- A highly selective phenothiazine-based fluorescence 'turn-on' indicator based on cyanide-promoted novel protection/deprotection mechanism
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A cyanide anion (CN-)-triggered deprotection of NH-protected phenothiazine, (E)-10-(10H-phenothiazin-3′-yl)propenal, has been discovered as a novel mechanism for the highly selective fluorescence detection of CN- under ambient conditions. The present protocol may pave the way for its broad application in organic synthesis in the near future. This journal is
- Garg, Bhaskar,Ling, Yong-Chien
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- More than just a GPCR ligand: Structure-based discovery of thioridazine derivatives as Pim-1 kinase inhibitors
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Pim-1 kinase is a serine/threonine kinase which plays an important role in cell proliferation and differentiation. The Pim-1 kinase expression is elevated in leukemia and prostate cancer. Accordingly, we employed a structure-based hierarchical virtual screening approach to identify potential unknown Pim-1 kinase activity for existing drugs. Among the LOPAC library of pharmacologically active compounds, one top-ranked drug molecule thioridazine, a well-known antipsychotic agent which exerted its biological function as a dopamine receptor antagonist, showed low micromolar activity in the Pim-1 enzymatic assay. We determined the co-crystal structure of thioridazine bound with Pim-1 kinase, and defined the key elements of the pharmacophore by analyzing the structure-activity relationship of thioridazine analogues. In addition, we also assessed our pharmacophore by successfully predicting the Pim-1 activity of the selective Akt inhibitor, 10-DEBC. Our discovery of the unknown Pim-1 inhibitory activity of thioridazine and 10-DEBC might provide novel insights into understanding their molecular mechanism of action, and inspire the computation-driven multiple-target drug discovery.
- Li, Wei,Wan, Xiaobo,Zeng, Fanqi,Xie, Yuting,Wang, Yanli,Zhang, Wei,Li, Li,Huang, Niu
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- 14N/15N isotope effect on the electron transfer process between phenothiazine and its radical cation
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An appreciable equilibrium isotope effect has been observed for electron transfer from phenothiazine (PT) to the radical cation of its 15N-substituted analogue ([15N]PT+?), i.e. equation presented via electron paramagnetic resonance analysis of the mixed radical cations formed from mixing the [15N]phenothiazine radical cation hexachloroantimonate and phenothiazine in acetonitrile (K=0·77±0·10 at 25 °C), and by physical separation of the neutral phenothiazines from the radical cation salts in the equilibrium mixture (K=0·83±0·10 at 25 °C). Infrared and Raman spectra of [14N]- and [15N]phenothiazines and their radical cations were measured to assign the vibrational frequency shifts caused by the heavy-atom substitution and radical cation formation, which gave an estimate of the enthalpy change of 441·7 J mol-1 for the electron transfer process. These results reveal that 15N substitution of phenothiazine decreases appreciably the ionization potential of the molecule, making it easier to lose an electron to form the corresponding radical cation in solution.
- Wu, Long-Min,Lue, Jian-Ming,Wen, Xiao-Lin,Jia, Xue-Qing,Liu, You-Cheng,Liu, Zhong-Li
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- Carbon- and SO2-Locked Diarylnitroxides: Quantum Chemical Consideration, Synthesis, and Electrochemistry
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Selection of linkers connecting two phenyl rings as a part of molecular design of diarylnitroxides with increased kinetic stability of redox forms was performed using quantum chemical estimation of the geometry and oxidation potential values. It revealed that introduction of the carbon bridge cannot be considered as efficient “instrument” for structural tuning of the nitroxide properties since altering neither the length of the bridge nor its position results in significant changes in the oxidation potential, in contrast to a heteroatomic bridge, which makes more perturbation in the electronic structure of diarylnitroxide. To support the prediction, new SO2-bridged diarylnitroxide was synthesized and characterized using spectral and electrochemical methods. It is extremely stable in benzene solution, exhibits the maximal anodic potential value achieved for reversibly oxidized nitroxides to date (1.33 V, Ag/AgCl/KCl) and seems promising as cathodic redox active material providing maximal potential gap as compared to the previously reported compounds.
- Levitskiy, Oleg A.,Dulov, Dmitry A.,Bogdanov, Alexey V.,Magdesieva, Tatiana V.
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- Sugarcane field weeding composition
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The invention discloses a weeding composition for a sugarcane field. The weeding composition is prepared from the following components in percentage by weight: 1-60% of triclopyr, 1-30% of metrazone-dinitrate, 1-50% of a weeding substance, 20-40% of silicon dioxide sol, 1-3% of a surfactant, 5-10% of triethanolamine, 3-10% of vegetable oil and the balance of a carrier. According to the invention, a pesticide application method that various herbicides such as triclopyr, Mesotrione, ametryn, cyanazine and atrazine are mixed together is adopted, so that the prevention and control effect of the herbicide is synergistic; The herbicide controlling spectrum can be greatly expanded, the number of times of pesticide application is reduced, the pesticide effect is improved, the proper period of pesticide application is prolonged, the pesticide damage to crops is reduced, the residual activity of the herbicide is reduced, and the occurrence and development of herbicide resistance of the herbicide are delayed. The silicon dioxide sol containing antioxidant groups is used for coating the weeding components, so that the application is safer, the antioxidant activity of the weeding composition is remarkably improved, and the weeding composition is easier to store.
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Paragraph 0018; 0033; 0042; 0051; 0060; 0069; 0077
(2021/06/26)
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- Phenacyl Phenothiazinium Salt as a New Broad-Wavelength-Absorbing Photoinitiator for Cationic and Free Radical Polymerizations
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A novel broad-wavelength-absorbing photoinitiator based on phenacyl phenothiazinium hexafluroantimonate (P-PTh) possessing both phenacyl and phenothiazine chromophoric groups was reported. P-PTh absorbs light at UV, Visible and Near-IR region. Photophysical, photochemical, and computational investigations revealed that P-PTh in solution decomposes at all wavelengths by homolytic and heterolytic cleavages and generates cationic and radical species, which could efficiently initiate cationic and free radical polymerizations. It is anticipated that the photoinitiator with such wavelength flexibility may open up new pathways in curing applications of formulations of pigment systems.
- Liu, Ren,Xu, Dandan,Yagci, Yusuf,Zhang, Yuchao,Zhou, Yufan,Zhu, Yi
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supporting information
p. 16917 - 16921
(2021/06/28)
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- One-Pot Tandem Access to Phenothiazine Derivatives from Acetanilide and 2-Bromothiophenol via Rhodium-Catalyzed C-H Thiolation and Copper-Catalyzed C-N Amination
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A one-pot and step economic reaction involving Rh(III)-catalyzed C-H thiolation and relay Cu(II)-catalyzed C-N amination of acetanilide and 2-bromothiophenol is reported here, with several valuable phenothiazine products obtained. This synthesis protocol proceeds from easily starting materials, demonstrating high atom economy, broad substrate scope, and good yield. Furthermore, the directing group can be easily eliminated, and chlorpromazine is provided in a large scale; thus this synthesis protocol could be utilized to construct phenothiazine scaffolds.
- Rui, Xiyan,Wang, Chao,Si, Dongjuan,Hui, Xuechao,Li, Keting,Wen, Hongmei,Li, Wei,Liu, Jian
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p. 6622 - 6632
(2021/05/29)
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- Combined KOH/BEt3Catalyst for Selective Deaminative Hydroboration of Aromatic Carboxamides for Construction of Luminophores
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The selective catalytic C-N bond cleavage of amides into value-added amine products is a desirable but challenging transformation. Molecules containing iminodibenzyl motifs are prevalent in pharmaceutical molecules and functional materials. Here we established a combined KOH/BEt3 catalyst for deaminative hydroboration of acyl-iminodibenzyl derivatives, including nonheterocyclic carboxamides, to the corresponding amines. This novel transition-metal-free methodology was also applied to the construction of Clomipramine and luminophores.
- Li, Jinshan,Wang, Jiali,Yang, Jianguo,Yao, Wubing,Zhong, Aiguo
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supporting information
p. 8086 - 8090
(2020/11/03)
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- A NaH-promoted N-detosylation reaction of diverse p-toluenesulfonamides
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A NaH-mediated detosylation reaction of various Ts-protected indoles, azaheterocycles, anilines and dibenzylamine was reported. The method features cheap reagent, convenient operations, mild reaction conditions and broad substrate scope. Moreover, this study revealed that the loading of NaH in tosylation reactions of nitrogen-containing compounds with NaH as a base in DMA or DMF should be controlled due to the possibility of adverse detosylation.
- Sun, Wanwan,Chen, Xiaobei,Hu, Ying,Geng, Huihui,Jiang, Yuanrui,Zhou, Yuxin,Zhu, Wenjing,Hu, Min,Hu, Haohua,Wang, Xingyi,Wang, Xinli,Zhang, Shilei,Hu, Yanwei
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supporting information
(2020/10/05)
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- Synthesis of phenoxathiins and phenothiazines by aryne reactions with thiosulfonates
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Novel synthetic methods for phenoxathiins and phenothiazines by aryne reactions are disclosed. We found that phenoxathiins were efficiently prepared by the reaction between aryne intermediates and S-(2-hydroxyaryl) 4-toluenethiosulfo-nates. A synthetic method for phenothiazines was also developed by the reaction of arynes with S-(2-aminoaryl) 4-toluenethiosulfonates.
- Hosoya, Takamitsu,Kanemoto, Kazuya,Sakata, Yuki,Yoshida, Suguru
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supporting information
p. 593 - 596
(2020/05/19)
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- Efficient and regioselective synthesis of phenothiazine via ferric citrate catalyzed C-S/C-N cross-coupling
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Efficient C-S and C-N cross-coupling reactions have been developed for regioselective, scalable and environmentally benign synthesis of substituted phenothiazine derivatives. Cross-coupling reactions were demonstrated on various challenging substrates using non-toxic, highly economical, readily available ferric citrate as a catalyst to get desired product with high regioselectivity. Atom economy is the added advantage of this protocol since additional N-protection step before coupling and eventual deprotection of the same to obtain the desired product arenot required. To the best of our knowledge, this is the first report on the use of inexpensive ferric citrate as a catalyst without involving any ligand for the synthesis of regioselectively substituted phenothiazine.
- Das, Tonmoy Chitta,Quadri, Syed Aziz Imam,Farooqui, Mazahar
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supporting information
p. 16 - 24
(2019/05/04)
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- Hydride-catalyzed selectively reductive cleavage of unactivated tertiary amides using hydrosilane
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The first hydride-catalyzed reductive cleavage of various unactivated tertiary amides, including the biologically active aryl-phenazine carboxamides and the challenging non-heterocyclic carbonyl functions, using low-cost hydrosilane as a reducing reagent has been developed. The novel catalyst system exhibits high efficiency and exclusive selectivity, providing the desired amines in useful to excellent yields under mild conditions. Overall, this transition metal-free process may offer a versatile alternative to currently employed expensive reducing reagents, high-pressure hydrogen or metal systems for the selective reductive cleavage of amides.
- Yao, Wubing,Li, Rongrong,Yang, Jianguo,Hao, Feiyue
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p. 3874 - 3878
(2019/08/07)
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- Hydrogen bonding promoted simple and clean photo-induced reduction of C-X bond with isopropanol
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We herein report a simple and clean photo-induced metal-free reduction of C-X bond under an atmosphere of air at room temperature. Isopropanol is used as both the reducing reagent and solvent. Various functional groups (acids, esters, alcohols, anilines, phenols, indoles, pyridines, cyano and trifluoromethyl groups) and other heterocyclic compounds are tolerated. Different organic halides (including C-I, C-Br and C-Cl bonds) can be dehalogenated with moderate to excellent yields. Polyhalides are also reduced chemoselectively and efficiently. DFT calculation suggests a six-membered ring transition state via C-X H-O hydrogen bonding to decrease the activation energy.
- Cao, Dawei,Yan, Chaoxian,Zhou, Panpan,Zeng, Huiying,Li, Chao-Jun
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supporting information
p. 767 - 770
(2019/01/21)
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- Synthesis and microbiological evaluation of some new phenothiazine derivatives
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A new series of 4-(10-acetyl-10H-phenothiazine-3-yl)-1-phenylazetidine-2-ones (6a-g) was prepared by intermolecular cyclization of Schiff bases (5a-g) and chloroacetyl chloride in the presence of base catalyst triethylamine. The microbiological evaluations of the compounds 6a-g were performed, and the compounds 6a, 6b, 6d, 6f, and 6g showed significant antimicrobial activities.
- Sen, Sandip,De, Biplab,Mallik, Arunabha,Roy, Biswabara,Kumar, Deepak
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p. 221 - 226
(2018/09/14)
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- Synthesis of diverse phenothiazines by direct thioamination of arynes with S-(o-bromoaryl)-S-methylsulfilimines and subsequent intramolecular BuchwaldHartwig amination
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A facile method for the synthesis of diverse phenothiazines has been achieved by direct thioamination of aryne intermediates with S-(o-bromoaryl)-S-methylsulfilimines and subsequent intramolecular BuchwaldHartwig amination. Since various sulfilimines could be prepared easily by odorless copper-catalyzed ipso-thiolation of readily available o-bromoarylboronic acids followed by imination and hydrolysis, this approach enables the synthesis of a wide variety of multisubstituted phenothiazines.
- Matsuzawa, Tsubasa,Uchida, Keisuke,Yoshida, Suguru,Hosoya, Takamitsu
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p. 825 - 828
(2018/07/05)
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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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- A disubstituted amide derivatives decarbonylation hydrogenation green new method (by machine translation)
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The invention relates to a high efficiency, high selectivity of the disubstituted amide derivatives of decarbonylation hydrogenation reaction green new method. For the first time to the metallic compound triethylborane as catalyst, under mild conditions can be conveniently catalytic N, N - di-aryl substituted amide and its derivative and cheap and easy to obtain organic silicon reagent selective preparation of secondary organic amine product. Compared with the traditional method, the new method generally has the wide substrate universality, functional group compatibility outstanding, simple operation and the like. For the first time in order to realize the organic silicon reagent as reducing agent and amide compounds decarbonylation hydrogenation reaction, is the reduction of amides and derivatives thereof, in particular the organic light-emitting diodes (OLEDs) material unit - diaryl amine compound of the laboratory preparation or industrial production provides a brand-new "green" response strategies. (by machine translation)
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Paragraph 0058; 0059; 0060; 0061
(2018/02/04)
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- Iron catalytic phenothiazine synthetic method of compound
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The invention provides a synthetic method of an iron-catalyzed phenothiazine compound. The synthetic method comprises the following step: in the presence of an iron salt catalyst, a ligand and an alkali, carrying out C-S coupling, C-N coupling and deacylation reaction on raw materials (N-(2-sulfydryl phenyl) acetamide and o-dibromobenzene) at a certain temperature to obtain the phenothiazine compound. The synthetic method provided by the invention is simple in operation, mild in condition, wide in application range, relatively high in yield and short in reaction time and has a good industrial prospect.
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Paragraph 0018; 0019; 0022; 0023
(2017/04/08)
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- Transition-metal-free synthesis of phenothiazines from S-2-acetamidophenyl ethanethioate and ortho-dihaloarenes
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An efficient cesium carbonate-mediated synthesis of phenothiazine derivatives from S-2-acetamidophenyl ethanethioates and ortho-dihaloarenes has been developed. This protocol affords an efficient approach for the construction of phenothiazine derivatives without the need of transition-metal catalyst or ligand. A plausible mechanism is proposed.
- Zhou, Yue,Zeng, Qingle,Zhang, Li
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supporting information
p. 710 - 715
(2017/03/27)
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- Synthetic method and application of phenothiazine and/or derivative thereof
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The invention discloses a synthetic method for phenothiazine and/or a derivative thereof. The synthetic method comprises the following steps: mixing diphenylamine and/or a diphenylamine derivative, sulphur and a solid acid catalyst; then subjecting the obtained mixture to full reaction in a protective atmosphere; and then carrying out post-treatment so as to obtain phenothiazine and/or the derivative thereof. The invention also discloses application of phenothiazine and/or the derivative thereof. The synthetic method for phenothiazine and/or the derivative thereof is a safe, energy-saving, green and environment-friendly process which is simple to operate, mild in reaction conditions, short in reaction period, convenient to control, high in process security, low in production energy consumption and high in yield; the prepared phenothiazine and/or the derivative thereof has high purity; water, organic solvents and the like are not needed in the reaction process; post-treatment is simple; raw materials, the solid acid catalyst and the like are widely and easily available and cheap; the solid acid catalyst can be recovered and reused; and the method has low cost and is applicable to large scale production.
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Paragraph 0063
(2016/11/24)
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- Hydrodeoxygenation of sulfoxides to sulfides by a Pt and MoOx co-loaded TiO2 catalyst
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Supported metal nanoparticle catalysts were studied for the hydrodeoxygenation of sulfoxides to sulfides under solvent-free and mild conditions (50-155 °C, 1 or 7 atm H2). The catalytic activity for the model reaction of diphenyl sulfoxide depended on the type of metals, support materials and co-loaded oxides of transition metals (V, Nb, Mo, W, Re). Pt and MoOx co-loaded TiO2 (Pt-MoOx/TiO2) showed the highest activity. Pt-MoOx/TiO2 was reusable after the reaction and was effective for the reduction of various sulfoxides and showed a higher turnover number (TON) than previously reported catalysts. Using Pt-MoOx/TiO2, benzylphenylsulfone was reduced by H2 to give phenylbenzyl sulfide via benzylphenyl sulfoxides, which represented the first example of catalytic conversion of a sulfone to a sulfide by H2. Characterization studies of Pt-MoOx/TiO2 show that the surface of TiO2 is covered by small (or thin layer) Mo oxide species with exposed Mo cations as Lewis acid sites, and 4-5 nm sized Pt metal nanoparticles are supported on the Mo oxide-covered TiO2.
- Touchy, Abeda Sultana,Hakim Siddiki,Onodera, Wataru,Kon, Kenichi,Shimizu, Ken-Ichi
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p. 2554 - 2560
(2016/05/19)
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- Potassium carbonate-mediated tandem C-S and C-N coupling reaction for the synthesis of phenothiazines under transition-metal-free and ligand-free conditions
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An efficient potassium carbonate-mediated tandem C-S and C-N coupling reaction between N-(2-iodophenyl)acetamides and 2-halo-benzenethiols has been developed. This protocol affords a simple and efficient approach for the construction of phenothiazine derivatives without the need for addition of transition-metal catalyst or ligand for the first time. Furthermore, the reaction can be easily performed on a large scale.
- Wu, San,Hu, Wei-Ye,Zhang, Song-Lin
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p. 24257 - 24260
(2016/03/15)
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- A method of synthesizing phenoxthine compounds
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The invention develops a method for synthesizing phenothiazine compounds by using benzothiazole and derivatives thereof as well as 1-bromo-2-iodobenzene and derivatives thereof as raw materials and copper or copper salt/N-alkoxy-1H-pyrrolic amide system as a copper catalyst. The method is a brand-new method for synthesizing phenothiazine compounds. The method has the characteristics of low temperature, short reaction time, low solvent toxicity and wide substrate adaptability, and has wide application prospects in the aspect of preparation of medicines, pesticides and materials.
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Paragraph 0024; 0025; 0026; 0027
(2016/10/17)
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- Radical Route to 1,4-Benzothiazine Derivatives from 2-Aminobenzenethiols and Ketones under Transition-Metal-Free Conditions
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Transition-metal-free radical access to 1,4-benzothiazine derivatives from o-aminobenzenethiols is disclosed. This procedure is available for various ketones including α,β-unsaturated, cyclic, linear, and fluoroalkyl ketones to generate a number of 1,4-benzothiazines, which exist in numerous bioactive and natural molecules, rendering this protocol attractive to both synthetic and medicinal chemistry.
- Lin, Ya-mei,Lu, Guo-ping,Wang, Rong-kang,Yi, Wen-bin
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supporting information
p. 6424 - 6427
(2016/12/23)
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- Copper-Catalyzed Domino Reactions for the Synthesis of Phenothiazines
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A method for the one-pot synthesis of phenothiazines from benzothiazoles and aryl ortho-dihalides was explored. Preliminary work on the mechanism of the reaction suggested that it follows a domino process, including the hydrolysis of benzothiazoles followed by C-S coupling and C-N coupling. The low loading of the catalyst system (5 mol-% for both copper and ligand), the mild experimental conditions (90 °C, 12 h), and the use of a green reaction medium make this synthesis very attractive to academia and industry. A copper-catalyzed domino reaction consisting of the hydrolysis of benzothiazoles followed by C-S and C-N couplings for the synthesis of phenothiazines from benzothiazoles and aryl ortho-dihalides is described. The low loading of the catalyst system, mild experimental conditions, and the use of polyethylene glycol as the solvent make this synthetic approach very attractive to academia and industry.
- Huang, Manna,Huang, Dongting,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 4835 - 4839
(2015/08/03)
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- N-substituted phenothiazine derivatives: How the stability of the neutral and radical cation forms affects overcharge performance in lithium-ion batteries
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Phenothiazine and five N-substituted derivatives were evaluated as electrolyte additives for overcharge protection in LiFePO4/synthetic graphite lithium-ion batteries. We report on the stability and reactivity of both the neutral and radical-cation forms of these six compounds. While three of the compounds show extensive overcharge protection, the remaining three last for only one to a few cycles. UV/Vis studies of redox shuttle stability in the radical cation form are consistent with the overcharge performance: redox shuttles with spectra that show little change over time exhibit extensive overcharge performance, whereas those with changing spectra have limited overcharge protection. In one case, we determined that a C-N bond cleaves upon oxidation, forming the phenothiazine radical cation and leading to premature overcharge protection failure; in another case, poor solubility appears to limit protection.
- Narayana, Kishore Anand,Casselman, Matthew D.,Elliott, Corrine F.,Ergun, Selin,Parkin, Sean R.,Risko, Chad,Odom, Susan A.
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p. 1179 - 1189
(2015/04/27)
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- Method for the Synthesis of Phenothiazines via a Domino Iron-Catalyzed C-S/C-N Cross-Coupling Reaction
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An environmentally benign and efficient method has been developed for the synthesis of phenothiazines via a tandem iron-catalyzed C-S/C-N cross-coupling reaction. Some of the issues typically encountered during the synthesis of phenothiazines in the presence of palladium and copper catalysts, including poor substrate scope, long reaction times and poor regioselectivity, have been addressed using this newly developed iron-catalyzed method.
- Hu, Weiye,Zhang, Songlin
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p. 6128 - 6132
(2015/06/30)
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- A catalyst system, copper/ N -methoxy-1 H -pyrrole-2-carboxamide, for the synthesis of phenothiazines in poly(ethylene glycol)
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A copper/N-methoxy-1H-pyrrole-2-carboxamide catalyst system has been established for the preparation of phenothiazines in good yields by two routes, starting from 2-iodoanilines and 2-bromobenzenethiol and from aryl ortho-dihalides and o-aminobenzenethiols, by conducting the reaction at 90 °C in poly(ethylene glycol)-100 (PEG-100). In addition, the catalyst system was useful for promoting direct arylation of various aryl amines, aliphatic amines, and aqueous ammonia. The simple experimental operation, low loading of catalyst system together with the use of green solvent, makes it attractive for the versatile syntheses of phenothiazines and various amines.
- Huang, Manna,Hou, Jianying,Yang, Ruiqiao,Zhang, Liting,Zhu, Xinhai,Wan, Yiqian
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supporting information
p. 3356 - 3364
(2015/02/02)
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- Synthesis of phenothiazines from cyclohexanones and 2-aminobenzenethiols under transition-metal-free conditions
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A convenient method for the synthesis of various substituted phenothiazines from cyclohexanones and 2-aminobenzenethiols using molecular oxygen as hydrogen acceptor in the absence of transition-metals is described. For the first time cyclohexanones were used as coupling partners for the construction of phenothiazines.
- Liao, Yunfeng,Jiang, Pengcheng,Chen, Shanping,Xiao, Fuhong,Deng, Guo-Jun
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p. 18605 - 18608
(2013/10/21)
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- Copper oxide nanoparticles supported on graphene oxide-Catalyzed S-arylation: An efficient and ligand-free synthesis of aryl sulfides
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Copper oxide nanoparticles that are supported on graphene oxide as a catalytic system have been utilized for ligand-free and solvent-free C-S cross-coupling reactions with weak bases such as tri- ethylamine. Symmetrical/unsymmetrical aryl sulfides have been synthesized by the coupling of different aryl halides with aromatic as well as aliphatic sulfides. Surprisingly, aryl chlorides also well reacted with different types of sulfides in the presence of dimethyl sulfoxide and cesium carbonate. Besides, this catalytic system is suitable for the synthesis of phenothiazines via cascade C-S and C-N cross-coupling of ortho-dihalides and ortho-aminobenzothiazoles. In addition, this alternative approach is extremely useful for the synthesis of a variety of symmetrical diaryl sulfides by using thiourea as a sulfur source that is devoid of the foul smell of thiols. Indeed, the calculated E-factor value of our present protocol is 2.52. Furthermore, this protocol is particularly attractive as an environmentally benign and practical method for the synthesis of different aryl sulfides. Moreover, the heterogeneous catalytic system described in this process represents not only a greener approach but retains its significant activity for up to six catalytic cycles.
- Kamal, Ahmed,Srinivasulu, Vunnam,Murty,Shankaraiah, Nagula,Nagesh, Narayana,Reddy, T. Srinivasa,Subba Rao
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p. 2297 - 2307
(2013/10/01)
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- Synthesis of phenothiazines via ligand-free CuI-catalyzed cascade C-S and C-N coupling of aryl ortho-dihalides and ortho-aminobenzenethiols
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A ligand-free CuI-catalyzed cascade C-S and C-N cross coupling of (hetero)aryl ortho-dihalides and ortho-aminobenzenethiols has been developed, and various phenothiazines were synthesized with excellent regioselectivity. A possible mechanism is proposed for the cascade coupling.
- Dai, Chuan,Sun, Xiaofei,Tu, Xingzhao,Wu, Li,Zhan, Dan,Zeng, Qingle
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experimental part
p. 5367 - 5369
(2012/06/04)
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- Ligand-free copper-catalyzed synthesis of diaryl thioethers from aryl halides and thioacetamide
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Diaryl thioethers can be prepared via a copper-catalyzed cross-coupling between aryl halides and thioacetamide using Cs2CO3 as a base and DMSO-H2O as a solvent at 120 °C. Georg Thieme Verlag Stuttgart - New York.
- Tao, Chuanzhou,Lv, Aifeng,Zhao, Nan,Yang, Shuai,Liu, Xiaolang,Zhou, Jian,Liu, Weiwei,Zhao, Jing
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supporting information; experimental part
p. 134 - 138
(2011/03/22)
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- Assembly of substituted phenothiazines by a sequentially controlled CuI/L-proline-catalyzed cascade C-S and C-N bond formation
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(Chemical equation presented) In the pro-line of fire: A general and efficient cascade reaction approach to substituted phenothiazines, which relies on controlled sequential Cul/L-prolinecatalyzed C-S and C-N bond formations, is described. DMSO = dimethylsulfoxide.
- Dawei, Ma.,Geng, Qian,Zhang, Hui,Jiang, Yongwen
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supporting information; experimental part
p. 1291 - 1294
(2010/05/17)
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- NOVEL AROMATIC COMPOUND AND POLYARYLENE COPOLYMER HAVING NITROGEN-CONTAINING HETEROCYCLE INCLUDING SULFONIC ACID GROUP IN SIDE CHAIN
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Provided is a solid polymer electrolyte having increased heat resistance and high proton conductivity and a proton conductive membrane composed of the electrolyte. Also provided is a copolymer having a sulfonic acid group. The copolymer includes a repeating unit represented by Formula (1): (in the formula, Y denotes at least one kind of structure selected from the group consisting of —CO—, —SO2—, —SO—, —CONH—, —COO—, —(CF2)l— (l is an integer of 1 to 10), and —C(CF3)2—; W denotes at least one kind of structure selected from the group consisting of a direct bond, —CO—, —SO2—, —SO—, —CONH—, —COO—, —(CF2)l— (l is an integer of 1 to 10), —C(CF3)2—, —O—, and —S—; Z denotes a direct bond or at least one kind of structure selected from the group consisting of —(CH2)l—(l is an integer of 1 to 10), —C(CH3)2—, —O—, —S—, —CO—, and —SO2—; R30 denotes a nitrogen-containing aromatic ring having a substituent represented by —SO3H, —O(CH2)hSO3H, or —O(CF2)hSO3H (h is an integer of 1 to 12); p is an integer of 0 to 10; q is an integer of 0 to 10; r is an integer of 1 to 5; and k is an integer of 0 to 4).
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- Photodegradation of 2-chloro substituted phenothiazines in alcohols
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The mechanisms that trigger the phototoxic response to 2- chlorophenothiazine derivatives are still unknown. To better understand the relationship between the molecular structure of halogenated phenothiazines and their phototoxic activity, their photophysics and photochemistry were studied in several alcohols. The photodestruction quantum yields were determined under anaerobic conditions using monochromatic light (313 nm). Absorption- and emission-spectroscopy, 1H- and 13C-NMR and GC-MS were used to characterize the photoproducts and reference compounds. An electron transfer mechanism had been previously proposed by Bunce et al. (J. Med. Chem. 22, 202-204) to explain the large difference between the photodestruction quantum yield of 2-chlorpromazine (φ = 0.46) and 2-chlorphenothiazine (φ = 0.20). According to these authors, the alkylamino chain transfers an electron to the phenothiazine moiety. Our results demonstrate that this mechanism is incorrect, because the photodestruction quantum yields of all chlorinated derivatives of this study are the same under the same conditions of solvent and irradiation wavelength. The quantum yield has no dependence on the 10-substituent, but it depends on the solvent. The percentage of each photoproduct, on the other hand, strongly depends on that substituent, but not very much on the solvent. Finally, it is demonstrated that the phototoxic effect of chlorinated phenothiazines is not related to the photodechlorination, although both processes share the same transient.
- Garcia, Carmelo,Pinero, Luis,Oyola, Rolando,Arce, Rafael
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body text
p. 160 - 170
(2009/04/10)
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- Heterocyclization of N-propenyl-substituted phenothiazines and phenoxazines using electrophiles in an anhydrous medium
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10-Propenylphenothiazine reacts with a catalytic amount of BF 3·Et2O in dry ethyl acetate via intramolecular heterocyclization of an intermediate dimeric cation to give mainly 1-ethyl-2-methyl-3-(phenothiazin-10-yl)-2,3-dihydro-1H-pyrido[3,2,1-k,l] phenothiazine and a minor product through fission of phenothiazine which is 1-ethyl-2-methyl-1H-pyrido[3,2,1-k,l]phenothiazine. Under similar conditions 10-propenylphenoxazine gave an oligomer (degree of polymerization 4.4) and the minor product 1-ethyl-2-methyl-1H-pyrido[3,2,1-k,l]phenoxazine likely formed similarly to the phenothiazine analog from the corresponding product of intramolecular heterocyclization (the latter not being observed in the reaction mixture).
- Sirotkina,Khlebnikov,Napilkova
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experimental part
p. 1505 - 1509
(2009/07/04)
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- The singlet oxygen oxidation of chlorpromazine and some phenothiazine derivatives. Products and reaction mechanisms
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(Chemical Equation Presented) A kinetic and product study of the reactions of chlorpromazine 1, N-methylphenothiazine 2, and N-ethylphenothiazine 3 with singlet oxygen was carried out in MeOH and MeCN. 1 undergoes exclusive side-chain cleavage, whereas the reactions of 2 and 3, in MeOH, afforded only the corresponding sulfoxides. A mechanism for the reaction of 1 is proposed where the first step involves an interaction between singlet oxygen and the side-chain dimethylamino nitrogen. This explains why no side-chain cleavage is observed for 2 and 3.
- Baciocchi, Enrico,Del Giacco, Tiziana,Lanzalunga, Osvaldo,Lapi, Andrea,Raponi, Daniele
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p. 5912 - 5915
(2008/02/10)
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- Bridged charge transport materials having a central sulfur atom linkage
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The present invention provides organophotoreceptors comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:(a) a charge transport material having the formula ???where Z1 and Z2 comprise, each independently, a bond, a vinyl group, a - CR1=N-NR2- group, or a -CR3=N-N=CR4- group; ???Y1 and Y2 comprise, each independently, an aromatic group; ???X1 and X2 are, each independently, a linking group; ???W1 and W2 are, each independently, a -(CH2)n- group or a -(CH2)n-1-C(=O)-group, where n is an integer between 1 and 10, inclusive; ???Q1 and Q2 are, each independently, O, S, or NR; and ???R1, R2, R3, R4, R, R', and R" comprise, each independently, H, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, a heterocyclic group, or an aromatic group; and(b) a charge generating compound. Corresponding electrophotographic apparatuses and imaging methods are described, as are charge transport materials and methods of preparing a bridged charge transport material.
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- Novel derivatives and analogues of galanthamin
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New compounds of general formula I 1
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- Piperadinyl-substituted pyridylalkane, alkene and alkine carboxamides
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The invention relates to new piperidinyl-substituted pyridyl carboxamides of the general formula (I), wherein the structure element E has meanings (E1) or (E2) and whereby the heterocyclic ring can optionally have a double bond. These substances have especially high cytostatic activities and pronounced immunosuppressive properties which make them suitable for therapeutic treatment in broad tumor spectrum.
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- Alcoholysis of 2,2-dichloropropyl derivatives of carbazole, phenothiazine, and phenoxazine
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Reactions of 9-(2,2-dichlorocyclopropyl)carbazole, 10-(2,2-dichlorocyclopropyl)phenothiazine, and 10-(2,2-dichlorocyclopropyl)phenoxazine with alcohols in the system t-BuOK-DMSO yield the corresponding N-(1-alkoxy-2-propynyl) derivatives. Hydrolysis of 9-(1-methoxy-2-propynyl)carbazole and 10-(1-methoxy-2-propynyl)phenothiazine in 60% aqueous dioxane in the presence of sulfuric acid gives the corresponding heterocyclic amine and 2-propynal. ? Deceased.
- Anfinogenov,Okhtemenko,Khlebnikov,Ogorodnikov
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p. 112 - 115
(2007/10/03)
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- Investigation on the reaction of 2-chloro-10H-phenothiazine under aryne forming conditions
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The reaction of 2-chloro-10H-phenothiazine with a variety of arylacetonitriles and α-cyano-o-tolunitrile in the presence of LTMP gave 2- arylmethyl-10H-phenothiathiazine-1-carbonitriles and 13-amino-14H- naphtho[2,3-b]phenothiazine-8-carbonitrile, respectively. Interestingly, LTMP effectively trapped 10-lithio-1,2-didehydrophenothiazine to give 2-(2,2,6,6- tetramethylpiperidin-1-yl)-10H-phenothiazine.
- Wang, Anlai,Zhang, Hongming,Biehl, Edward R.
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p. 373 - 380
(2007/10/03)
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- Microwave-assisted phenothiazines preparation by thionation of diphenylamines
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A preparation in 'dry media' of phenothiazine derivatives by thionation of diphenylamines using microwave-activation is presented. This method allowed the preparation of 2,4,6,8-tetra-tert-butyl-10H-phenothiazine 2e, the first 2,4,6,8-tetra-substituted derivative of this heterocycle, practically inaccessible by other thionation procedure.
- Filip, Sorin V.,Silberg, Ioan A.,Surducan, Emanoil,Vlassa, Mircea,Surducan, Vasile
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p. 337 - 345
(2007/10/03)
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- N-Hetarylethylenes. XII. Influence of the Substituent at the Double Bond and the Nature of the Heterocycle on the Acid Hydrolysis of N-Alkenyl Derivatives of Phenoxazine, Phenothiazine, and Carbazole
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The kinetics of acid hydrolysis of N-vinylphenothiazine, N-vinylphenoxazine, N-isopropenylcarbazole, N-isopropenylphenoxazine, N-(1-phenylvinyl)phenothiazine, and N-(1-phenylvinyl)phenoxazine in 60% aqueous dioxane have been studied. The activation parameters and kinetic isotope effects (kH/kD = 3.1-5.2) indicate that the hydrolysis follows ASE2 mechanism with proton transfer from the medium to substrate in the rate-determining stage. The results are compared with the previous data for N-alkenyl derivatives of carbazole, phenothiazine, and phenoxazine. The existence of isokinetic relationship in the coordinates In k (313 K) - In k (334 K) provides an additional evidence for the similarity of the mechanisms of hydrolysis of these compounds. 10-Phenothiazinyl substituent exerts the strongest activating effect on the double bond. In the series of compounds with the same substituents, the rate of hydrolysis increases in going from cis to trans and then to geminal arrangement of the substituents at the double bond.
- Anfinogenov,Okhtemenko,Khlebnikov,Filimonov
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p. 1027 - 1032
(2007/10/03)
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- Pyrimidine derivatives for labeled binding partners
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A compound having the structure: STR1 wherein R1 is an oligonucleotide; a is 1 and b is 0; A is C or CH; X is S, O, NH or NCH2 R6 ; Z is taken together with A to form an aryl ring structure comprising 6 ring atoms wherein the aryl ring carbon atoms are unsubstituted with other than H or at least 1 nonbridging ring carbon atom is substituted with R6 or =O; R6 is independently H, C1 -C6 alkyl, C2 -C6 alkenyl, C2 -C6 alkynyl, NO2, N(R3)2, C N or halo, or an R6 is taken together with an adjacent Z group R6 to complete a phenyl ring; and R3 is a protecting group or H; and tautomers, solvates and salts thereof.
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- Binding compentent oligomers containing unsaturated 3',5' and 2',5' linkages
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Oligonucleotide analogs having one or more substitute linkages of the formula 2'/3'--S--CH2 --CH=5' or 2'/3'--O--CH2 --CH=5' between adjacent nucleomonomers are disclosed. The substitute linkage replace the usual phosphodiester linkage found in unmodified nucleic acids. The oligonucleotide analogs are easy to synthesize, stable in vivo, resistant to endogenous nucleases and are able to hybridize to target nucleic acid sequences in a sequence specific manner.
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- Chemical and electrochemical oxidation of phenothiazine
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The oxidation of phenothiazine in dilute solutions of sulphuric acid leads to the corresponding cation radical.Using a potentiometric technique, a pKa value of 5.72 +/-0.05 was determined for phenothiazine.The kinetics has been studied and participation of both protonated and unprotonated oxidant in the oxidation reaction has been confirmed.Using a voltammetric technique with a rotating disk electrode, the anodic oxidation of phenothiazine was shown to be a one-electron diffusion-controlled process.A quantum chemical explanation was found for the direction of phenothiazine protonation and the absence of a dimerization stage oxidation.
- Pankratov, Alexei N.,Uchaeva, Inna M.,Stepanov, Alexander N.
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p. 674 - 677
(2007/10/02)
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- Reactivity of Diselenide Dication Salt, 1,5-Diselenoniabicyclooctane Bis(hexafluorophosphate) toward Aromatics. A New Mode of Aromatic Substitution and Redox Reaction
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A new diselenide dication salt, 1,5-diselenoniabicyclooctane bis(hexafluorophosphate) was reacted with several aromatics to afford either the substitution or redox products.The reaction mode depends on the oxidation potential of aromatics.
- Fujihara, Hisashi,Nakamura, Akiko,Akaishi, Ryouichi,Furukawa, Naomichi
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p. 393 - 396
(2007/10/02)
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