- Aluminium Oxide Supported on SBA-15 Molecular Sieves as Potential Lewis Acid Catalysts for Epoxide Ring Opening Using Aniline
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Abstract: A series of aluminium oxide (Al2O3)-supported SBA-15 molecular sieves were prepared using a one-step wet-impregnation method. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared spectroscopy and ammonia TPD were used to investigate the structures and chemical natures of the surface-bound species. The FT-IR studies of metal-impregnated SBA-15 materials revealed strong covalent interaction of Al2O3 on SBA-15 materials with strong Lewis acidic properties, evident from ammonia-TPD studies. The metal oxide-supported SBA-15 catalysts are active for epoxide ring opening with aniline at room temperature, and showed remarkably high stability and selectivity towards mono-alkylated products (about 86%) viz., 1-(phenylamino)propan-2-ol and 2-(phenylamino)propan-1-ol. The catalytic activities remained intact after several recycles. The observed activities and selectivities were compared with other metal oxide-loaded SBA-15 catalysts obtained by similar preparation methods. Graphical Abstract: Aluminium oxide supported SBA-15 molecular sieves were prepared using a one-step wet-impregnation method. The materials showed strong Lewis acidic sites and promising catalytic activity for epoxide ring opening with aniline at room temperature. [Figure not available: see fulltext.]
- Yadav, Rekha,Muralidhar, Akhila,Shamna,Aghila,Gurrala, Lakshmiprasad,Sakthivel, Ayyamperumal
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- Mesoporous Zr-Beta zeolites prepared by a post-synthetic strategy as a robust Lewis acid catalyst for the ring-opening aminolysis of epoxides
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Mesoporous zirconosilicate, stannosilicate, and titanosilicate with the BEA structure framework have been prepared from the commercially available Beta zeolite via acid-alkaline treatments and subsequent dry impregnation of appropriate organometallic prec
- Tang, Bo,Dai, Weili,Sun, Xiaoming,Wu, Guangjun,Guan, Naijia,Hunger, Michael,Li, Landong
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- In situ preparation, characterization, and catalytic application of various amine functionalized microporous SAPO-37
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A series of monoamine, diamine, and aniline functionalized microporous silicoaluminophosphate molecular sieves (SAPO-37) was prepared by introduction of organo-silane ligand during hydrothermal synthesis. The template was selectively removed by the solvent extraction method in the presence of sodium nitrate salt. The effective removal of the template was evident from FT-IR, and 13C MAS-NMR studies. The retention of high crystallinity was evident from the powder XRD pattern of the template-removed functionalized SAPO-37 materials. The functionalized materials showed a high surface area in the range of 200-300 m2g-1 with a pore volume of 0.2-0.4 cm3g-1. The functionalized SAPO-37 was found to be a potential catalyst for epoxide ring opening with aniline.
- Ahmed, Maqsood,Yadav, Rekha,Sakthivel, Ayyamperumal
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Read Online
- Post-synthesis of Zr-MOR as a robust solid acid catalyst for the ring-opening aminolysis of epoxides
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Zirconosilicate with the MOR topology (Zr-MOR) was successfully prepared using a two-step post-synthesis strategy from pre-dealumination of a H-MOR zeolite and subsequent dry impregnation of Cp2ZrCl2. The incorporated Zr species main
- Tang, Bo,Song, Wei-Chao,Li, Sheng-Yang,Yang, En-Cui,Zhao, Xiao-Jun
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p. 13503 - 13511
(2018/08/21)
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- Highly Enantioselective Hydrogenation of Amides via Dynamic Kinetic Resolution Under Low Pressure and Room Temperature
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High-throughput screening and lab-scale optimization were combined to develop the catalytic system trans-RuCl2((S,S)-skewphos)((R,R)-dpen), 2-PrONa, and 2-PrOH. This system hydrogenates functionalized α-phenoxy and related amides at room temperature under 4 atm H2 pressure to give chiral alcohols with up to 99% yield and in greater than 99% enantiomeric excess via dynamic kinetic resolution.
- Rasu, Loorthuraja,John, Jeremy M.,Stephenson, Elanna,Endean, Riley,Kalapugama, Suneth,Clément, Roxanne,Bergens, Steven H.
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supporting information
p. 3065 - 3071
(2017/03/11)
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- A solvent free method for preparation of β-amino alcohols by ring opening of epoxides with amines using MCM-22 as a catalyst
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β-amino alcohols were synthesized at room temperature employing microporous MCM-22 zeolite as catalyst in an eco-friendly manner without using solvent. The zeolite MCM-22 showed promising activity for the conversion of primary and secondary amines into β-amino alcohols under mild reaction conditions. The catalytic activity remains intact for three recycles.
- Baskaran, Thangaraj,Joshi, Akanksha,Kamalakar, Gunda,Sakthivel, Ayyamperumal
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- Catalyst-free regioselective ring opening of epoxides with aromatic amines in water and solvent-free conditions
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Without using any catalysts, a variety of epoxides undergo ring-opening by aromatic amines to afford the corresponding 1,2-amino alcohols in high to excellent yields with good regioselectivity in the presence of water as solvent and under solvent-free con
- Ziyaei-Halimehjani,Gholami,Saidi
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- Highly efficient nanocrystalline zirconosilicate catalysts for the aminolysis, alcoholysis, and hydroamination reactions
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Nanocrystalline zirconosilicates and titanosilicates with MFI framework structure were hydrothermally synthesized by the addition of organosilanes in the synthesis composition of conventional zirconosilicate and titanosilicate materials. Materials were characterized by a complementary combination of X-ray diffraction, nitrogen sorption, scanning/transmission electron microscopy (S/TEM), ammonia temperature-programmed desorption (TPD), Fourier transform infrared (FT-IR) spectroscopy, and ultraviolet-visible (UV-vis) spectroscopic investigations. Nanocrystalline zeolite catalysts of the present study are reusable. They exhibit significantly higher catalytic activities in aminolysis and alcoholysis compared with the hitherto known catalysts. A range of β-amino alcohols/β-alkoxy alcohols with high regioselectivity were synthesized using zirconosilicates. Application of these materials was also extended in the synthesis of aminoesters by the hydroamination reaction of methyl acrylates and amines. Structure activity relationship was explained based on acidity measurements, reactivity of amines/alcohols, and adsorption of reactants on catalysts.
- Kore, Rajkumar,Srivastava, Rajendra,Satpati, Biswarup
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p. 2891 - 2904
(2014/01/06)
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- Synthesis and structure of an air-stable organobismuth triflate complex and its use as a high-efficiency catalyst for the ring opening of epoxides in aqueous media with aromatic amines
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An air-stable organobismuth triflate complex with a novel 5,6,7,12-tetrahydrodibenzo[c,f]-[1,5]oxabismocine framework was synthesized and characterized by spectroscopic and single-crystal X-ray diffraction techniques. The organobismuth framework is cationic, and the complex shows relatively strong Lewis acidity (0.8 o ≤ 3.3). It was found to exhibit high catalytic activity towards the ring-opening reaction of epoxides in aqueous media with aromatic amines at room temperature. This catalyst shows good stability, recyclability and reusability. The catalytic system affords a simple and efficient method for the synthesis of β-amino alcohols.
- Tan, Nianyuan,Yin, Shuangfeng,Li, Yuefang,Qiu, Renhua,Meng, Zhengong,Song, Xingxing,Luo, Shenglian,Au, Chak-Tong,Wong, Wai-Yeung
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experimental part
p. 1579 - 1583
(2011/05/14)
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- The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: The catalytic effect of phosphonium-based ionic liquids
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At T ≥ 140 °C, different primary aromatic amines (pX-C 6H4NH2; X = H, OCH3, CH3, Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C 6H4N(CH2CH(R)OH)2; R = H, CH 3] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by 13C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.
- Selva, Maurizio,Fabris, Massimo,Lucchini, Vittorio,Perosa, Alvise,Noe, Marco
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experimental part
p. 5187 - 5198
(2010/12/25)
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- Reduction of 2-chloro-N-phenylpropanamide and 2-methyl-N-phenylaziridine with lithium aluminium hydride
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The reduction of 2-chloro-N-phenylpropanamide with LiAlH4 has been re-examined. In contrast to previous findings, we obtain in almost equal quantities two amines from this reaction, namely N-propylaniline and the rearranged product N-isopropylaniline. 2-Methyl-N-phenylaziridine is an intermediate in the reduction and can be isolated from reactions with less LiAlH4. Reduction of 2-methyl-N-phenylaziridine itself proceeds non-regioselectively to provide a mixture of propyl- and isopropylanilines. Formation of the amines by reduction of the aziridine is much slower than formation by reduction of the 2-chloropropanamide, which indicates that Lewis acid catalysis (by aluminium chlorohydrides) facilitates the reduction of the aziridine. In addition, Lewis acid catalysis increases the relative yield of the propylamine product. The reduction of 2-chloro-N-phenylpropanamide furnishes 2-phenylamino-1-propanol as a by-product, rather than the previously proposed 1-phenylamino-2-propanol. The Royal Society of Chemistry.
- Vilhelmsen, Mie Hojer,stergaard, Lars Frosig,Nielsen, Mogens Brondsted,Hammerum, Steen
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experimental part
p. 1773 - 1778
(2008/10/09)
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- A new one-pot, four-component synthesis of 1,2-amino alcohols: TiCl 3/t-BuOOH-mediated radical hydroxymethylation of imines
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(Chemical Equation Presented) An amine, an aldehyde, and methanol can be readily assembled in one pot under very mild conditions through a free-radical multicomponent reaction by using an aqueous acidic TiCl3/t-BuOOH system to afford 1,2-amino alcohols in fair to excellent yields.
- Clerici, Angelo,Ghilardi, Alessandra,Pastori, Nadia,Punta, Carlo,Porta, Ombretta
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supporting information; experimental part
p. 5063 - 5066
(2009/05/31)
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- Highly efficient ring opening reactions of epoxides with deactivated aromatic amines catalyzed by heteropoly acids in water
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Heteropoly acid was found to be an effective and efficient catalyst for the ring opening reaction of epoxides with various aromatic amines to produce the corresponding β-amino alcohols in moderate to excellent yields in water. This method provides a new and efficient protocol in terms of mild reaction conditions, clean reaction profiles, small quantity of catalyst, and simple work-up procedure.
- Azizi, Najmedin,Saidi, Mohammad R.
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p. 888 - 891
(2007/10/03)
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- Activation and reactivity of epoxides on solid acid catalysts
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The aminolysis of epoxides over novel solid catalysts (Broensted-acidic SBA-15 functionalized with propylsulfonic acid and Lewis-acidic Ti-MCM-41) is reported. The acidic properties of these catalysts were determined by FTIR spectroscopy and temperature-programmed desorption of pyridine and NH3, respectively. The mesoporous solid acids of the present study are reusable and exhibit significantly higher catalytic activities than known catalysts for opening of the oxirane ring with nitrogen (aromatic and aliphatic amines)-containing and oxygen (alcohols)-containing nucleophiles. A range of β-amino alcohols with high regioselectivity and stereoselectivity were synthesized. Adsorption studies as well as the sigmoid shape of the conversion-versus-time plots show that the epoxide and amine compete for adsorption on the acidic sites ({single bond}SO3H or Ti4+) on the catalyst surface. Epoxide adsorption and activation on acid sites are the more critical processes. Catalytic activity decreases with increasing basicity of the amines and/or the alcohol, as well as the dielectric constant of the solvent.
- Saikia,Satyarthi,Srinivas,Ratnasamy
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p. 148 - 160
(2008/09/18)
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- Synthesis of β-amino alcohols from aromatic amines and alkylene carbonates using Na-Y zeolite catalyst
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A simple, efficient, and environmentally benign methodology for the synthesis of β-amino alcohols from aromatic amines and alkylene carbonates in the presence of the highly active and reusable solid base catalyst Na-Y zeolite is demonstrated. Georg Thieme Verlag Stuttgart.
- Shivarkar, Anandkumar B.,Gupte, Sunil P.,Chaudhari, Raghunath V.
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p. 1374 - 1378
(2007/10/03)
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- Lewis acids catalyzed ring-opening reactions of methylenecyclopropanes and epoxides in supercritical carbon dioxide or modified supercritical carbon dioxide with perfluorocarbon
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The reactions of methylenecyclopropanes (MCPs) and epoxides with alcohols and aromatic amines can be carried out in supercritical carbon dioxide (scCO2) or modified scCO2 with perfluorocarbon which offer a way to synthesize various alcohols, amino-alcohols, homoallylic ethers, and amines under an environmentally benign condition.
- Shi, Min,Chen, Yu
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p. 219 - 227
(2007/10/03)
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- Synthesis of derivatives of 2-(indol-1-yl)propionic acids
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We have developed a method for synthesis of N-substituted derivatives of indole from N-phenylalanine, including Fischer cyclization of the corresponding arylalkylhydrazones. The starting hydrazines were obtained by reduction of the corresponding nitrosami
- Kurkin,Golantsov,Karchava,Yurovskaya
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- Mechanistic investigation of an anomalous anchimeric assistance in the acid hydrolysis of the ether linkage. Part 4
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Kinetic investigation of the acid hydrolysis of N-(methoxyprop-2-yl)benzanilide (1) was performed in 8.84 M HCl and/or DCl at 75.1°C. The formation of 2-(N-phenylamino)propanol (4) was explained and the mechanism, involving an initial ether cleavage anchimerically assisted by the amide group, was clarified. The overall process evolves through three steps involving two intermediates. The rate constants of the individual processes have been determined by UV and 1H NMR spectroscopic techniques.
- Arcelli, Antonio,Cecchi, Romina,Porzi, Gianni,Rinaldi, Samuele,Sandri, Sergio
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p. 4039 - 4043
(2007/10/03)
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- Kinetics and mechanism of thermal gas-phase elimination of α-substituted carboxylic acids: Role of relative basicity of α-substituents and acidity of incipient proton
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2-Phenoxypropanoic acid together with five of its aryl derivatives, its phenylthio and its N-phenylamino analogues were pyrolyzed at 494-566 K. The reactions were homogeneous, polar and free from catalytic and radical pathways, and obeyed a first-order rate equation. The limits of the Arrhenius log A (s-1) and E (kJ mol-1) values obtained for these reactions averaged 11.98 ± 1.71 and 158.1 ± 17.4, respectively. Analysis of the pyrolysates showed the elimination products to be carbon monoxide, acetaldehyde and the corresponding phenol, thiophenol or aniline compounds. The pyrolysis of 2-phenoxy- and 2-(N-phenylamino)-1-propanol was also investigated over the temperature range 638-792 K. The kinetic results and products analysis lend support to a reaction pathway involving a five-membered cyclic polar transition state. Copyright
- Al-Awadi, Nouria A.,Kaul, Kamini,El-Dusouqui, Osman M. E.
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p. 499 - 504
(2007/10/03)
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- The Stereochemical Investigation of 3-Aryl-.4-methyl-1,2,3-oxathiazolidine 2-oxides Using NMR
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The title compounds were prepared by the reaction of the corresponding N-2-hydroxyisopropylanilines with thionyl chloride in the presence of triethylamine, and their pmr and cmr spectra were examined.On the basis of the chemical shifts due to the γ and δ-effects, the stereochemical structures are discussed.
- Nishiyama, Tomihiro,Takahama, Yasumitsu,Yamada, Fukiko
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p. 195 - 197
(2007/10/02)
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- β-Substituted Organoalkaline Tri- and Tetra-anions; Preparation, Stability, and Reactivity
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New β,γ-, β,β'-disubstituted organometallic trianions of the type C(Y)C(Y')C(8) and C(Y)CC(Y') (18) (Y = or (*) Y' = O, PhN), β-substituted organodimetallic trianions of the type CC(PhN)C (25) with alkali-metal cations (Li, Na, and K), and a lithiated tetra-anion of the type CC(PhN)C(PhN)C (32) are obtained from the corresponding substituted organomercury(II) compounds via low-temperature mercury-alkali metal transmetallation.The starting organomercurials can be obtained by solvomercuriation from suitable unsaturated systems.These polyanion derivatives are stable species only at temperatures in the range -78 to -100 deg C; at higher temperatures rapid decomposition takes place via either a β-elimination process or proton abstraction from the reaction media.The new polyanionic compounds are characterized by transformation into their deuterio derivatives with deuterium oxide at low temperature.The thermal decomposition of these organometallic intermediates is also reported.The reactivity of the lithiated trianion derived from isopropylaniline (25a) with different agents (ethyl bromide, dimethyl disulphide, and trimethylchlorosilane) in a successive or simultaneous way is studied; this process occurs in a regioselective manner.
- Barluenga, Jose,Fananas, Francisco J.,Villamana, Jorge,Yus, Miguel
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p. 2685 - 2692
(2007/10/02)
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- Structural Information from Tandem Mass Spectrometry for China White and Related Fentanyl Derivatives
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The potential of tandem mass spectrometry utilizing collisionally activated dissociation (CAD) for molecular structure determination is illustrated with α-methylfentanyl ("China White"), whose complex structure required several methods for its original el
- Cheng, Michael T.,Kruppa, Gary H.,McLafferty, Fred W.,Cooper, Donald A.
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p. 2204 - 2207
(2007/10/02)
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