- Synthesis of N-Aryl-3,5-dichloro-4H-1,2,6-thiadiazin-4-imines from 3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine
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Condensation of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine with a range of anilines gave 22 N-aryl-3,5-dichloro-4H-1,2,6-thiadiazin-4-imines in 43-96% yields. The scope and limitations of this condensation are briefly investigated. Furthermore, mono- and bis-substitution of the C-3 and C-5 chlorines of 3,5-dichloro-N-phenyl-4H-1,2,6-thiadiazin-4-imine by amine and alkoxide nucleophiles is explored. Finally, Stille coupling chemistry is used to prepare several N-phenyl-3,5-diaryl-4H-1,2,6-thiadiazin-4-imines.
- Kalogirou, Andreas S.,Manoli, Maria,Koutentis, Panayiotis A.
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- Anilinium dihydrogen phosphate
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The triclinic structure of the title compound, C6H 8N+·H2PO4-, with three symmetry-independent structural units (Z′ = 3), is formed of separate organic and inorganic layers alternating along the b axis. The building blocks of the inorganic layer are deformed H2PO4 tetra-hedra assembled into infinite ladders by short and hence strong hydrogen bonds. The anilinium cations forming the organic layer are not hydrogen bonded to one another, but they are anchored by four N-H...O crosslinks between the dihydrogen phosphate chains of adjacent ladders. Two H atoms of each-NH3 group then form one normal and one bifurcated N-H...O hydrogen bond to the P=O oxygens of two tetra-hedra of one chain, while the third H atom is hydrogen bonded to the nearest O atom of an adjacent chain belonging to another dihydrogen phosphate ladder.
- Kaman, Ondej,Smrcok, Lubomir,Gyepes, Robert,Havlicek, David
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- Effect of Solvents on Acid-Catalyzed Claisen Amino Rearrangement in N-(1-Methyl-2-butenyl)aniline
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Abstract: The effect solvents have on the processes of rearrangement and elimination in N-(1-methyl-2-butenyl)aniline (I) in the presence of HCl is studied. It is shown that the dependence of the rearrangement and elimination rate constants of (I) · HCl on the nature of solvents are described perfectly by the Koppel–Palm equation, which considers both nonspecific and specific solvation. The inhibitory effect of solvent nucleophilicity is explained by the complexation between (I) · HCl and solvent molecules. Analysis of the (I) · HCl conversion products obtained in a mixed solvent (m-toluidine + nitrobenzene) demonstrates the intermolecular transfer of the allyl moiety, confirming the formation of allyl cations in the Claisen amino rearrangement.
- Abdrakhmanov,Sharafutdinov,Mustafin,Zimin, Yu. S.,Daminev
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- Cyclometalated Ruthenium(II) NHC Complexes with Imidazo[1,5-a]pyridine-Based (C^C*) Ligands – Synthesis and Characterization
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We present the synthesis and characterization of cyclometalated ruthenium(II) NHC complexes with phenyl-substituted imidazo[1,5-a]pyridine C^C* ligands. The corresponding p-cymene complexes can be reacted with bipyridine to form bisheteroleptic ruthenium(II) dyes. The compounds have been characterized by one- and two-dimensional 1H/13C NMR spectroscopy, elemental analysis, cyclic voltammetry, infrared spectroscopy, as well as solid-state structure (X-ray) analysis.
- Schleicher, David,Tronnier, Alexander,Soellner, Johannes,Strassner, Thomas
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- Iron-catalyzed selective reduction of nitro compounds to amines
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An efficient reduction of the nitro group with a catalytic amount of Fe(acac)3 and TMDS in THF at 60 °C affording the corresponding amine is described.
- Pehlivan, Leyla,Métay, Estelle,Laval, Stéphane,Dayoub, Wissam,Demonchaux, Patrice,Mignani, Gérard,Lemaire, Marc
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- Semi-organic salts of aniline with inorganic acids: Prospective materials for the second harmonic generation
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Three novel inorganic salts of aniline with sulfuric and selenic acids were prepared and characterized by X-ray structural analysis. Anilinium(1+) selenate, (C6H5NH3 +) 2SeO4 2-, and anilinium sulfate, (C 6H5NH3 +)2SO 4 2-, crystallize in the monoclinic space group C2. The crystal structures are based on hydrogen bonded layers of alternating anilinium cations and inorganic anions. Anilinium(1+) selenate dihydrate, (C 6H5NH3 +)2SeO 4 2-·2H2O, crystallizes in the monoclinic space group C2/c. The crystal structure is formed by a network of alternating anilinium cations, selenate anions and water molecules connected by a system of intermolecular hydrogen bonds. The FTIR and Raman spectra of all the compounds have been recorded and discussed as well as their crystal structures. According to the DSC curves and temperature dependence of lattice parameters, anilinium sulfate exhibits phase transitions at 217 and 182 K. The appropriate changes of vibrational spectra were also recorded during cooling of the sample especially in the N-H stretching and sulfate antisymmetric stretching (ν3 SO4 2-) spectral regions. The quantitative measurements of the second harmonic generation at 1064 nm were performed using powdered samples of anilinium sulfate, anilinium chloride and anilinium selenate, and the relative efficiencies deff = 0.05dKDP, deff = 2.33dKDP and deff = 0.05dKDP (KDP; i.e. KH 2PO4) have been observed, respectively.
- Matulková, Irena,Cihelka, Jaroslav,Fejfarová, Karla,Duek, Michal,Pojarová, Michaela,Vank, Pemysl,Kroupa, Jan,ála, Michal,Krupková, Radmila,Němec, Ivan
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- Synthesis and experimental and theoretical characterization of m-fluorosulfinylaniline
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The synthesis of m-fluorosulfinylaniline together with a tentative assignment of the vibrational, NMR and mass spectra are reported. Quantum chemical calculations predict two stable conformers, with very similar energies, both of which possess in the liquid phase syn structure of the -NSO moiety (syn of the SO double bond relative to the C-N single bond). Both conformers belong to the CS symmetry group and differ by the relative orientation of the fluorine atom and the NSO group. However, the FT-IR, FT-Raman and NMR spectra do not allow a distinction between these two conformers. The experimentally observed spectral data (FT-IR, FT-Raman, 1H and 13C and GC-mass spectrometry) of the title compound are compared with the spectral data obtained by quantum chemical calculations and the gauge including atomic orbital (GIAO) method (DFT/B3LYP approximation using 6-311+G(df), 6-311++G(df,pd) and cc-pVTZ basis sets). Moreover, natural bond orbital (NBO) analysis is applied for studying the stability of the molecule upon charge delocalization in order to provide an explanation of its electronic properties.
- Páez Jerez, Ana L.,Chemes, Doly M.,Cutin, Edgardo H.,Oberhammer, Heinz,Robles, Norma L.
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- Amine Catalysis of the Hydrolysis of Trifluoroacetanilide
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Only hydrolysis products could be isolated from the reaction of trifluoroacetanilide I with aqueous n-butylamine buffer at pH 10.5.Kinetic studies of the decomposition of trifluoroacetanilide I in aqueous morpholine, n-butylamine, piperidine and trimethylamine buffers were also conducted.The most reasonable scheme for the reaction mechanism, compatible with all data, is presented in Scheme I and involves the general-base-catalyzed decomposition of the intermediate III which can be formed by hydroxide ion or water addition to I.Utilizing the constants of Table I, eq 6 is capable of predicting observed rate constants with an error of l ess than 9 percent (see Tables II an III).Some variation in values for these constants for trimethylamine buffers is observed and attributed to possible activity changes for the solutions.Deuterium isotope rate effects were determined for these constants in morpholine buffers.A value of k1H2O/k2D2O of 0.39 was obtained and may indicate the presence of a third pathway for the generation of III (eq 9), involving the hydration of the anion II.A value of k4H2O/k4D2O of 1.65 and a Broensted β value of 0.23 for k4 are interpreted to indicate general-base catalysis by the amine buffer.The low values for these quantities are indicative of a transition state involving an early proton transfer.General-base catalysis of proton transfer for the k4 step is also indicated by the fact that trimethylamine appears to behave mechanistically, similar to the other amines used.The value of 8.8 obtained for k3H2O/k3D2O clearly shows proton transfer to be occuring in this step as well.The results of this study thus support those suggested previously in that the hydrolysis of I undergoes a change in rate-determining step in mild alkaline aqueous solutions.This occurs because of the combination of the poor leaving ability of the anilinium ion and acyl activation present in the substrate trifluoroacetanilide.
- Huffman, Robert W.
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- Solvent-freeN-Boc deprotection byex situgeneration of hydrogen chloride gas
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An efficient, scalable and sustainable method for the quantitative deprotection of thetert-butyl carbamate (N-Boc) protecting group is described, using down to near-stoichiometric amounts of hydrogen chloride gas in solvent-free conditions. We demonstrate theex situgeneration of hydrogen chloride gas from sodium chloride and sulfuric acid in a two-chamber reactor, introducing a straightforward method for controlled and stoichiometric release of HCl gas. The solvent-free conditions allow deprotection of a wide variety ofN-Boc derivatives to obtain the hydrochloride salts in quantitative yields. The procedure obviates the need for any work-up or purification steps providing an uncomplicated green alternative to standard methods. Due to the solvent-free, anhydrous conditions, this method shows high tolerance towards acid sensitive functional groups and furnishes expanded functional group orthogonality.
- De Borggraeve, Wim M.,Gilles, Philippe,Van Mileghem, Seger,Verschueren, Rik H.
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p. 5782 - 5787
(2021/07/12)
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- Direct Amidation of Esters by Ball Milling**
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The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
- Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
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supporting information
p. 21868 - 21874
(2021/09/02)
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- Selective and Additive-Free Hydrogenation of Nitroarenes Mediated by a DMSO-Tagged Molecular Cobalt Corrole Catalyst
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We report on the first cobalt corrole that effectively mediates the homogeneous hydrogenation of structurally diverse nitroarenes to afford the corresponding amines. The given catalyst is easily assembled prior to use from 4-tert-butylbenzaldehyde and pyrrole followed by metalation of the resulting corrole macrocycle with cobalt(II) acetate. The thus-prepared complex is self-contained in that the hydrogenation protocol is free from the requirement for adding any auxiliary reagent to elicit the catalytic activity of the applied metal complex. Moreover, a containment system is not required for the assembly of the hydrogenation reaction set-up as both the autoclave and the reaction vessels are readily charged under a regular laboratory atmosphere.
- Sch?fberger, Wolfgang,Timelthaler, Daniel,Topf, Christoph
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supporting information
p. 2114 - 2120
(2021/07/22)
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- Cobalt-Catalyzed Deoxygenative Hydroboration of Nitro Compounds and Applications to One-Pot Synthesis of Aldimines and Amides
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The commercially available and bench-stable Co(acac)2 ligated with bis[(2-diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h?1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N-borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one-pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.
- Gudun, Kristina A.,Hayrapetyan, Davit,Khalimon, Andrey Y.,Segizbayev, Medet,Slamova, Ainur,Zakarina, Raikhan
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- Synthesis, characterization and electropolymerization of functionalized organic salt–anilinium saccharinate and electrochemically controlled release of saccharinate anions
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In this work, a novel functionalized organic salt ? anilinium saccharinate ([HANI][Sac]) was synthesized by the ion exchange method, and its composition and properties were characterized by 1H NMR, 13C NMR, ESI/MS and TG-DSC techniques. [HANI][Sac] can be used as both monomer and supporting electrolyte for efficient electrosynthesis of polyaniline (PANI) in acetonitrile. The obtained PANI has hierarchical porous structure and its doping degree with saccharinate anion ([Sac]-) is as high as 33.5%. The resulting [Sac]--doped-PANI (PANI-[Sac]) can be used as an electrochemically controlled drug delivery system. The in vitro release kinetics of [Sac]- under different potential stimuli conditions showed that, at a given time, the release rate of [Sac]- and its release percentage (ratio of the amount released to that loaded) increase with the negative shift of the applied potential. The amount of [Sac]- loaded and/or released can also be regulated by varying the charge for PANI electropolymerization. The present work provides a new strategy for the facile construction of conducting polymer-based electrochemically controlled drug release system.
- Shen, Lanbo,Gao, Na,Huang, Xirong
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- METHOD FOR PREPARING AN AMINE HYDROCHLORIDE SUSPENSION
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The invention relates to a method for preparing a suspension of a hydrochloride of an organic amine, comprising the following steps of (i) initially charging at least one organic solvent in a reaction vessel to form a liquid level, (ii) adding hydrogen chloride, (iii) adding the organic amine, wherein the organic amine is added below the liquid level present in the reaction vessel and steps (ii) and (iii) are at least partly carried out simultaneously. Furthermore, the present invention also relates to a method wherein the suspension obtained after step (iii) is reacted in a step (iv) with phosgene to obtain the organic isocyanate corresponding to the organic amine used, to the corresponding organic isocyanate and to the use of the organic isocyanate for producing polyisocyanates.
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Paragraph 0093
(2020/12/25)
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- Preparation and application methods for ionic liquid inhibitor used for water-based drilling fluid
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The invention discloses preparation and application methods for an ionic liquid inhibitor used for a water-based drilling fluid. The preparation method comprises the following steps: (1) allowing a cation raw material to react with concentrated acid so as to generate corresponding salt, wherein the cation raw material is one selected from the group consisting of alkylamine, phenol and aniline, andthe concentrated acid is one selected from the group consisting of concentrated hydrochloric acid and concentrated phosphoric acid; and (2) allowing the salt to react with an anion raw material in asolvent so as to obtain a target ionic liquid inhibitor, wherein the anion raw material is one selected from the group consisting of AlCl3, FeCl3 and ZnCl2, or a salt containing one group selected from the group consisting of RCOO- and SbF6-. The ionic liquid inhibitor provided by the invention has good compatibility with a drilling fluid and excellent inhibition performance; under the same conditions, the recovery rate of the ionic liquid inhibitor is 39% higher compared with clear water and 13% higher compared with KCl slurry having a concentration of 5%; and the ionic liquid inhibitor is close to an amine-based inhibitor and free of the problem of generation of foam.
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Paragraph 0019-0020
(2019/03/26)
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- Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution
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Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.
- Lardy, Samuel W.,Luong, Kristine C.,Schmidt, Valerie A.
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supporting information
p. 15267 - 15271
(2019/12/11)
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- Reversible capture and release of aromatic amines by vicinal tricarbonyl compound
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In this paper, we report reversible capture and release of aromatic amines by diphenylpropanetrione (DPPT). Addition of aromatic amines to the central carbonyl group occurred readily at ambient temperature to provide the aromatic amine adducts of DPPT (DPPT-aromatic amines), which has a hemiaminal structure. On the other hand, washing a solution of DPPT-aromatic amine with diluted hydrochloric acid (HCl) enabled successful recovery of DPPT to demonstrate the reversible nature of this system.
- Yuki, Tatsuya,Yonekawa, Morio,Furusho, Yoshio,Sei, Yoshihisa,Tomita, Ikuyoshi,Endo, Takeshi
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p. 2868 - 2873
(2016/05/19)
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- High graphite N content in nitrogen-doped graphene as an efficient metal-free catalyst for reduction of nitroarenes in water
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Four kinds of nitrogen-doped graphene (NG) as metal-free catalysts are synthesized by a one-step hydrothermal reaction and thermal treatment using graphene oxide and urea as precursors. It is found that the reduction of nitroarenes can be catalyzed by using a low NG loading and a small amount of NaBH4 in water with high yield. The type of nitrogen species in NG has an important effect on the reduction reaction. The NG catalyst containing the most graphite N shows the highest catalytic activity during reduction of nitroarenes, which demonstrates that the graphite N of NG plays a key role in impelling this reaction. The reaction mechanism is proven by GC-MS experiments, and DFT calculations reveal the reasons for the graphite N showing better catalytic activity. It is worth noting that no dehalogenation phenomenon occurs during the reduction process for halogen-substituted nitroarenes in contrast to conventional metal catalysts. In addition, the NG catalyst can be simply recycled and efficiently used for eight consecutive runs with no significant decrease in activity.
- Yang, Fan,Chi, Cheng,Wang, Chunxia,Wang, Ying,Li, Yongfeng
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supporting information
p. 4254 - 4262
(2016/08/02)
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- Direct cycle between co-product and reactant: An approach to improve the atom economy and its application in the synthesis and protection of primary amines
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Two important goals of green chemistry are to maximize the efficiency of reactants and to minimize the production of waste. In this study, a novel approach to improve the atom economy of a chemical process was developed by incorporating a direct cycle between a co-product and a reactant of the same reaction. To demonstrate this concept, recoverable 3,4-diphenylmaleic anhydride (1) was designed and used for the atom-economical synthesis of aliphatic primary amines from aqueous ammonia. In each individual cycle, only ammonia and alkyl halide were consumed, and 1 was recovered in nearly a quantitative yield. In this approach for developing atom-economical protecting agents, 1 showed good performance as a recoverable protecting agent for primary amines. The broad substrate scope, good tolerance to various reaction conditions, and high reaction and recovery rates make 1 a valuable complement to conventional primary amine protecting agents.
- Guan, Qi,Jiang, Mingyang,Wu, Junhui,Zhai, Yanpeng,Wu, Yue,Bao, Kai,Zhang, Weige
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supporting information
p. 5794 - 5799
(2016/11/06)
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- Metal-Free Intermolecular Coupling of Arenes with Secondary Amides: Chemoselective Synthesis of Aromatic Ketimines and Ketones, and N-Deacylation of Secondary Amides
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The direct transformation of common secondary amides into aromatic ketimines and aromatic ketones with C-C bond formation is described. The reaction can also be used for N-deacylation of secondary amides to release amines. This method consists of in situ amide activation with triflic anhydride and intermolecular capture of the resulting highly electrophilic nitrilium intermediate with an arene. The reaction is applicable to various kinds of secondary amides (electrophiles), but only electron-rich and moderately electron-rich arenes can be used as nucleophiles. Thanks to the use of bench stable arenes instead of reactive and basic organometallics as nucleophiles, the reaction proceeded with high chemoselectivity at the secondary amido group in the presence of a series of sensitive functional groups such as aldehyde, ketone, ester, cyano, nitro, and tertiary amido groups. The reaction can be viewed as a Friedel-Crafts-type reaction using secondary amides as acylating agents or as an intermolecular version of the Bischler-Napieralski reaction.
- Huang, Pei-Qiang,Huang, Ying-Hong,Xiao, Kai-Jiong
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p. 9020 - 9027
(2016/10/17)
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- High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation
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We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with a Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on a larger scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers at the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).
- Abdelhamid, Muhammad E.,Murdoch, Timothy,Greaves, Tamar L.,O'Mullane, Anthony P.,Snook, Graeme A.
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p. 17967 - 17972
(2015/07/07)
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- The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
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The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
- Desai, Salil Dileep,Kirsch, Lee E.
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p. 471 - 488
(2015/06/30)
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- PRODUCTION METHOD FOR COMPOUND COMPRISING AMINO GROUP AND/OR HYDROXYL GROUP
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Disclosed is a method for producing a compound having an amino group and/or a hydroxyl group from a substrate compound having an atomic group containing CO or CS by eliminating said atomic group. The substrate compound having an atomic group containing CO or CS (for example, an amide, a carbamate, or the like) is allowed to react with a compound expressed by formula (I) below, at a temperature of 120°C or lower, preferably in the presence of an ammonium salt, to eliminate said atomic group containing CO or CS. In formula (I) A may not be present, and in a case where A is present, A represents an alkyl group having 1 to 6 carbon atoms. ????????H2N-A-NH2?????(I)
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Paragraph 0105
(2015/01/18)
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- Continuous-flow hydrogenation of olefins and nitrobenzenes catalyzed by platinum nanoparticles dispersed in an amphiphilic polymer
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A method for the flow hydrogenation of olefins and nitrobenzenes in a continuous-flow reactor containing platinum nanoparticles dispersed on an amphiphilic polystyrene-poly(ethylene glycol) resin (ARP-Pt) was developed. The hydrogenation of olefins and nitrobenzenes was completed within 31 seconds in the continuous-flow system containing ARP-Pt, giving the corresponding hydrogenated products in up to 99% yield with good chemoselectivity. Moreover, long-term (63-70 h) continuous-flow hydrogenation of styrene and nitrobenzene produced more than ten grams of ethylbenzene and aniline, respectively, without significant loss of catalytic activity. The flow hydrogenation system provides an efficient and practical method for the chemoselective reduction of olefins and nitrobenzenes. This journal is
- Osako, Takao,Torii, Kaoru,Tazawa, Aya,Uozumi, Yasuhiro
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p. 45760 - 45766
(2015/06/08)
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- Mild N-deacylation of secondary amides by alkylation with organocerium reagents
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Secondary amides are a class of highly stable compounds serving as versatile starting materials, intermediates and directing groups (amido groups) in organic synthesis. The direct deacylation of secondary amides to release amines is an important transformation in organic synthesis. Here, we report a protocol for the deacylation of secondary amides and isolation of amines. The method is based on the activation of amides with Tf2O, followed by addition of organocerium reagents, and acidic work-up. The reaction proceeded under mild conditions and afforded the corresponding amines, isolated as their hydrochloride salts, in good yields. In combination with the C-H activation functionalization methodology, the method is applicable to the functionalization of aniline as well as conversion of carboxylic derivatives to functionalized ketones.
- Wang, Ai-E.,Chang, Zong,Liu, Yong-Peng,Huang, Pei-Qiang
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supporting information
p. 1055 - 1058
(2015/09/01)
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- Spectroscopic studies on gallic acid and its azo derivatives and their iron(III) complexes
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Azo gallic derivatives and their iron(III) complexes were synthesized and characterized. The stereochemistry and the mode of bonding of the complexes were achieved based on elemental analysis, UV-Vis and IR. The thermal behaviors of the complexes were studied. The effect of pH on the electronic absorption spectra of gallic acid and its azo derivatives are discussed. Different spectroscopic methods (molar ratio, straight line method, continuous variation, slope ratio and successive method) are applied for determination of stoichiometry and pK values for the complex formation of gallic acid with iron(III) in aqueous media. Iron(III) complexes of gallic acid is formed with different ratio: 1:1, 1:2, 1:3 and 1:4 (M:L).
- Masoud, Mamdouh S.,Ali, Alaa E.,Haggag, Sawsan S.,Nasr, Nessma M.
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p. 505 - 511
(2013/12/04)
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- Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)3 and NaBH4
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An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions. This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield). Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.
- MacNair, Alistair J.,Tran, Ming-Ming,Nelson, Jennifer E.,Sloan, G. Usherwood,Ironmonger, Alan,Thomas, Stephen P.
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supporting information
p. 5082 - 5088
(2014/07/08)
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- Selective monomethylation of primary amines with simple electrophiles
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Direct monomethylation of primary amines with methyl triflate was achieved with high selectivity (up to 96%). The key point of this single methyl transfer stems from the use of HFIP as the solvent that interferes with amines and avoids overmethylation.
- Lebleu, Thomas,Ma, Xiaolu,Maddaluno, Jacques,Legros, Julien
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supporting information
p. 1836 - 1838
(2014/02/14)
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- Phenylimino-2H-chromen-3-carboxamide derivatives as novel small molecule inhibitors of β-secretase (BACE1)
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The inhibition of β secretase (BACE1) is potentially important approach to treatment of Alzheimer disease (AD). A novel series of 4-bromophenyl piperazine derivatives coupled to the phenylimino-2H-chromen-3-carboxamide scaffold were investigated as BACE1 inhibitors in this study. Docking study suggested that the phenyl-imino group of the scaffold establishes favorable π-π stacking interaction with side chain of Phe108 of flap pocket. Some of the docking proposed derivatives were synthesized and evaluated for BACE1 inhibitory activity using a FRET-based assay. High BACE1 inhibitory activities were observed from derivatives containing fused heteroaromtic groups attached through the aliphatic linkage to the N4-piperazine moiety, which may be attributed to the engagement of effective interactions with S1-S′1 sub-pocket residues. Of the most potent compounds, 9e displayed an IC 50 value for BACE1 of 98 nM. Some of these derivatives demonstrated good inhibitory activity on Aβ production in N2a-APPswe cells at 5 and 10 μM. These compounds might be considered as promising BACE1 inhibitory agents that could lower Aβ production in AD.
- Edraki, Najmeh,Firuzi, Omidreza,Foroumadi, Alireza,Miri, Ramin,Madadkar-Sobhani, Armin,Khoshneviszadeh, Mehdi,Shafiee, Abbas
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p. 2396 - 2412
(2013/05/21)
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- 1,2,3-Trimethoxypropane, a glycerol-based solvent with low toxicity: New utilization for the reduction of nitrile, nitro, ester, and acid functional groups with TMDS and a metal catalyst
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1,2,3-Trimethoxypropane (1,2,3-TMP) was prepared from glycerol in one step in good yield and selectivity by phase transfer catalysis. According to OECD guidelines, a toxicity study was realized for this compound. It revealed that 1,2,3-TMP has a low acute toxicity, no skin sensitization, no mutagenicity and no ecotoxicity in an aquatic environment. This compound was also used as a solvent for the reduction of organic functions using either aluminium hydride or 1,1,3,3-tetramethyldisiloxane (TMDS) as a benign hydride source. In particular, a new process for the reduction of nitriles to amines in 2-MeTHF and in 1,2,3-TMP was developed, using TMDS in combination with copper triflate (Cu(OTf)2).
- Sutter, Marc,Pehlivan, Leyla,Lafon, Romain,Dayoub, Wissam,Raoul, Yann,Metay, Estelle,Lemaire, Marc
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supporting information
p. 3020 - 3026
(2013/11/06)
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- A facile and efficient method for the selective deacylation of N-arylacetamides and 2-chloro-Narylacetamides catalyzed by SOCl2
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Thionyl chloride efficiently and selectively promoted the deacylation of N-arylacetamides and 2-chloro-N-arylacetamides, under anhydrous conditions, without effecting the ester group, aminosulfonyl group, or benzyloxyamide group. This method, which has been successfully applied to a variety of substrates including different N-arylacetamides and 2-chloro-N-arylacetamides, has the attractive advantages of inexpensive reagents, satisfactory selectivity, excellent yields, short reaction time, and convenient workup. This new method can probably be used to selectively deacylate between aromatic amides and alkyl amides. Springer Science+Business Media B.V. 2011.
- Wang, Gong-Bao,Wang, Lin-Fa,Li, Chao-Zhang,Sun, Jing,Zhou, Guang-Ming,Yang, Da-Cheng
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- Fluorescence ratiometry and fluorescence lifetime imaging: Using a single molecular sensor for dual mode imaging of cellular viscosity
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Intracellular viscosity strongly influences transportation of mass and signal, interactions between the biomacromolecules, and diffusion of reactive metabolites in live cells. Fluorescent molecular rotors are recently developed reagents used to determine the viscosity in solutions or biological fluid. Due to the complexity of live cells, it is important to carry out the viscosity determinations in multimode for high reliability and accuracy. The first molecular rotor (RY3) capable of dual mode fluorescence imaging (ratiometry imaging and fluorescence lifetime imaging) of intracellular viscosity is reported. RY3 is a pentamethine cyanine dye substituted at the central (meso-) position with an aldehyde group (CHO). In nonviscous media, rotation of the CHO group gives rise to internal conversion by a nonradiative process. The restraining of rotation in viscous or low-temperature media results in strong fluorescence (6-fold increase) and lengthens the fluorescence lifetime (from 200 to 1450 ps). The specially designed molecular sensor has two absorption maxima (λabs 400 and 613 nm in ethanol) and two emission maxima (in blue, λem 456 nm and red, 650 nm in ethanol). However it is only the red emission which is markedly sensitive to viscosity or temperature changes, providing a ratiometric response (12-fold) as well as a large pseudo-Stokes shift (250 nm). A mechanism is proposed, based on quantum chemical calculations and 1H NMR spectra at low-temperature. Inside cells the viscosity changes, showing some regional differences, can be clearly observed by both ratiometry imaging and fluorescence lifetime imaging (FLIM). Although living cells are complex the correlation observed between the two imaging procedures offers the possibility of previously unavailable reliability and accuracy when determining intracellular viscosity.
- Peng, Xiaojun,Yang, Zhigang,Wang, Jingyun,Fan, Jiangli,He, Yanxia,Song, Fengling,Wang, Bingshuai,Sun, Shiguo,Qu, Junle,Qi, Jing,Yan, Meng
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supporting information; experimental part
p. 6626 - 6635
(2011/06/27)
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- Synthesis, insecticidal activities, and molecular docking studies of 1,5-disubstituted-1,3,5-hexahydrotriazine-2-(N-nitro)imines
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Figure represented. A series of novel neonicotinoids analogs were designed by modifying the pharmacophore of imidacloprid to 1,3,5-hexahydrotriazine conjugated to nitroimine (iNNO2) and introducing the phenyl or arylmethyl at the 5-position, and their insecticidal activities were evaluated. Introducing a heterocyclic methyl at 5-position increased the insecticidal activities, whereas other phenyl, phenylmethyl or phenylethyl substituents were unfavorable to activities. Molecular docking study was also performed to clarify the interactions of the most potent analog 1-((6-chloropyridin-3-yl)methyl)-5- (3-pyridylmethyl)-1,3,5-hexahydrotriazine-2-(N-nitro) imine (7s) with the target nicotinic acetylcholine receptor, which explained the structure-activity relationships observed in vitro, and revealed further possibilities for insecticide development.
- Sun, Chuan-Wen,Wang, Hai-Feng,Zhu, Jun,Yang, Ding-Rong,Jin, Jia,Xing, Jia-Hua
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experimental part
p. 829 - 835
(2011/09/16)
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- Alternative method for the reduction of aromatic nitro to amine using TMDS-iron catalyst system
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The system 1,1,3,3-tetramethyldisiloxane (TMDS)/Fe(acac)3 is reported here as a new method to obtain amines from aromatic nitro compounds. Amines are synthetized in a straightforward step and are isolated as hydrochloride salts with good to excellent yields. This system has shown a good selectivity toward aryl-chloride, aryl-bromide, ester, carboxylic acid, and cyano groups. The reduction of alkylnitro compounds was unfortunately not possible using this method, only a mixture of mono and dialkylated amine was obtained.
- Pehlivan, Leyla,Métay, Estelle,Laval, Stéphane,Dayoub, Wissam,Demonchaux, Patrice,Mignani, Gérard,Lemaire, Marc
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experimental part
p. 1971 - 1976
(2011/04/22)
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- Kinetics and mechanism of the anilinolysis of dicyclohexyl phosphinic chloride in acetonitrile
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The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; cHex2P(=O)Cl] with substituted anilines (XC6H 4NH2) and deuterated anilines (XC6H 4ND2) are investigated kinetically in acetonitrile at 60.0 °C. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal (kH/kD > 1; max kH/kDt = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse (kH/kDt H/k Dt = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted SN2 mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.
- Ul Hoque, Md. Ehtesham,Lee, Hai Whang
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experimental part
p. 1997 - 2002
(2012/02/01)
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- Selective N-alkylation of amines with alcohols by using non-metal-based acid-base cooperative catalysis
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Learning to cooperate: A straightforward method for the selective N-mono- and dialkylation of amines with alcohols by means of non-metal-based catalysis promoted by TAPC is reported (see scheme). Selectivity of the N-mono- and dialkylation, substrate scope and functional-group tolerance are highlighted with respect to each amine (1° and 2°; aromatic and aliphatic) and alcohol (1°, 2° and 3°; benzylic and aliphatic) component. Copyright
- Du, Ya,Oishi, Shunsuke,Saito, Susumu
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supporting information; experimental part
p. 12262 - 12267
(2011/11/29)
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- A PROCESS FOR PREPARATION OF POLYMETHYLENE POLYPHENYL POLYAMINE
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The present invention provides a method of preparing polymethylene-polyphenyl-polyamine (briefly referred to as polyamine, DAM), in which a high gravity rotating bed is used as the mixing reactor of formaldehyde and aniline hydrochloride, the mixing solution of aniline hydrochloride and circulation solution and the formaldehyde are fed into the high gravity rotating bed reactor proportionally to carry out mixing and condensation reaction under a condition of a very high gravity; the materials leaving the high gravity rotating bed reactor is introduced into a stirred vessel to proceed with the pre-condensation reaction and obtain a condensation solution; and the process steps of heating, molecular rearrangement, neutralization, water washing and purification, etc. are completed to obtain the refined DAM. With the method according to the present invention, the main by-products is obviously reduced in the condensation process, the phenomenon of deposit attaching to the inner walls of circulation pipes and heat exchange and blockage are prevented in the condensation process, the impurity content is low in the refined DAM, and the subsequent product MDI has a lighter color, the product quality is stable and may be improved to a certain extent.
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Page/Page column 6
(2010/02/17)
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- EPR and ENDOR spectroscopic study of the reactions of aromatic azides with gallium trichloride
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The reactions of gallium trichloride with phenyl and deuterio-phenyl azides, as well as with 4-methoxyphenyl azide and deuterium isotopomers, were examined by product analysis, CW EPR spectroscopy and pulsed ENDOR spectroscopy. The products included the corresponding anilines together with 4-aminodiphenylamine type dimers, and polyanilines. Complex CW EPR spectra of the radical cations of the dimers [ArNHC6H4NH 2]+ and trimers [ArNHC6H4NHC 6H4NH2]+ were obtained. These EPR spectra were analysed with the help of data from the deuterium-substituted analogues as well as the pulse Davies ENDOR spectra. DFT computations of the radical cations provided corroborating evidence and suggested the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed.
- Bencivenni, Giorgio,Cesari, Riccardo,Nanni, Daniele,El Mkami, Hassane,Walton, John C.
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supporting information; experimental part
p. 5097 - 5104
(2010/12/24)
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- Highly chemo- and regioselective reduction of aromatic nitro compounds using the system silane/oxo-rhenium complexes
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(Chemical Equation Presented) The reduction of aromatic nitro compounds to the corresponding amines with silanes catalyzed by high valent oxo-rhenium complexes is reported. The catalytic systems PhMe2SiH/ReIO 2(PPh3)2 (5 mol %) and PhMe2SiH/ ReOCl3(PPh3)2 (5 mol %) reduced efficiently a series of aromatic nitro compounds in the presence of a wide range of functional groups such as ester, halo, amide, sulfone, lactone, and benzyl. This methodology also allowed the regioselective reduction of dinitrobenzenes to the corresponding nitroanilines and the reduction of an aromatic nitro group in presence of an aliphatic nitro group. 2009 American Chemical Society.
- De Noronha, Rita G.,Romao, Carlos C.,Fernandes, Ana C.
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supporting information; experimental part
p. 6960 - 6964
(2010/03/03)
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- Concurrent primary and secondary deuterium kinetic isotope effects in anilinolysis of O-aryl methyl phosphonochloridothioates
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The nucleophilic substitution reactions of Y-O-aryl methyl phosphonochloridothioates with substituted anilines (XC6H 4NH2) and deuterated anilines (XC6H 4ND2) are investigated kinetically in acetonitrile at 55.0°C. The Hammett and Bronsted plots for substituent (X) variations in the nucleophiles are biphasic concave downwards with a break region between X = H and 4-Cl. The deuterium kinetic isotope effects (DKIEs) are primary normal (kH/kD = 1.03-1.30) for stronger nucleophiles (X = 4-MeO, 4-Me and H), and extremely large secondary inverse (kH/kD = 0.367-0.567) for weaker nucleophiles (X = 4-Cl, 3-Cl and 3-NO2). The cross-interaction constants are negative (ρXY(H) = -0.95 and ρXY(D) = -1.11) for stronger nucleophiles, while positive (ρXY(H) = +0.77 and ρXY(D) = +0.21) for weaker nucleophiles. These kinetic results indicate that the mechanism changes from a concerted process involving frontside nucleophilic attack for stronger nucleophiles to a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving backside attack for weaker nucleophiles. A hydrogen-bonded, four-center-type transition state (TS) is suggested for a frontside attack, while a trigonal bipyramidal pentacoordinate TS is suggested for a backside attack. The unusually small DKIEs, as small as or equal to 0.4, for weaker nucleophiles seem to be ascribed to severe steric congestion in the TS.
- Ul Hoque, Md. Ehtesham,Guha, Arun Kanti,Kim, Chan Kyung,Lee, Bon-Su,Lee, Hai Whang
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experimental part
p. 2919 - 2925
(2011/02/28)
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- Kinetics and mechanism of the aminolysis of dimethyl and methyl phenyl phosphinic chlorides with anilines
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The reactions of dimethyl phosphinic chloride (1) and methyl phenyl phosphinic chloride (2) with X-anilines have been studied kinetically in acetonitrile at 15.0 and 55.0 °C, respectively. The deuterium kinetic isotope effects (KIEs) involving deuterated aniline nucleophiles (XC 6H4ND2) are also reported for the same reactions. The obtained KIEs for 1 are secondary inverse (kH/k D=0.703-0.899H/kD=1.62-2.10> 1). A concerted mechanism involving predominantly backside nucleophilic attack is proposed for the anilinolysis of 1. A concerted mechanism involving predominantly frontside attack via a hydrogen-bonded four-center-type transition state is proposed for the anilinolysis of 2. The degree of steric hindrance is the major factor that determines both the reactivity of the phosphinates and the direction of the nucleophilic attack on the phosphinates. Copyright
- Dey, Nilay Kumar,Hoque, Md. Ehtesham Ul,Kim, Chan Kyung,Lee, Bon-Su,Lee, Hai Whang
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experimental part
p. 425 - 430
(2010/04/30)
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- Synthesis of 3-alkoxymethylcoumarin from 3-cyanochromene via a novel intermediate 2-phenylimino-3-alkoxymethylchromene
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(Chemical Equation Presented) In this paper a concise, efficient, and environmentally benign method for the synthesis of 3-alkoxymethylcoumarin is described. From the reaction of 3-cyanochromene with an alkoxide and arylamine in THF, (Z)-2-phenylimino-3-a
- Tsai, Jui-Chi,Li, Sie-Rong,Chiang, Michael Y.,Chen, Lian-Yeu,Chen, Po-Yuan,Lo, Yi-Fang,Wang, Chen-Hao,Lin, Chun-Nan,Wang, Eng-Chi
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supporting information; experimental part
p. 8798 - 8801
(2010/03/01)
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- PROCESS FOR PREPARING DIAMINODIPHENYLMETHANES
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Process for preparing diamino diphenyl methane and poly-(diamino diphenyl methane) comprising reacting aniline with formaldehyde in the presence of hydrogen chloride added in the gaseous form wherein the aniline contains 0.1 to 7 wt%, preferably 2 to 5 wt% of a protic chemical, preferably water.
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(2008/06/13)
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- Platelet ADP receptor inhibitors
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Novel compounds of formulae (I) to (VIII), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I) to (VIII), or a pharmaceutically acceptable salt thereof.
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- Synthesis of primary amines by the electrophilic amination of Grignard reagents with 1,3-dioxolan-2-one O-sulfonyloxime
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(Chemical equation presented) Primary amines are prepared by the electrophilic amination of Grignard reagents with 4,4,5,5-tetramethyl-1,3- dioxolan-2-one O-phenylsulfonyloxime and the acidic hydrolysis of the resulting imines.
- Kitamura, Mitsuru,Suga, Takahiro,Chiba, Shunsuke,Narasaka, Koichi
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p. 4619 - 4621
(2007/10/03)
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- Synthesis of primary amines and N-methylamines by the electrophilic amination of Grignard reagents with 2-imidazolidinone O-sulfonyloxime
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2-Imidazolidinone O-sulfonyloxime reacts with various aryl and alkyl Grignard reagents as an electrophilic amination reagent, giving N-alkylated imines. The resulting imines are transformed to primary amines and N-methyl secondary amines by hydrolysis with CsOH and LiAlH4 reduction, respectively.
- Kitamura, Mitsuru,Chiba, Shunsuke,Narasaka, Koichi
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p. 1063 - 1070
(2007/10/03)
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- Naphthylsalicylanilides as antimicrobial and antiinflammatory agents
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The present invention discloses novel naphthylsalicylanilides of the general formula wherein W is a substituted or unsubstituted naphthyl ring. The substitution on W includes replacing one or more —H with —OH, alkyl, O-alkyl, branched alkyl, or cycloalkyl, containing 1-6 carbon atoms or combinations thereof. Y is a substituted or unsubstituted phenyl ring or substituted or unsubstituted naphthyl ring. The substitution for Y includes replacement of one or more —H atoms with CN, CF3, NO2, methoxy, benzoyl, phenoxy, phenoxymethyl or combinations thereof. These compounds are useful as antibacterial against gram negative and gram positive bacteria and as antiinflammatory agents.
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Page column 7
(2008/06/13)
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- Negative photoresist composition using polymer having 1,2-diol structure and process for forming pattern using the same
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It is an object of the present invention to provide a negative photoresist composition for lithography, using short-wavelength light such as ArF excimer laser beam as a light source. The negative photoresist composition of the present invention is a negative photoresist composition comprising at least a polymer having a unit represented by the general formula (1) a crosslinking agent and a photo-acid generating agent, and the crosslinking agent is capable of crosslinking the polymer in the presence of an acid catalyst, whereby the polymer is insolubilized in a developer. Since the negative resist composition of the present invention is insolubilized in the developer by an action of an acid produced from the photo-acid generating agent at the exposed portion, a negative pattern can be obtained. Since the polymer has not a benzene ring, unlike a base polymer of a conventional negative resist, the polymer has high transparency to ArF excimer laser beam and also has high etching resistance because of its bridged alicyclic group.
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- NAPHTHYLSALICYLANILIDES AS ANTIMICROBIAL AND ANTIINFLAMMATORY AGENTS
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The present invention discloses novel naphthylsalicylanilides of the general formula wherein W is a substituted or unsubstituted naphthyl ring. The substitution on W includes replacing one or more —H with —OH, alkyl, O-alkyl, branched alkyl, or cycloalkyl, containing 1-6 carbon atoms or combinations thereof. Y is a substituted or unsubstituted phenyl ring or substituted or unsubstituted naphthyl ring. The substitution for Y includes replacement of one or more —H atoms with CN, CF3, NO2, methoxy, benzoyl, phenoxy, phenoxymethyl or combinations thereof. These compounds are useful as antibacterial against gram negative and gram positive bacteria and as antiinflammatory agents.
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