- Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
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The invention discloses a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method of the ligand, a catalyst composition taking the complex as an active component and application of the catalyst composition. According to the pincerlike manganese complex, a cycloalkyl ring is introduced into a ligand framework, and by regulating and controlling the cyclic tension, flexibility and steric hindrance of the cycloalkyl ring, the reactivity and stability of the manganese metal center can be effectively adjusted, and the catalytic activity and substrate applicability of a manganese metal system are remarkably improved. The catalyst composition taking the pincerlike manganese complex as an active component has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of preparing quinoline or pyridine derivatives by catalyzing dehydrogenation coupling reaction of o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol; and the synthesis advantages of low cost and stable performance are embodied, the operation is simple, and the yield is high.
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Paragraph 0159-0165
(2021/07/31)
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- Direct synthesis of ring-fused quinolines and pyridines catalyzed byNNHY-ligated manganese complexes (Y = NR2or SR)
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Four cationic manganese(i) complexes, [(fac-NNHN)Mn(CO)3]Br (Mn-1-Mn-3) and [(fac-NNHS)Mn(CO)3]Br (Mn-4) (whereNNHis a 5,6,7,8-tetrahydro-8-quinolinamine moiety), have been synthesized and evaluated as catalysts for the direct synthesis of quinolines and pyridines by the reaction of a γ-amino alcohol with a ketone or secondary alcohol;NNHS-ligatedMn-4proved the most effective of the four catalysts. The reactions proceeded well in the presence of catalyst loadings in the range 0.5-5.0 mol% and tolerated diverse functional groups such as alkyl, cycloalkyl, alkoxy, chloride and hetero-aryl. A mechanism involving acceptorless dehydrogenation coupling (ADC) has been proposed on the basis of DFT calculations and experimental evidence. Significantly, this manganese-based catalytic protocol provides a promising green and environmentally friendly route to a wide range of synthetically important substituted monocyclic, bicyclic as well as tricyclicN-heterocycles (including 50 quinoline and 26 pyridine examples) with isolated yields of up to 93%.
- Han, Mingyang,Lin, Qing,Liu, Qingbin,Liu, Song,Ma, Ning,Solan, Gregory A.,Sun, Wen-Hua,Wang, Zheng,Yan, Xiuli
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p. 8026 - 8036
(2021/12/27)
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- Cu-Catalyzed Pyridine Synthesis via Oxidative Annulation of Cyclic Ketones with Propargylamine
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A Cu-catalyzed, easily scalable one-pot synthesis of fused pyridines by the reaction of cyclic ketones with propargylamine is described. The protocol was optimized based on the results of more than 30 experiments. The highest product yields were achieved in i-PrOH as a solvent in the presence of 5.0 mol % CuCl2 in air. In contrast to the well-known Au-catalyzed protocol, our procedure is "laboratory friendly", cost-effective, and suitable for preparing dozens of grams of fused pyridine-based building blocks and does not require a high-pressure autoclave technique. Decreasing the catalyst amount in the reaction to 1.25 mol % CuCl2 provided a yield comparable to that achieved with 5 mol % catalyst, though a longer reaction time was required. A plausible reaction mechanism was proposed. The scope and limitation of the reaction were studied using 24 different cyclic ketones as starting materials. The fused pyridine yield decreased among cyclic ketones in the following order: six-membered ? eight-membered > five-membered ~seven-membered. The elaborated reaction conditions demonstrated tolerance to a number of protective functional groups in ketone such as ester, tert-butoxycarbonyl (Boc)-protected amine, and acetal moieties.
- Sotnik, Svitlana O.,Subota, Andrii I.,Kliuchynskyi, Anton Y.,Yehorov, Dmytro V.,Lytvynenko, Anton S.,Rozhenko, Alexander B.,Kolotilov, Sergey V.,Ryabukhin, Sergey V.,Volochnyuk, Dmitriy M.
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p. 7315 - 7325
(2021/05/29)
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- Palladium acetate-catalyzed one-pot synthesis of mono- And disubstitued pyridines
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A Pd-catalyzed one-pot synthesis of mono- and disubstituted pyridines was developed. The substituted pyridines were obtained from ketones or an aldehyde and 1,3-diaminopropane using a combination of catalytic Pd(OAc)2 and Cu(OAc)2. High-concentration reaction conditions enabled this catalytic reaction to be acid-free.
- Mikami, Shunya,Toyota, Masahiro
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p. 1315 - 1321
(2019/08/01)
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- Production process of 2,3- cyclopenteno pyridine
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2,3-cyclopenteno pyridine has physiological activity of resisting ulcer and resisting cancer, is an important medical intermediate and alkaloid, is also used for preparing plant protective agents, synthetic resin, antioxidants and the like, and is currently used for the side chains of a fourth-generation injection-use aminothiazole cephalosporins, which is cefpirome, and the quantity demanded in developing countries, such as China and India, is growing rapidly at present. The invention provides a production process of the 2,3- cyclopenteno pyridine. The specific process is as follows: (1) preparation of 4,5,6,7-tetrahydro-2-oxo-3-formyl cyclopenteno pyridine, (2) preparation of 2-chloro-2,3-cyclopenteno pyridine, and (3) preparation of the 2,3-cyclopenteno pyridine.
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Paragraph 0005; 0006
(2018/09/08)
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- 2 - (b benzene phosphine base ethyl) - (5, 6, 7, 8 - tetrahydro quinolyl) amine ruthenium complex preparation method and application thereof
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The invention discloses a preparation method and application of 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complexes. A ligand 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine is firstly prepared, and then reacted with RuHCl(CO)(PPh3)3 and RuCl2(PPh3)3 for preparing a complex 1 and a complex 2 which are different in structure, and then the 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complex 1 or complex 2 is used to catalyze a condensation reaction of an amino alcohol and a secondary alcohol or a ketone, so that pyridine and quinoline derivatives are synthesized. The preparation method is simple, good in stability, and the catalyst is high in catalytic activity and has the usage amount only being 0.025% by molar of a substrate. The preparation method is applied to production of pyridine and quinoline derivatives, the method is simple, environmental pollution is small, the yield is high and the cost is low.
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Paragraph 0055; 0056; 0057; 0058; 0059
(2017/06/19)
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- An ion liquid law synthesis of pharmaceutical intermediates 6, 7 - dihydro - 5H - cyclopenta (b) pyridine preparation method (by machine translation)
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The invention relates to the preparation of the intermediate compound, in particular to a pharmaceutical intermediate ion liquid law synthesis of 6, 7 - dihydro - 5H - cyclopenta (b) pyridine of the preparation method. The preparation method comprises: (1) ion the liquid carries catalyst BMImZnCl3 Preparation, (2) in order to cyclopentanone and propiolic as raw materials, in BMImBF4 /BMImZnCl3 Under catalytic system, microwave heating to synthesize medicine intermediate 6, 7 - dihydro - 5H - cyclopentane (b) pyridine, after the reaction the reaction liquid organic solvent extraction, drying, distillation, to get the content in the range of 99.0% product of the above, the yield is 70% -75%. The invention in the ionic liquid microwave synthesis of 6, 7 - dihydro - 5H - cyclopentane and [b] pyridine, mild reaction conditions, the reaction time is short, reaction selectivity and high yield, the ionic liquid catalyst can be recycled, operation and after treatment is simple, and is a highly efficient, environment-friendly synthetic method. (by machine translation)
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Paragraph 0013; 0014; 0016; 0018; 0020
(2017/08/27)
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- Preparation method of cefpirome intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine
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The invention relates to preparation of a medical intermediate, in particular to a preparation method of a cefpirome intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine. Cyclopentanone and propargylamine are used as raw materials, a key intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine of cefpirome is synthesized in an autoclave and an organic solvent by taking a ferric nitrate activated carbon carrier as a catalyst, reaction liquid is filtered and then is adjusted to be alkalescent by using ammonia water, an organic layer is rectified to obtain a product of which the content is 99.0% or more, and the yield reaches 68-72%. The preparation method provided by the invention takes the ferric nitrate activated carbon carrier as the catalyst for high-pressure synthesis, the reaction condition is mild, the reaction time is short, the operation is simple and convenient, the after-treatment is simple, the yield is high, the obtained product contains few impurities, the content is 99.0% or more, and meanwhile, the catalyst and the solvent are easy to recycle.
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Paragraph 0014; 0015; 0016; 0017; 0018; 0019; 0020; 0021
(2017/08/27)
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- Au-complex containing phosphino and imidazolyl moieties as a bi-functional catalyst for one-pot synthesis of pyridine derivatives
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The complex of Au-L1 containing imidazolyl ring and the phosphine-ligated-Au moiety was synthesized and applied as the efficient bi-functional catalyst for the one-pot sequential condensation/annulation reaction for the synthesis of pyridine derivatives. It was found that, as for Au-L1, the involved imidazolyl group acted as a Lewis base to catalyze the condensation of carbonyl compounds with propargylamine to form the imino intermediate, and the involved Au+-complex species with alkynophilicity corresponded to the subsequent activation of imino-tailed alkynyl to afford dehydropyridine intermediate. The latter proceeded auto-oxidation reaction to afford the pyridine derivatives. The observed sequential catalysis over Au-L1 proved more efficient than that over the mechanical mixtures of the Au-complex (Au-L2) and N-methylimidazole, because the free N-methylimidazole as an N-containing donor competed with the alkyne substrate to coordinate to Au-center. Moreover, Au-L1 exhibited good generality to a wide range of the substrates for the synthesis of 2,3-fused pyridine derivatives and 2-aryl(heteroaryl)-substituted pyridines.
- Yang, Da,Liu, Huan,Wang, Dong-Liang,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
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p. 323 - 330
(2016/09/23)
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- A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of - Amino Alcohols and Secondary Alcohols
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The ruthenium complex (8-(2-diphenylphosphinoethyl)aminotrihydroquinolinyl)(carbonyl)(hydrido)ruthenium chloride exhibited extremely high efficiency toward the coupling cyclization of -amino alcohols with secondary alcohols. The corresponding products, pyridine or quinoline derivatives, are obtained in good to high isolated yields. On comparison with literature catalysts whose noble-metal loading with respect to -amino alcohols reached 0.5-1.0 mol % for Ru and a record lowest of 0.04 mol % for Ir, the current catalyst achieves the same efficiency with a loading of 0.025 mol % for Ru. The mechanism of acceptorless dehydrogenative condensation (ADC) was proposed on the basis of DFT calculations; in addition, the reactive intermediates were determined by GC-MS, NMR, and single-crystal X-ray diffraction. The catalytic process is potentially suitable for industrial applications.
- Pan, Bing,Liu, Bo,Yue, Erlin,Liu, Qingbin,Yang, Xinzheng,Wang, Zheng,Sun, Wen-Hua
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p. 1247 - 1253
(2016/02/18)
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- A simple iridicycle catalyst for efficient transfer hydrogenation of n-heterocycles in water
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A cyclometalated iridium complex is shown to catalyse the transfer hydrogenation of various nitrogen heterocycles, including but not limited to quinolines, isoquinolines, indoles and pyridinium salts, in an aqueous solution of HCO2H/HCO2Na under mild conditions. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), with catalyst loadings as low as 0.01 mol % being feasible. Mechanistic investigation of the quinoline reduction suggests that the transfer hydrogenation proceeds via both 1,2- and 1,4-addition pathways, with the catalytic turnover being limited by the step of hydride transfer. An easily accessible iridicycle catalyst effects the transfer hydrogenation of a wide variety of N-heterocycles in water, including quinolines, isoquinolines, indoles, quinoxalines, and pyridines. The catalyst shows excellent functional-group compatibility and high turnover number (up to 7500), even with low catalyst loadings.
- Talwar, Dinesh,Li, Ho Yin,Durham, Emma,Xiao, Jianliang
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supporting information
p. 5370 - 5379
(2015/03/30)
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- Direct synthesis of pyridines and quinolines by coupling of γ-amino-alcohols with secondary alcohols liberating H2 catalyzed by ruthenium pincer complexes
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A novel, one-step synthesis of substituted pyridine- and quinoline-derivatives was achieved by acceptorless dehydrogenative coupling of γ-aminoalcohols with secondary alcohols. The reaction involves consecutive C-N and C-C bond formation, catalyzed by a bipyridyl-based ruthenium pincer complex with a base.
- Srimani, Dipankar,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 6632 - 6634
(2013/07/26)
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- Scope of the inverse electron demand Diels-Alder reactions of 1,2,3-triazine
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Chemical equations presented. An examination of the scope of the inverse electron demand Diels-Alder reactions of the parent unsubstituted 1,2,3-triazine is described including the first report of its unique capabilities for participating in previously unexplored [4 + 2] cycloaddition reactions with heterodienophiles.
- Anderson, Erin D.,Boger, Dale L.
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supporting information; experimental part
p. 2492 - 2494
(2011/07/09)
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- Inverse electron demand diels-alder reactions of 1,2,3-triazines: Pronounced substituent effects on reactivity and cycloaddition scope
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A systematic study of the inverse electron demand Diels-Alder reactions of 1,2,3-triazines is disclosed, including an examination of the impact of a C5 substituent. Such substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 1,2,3-triazine without altering, and perhaps even enhancing, the intrinsic cycloaddition regioselectivity. The study revealed not only that the reactivity may be predictably modulated by a C5 substituent (R = CO2Me > Ph > H) but also that the impact is of a magnitude to convert 1,2,3-triazine (1) and its modest cycloaddition scope into a heterocyclic azadiene system with a reaction scope that portends extensive synthetic utility, expanding the range of participating dienophiles. Significantly, the studies define a now powerful additional heterocyclic azadiene, complementary to the isomeric 1,2,4-triazines and 1,3,5-triazines, capable of dependable participation in inverse electron demand Diels-Alder reactions, extending the number of complementary heterocyclic ring systems accessible with implementation of the methodology.
- Anderson, Erin D.,Boger, Dale L.
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supporting information; experimental part
p. 12285 - 12292
(2011/09/16)
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- Cross-linked glycopeptide-cephalosporin antibiotics
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This invention provides cross-linked glycopeptide-cephalosporin compounds and pharmaceutically acceptable salts thereof which are useful as antibiotics. This invention also provides pharmaceutical compositions containing such compounds; methods for treating bacterial infections in a mammal using such compounds; and processes and intermediates useful for preparing such compounds.
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- Sequential amination/annulation/aromatization reaction of carbonyl compounds and propargylamine: A new one-pot approach to functionalized pyridines
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A general one-pot synthesis of pyridines 4a-t from the reaction of dialkyl acyclic/cyclic ketones 1a-i, methyl, aryl/heteroaryl ketones 1m-r, and aldehydes bearing α-hydrogens 1s,t with propargylamine 2 is described. Gold and copper salts are efficient catalysts for the reaction of ketones with 2. The formation of the pyridines 4 is suggested to proceed through the sequential amination of carbonyl compounds followed by regioselective 6-endo-dig cyclization of the N-propargylenamine (N-propargyldienamine) intermediate 3(5) and aromatization reaction. Whereas the preparation of linear polycyclic pyridine 4i can be carried out by reacting cholestan-3-one 1i with 2, the angular polycyclic pyridine 4j has been obtained starting from cholest-5-en-3-one 1j. Selectivity of the reaction of polycyclic dicarbonyls 1k,1 with 2 has also been investigated.
- Abbiati, Giorgio,Arcadi, Antonio,Bianchi, Gabriele,Di Giuseppe, Sabrina,Marinelli, Fabio,Rossi, Elisabetta
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p. 6959 - 6966
(2007/10/03)
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- INTRAMOLECULAR DIELS-ALDER REACTIONS OF 2-(ALKYNYL)PYRIMIDINES AND 2-(ALKYNYL)PYRIDINES
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Pyrimidines 3,7 and 13 carrying an ο-alkynyl side-chain -CR2(CH2)nCH2CCH (R=H, CN; n=1,2) at the 2-position undergo intramolecular inverse electron demand Diels-Alder reactions across the C-2 and C-5 positions.Loss of hydrogen cyanide, caused by a retro-Diels-Alder reaction, from the intermediate cycloadducts leads to annelated pyridines 5,9 and 15, respectively.Similarly, from the nitropyridines 16 the 2,3-dihydronitro-1H-indenes 18 are obtained.The influence of electronic and steric effects on the rate of cycloaddition is discussed.Gem-disubstitution on the chain connecting the reaction centers leads to a considerable rate enhancement for compounds 3 vs 13.Compounds 7, having an extra methylene group in the tether between diene and dienophile, react much slower than compounds 3 due to decreased entropic assistance.
- Frissen, A. E.,Marcelis, A. T. M.,Geurtsen, G.,Bie, D. A. de,Plas, H. C. van der
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p. 5151 - 5162
(2007/10/02)
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- Cephalosporin derivatives and bactericides containing the same
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Cephalosporin compounds represented by the following formula (I) and pharmaceutically acceptable salts thereof have a broad bactericidal spectrum against various pathogenic bacteria including Psuedomonas aeruginosa and are useful as bactericidal remedies for pathogenic diseases of human and animals: STR1 wherein A represents an unsubstituted or substituted pyridylthio group of a formula (I-1); STR2 or an unsubstituted or substituted pyridiniumthio group of a formula (I-2): STR3 or an unsubstituted or substituted pyridinium group of a formula (I-3); STR4 or a 5- or 6-membered heterocyclicthio or bicycloheterocyclicthio group of a formula (I-4):
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- 1,2,3-Triazines,III. - Synthesis of N-Aminopyrazoles and their Oxidation to 1,2,3-Triazines. Molecular Structure of 1,2,3-Triazine
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Oxidation of the N-aminopyrazoles 4a-i affords the 1,2,3-triazines 5a-i.Spectra and reactions - such as oxidation, reduction, and cycloaddition reactions - of some 1,2,3-triazines 5 are described.The X-ray analysis of 5a is presented.
- Neunhoeffer, Hans,Clausen, Monika,Voetter, Hans-Dieter,Ohl, Harald,Krueger, Carl,Angermund, K.
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p. 1732 - 1751
(2007/10/02)
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- Process for recovering oxygenated organic compounds from dilute aqueous solutions employing liquid extraction media
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A thermally efficient process for recovering an oxygenated organic material, such as ethanol, present in dilute aqueous solution is disclosed which comprises contacting said dilute aqueous solution with at least one inert extractant which is liquid at ambient temperature and pressure, said extractant being selected from the group consisting of unsubstituted and substituted cyclic secondary amines and unsubstituted and substituted aromatic cyclic amines having a distribution coefficient of at least about 0.70 or a separation factor of at least about 1.0. The invention further provides a process for obtaining substantially anhydrous oxygenated organic material from a dilute aqueous solution thereof in which the stream is subjected to liquid-liquid extraction to provide an oxygenated organic material poor raffinate phase and an oxygenated organic material rich extract phase, the oxygenated organic material present in said latter phase is concentrated in a rectifying column to provide an aqueous oxygenated organic material of high concentration and, if desired or necessary, the concentrated stream is azeotropically distilled in an anhydrous column operated under substantially superatmospheric pressure with thermal values recovered from said anhydrous column being used to satisfy part of all of the thermal operating requirements of the rectifying column.
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- Thermolysis of Oxime O-Allyl Ethers: A New Method for Pyridine Synthesis
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Thermolysis of cycloalkanone oxime O-allyl ethers in air gave the corresponding cycloalkenopyridines, providing a new method for the synthesis of cycloalkenopyridine derivatives.Keywords - cycloalkanone oxime O-allyl ether; cycloalkenopyridine; thermolysis; O-allylhydroxylamine; cyclohexanone; tetrahydroquinoline
- Koyama, Junko,Sugita, Teruyo,Suzuta, Yukio,Irie, Hiroshi
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p. 2601 - 2606
(2007/10/02)
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- Process for recovering ethanol from dilute aqueous solutions employing liquid extraction media
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A thermally efficient process for recovering ethanol present in dilute aqueous solution is disclosed which comprises contacting said dilute aqueous ethanol solution with at least one inert extractant which is liquid at ambient temperature and pressure, said extractant being selected from the group consisting of unsubstituted and substituted cyclic secondary amines and unsubstituted and substituted aromatic cyclic amines having a distribution coefficient of at least about 0.70 or a separation factor of at least about 1.0. The invention further provides a process for obtaining substantially anhydrous ethanol from a dilute aqueous ethanol solution in which the ethanol stream is subjected to liquid-liquid extraction to provide an ethanol-poor raffinate phase and an ethanol-rich extract phase, the ethanol present in said latter phase is concentrated in a rectifying column to provide an aqueous ethanol of high proof and the concentrated ethanol is azeotropically distilled in an anhydrous column operated under substantially superatmospheric pressure with thermal values recovered from said anhydrous column being used to satisfy part of all of the thermal operating requirements of the rectifying column.
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- The Decomposition of β-Phenethylsulfonyl Azides. Solution Chemistry and Flash Vacuum Pyrolysis
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The intramolecular cyclization of the parent title compound and a number of para-substituted derivatives (1) in solution was found to take place in low yield and to be accompanied by products of intermolecular reactions, namely, C-H insertion (4) and hydrogen abstraction (3).The use of an excess of a relatively inert solvent Freon 113 led to a better yield of the desired 3,4-dihydro-2,1-benzothiazine 2,2-dioxides (2).Flash vacuum pyrolysis (FVP) of 1 at 250-300 deg C also gave some 2, but the use of higher temperatures led to the formation of styrenes (8), indolines (9), indoles (10), sulfur dioxide, and the remarkable transformation products, the 4-substituted 6,7-dihydro-5H-1-pyrindines (7), in good yield.The styrenes result from the elimination of HN3 and SO2 from the azides, and indolines are formed in good yield by FVP of 2 at 650 deg C.The dihydropyrindines are not obtained from 2, and β-phenethynitrene is not a source of any of the above observed products.A mechanism is proposed for the formation of 7 from β-arylethylsulfonylnitrenes.Consistent with the mechanism is the observation that both 1- and 2-phenylpropanesulfonyl azide give a mixture of 6- and 7-methyl-6,7-dihydro-5H-1-pyrindines in the same ratio on FVP at 650 deg C.Thermolysis of 1a in benzene at 100 deg C gives an N-sulfonylazepine derivative.The FVP of 1 and 2 at 650 deg C are preparative routes to 7 and 9, respectively.
- Abramovitch, Rudolph A.,Holcomb, William D.,Wake, Shigeo
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p. 1525 - 1533
(2007/10/02)
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