9-acridinone. This relatively rapid process influences to a substantial extent the intensity of the chemiluminescence. The prospects for the analytical application of 9-cyano-10-methylacridinium salts are briefly outlined.
- Wroblewska,Huta,Midyanyj,Patsay,Rak,Blazejowski
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- Sulfonation of 10-carboxymethylene-9-acridanone under thermal and microwave conditions. Comparison of kinetic parameters
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Sulfonation of 10-carboxymethylene-9-acridanone under thermal and microwave conditions was studied. The rate constants of the accumulation of the desired product in the reaction conditions were measured.
- Markovich,Kudryavtseva,Markovich,Koroleva
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- Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution
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The chemiluminescence (CL) of lucigenin (Luc2+) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2?-) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2?- production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc2+ into lucigenin cation radicals (Luc?+), which react with O2?- to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution.
- Chi, Quan,Chen, Wanying,He, Zhike
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- Acid-catalyzed oxidative cross-coupling of acridans with silyl diazoenolates and a Rh-catalyzed rearrangement: two-step synthesis of γ-(9-acridanylidene)-β-keto esters
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A MsOH-catalyzed oxidative cross-coupling of acridans and silyl diazoenolates and a Rh2(OAc)4-catalyzed rearrangement of the resultant diazo products are described. The reactions provide various γ-(9-acridanylidene)-β-keto esters in good yields, which bear an active α-methylene unit for further functionalization.
- Li, Weiyu,Xu, Hao,Zhou, Lei
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p. 5649 - 5657
(2021/07/02)
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- Design, synthesis and evaluation of novel 9-arylalkyl-10-methylacridinium derivatives as highly potent FtsZ-targeting antibacterial agents
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With the increasing incidence of antibiotic resistance, new antibacterial agents having novel mechanisms of action hence are in an urgent need to combat infectious diseases caused by multidrug-resistant (MDR) pathogens. Four novel series of substituted 9-arylalkyl-10-methylacridinium derivatives as FtsZ inhibitors were designed, synthesized and evaluated for their antibacterial activities against various Gram-positive and Gram-negative bacteria. The results demonstrated that they exhibited broad-spectrum activities with substantial efficacy against MRSA and VRE, which were superior or comparable to the berberine, sanguinarine, linezolid, ciprofloxacin and vancomycin. In particular, the most promising compound 15f showed rapid bactericidal properties, which avoid the emergence of drug resistance. However, 15f showed no inhibitory effect on Gram-negative bacteria but biofilm formation study gave possible answers. Further target identification and mechanistic studies revealed that 15f functioned as an effective FtsZ inhibitor to alter the dynamics of FtsZ self-polymerization, which resulted in termination of the cell division and caused cell death. Further cytotoxicity and animal studies demonstrated that 15f not only displayed efficacy in a murine model of bacteremia in vivo, but also no significant hemolysis to mammalian cells. Overall, this compound with novel skeleton could serve as an antibacterial lead of FtsZ inhibitor for further evaluation of drug-likeness.
- Song, Di,Zhang, Nan,Zhang, Panpan,Zhang, Na,Chen, Weijin,Zhang, Long,Guo, Ting,Gu, Xiaotong,Ma, Shutao
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- Aromatic heterocycle substituted acridine quaternary ammonium salt derivative as well as preparation method and application thereof
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The invention belongs to the technical field of pharmaceutical compounds, relates to an aromatic heterocyclic substituted acridine quaternary ammonium salt derivative and a preparation method and application thereof, and has the structure shown in a formula (I). In-flight R1 A compound selected from the group consisting of aryl and heteroaryl. Substituted aryls. X Is a halogen or benzenesulfonate anion. The invention provides an aromatic heterocyclic substituted acridine quaternary ammonium salt derivative as well as a preparation method and application thereof, and is designed to synthesize an aromatic heterocyclic substituted acridine quaternary ammonium salt derivative through a simplified structure, and is designed to synthesize an aromatic heterocyclic substituted acridine quaternary ammonium salt derivative so as to achieve the unique antibacterial effect by inhibiting the bacteria FtsZ and bacterial biofilm.
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- Acylalkylation of Arynes Generated from o-Iodoaryl Triflates with Hydrosilanes and Cesium Fluoride
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An efficient method to generate aryne intermediates from o-iodoaryl triflates triggered by triethylsilane and cesium fluoride is disclosed. This method realized the acylalkylation of arynes using easily available o-iodoaryl triflate-type precursors, which was difficult when using conventional nucleophilic activators. A wide range of (hetero)arenes including various fused benzothiazoles were successfully synthesized from o-iodoaryl triflates by virtue of their good accessibility and divergent transformations of aryne intermediates.
- Minoshima, Mai,Uchida, Keisuke,Nakamura, Yu,Hosoya, Takamitsu,Yoshida, Suguru
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supporting information
p. 1868 - 1873
(2021/03/08)
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- Synthesis of xanthones, thioxanthones and Acridones by a metal-free photocatalytic oxidation using visible light and molecular oxygen
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9H-Xanthenes, 9H-thioxanthenes and 9,10-dihydroacridines can be easily oxidized to the corresponding xanthones, thioxanthones and acridones, respectively, by a simple photo-oxidation procedure carried out using molecular oxygen as oxidant under the irradiation of visible blue light and in the presence of riboflavin tetraacetate as a metal-free photocatalyst. The obtained yields are high or quantitative.
- Chinchilla, Rafael,Torregrosa-Chinillach, Alejandro
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- Ultraviolet-light-induced aerobic oxidation of benzylic C(sp3)-H of alkylarenes under catalyst- and additive-free conditions
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A mild and efficient system has been discovered for the synthesis of α-aryl carbonyl compounds via oxidation of benzylic C–H to C[dbnd]O bonds. This ultraviolet-light-mediated oxygenation reaction exhibited excellent substrate scope including various xanthenes, thioxanthenes and 9, 10-dihydroacridines and afforded the corresponding ketones with good to excellent yields under catalyst- and additive-free conditions at room temperature.
- Zhou, Jiacheng,Li, Meichao,Li, Tianci,Li, Chunmei,Hu, Xinquan,Jin, Liqun,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu
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- The embedding of fluorescent: N -methyl-9-acridone into a topological new layered aluminophosphate SYSU-2 by one-pot synthesis
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A layered aluminophosphate |C14H11NO|2[Al4(HPO4)4F4(H2O)2] (denoted as SYSU-2) with a new topology has been hydrothermally synthesized with N-methyl-9-acridone (NMA) as the organic structure-directing agent. Single-crystal X-ray diffraction analysis reveals that SYSU-2 crystallizes in a triclinic space group P1, with the inorganic sheets stacked in an AA sequence. Hydrogen bonds are responsible for the neutral inorganic-organic layer connection. The layer structure of SYSU-2 is constructed by alternating AlO4F2 octahedra and PO4 tetrahedra. The topological analysis of SYSU-2 indicates an independent topology. The NMA layers are self-assembled with π-π interaction. SYSU-2 crystals show interesting dual-band emission fluorescence properties compared with NMA crystals. Under 406 nm UV irradiation, SYSU-2 crystals emit yellow light with two emission bands at 477 and 566 nm, while NMA crystals emit blue light with only one band at 473 nm. The differences may be derived from the difference of stacking orders and distance of NMA molecule layers between the two crystals
- Jiang, Jiuxing,Liang, Weichi,Wen, Jiali,Zhang, Meng,Zhao, Yukai
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p. 17033 - 17038
(2020/12/18)
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- Organic compound with acridine-derived triarylamine structure and application of organic compound
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The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an organic compound with an acridine-derived triarylamine structure and application of theorganic compound. The compound provided by the invention has the acridine-derived triarylamine structure, and because the triarylamine structure has very high hole migration efficiency, the evaporation temperature of the compound is obviously reduced; besides, the compound provided by the invention can maintain good thermodynamic stability while the evaporation temperature is reduced, and the compound provided by the invention is suitable for being used as a hole transport layer in an OLED device. The preparation process of the compound is simple and feasible, raw materials are easy to obtain,and the compound is suitable for mass production.
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Paragraph 0028-0032; 0048-0052
(2020/06/20)
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- Boron trifluoride etherate promoted microwave-assisted synthesis of antimalarial acridones
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A microwave-assisted, rapid and efficient method using boron trifluoride etherate (BF3.Et2O) for the synthesis of acridones, via an intramolecular acylation of N-phenylanthranilic acid derivatives, has been developed. The reaction proceeds under solvent-free conditions, tolerates a wide range of functional groups, and provides rapid access to a range of acridones in good to excellent yields. Several of the synthesized acridones exhibited potent antimalarial activities against CQ sensitive and multi-drug resistant (MDR) parasites.
- Kancharla, Papireddy,Dodean, Rozalia A.,Li, Yuexin,Kelly, Jane X.
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p. 42284 - 42293
(2020/01/08)
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- Stabilized Carbenium Ions as Latent, Z-type Ligands
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Controlling the reactivity of transition metals using secondary, σ-accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o-Ph2P(C6H4)Acr)AuCl]+ ([3]+; Acr=9-N-methylacridinium) and [(o-Ph2P(C6H4)Xan)AuCl]+ ([4]+; Xan=9-xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [4]+ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative (7) in which the metal atom is covalently bound to the former carbocationic center. This anion-induced AuI/AuIII oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [4]+ into an X-type ligand in 7. We conclude that the carbenium moiety of this complex acts as a latent Z-type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.
- Wilkins, Lewis C.,Kim, Youngmin,Litle, Elishua D.,Gabba?, Fran?ois P.
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supporting information
p. 18266 - 18270
(2019/11/14)
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- Improvement of Preparation Process for Key Intermediate of Chemiluminescence APS-5
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The invention relates to a key intermediate of a compound APS-5 which reacts with phosphatase to generate chemiluminescence, in particular to a preparation method of 10-methyl-9,10-dihydroacridine-9-thiocarboxylic acid-4-chlorophenyl ester.
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Paragraph 0010
(2019/07/05)
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- Acridone Derivate Simultaneously Featuring Multiple Functions and Its Applications
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Compared with plenty of single-functional molecules, multifunctional molecules are scarce and have high demand in further research. In this work, a multifunctional molecule called 10-methyl-2-amino-acridone (MAA) is presented. Interestingly, MAA simultaneously features electrochemistry, two-photon fluorescence, visible-light-induced oxidase mimic, and photoelectrochemistry (PEC) activity, and the related properties are studied in detailed. Multiple functions integrated into one molecule allow MAA to become a versatile signal probe. Therefore, the MAA acted as an electrochemical indicator to detect exosomal total protein with high sensitivity at first. In addition, MAA is used for one- or two-photon fluorescence imaging in vitro and in vivo, including cells, three-dimensional (3D) tumor spheroids, zebrafish, and exosomes. The results suggest that MAA not only possesses favorable photostability, but it is also suitable for imaging in deep tissue. Furthermore, the visible-light-induced oxidase mimic and photoelectrochemical activities of MAA are selectively inhibited by Cu2+, and the relevant mechanism is carefully analyzed. On the basis of this phenomenon, we develop a dual-modal detection strategy for detection of Cu2+ in river water. Compared with a single signal readout model, this strategy is able to avoid false positive and negative detection through two series of data mutually validating each other. Therefore, our study shows that the "multiple-in-one" MAA provides a blueprint for the investigation and application of a multifunctional organic molecule.
- Xia, Yaokun,He, Wenhui,Li, Juan,Zeng, Lupeng,Chen, Tingting,Liao, Yijuan,Sun, Weiming,Lan, Jianming,Zhuo, Shuangmu,Zhang, Jing,Yang, Huanghao,Chen, Jinghua
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p. 8406 - 8414
(2019/06/17)
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- Assessment of dna topoisomerase i unwinding activity, radical scavenging capacity, and inhibition of breast cancer cell viability of n-alkylacridones and n,n′-dialkyl-9,9′-biacridylidenes
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The anticancer activity of acridone derivatives has attracted increasing interest, therefore, a variety of substituted analogs belonging to this family have been developed and evaluated for their anti-cancer properties. A series of N-alkyl-acridones 1–6 and N,N′-dialkyl-9,9′-biacridylidenes 7–12 with variable alkyl chains were examined for their topoisomerase I activity at neutral and acidic conditions as well as for their binding capacity to calf thymus and possible radical trapping antioxidant activity. It was found that at a neutral pH, topoisomerase I activity of both classes of compounds was similar, while under acidic conditions, enhanced intercalation was observed. Nalkyl- acridone derivatives 1–6 exhibited stronger, dose-dependent, cytotoxic activity against MCF- 7 human breast epithelial cancer cells than N,N′-dialkyl-9,9′-biacridylidenes 7–12, revealing that conjugation of the heteroaromatic system plays a significant role on the effective distribution of the compound in the intracellular environment. Cellular investigation of long alkyl derivatives against cell migration exhibited 40–50% wound healing effects and cytoplasm diffusion, while compounds with shorter alkyl chains were accumulated both in the nucleus and cytoplasm. All N,N′-dialkyl- 9,9′-biacridylidenes showed unexpected high scavenging activity towards DPPH or ABTS radicals which may be explained by higher stabilization of radical cations by the extended conjugation of heteroaromatic ring system.
- Krokidis, Marios G.,Molphy, Zara,Efthimiadou, Eleni K.,Kokoli, Marianna,Argyri, Smaragda-Maria,Dousi, Irini,Masi, Annalisa,Papadopoulos, Kyriakos,Kellett, Andrew,Chatgilialoglu, Chryssostomos
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- Visible-Light-Induced Aerobic Oxidation of Benzylic C(sp 3)-H of Alkylarenes Promoted by DDQ, tert -Butyl Nitrite, and Acetic Acid
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A visible-light photocatalytic aerobic oxidation of benzylic C(sp 3)-H bonds proceeded in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tert -butyl nitrite, and acetic acid. Advantages of this aerobic oxidation method include its relatively mild conditions, the use of visible-light irradiation instead of conventional thermal methods, the use of a low catalyst loading, and the ability to oxidize a range of alkylarenes, including xanthenes, thioxanthenes, and 9,10-dihydroacridines, to the corresponding ketones in excellent yields.
- Pan, Decheng,Wang, Yiqing,Li, Meichao,Hu, Xinquan,Sun, Nan,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu
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p. 218 - 224
(2019/01/14)
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- Photocatalytic oxidation synthesis method of acridone compound
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The invention discloses a photocatalytic oxidation synthesis method of an acridone compound. According to the method, a 9,10-dihydroacridine compound is used as a reaction substrate, 2,3-dichloro-5,6-dinitrile group-1,4-benzoquinone (DDQ) and tert-butyl nitrite (TBN) are used as catalysts, acetic acid is used as a reaction aid, oxygen is used as an oxidant, the reaction substrate reacts in a 1,2-dichloroethane solvent at normal temperature and pressure under blue light irradiation, and after the completion of the reaction, the acridone compound is obtained by separation treatment. According tothe synthesis method provided by the invention, a traditional heating reaction is replaced with an illumination reaction, thereby saving energy; no transition metal catalyst is used; and the productyield is high under optimized conditions.
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Paragraph 0025-0042
(2019/02/26)
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- Synthesis method of acridone derivative
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The application relates to a synthesis method of an acridone derivative. The synthesis method comprises the following steps: mixing a compound shown in a formula (I), a photocatalyst and a solvent, reacting under the conditions of oxygen and lighting and obtaining the acridone derivative. The synthesis method of the acridone derivative has the beneficial effects that the photocatalyst can catalyzethe compound shown in the formula (I) to carry out intramolecular hydrocarbon ammoniation reaction under the conditions of oxygen and lighting so as to synthesize the acridone derivative, and the pretreatment for the compound shown in the formula (I) is not needed; the operation is simple and convenient, and the condition is mild, the yield is high; the synthesis method conforms to the economic and environment-friendly characteristics of atoms and has high practical value for industrial preparation of the acridone derivative.
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Paragraph 0047-0049; 0116-0118; 0123-0125; 0054-0056
(2019/01/05)
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- Synthesis of 2-aminobenzophenones through acylation of anilines with α-oxocarboxylic acids assisted by: Tert -butyl nitrite
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In this paper, a regioselective, efficient and convenient synthesis of 2-aminobenzophenones through acylation of anilines with α-oxocarboxylic acids assisted by tert-butyl nitrite is presented. Interestingly, tert-butyl nitrite acts as not only an efficient and mild nitrosation reagent, but also a sustainable oxidant required in the Pd(ii)-catalyzed decarboxylative acylation. Meanwhile, the NO unit turned out to be an easily introduced and readily removable directing group for the regioselective acylation.
- Wang, Qianqian,Zhang, Xinying,Fan, Xuesen
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p. 7737 - 7747
(2018/11/02)
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- Transition-Metal-Free Synthesis of Acridones via Base-Mediated Intramolecular Oxidative C?H Amination
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Intramolecular oxidative C?H amination of 2-aminobenzophenones was achieved in the presence of potassium tert-butoxide and dimethyl sulfoxide. A series of functionalized acridones were prepared in moderate to excellent yields in a mild, efficient, and transition-metal-free manner. (Figure presented.).
- Wei, Wen-Tao,Sheng, Jian-Fei,Miao, Hui,Luo, Xiang,Song, Xian-Heng,Yan, Ming,Zou, Yong
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p. 2101 - 2106
(2018/06/14)
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- Synthesis and Properties of Acridine and Acridinium Dye Functionalized Bis(terpyridine) Ruthenium(II) Complexes
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We present first principle studies on the rational design of an acridine/N-methylacridinium dye (Acr/MeAcr+) substituted terpyridine ligand to investigate if these chromophores can act as triplet-energy storage units in bis(terpyridine) ruthenium(II) complexes. We studied the influence of the dye form (Acr/MeAcr+) as well as the interconnecting linker unit (none, 4-phenyl, or 5-thien-2-yl) and investigated these aspects by steady-state/time-resolved spectroscopy, cyclic voltammetry, X-ray structure analysis, and DFT calculations.
- Eberhard, Jens,Peuntinger, Katrin,Fr?hlich, Roland,Guldi, Dirk M.,Mattay, Jochen
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p. 2682 - 2700
(2018/06/04)
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- A chemically-responsive bis-acridinium receptor
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A dicationic receptor based on two acridinium moieties linked by a triphenylene spacer was studied in solution and in the solid state. Recognition moieties, namely acridiniums, were exploited to evidence a host-guest response of the receptor with electron rich guests. Upon addition of methoxide anions, the formation of the bis-acridane form of the receptor was observed. The chemical responsiveness of the receptor to these anions inhibits its recognition properties towards π-donor guests. In addition, the reversibility of the chemical response was demonstrated under acidic conditions.
- Gosset,Xu,Maurel,Chamoreau,Nowak,Vives,Perruchot,Heitz,Jacquot De Rouville
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supporting information
p. 4728 - 4734
(2018/03/21)
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- Photocatalytic Construction of S-S and C-S Bonds Promoted by Acridinium Salt: An Unexpected Pathway to Synthesize 1,2,4-Dithiazoles
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An unexpected cyclization of thioamides with p-quinone methides promoted by acridinium salt under the irradiation of visible light furnished 1,2,4-dithiazoles in moderate to good yields. In addition, the reaction of the obtained 1,2,4-dithiazoles with isocyanides offered a new entry for the synthesis of thiazol-5(4H)-imines in moderate yields.
- Huang, Xiao-Ying,Ding, Rui,Mo, Zu-Yu,Xu, Yan-Li,Tang, Hai-Tao,Wang, Heng-Shan,Chen, Yan-Yan,Pan, Ying-Ming
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supporting information
p. 4819 - 4823
(2018/08/24)
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- Novel Oxidative Ugi Reaction for the Synthesis of Highly Active, Visible-Light, Imide-Acridinium Organophotocatalysts
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A newly designed class of acridinium-based organophotocatalysts bearing an imide group at the C9-position is presented. To achieve these unprecedented structures, a synthetic strategy based on a novel straightforward oxidative Ugi-type reaction at the benzylic position of C9-unsubstituted acridanes was developed. The introduction of the imide-unit affords a notable photocatalytic activity enhancement, allowing efficient transformations in different oxidative and reductive visible-light catalytic reactions.
- Gini, Andrea,Uygur, Mustafa,Rigotti, Thomas,Alemán, José,García Manche?o, Olga
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supporting information
p. 12509 - 12514
(2018/09/10)
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- Preparation method of acridone and derivatives thereof
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The invention discloses a preparation method of acridone and derivatives thereof. The method is characterized in that 2-halogenated diphenylamine compounds are used as a substrate, and the acridone and the derivatives thereof are prepared by means of a palladium catalyzed carbonylation reaction under a carbon monoxide atmosphere. The reaction raw materials of the method are relatively easy to obtain, and the reaction conditions are mild; this method breaks the limitation that the substrate needs to be introduced into a precursor of a carbonyl functional group in advance in the conventional preparation method; the carbon monoxide is used as a direct source of the carbonyl group, and two C-C bonds are constructed by means of the carbonylation reaction in one step, so that the method is bestin line with the concepts of atomic economy, synthetic process economy and green chemistry in organic synthesis; organic methodologies is developed, and the efficient preparation of acridone compoundsis also realized.
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Paragraph 0061; 0062
(2018/07/30)
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- Synthesis of acridones through palladium-catalyzed carbonylative of 2-bromo-diarylamines
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A facile protocol for the synthesis of acridone derivatives has been developed through palladium-catalyzed carbonylation/C–H activation sequence from 2-bromo-diarylamines in moderate to excellent yields. The reactions occurred smoothly and allowed both el
- Song, Juan,Ding, Keran,Sun, Wei,Wang, Songjiang,Sun, Haisen,Xiao, Kang,Qian, Yan,Liu, Chao
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supporting information
p. 2889 - 2892
(2018/06/25)
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- Method for construction of C-N bond for synthesis of acridone derivative by intramolecular decarboxylation coupling
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The present invention provides a method for construction of a C-N bond for synthesis of an acridone derivative by intramolecular decarboxylation coupling, the synthesis process is as follows: a formula (I) compound, anhydrous 1, 10-phenanthroline, copper acetate, palladium acetate and silver carbonate are added to solvent anhydrous DMF, and heated in O2 atmosphere to 120 to 160 DEG C for reaction for 12-16h, and after postprocessing of a reaction liquid, the acridone derivative shown as a formula (II) can be obtained; the C-N bond can be constructed in one step for synthesis of an acridone product, the method has the advantages of high efficiency, low cost and good yield, conventional reagents are used in the reaction, and the conventional reagents are low-toxicity, environmental-friendly and economic.
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Paragraph 0020; 0021; 0022
(2017/10/07)
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- A Chromium(III)-Superoxo Complex as a Three-Electron Oxidant with a Large Tunneling Effect in Multi-Electron Oxidation of NADH Analogues
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Metal-superoxo species are involved in a variety of enzymatic oxidation reactions, and multi-electron oxidation of substrates is frequently observed in those enzymatic reactions. A CrIII-superoxo complex, [CrIII(O2)(TMC)(Cl)]+ (1; TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), is described that acts as a novel three-electron oxidant in the oxidation of dihydronicotinamide adenine dinucleotide (NADH) analogues. In the reactions of 1 with NADH analogues, a CrIV-oxo complex, [CrIV(O)(TMC)(Cl)]+ (2), is formed by a heterolytic O?O bond cleavage of a putative CrII-hydroperoxo complex, [CrII(OOH)(TMC)(Cl)], which is generated by hydride transfer from NADH analogues to 1. The comparison of the reactivity of NADH analogues with 1 and p-chloranil (Cl4Q) indicates that oxidation of NADH analogues by 1 proceeds by proton-coupled electron transfer with a very large tunneling effect (for example, with a kinetic isotope effect of 470 at 233 K), followed by rapid electron transfer.
- Devi, Tarali,Lee, Yong-Min,Jung, Jieun,Sankaralingam, Muniyandi,Nam, Wonwoo,Fukuzumi, Shunichi
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p. 3510 - 3515
(2017/03/21)
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- Two-photon fluorescent probe 10-methyl-2-amino-acridone as well as preparation method and application thereof
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The invention discloses two-photon fluorescent probe 10-methyl-2-amino-acridone as well as a preparation method and application thereof. The 10-methyl-2-amino-acridone is used as a fluorescent probe and is used for living imaging of cells and zebra fishes. The structural formula of the 10-methyl-2-amino-acridone is shown in the description. The compound has good water solubility; emission wavelength of the compound is a green light wave band; with good two-photon activity, bioautofluorescence and self-absorption can be well reduced, and the compound is successfully applied to imaging of the cells and the zebra fishes; meanwhile, the compound has good electrochemical activity, and is expected to be applied to the field of electrochemical sensing as a novel electro-active indicator.
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Paragraph 0014
(2017/11/30)
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- Substrate-Controlled Selectivity Switch in the Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and CO2
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The transition-metal-free multicomponent coupling involving arynes, aromatic tertiary amines, and CO2 is reported. The reaction exhibits switchable selectivity depending on the electronic nature of the aromatic amines used. With amines bearing electron-releasing/neutral groups as the nucleophilic trigger, the reaction afforded 2-arylamino benzoates via a nitrogen to oxygen alkyl group migration. Employing electron-deficient amines in the reaction furnished 2-aminoaryl benzoates proceeding via the aryl to aryl amino group migration resembling a Smiles rearrangement.
- Bhojgude, Sachin Suresh,Roy, Tony,Gonnade, Rajesh G.,Biju, Akkattu T.
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p. 5424 - 5427
(2016/11/04)
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- Synthesis, photophysical and electrochemical studies of acridone-amine based donor-acceptors for hole transport materials
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A series of new donor-acceptor molecules based on acridone-amine containing four aryl substituted 2,7-diaminoacridones (1-4) and morpholine substituted acridone compounds (5) were synthesized in good yields using palladium catalysed Buchwald-Hartwig C-N amination. Their absorption, photoluminescence and electrochemical properties were investigated in solution and in thin films. Photophysical properties were found to be affected by the electron donating capability of the substituents on the diaryl amines. Absorption showed intramolecular charge transfer transitions (ICT) in a range of 447-479 nm. These acridone amine derivatives emit in the green region (500-527 nm). Reversible oxidation waves were observed for compounds 1-5 in cyclic voltammetry. The HOMO (-4.95 to -5.11 eV) and LUMO (-2.36 to -2.56 eV) energy levels of 1-5 were calculated. The EHOMO for compounds 1-5 are similar with the most widely used hole transporting materials NPD, TPD and spiro-OMe-TAD. Hence we believe that these compounds have the potential to be used as hole transporting materials in optoelectronic devices.
- Sharma, Bharat K.,Shaikh, Azam M.,Agarwal, Neeraj,Kamble, Rajesh M.
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p. 17129 - 17137
(2016/02/20)
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- Synthesis of 1,2-Dioxetanes as Thermochemiluminescent Labels for Ultrasensitive Bioassays: Rational Prediction of Olefin Photooxygenation Outcome by Using a Chemometric Approach
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Great interest in new thermochemiluminescent (TCL) molecules, for example, in bioanalytical assays, has prompted the design and synthesis of a small library of more than 30 olefins to be subjected to photooxygenation, with the aim of obtaining new 1,2-dioxetane-based TCL labels with optimized properties. Fluorine atoms on the acridan system remarkably stabilize 1,2-dioxetanes when they are located in the 3- and/or 6-position (4 h and 4 i). On the other hand, 2,7-difluorinated acridan dioxetane (4 j) showed a significantly enhanced fluorescence quantum yield with respect to the unsubstituted dioxetane (4 a). Some of the synthesized olefins did not undergo singlet oxygen addition and a rationale was sought to ease the photooxygenation step, leading to the TCL dioxetanes. A chemometric approach has been adopted to exploit principal component analysis and linear discriminant analysis of the structural and electronic molecular descriptors obtained by DFT optimizations of olefins 3. This approach allows the steric and electronic parameters that govern dioxetane formation to be revealed.
- Andronico, Luca A.,Quintavalla, Arianna,Lombardo, Marco,Mirasoli, Mara,Guardigli, Massimo,Trombini, Claudio,Roda, Aldo
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supporting information
p. 18156 - 18168
(2016/12/16)
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- Anisotropic Dissociation of π-π Stacking and Flipping-Motion-Induced Crystal Jumping in Alkylacridones and Their Dicyanomethylene Derivatives
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Ethylacridone (1 b) and dicyanomethylenated acridones 2 a,b,d showed crystal-jumping activity upon heating. This is the first example of thermosalient behavior in a simple aromatic ketone and its derivatives. A systematic investigation of the jumping behavior of derivatives with different alkyl chains by variable-temperature X-ray crystal-structure analyses revealed the mechanism of this phenomenon. Anisotropic dissociation of π stacking in a dimer was important for inducing crystal jumping in 1 b, whereas the collective fluctuation/flipping motion of a dicyanomethylene unit induced crystal jumping in 2.
- Takeda, Takashi,Akutagawa, Tomoyuki
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p. 7763 - 7770
(2016/06/08)
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- Oxidative SNH amidation of acridine and tautomerism of N-(acridin-9-yl)benzamides
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[Figure not available: see fulltext.] Direct oxidative nucleophilic substitution of hydrogen atom in acridine molecule was used to synthesize 9-acylaminoacridines. The prototropic amine-imine tautomerism of these compounds was studied.
- Demidov, Oleg P.,Borovlev, Ivan V.,Amangasieva, Gulminat A.,Avakyan, Elena K.
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p. 104 - 109
(2016/07/06)
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- A one-pot construction of acridones by rhodium catalyzed reaction of N-phenyl-2-(1-sulfonyl-1H-1,2,3-triazol-4-yl)aniline
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A one-pot synthesis of N-alkyl acridone via rhodium catalyzed decomposition of N-phenyl-2-(1-sulfonyl-1H-1,2,3-triazol-4-yl)aniline and subsequent oxidative C–C bond fragmentation has been developed. 14 examples are presented and the yields range from 30% to 80%.
- Xu, Hua-Dong,Pan, Ying-Peng,Ren, Xin-Tao,Zhang, Ping,Shen, Mei-Hua
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supporting information
p. 6734 - 6737
(2018/05/14)
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- Ligand controlled regiodivergent C1 insertion on arynes for construction of phenanthridinone and acridone alkaloids
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A palladium-catalyzed regiodivergent C1 insertion multicomponent reaction involving aryne, CO, and 2-iodoaniline is established to construct the scaffolds of phenanthridinone and acridone alkaloids. Regioselective control is achieved under the guidance of selective ligands. The phenanthridinones are solely obtained under ligand-free condition. In comparison, application of the electron-abundant bidentate ligand dppm afforded the acridones with high efficiency. The release rate of the aryne from the precursor assists the regioselectivity of insertion as well, which was revealed through interval NMR tracking. A plausible mechanism was suggested based on the control experiments. Representative natural products and two types of natural product analogues were synthesized divergently through this tunable method. Divergent alkaloid synthesis: A multicomponent, regioselective approach for palladium-catalyzed C1 insertion is described. This reaction was applied in the divergent synthesis of phenanthridinone and acridone natural product core scaffolds.
- Feng, Minghao,Tang, Bingqing,Wang, Nengzhong,Xu, Hong-Xi,Jiang, Xuefeng
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p. 14960 - 14964
(2016/02/05)
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- Oxidative C-H bond functionalization and ring expansion with TMSCHN2: A copper(I)-catalyzed approach to dibenzoxepines and dibenzoazepines
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Tricyclic dibenzoxepines and dibenzazepines are important therapeutic agents for the pharmaceutical industry and academic research. However, their syntheses are generally rather tedious, requiring several steps that involve a Wagner-Meerwein-type rearrangement under harsh conditions. Herein, we present the first copper(I)-catalyzed oxidative C-H bond functionalization and ring expansion with TMSCHN2 to yield these important derivatives in a facile and straightforward way. Cut a long story short: Tricyclic dibenzoxepines and dibenzazepines are important therapeutic agents for pharmaceuticals, but their syntheses are generally rather tedious. A copper(I)-catalyzed oxidative C-H bond functionalization and ring expansion sequence with TMSCHN2 has been developed to yield these important derivatives in a facile and straightforward way.
- Stopka, Tobias,Marzo, Leyre,Zurro, Mercedes,Janich, Simon,Würthwein, Ernst-Ulrich,Daniliuc, Constantin G.,Alemán, José,Manche?o, Olga García
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supporting information
p. 5049 - 5053
(2015/04/27)
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- PhI(OAc)2-mediated intramolecular oxidative aryl-aldehyde C sp 2-C sp 2 bond formation: Metal-free synthesis of acridone derivatives
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A metal-free protocol for direct aryl-aldehyde Csp2-Csp 2 bond formation via a PhI(OAc)2-mediated intramolecular cross-dehydrogenative coupling (CDC) of various 2-(N-arylamino)aldehydes was developed. The novel methodology requires no need of preactivation of the aldehyde group, is applicable to a large variety of functionalized substrates, and most of all provides a convenient approach to the construction of biologically important acridone derivatives.
- Zheng, Zisheng,Dian, Longyang,Yuan, Yucheng,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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p. 7451 - 7458
(2014/09/17)
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- Sc(OTf)3-catalyzed dehydrogenative cyclization for synthesis of N-methylacridones
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A novel method has been developed for the synthesis of substituted N-methylacridones from 2-(N-methyl-N-phenylamino)benzaldehydes via dehydrogenative cyclization. This transformation involves two primary processes: the aldehyde first coordinates with Sc(OTf)3 and induces the aromatic electrophilic substitution (SEAr) reaction to form the active intermediate N-methyl-acridin-9-ol, which is then quickly oxidized in situ to afford the acridones. Furthermore, the procedure involved is both environmental friendly and atom efficient; H2O is the only byproduct in this reaction.
- Li, Xi-An,Wang, Hong-Li,Yang, Shang-Dong
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p. 1794 - 1797
(2013/05/23)
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- Copper-catalyzed intramolecular oxidative C-H functionalization and C-N formation of 2-aminobenzophenones: Unusual pseudo-1,2-shift of the substituent on the aryl ring
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A good move: A copper-catalyzed intramolecular oxidative C-H functionalization of 2-aminobenzophenone affords two regioisomeric acridones (see scheme). The reaction involves an unusual pseudo-1,2-migration of R 2 group(s) on the arene ring (bpy=2,2-bipyridine, DMAc=dimethylacetimide). Copyright
- Huang, Pang-Chi,Parthasarathy, Kanniyappan,Cheng, Chien-Hong
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supporting information
p. 460 - 464
(2013/02/23)
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- Synthesis of 10-methylacridin-9(10H)-ones through Cu-Catalyzed Intramolecular Oxidative C(sp2)-H Amination of 2-(Methylamino) benzophenones
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An efficient synthesis of a diverse set of 10-methylacridin-9(10H)-ones from 2-(methylamino)benzophenones has been developed. The reaction proceeds though Cu-catalyzed intramolecular aromatic C-H amination by using O2 as the sole oxidant to provide the desired products in moderate to good yields. In addition, 2-allylamino- and 2-(benzylamino)benzophenones as well as unprotected substrates can also undergo the C-H amination reaction to deliver the corresponding cyclization products smoothly. Preliminary mechanistic studies suggest that C-H activation is involved in a rate-limiting step. An efficient synthesis of a diverse set of 10-methylacridin-9(10H)-ones from 2-(methylamino)benzophenones has been developed. The reaction proceeds through Cu-catalyzed intramolecular aromatic C-H amination by using O2 as the oxidant. Mechanistic studies suggest that a rate-limiting C-H activation step is involved in the C-N bond-formation process.
- Huang, Jinbo,Wan, Congqing,Xu, Ming-Fang,Zhu, Qiang
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supporting information
p. 1876 - 1880
(2013/04/24)
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- Synthesis of o -(dimethylamino)aryl ketones, acridones, acridinium salts, and 1 H -indazoles by the reaction of hydrazones and arynes
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A novel, efficient route to biologically and pharmaceutically important o-(dimethylamino)aryl ketones, acridones, acridinium salts, and 1H-indazoles has been developed starting from readily available hydrazones of aldehydes and o-(trimethylsilyl)aryl triflates. The reaction proceeds through arynes under mild conditions, tolerates a wide range of functional groups, and provides the final products in good to excellent yields.
- Dubrovskiy, Anton V.,Larock, Richard C.
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p. 11232 - 11256
(2013/02/23)
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- Formation of acridones by ethylene extrusion in the reaction of arynes with β-lactams and dihydroquinolinones
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N-Unsubstituted β-lactams react with a molecule of aryne by insertion into the amide bond to form a 2,3-dihydroquinolin-4-one, which subsequently reacts with another molecule of aryne to form an acridone by extrusion of a molecule of ethylene. 2,3-Dihydroquinolin-4-ones react under the same reaction conditions to afford identical results. This is the first example of ethylene extrusion in aryne chemistry.
- Fang, Yuesi,Rogness, Donald C.,Larock, Richard C.,Shi, Feng
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experimental part
p. 6262 - 6270
(2012/09/22)
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- A simple and efficient dual optical signaling chemodosimeter for toxic Hg(II)
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10-Methylthioacridone, designated as acrithion, has been employed as an easily accessible chemodosimeter for the optical targeting of toxic Hg 2+ in buffered aqueous DMSO. The Hg2+-mediated desulfurization of the probe is translated into selective dual signaling of Hg2+ by means of color bleaching and fluorescence amplification while several other metal ions, including potentially competing Ag+, Cu2+ and Pb2+, afford no significant interferences even in excess concentrations.
- Mashraqui, Sabir H.,Tripathi, Sapna A.,Ghorpade, Sushil S.,Britto, Smita R.
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supporting information
p. 1352 - 1357
(2012/10/29)
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- Metal-free TEMPO-catalyzed oxidative C-C bond formation from Csp 3-H bonds using molecular oxygen as the oxidant
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An efficient TEMPO-catalyzed oxidative C-C bond formation with two Csp 3-H bonds using molecular oxygen as the oxidant has been developed. The novel transformation provides a new strategy for the TEMPO-O2 catalysis to construct C-C bonds. The advantages of this method include: (1) relatively mild and neutral conditions; (2) simplicity and safety of operation; (3) a stoichiometric amount of dangerous oxidants, any transition metals, additives, even solvent, is not required.
- Zhang, Bo,Cui, Yuxin,Jiao, Ning
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supporting information; experimental part
p. 4498 - 4500
(2012/06/01)
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