- Gold(I)-catalyzed formation of furans from Y-acyloxyalkynyl ketones
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Various γ-acyloxyalkynyl ketones were efficiently converted into highly substituted furans with 2.5 mol % of triflimide (triphenyl-phosphine) gold(I) as a catalyst in dichloroethane at 70 °C.
- Hoffmann, Marie,Miaskiewicz, Solene,Weibel, Jean-Marc,Pale, Patrick,Blanc, Aurelien
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Read Online
- Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
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The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.
- Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
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p. 7284 - 7296
(2021/05/29)
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- Efficient heterogeneous hydroaminocarbonylation of olefins with ammonium chloride as amino source
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An efficient protocol for heterogeneous hydroaminocarbonylation of olefins with ammonium chloride without addition of acid additive has been developed for the first time. We successfully synthesized the Pd@POPs-PPh3 catalyst through a solvothermal synthetic method. Under this heterogeneous catalytic system, C2-C6 olefins displayed good yields and TON, and a yield of 66% of propionamide and TON = 1400 were obtained under mild reaction conditions (403 K, Pethylene = 0.5 MPa, PCO = 2.5 MPa), which is a little higher than those in the homogeneous system. This catalytic system has the advantage of easy separation of product and catalyst, as well as good stability. Uniform dispersion of Pd active sites, strong coordination bond between P and Pd, high surface area, large pore volume and hierarchical porosity of Pd@POPs-PPh3 were confirmed by a series of characterizations, which is believed to be the keys for the good activity and stability of hydroaminocarbonylation reaction.
- Sun, Zhao,Yan, Li,Ji, Guangjun,Wang, Guoqing,Ma, Lei,Jiang, Miao,Li, Cunyao,Ding, Yunjie
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- Half-Sandwich Iridium Complexes Based on β-Ketoamino Ligands: Preparation, Structure, and Catalytic Activity in Amide Synthesis
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A series of β-ketoamino-based N,O-chelate half-sandwich iridium complexes with the general formula [Cp*IrClL] have been prepared in good yields. These air-insensitive iridium complexes showed desirable catalytic activity in an amide preparation under mild conditions. A number of amides with diverse substituted groups were furnished in a one-pot reaction with good-to-excellent yields through an amidation reaction of NH2OH·HCl with aldehydes in the presence of these iridium(III) precursors. The excellent catalytic activity, mild reaction conditions, and broad substrate scope gave this type of iridium catalyst potential for use in industry. All of the obtained iridium complexes were well characterized by different spectroscopy techniques. The exact molecular structure of complex 3 has been confirmed by single-crystal X-ray analysis.
- Wang, Yang,Guo, Wen,Guan, Ai-Lin,Liu, Shuang,Yao, Zi-Jian
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p. 11514 - 11520
(2021/07/31)
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- Trash to treasure: Eco-friendly and practical synthesis of amides by nitriles hydrolysis in WepPA
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The hydration of nitriles to amides in a water extract of pomelo peel ash (WEPPA) was realized with moderate to excellent yields without using external transition metals, bases or organic solvents. This reaction features a broad substrate scope, wide functional group tolerance, prominent chemoselectivity, and good reusability. Notably, a magnification experiment in this bio-based solvent at 100 mmol further demonstrated its practicability.
- Sun, Yajun,Jin, Weiwei,Liu, Chenjiang
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supporting information
(2019/11/11)
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- Method for preparing amide by metallic sodium catalyzed ester ammonolysis reaction
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The invention discloses a method for preparing amide by metallic sodium catalyzed ester ammonolysis reaction. The method is characterized in that ester and liquid ammonia are taken as raw materials, and metallic sodium is taken as a catalyst to perform reaction at a temperature of 90-140 DEG C in a high-pressure kettle; a molar ratio of the ester to ammonium is 1: (1.2 to 5.0); molar weight of the metallic sodium is 4-10% that of the ester; when reaction pressure is not lowered any longer, reaction is stopped to recycle the ammonium which is not reacted; and an obtained reaction product is post-treated to obtain a product. The method can be used for efficiently preparing the amide; and moreover, the raw materials are cheap and are low in toxicity, reaction activity is relatively high, dose of the catalyst is small, reaction speed is high, a reaction conversion rate is high, and the product is easily separated.
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Paragraph 0066
(2017/08/30)
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- Transfer Hydrogenation of Nitriles, Olefins, and N-Heterocycles Catalyzed by an N-Heterocyclic Carbene-Supported Half-Sandwich Complex of Ruthenium
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In the presence of KOBut, N-heterocyclic carbene-supported half-sandwich complex [Cp(IPr)Ru(pyr)2][PF6] (3) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) catalyzes transfer hydrogenation (TH) of nitriles, activated N-heterocycles, olefins, and conjugated olefins in isopropanol at the catalyst loading of 0.5%. The TH of nitriles leads to imines, produced as a result of coupling of the initially formed amines with acetone (produced from isopropanol), and showed good chemoselectivity. Reduction of N-heterocycles occurs for activated polycyclic substrates (e.g., quinoline) and takes place exclusively in the heterocycle. The TH also works well for linear and cyclic olefins but fails for trisubstituted substrates. However, the C = C bond of α,β-unsaturated esters, amides, and acids is easily reduced even for trisubstituted species, such as isovaleriates. Mechanistic studies suggest that the active species in these catalytic reactions is the trihydride Cp(IPr)RuH3 (5), which can catalyze these reactions in the absence of any base. Kinetic studies are consistent with a classical inner sphere hydride-based mechanism of TH.
- Mai, Van Hung,Nikonov, Georgii I.
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p. 943 - 949
(2016/05/09)
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- Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(ii) complexes
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The (PCP)Ni-OH complexes 2R (R = iPr, tBu, Cy) are effective catalyst precursors for the selective hydration of nitriles to the corresponding amides under relatively mild conditions (80 °C) and low catalyst loadings (0.05-0.5%). Substrate scope includes aliphatic, vinylic and aromatic nitriles, but substrates with protic groups poison the catalyst abruptly. The catalysts are effective because the electron rich nature of the PCP ligands and their steric bulk renders the hydroxo group labile.
- Borau-Garcia,Gutsulyak,Burford,Piers
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p. 12082 - 12085
(2016/01/15)
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- Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
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Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
- Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
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p. 12152 - 12160
(2015/02/19)
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- One-pot synthesis of 2-alkyl-4(5)-aryl-1H-imidazoles from 1-aryl-2-bromoethanones, ammonium carbonate and aliphatic carboxylic acids
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A simple and efficient protocol for the preparation of 2-alkyl-4(5)-aryl- 1H-imidazoles starting from α-bromo aryl methyl ketones and aliphatic carboxylic acids in the presence of ammonium carbonate has been developed.
- Liu, Cong,Nie, Yijiao,Yao, Guowei,Dai, Rongji,Deng, Yulin
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p. 208 - 210
(2014/05/06)
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- Efficient and selective hydration of nitriles to amides in aqueous systems with Ru(II)-phosphaurotropine catalysts
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A simple and efficient synthesis of amides by selective hydration of aromatic and aliphatic nitriles is described. The catalysts are prepared in situ from easily available Ru-precursors and ligands using water as the solvent. The most active catalyst, is obtained from [RuCl2(dmso)4] and benzylated 1,3,5-triaza-7-phosphaadamantane. Of the 16 substrates examined, 92-99% conversions of 14 nitriles were achieved in one hour at reflux temperature.
- Bolyog-Nagy, Evelin,Udvardy, Antal,Joó, Ferenc,Kathó, ágnes
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supporting information
p. 3615 - 3617
(2014/06/23)
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- N-Acyl-N'-(pyridin-2-yl) Ureas and Analogs Exhibiting Anti-Cancer and Anti-Proliferative Activities
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Described are compounds of Formula I which find utility in the treatment of cancer, autoimmune diseases and metabolic bone disorders through inhibition of c-FMS (CSF-1R), c-KIT, and/or PDGFR kinases. These compounds also find utility in the treatment of other mammalian diseases mediated by c-FMS, c-KIT, or PDGFR kinases.
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Paragraph 0360
(2014/09/30)
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- Mechanistic investigations and secondary coordination sphere effects in the hydration of nitriles with [Ru(η6-arene)Cl2PR 3] complexes
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The mechanism of the nitrile-to-amide hydration reaction using [Ru(η6-arene)Cl2(PR3)] complexes as catalysts was investigated (η6-arene = C6H 6, p-cymene, C6Me6; R = NMe2, OMe, OEt, Et, iPr). Experiments showed that the mechanism involves the following general sequence of reactions: substitution of a chloride ligand by the nitrile substrate, intermolecular nucleophilic attack by water to form an amidate intermediate, and dissociation of the resulting amide. The effects of secondary coordination sphere interactions on the rates and yields of the hydration reaction were investigated. Ligands that are capable of acting as hydrogen bond acceptors with the entering water molecule result in faster rates and higher yields than non-hydrogen-bonding ligands. The faster rates are attributable to the H-bonding-facilitated deprotonation of the water as the oxygen of the water bonds to the coordinated nitrile. DFT calculations on the proposed H-bonding intermediates support this interpretation. Most homogeneous catalysts will not hydrate cyanohydrins because of the equilibrium amounts of cyanide that are present in solutions of cyanohydrins; the cyanide poisons the catalyst. Because of its increased catalytic reactivity due to secondary coordination sphere effects, the [Ru(η6-arene)Cl2(P(NMe2) 3)] catalyst gives significant yields of cyanohydrin hydration products with glycolonitrile, lactonitrile, acetone cyanohydrin, and mandelonitrile. A Taft plot showed that an increase in the steric bulk of the nitrile results in a decrease in the hydration rate, and a Hammett plot showed that electron-withdrawing groups facilitate nitrile hydration. The decrease in rate as the size of the cyanohydrin increases is likely due to both increased steric bulk and to the addition of electron-donating groups on the nitrile. The [Ru(η6-arene)Cl2(PR3)] catalysts are initially less susceptible to cyanide poisoning than other homogeneous nitrile hydration catalysts because [Ru(η6-p-cymene)(CN)(Cl)(P(NMe 2)3)] forms in the presence of cyanide. The electron-withdrawing cyanide ligand facilitates nucleophilic attack of water on a coordinated nitrile in this molecule.
- Knapp, Spring Melody M.,Sherbow, Tobias J.,Yelle, Robert B.,Zakharov, Lev N.,Juliette, J. Jerrick,Tyler, David R.
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supporting information
p. 824 - 834
(2013/03/28)
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- Catalytic nitrile hydration with [Ru(η6- p -cymene)Cl 2(PR2R′)] complexes: Secondary coordination sphere effects with phosphine oxide and phosphinite ligands
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The rates of nitrile hydration reactions were investigated using [Ru(η6-p-cymene)Cl2(PR2R′)] complexes as homogeneous catalysts, where PR2R′ = PMe 2(CH2P(O)Me2), PMe2(CH 2CH2P(O)Me2), PPh2(CH 2P(O)Ph2), PPh2(CH2CH 2P(O)Ph2), PMe2OH, P(OEt)2OH. These catalysts were studied because the rate of the nitrile-to-amide hydration reaction was hypothesized to be affected by the position of the hydrogen bond accepting group in the secondary coordination sphere of the catalyst. Experiments showed that the rate of nitrile hydration was fastest when using [Ru(η6-p-cymene)Cl2PMe2OH]: i.e., the catalyst with the hydrogen bond accepting group capable of forming the most stable ring in the transition state of the rate-limiting step. This catalyst is also active at pH 3.5 and at low temperatures - conditions where α-hydroxynitriles (cyanohydrins) produce less cyanide, a known poison for organometallic nitrile hydration catalysts. The [Ru(η6-p-cymene) Cl2PMe2OH] catalyst completely converts the cyanohydrins glycolonitrile and lactonitrile to their corresponding α-hydroxyamides faster than previously investigated catalysts. [Ru(η6-p-cymene) Cl2PMe2OH] is not, however, a good catalyst for acetone cyanohydrin hydration, because it is susceptible to cyanide poisoning. Protecting the -OH group of acetone cyanohydrin was shown to be an effective way to prevent cyanide poisoning, resulting in quantitative hydration of acetone cyanohydrin acetate.
- Knapp, Spring Melody M.,Sherbow, Tobias J.,Yelle, Robert B.,Juliette, J. Jerrick,Tyler, David R.
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supporting information
p. 3744 - 3752
(2013/07/26)
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- Clean synthesis of amides over bifunctional catalysts of rhodium-loaded titanosilicates
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Rhodium-loaded titanosilicates were prepared and employed as efficient bifunctional catalysts in the one-pot synthesis of benzamide from benzaldehyde, hydrogen peroxide, and ammonia, which took place through a tandem reaction including ammoximation of benzaldehyde to benzaldehydeoxime and a sequential dehydration-rehydration reaction to benzamide. Various parameters that influenced the activity and product selectivity were investigated, such as crystalline topologies of the titanosilicate supports, types of transition metals, rhodium content, reaction temperature, time, solvent, and NH3/benzaldehyde molar ratio. Ti-MWW was proved to be a suitable support for loading the Rh(OH)x species. Rh(OH)x/Ti-MWWgave 84.9% of benzaldehyde conversion and 86.9% of benzamide selectivity, and it was also catalytically active for the transformation of a variety of aldehydes to the corresponding amides. The reusability of the bifunctional catalyst was also investigated. The insitu FTIR technique confirmed that the one-pot reaction included Ti-catalyzed ammoximation of benzaldehyde to the benzaldehyde oxime intermediate and sequential rhodium hydroxide related dehydration-rehydration reaction of oximes to amides.
- Xu, Le,Li, Ningning,Peng, Hong-Gen,Wu, Peng
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p. 2462 - 2470
(2013/08/23)
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- Direct catalytic formation of primary and tertiary amides from non-activated carboxylic acids, employing carbamates as amine source
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The operationally simple titanium(IV)- or zirconium(IV)-catalyzed direct amidation of non-activated carboxylic acids with ammonium carbamates generates primary, and tertiary N,N-dimethyl-substituted amides in good to excellent yields. Copyright
- Tinnis, Fredrik,Lundberg, Helena,Adolfsson, Hans
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supporting information
p. 2531 - 2536
(2012/11/06)
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- LRRK2 INHIBITORS
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Provided herein are compounds that inhibit or partially inhibit the activity of leucine rich repeat kinases. Also provided herein are methods of treatment of CNS disorders comprising administration of inhibitors of leucine rich repeat kinases.
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Page/Page column 125
(2013/02/28)
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- Selective hydration of nitriles to amides promoted by an Os-NHC catalyst: Formation and X-ray characterization of κ2-amidate intermediates
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The complex [Os(η6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF3SO 3) reacts with benzonitrile and acetonitrile to afford the κ2-amidate derivatives [Os(η6-p-cymene) {κ2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η6-benzene)(OH)(CH3CN)IMe] + (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed.
- Buil, Maria L.,Cadierno, Victorio,Esteruelas, Miguel A.,Gimeno, Jose,Herrero, Juana,Izquierdo, Susana,Onate, Enrique
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p. 6861 - 6867
(2012/11/13)
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- Lead discovery, chemistry optimization, and biological evaluation studies of novel biamide derivatives as CB2 receptor inverse agonists and osteoclast inhibitors
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N,N′-((4-(Dimethylamino)phenyl)methylene)bis(2-phenylacetamide) was discovered by using 3D pharmacophore database searches and was biologically confirmed as a new class of CB2 inverse agonists. Subsequently, 52 derivatives were designed and synthesized through lead chemistry optimization by modifying the rings A-C and the core structure in further SAR studies. Five compounds were developed and also confirmed as CB2 inverse agonists with the highest CB2 binding affinity (CB2Ki of 22-85 nM, EC50 of 4-28 nM) and best selectivity (CB 1/CB2 of 235- to 909-fold). Furthermore, osteoclastogenesis bioassay indicated that PAM compounds showed great inhibition of osteoclast formation. Especially, compound 26 showed 72% inhibition activity even at the low concentration of 0.1 μM. The cytotoxicity assay suggested that the inhibition of PAM compounds on osteoclastogenesis did not result from its cytotoxicity. Therefore, these PAM derivatives could be used as potential leads for the development of a new type of antiosteoporosis agent.
- Yang, Peng,Myint, Kyaw-Zeyar,Tong, Qin,Feng, Rentian,Cao, Haiping,Almehizia, Abdulrahman A.,Alqarni, Mohammed Hamed,Wang, Lirong,Bartlow, Patrick,Gao, Yingdai,Gertsch, Jürg,Teramachi, Jumpei,Kurihara, Noriyoshi,Roodman, Garson David,Cheng, Tao,Xie, Xiang-Qun
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p. 9973 - 9987
(2013/01/16)
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- An efficient copper(II)-catalyzed direct access to primary amides from aldehydes under neat conditions
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A simple expeditious one-pot conversion of a wide assortment of aldehydes to corresponding primary amides in good to excellent yields has been accomplished employing hydroxylamine hydrochloride (1 mol equiv), sodium acetate (1.1 mol equiv), and copper sulfate pentahydrate (5 mol %) under neat conditions at 110 °C. The protocol based upon ligand-free copper (II)-catalysis avoids the use of relatively expensive late transition metal-based catalysts, and is performed under operationally simple conditions without any demanding procedure of isolation and purification of products.
- Ganguly, Nemai C.,Roy, Sushmita,Mondal, Pallab
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experimental part
p. 1413 - 1416
(2012/03/27)
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- Nitrile biotransformation by whole cells of Aspergillus sp. PTCC 5266
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Aspergillus sp. PTCC 5266 exhibited nitrile-hydrating activity over a broad pH range from 6.0 to 10.0 at 26°C. It hydrated 4-nitrophenylacetonitrile, 2-chlorobenzonitrile and 3-chlorobenzonitrile to their corresponding carboxylic acids and amides, while benzyl cyanide, benzonitrile, 4-tolunitrile, cyclohexanecarbonitrile, 4-chlorobutyronitrile and isobutyronitrile gave carboxylic acids as the sole products. The maximum whole-cell nitrile-hydrating activity was observed at pH 7.0.
- Yousefi,Mohammadi,Habibi,Cheraghi
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body text
p. 54 - 59
(2012/03/10)
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- Palladium-catalyzed one-pot conversion of aldehydes to amides
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The palladium-catalyzed one-pot conversion of aldehydes into primary amides in the presence of hydroxylamine hydrochloride in aqueous dimethyl sulfoxide (DMSO) at moderate temperature is described. The process is selective and free from the addition of an external chelating ligand.
- Ali, Md. Ashif,Punniyamurthy, Tharmalingam
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experimental part
p. 288 - 292
(2010/04/28)
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- RhI-catalyzed hydration of organonitriles under ambient conditions
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(Chemical Presented) New scoop on scope and selectivity: The hydration of organonitriles catalyzed by a RhI(OMe) species under nearly pH-neutral and ambient conditions (25°C, 1 atm) is chemoselective and high-yielding (93 to 99%), has a broad substrate scope, and may thus be complementary to enzymatic hydration methods for the introduction of a terminal amido group (CONH2) onto a carbon chain.
- Goto, Akihiro,Endo, Kohei,Saito, Susumu
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p. 3607 - 3609
(2008/12/23)
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- Magnesium nitride as a convenient source of ammonia: Preparation of primary amides
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(Chemical Equation Presented) The use of magnesium nitride (Mg 3N2) as a convenient source of ammonia has been explored for the direct transformation of esters to primary amides. Methyl, ethyl, isopropyl, and tert-butyl esters are converted to the corresponding carboxamides in good yields (75-99%).
- Veitch, Gemma E.,Bridgwood, Katy L.,Ley, Steven V.
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scheme or table
p. 3623 - 3625
(2009/05/07)
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- Benzodiazepine derivatives as app modulators
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A novel class of 1,4- and 1,5-benzodiazepines of formula (I) is disclosed. The compounds modulate the processing of amyloid precursor protein by γ-secretase, and hence find use in the treatment or prevention of conditions associated with the deposition of β-amyloid, such as Alzheimer's disease.
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- Superacidic activation of α,β-unsaturated amides and their electrophilic reactions
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The electrophilic reactivity of α,β-unsaturated amides towards weak nucleophiles such as arenes and cyclohexane, initiated either with triflic acid (CF3SO3H) or with excess AlCl3, has been studied. The amides generally condense readily with aromatics in the presence of AlCl3 to give 3-arylpropionamides and related compounds in excellent yields, while some amides also undergo selective ionic hydrogenation with cyclohexane to give saturated amides. The proposed mechanism of these reactions involves dicationic intermediates (superelectrophiles). The direct observation of a dicationic species (by low-temperature NMR) is reported. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Koltunov, Konstantin Yu.,Walspurger, Stephane,Sommer, Jean
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p. 4039 - 4047
(2007/10/03)
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- Method for delivery of molecules to intracellular targets
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Disclosed are β-peptides and β-peptide conjugates that are capable of diffusing or otherwise being transported across the cell membranes of living cells. The β-peptides contain at least six β-amino acid residues, at leastsix of which are preferably β3-homoarginine residues. It has been found that when pharmacologically-active agents are conjugated to these types of β-peptides, the resulting conjugates (also disclosed herein) are also capable of diffusing or otherwise being transported across the cell membranes of living cells, including mammalian cells.
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- Additives for inhibiting gas hydrate formation
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The invention relates to the use of compounds of the formula (1) in which R1is C1-C30-alkyl, C2-C30-alkenyl or a group of the formula —CH2—CO—NR2R3or a C6-C18-aryl radical which may be substituted by a C1-C12-alkyl group, R2, R3independently of one another, are hydrogen, C1-C6-alkyl or C5-C7-cycloalkyl, or R2and R3, including the nitrogen atom to which they are bonded, form a ring of 4 to 8 ring atoms, it being possible for the ring also to contain oxygen or nitrogen atoms in addition to carbon atoms, A is a C2-C4-alkylene radical and n is an integer from 1 to 20, as gas hydrate inhibitors.
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- Bicyclic heteroamatic compounds useful as LH agonists
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The invention relates to a bicyclic heteroaromatic derivative compound according to general formula (I), or a pharmaceutically acceptable salt thereof, wherein R1is NR5R6, OR5, SR5or R7; R5and R6are independently selected from H, (1-8C)alkyl, (2-8C)alkenyl, (2-8C)alkynyl, (3-8C)cycloalkyl, (2-7C)heterocycloalkyl, alkyl(1-8C)carbonyl, (6-14C)arylcarbonyl, (6-14C)aryl or (4-13C)heteroaryl, or R5and R6together are joined in a (2-7C)heterocloalkyl ring; R7is (3-8C)cycloalkyl, (2-7C)heterocycloalkyl, (6-14C)aryl or (4-13C)heteroaryl, R2is (1-8C)alkyl, (2-8C)alkenyl, (2-8C)alkynyl, or (6-14C)aryl or (4-13C)heteroaryl, both optionally substituted with one or more substituents selected from (1-8C)alkyl, (1-8C)alkylthio, (1-8C)(di)alkylamino, (1-8C)alkoxy, (2-8C)alkenyl, or (2-8C)alkynyl; R3is (1-8C)alkyl, (2-8C)alkenyl, (2-8C)alkynyl, (3-8C)cycloalkyl, (2-7C)heterocycloalkyl, or (6-14C)aryl or (4-13C)heteroaryl, both optionally substituted with one or more substituents selected from (1-8C)alkyl, (1-8C)(di)alkylamino or (1-8C)alkoxy; X is S, O or N(R4); R4is H, (1-8C)alkyl, (1-8C)alkylcarbonyl, (6-14C)arylcarbonyl or (6-14C)aryl(1-8C)alkyl; Y is CH or N; Z is NH2or OH; A is S, N(H), N(R9), O or a bond; R9can be selected from the same groups as described for R2and B is N(H), O or a bond. The compounds of the invention have LH receptor activating activity and can be used in fertility regulating therapies.
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- Substituted piperidines as melanocortin receptor agonists
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Certain novel substituted piperidine compounds are agonists of the human melanocortin receptor(s) and, in particular, are selective agonists of the human melanocortin-4 receptor (MC-4R). They are therefore useful for the treatment, control, or prevention of diseases and disorders responsive to the activation of MC-4R, such as obesity, diabetes, sexual dysfunction, including erectile dysfunction and female sexual dysfunction.
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- Oligomers and polymers of di-substituted cyclic imino carboxylic acids
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Disclosed are cyclic imino oligomers and polymers comprised of subunits of the formula: Also disclosed are combinatorial libraries and arrays of the cyclic imino compounds.
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- Tricyclic compounds
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The novel compounds of the present invention are those of structural formula I: or a pharmaceutically acceptable salt, ester, or stereoisomer thereof, which are inhibitors of 5 alpha -reductase. The compounds of formula I are useful in the oral, systemic, parenteral or topical treatment of hyperandrogenic conditions. Methods of using the compounds of formula I for the treatment of hyperandrogenic conditions such as acne vulgaris, seborrhea, androgenic alopecia, male pattern baldness, female hirsutism, benign prostatic hyperplasia, and the prevention and treatment of prostatic carcinoma, as well as the treatment of prostatitis the treatment of sweat-related conditions such as apocrine gland sweating, hyperhidrosis, and hydradenitis suppurativa, the treatment of polycystic ovary syndrome, the prevention and treatment of bone loss and related diseases, and the prevention and treatment of premature labor are provided, as well as pharmaceutical compositions for the compounds of formula I.
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- α-Aminonitrile hydration in the presence of hydrogen peroxide in aqueous basic medium
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α-Aminonitriles are hydrated into α-aminoamides in the presence of hydrogen peroxide in sodic or ammoniacal basic medium. While the hydration mechanism is close to the mechanism described previously in the case of aromatic nitrites, we showed that, in weakly basic conditions, the amine function of α-aminonitrile is competitively oxidized via a peroxyimidic acid by an intramolecular process. In the case of 2-aminopropanenitrile, this reaction leads to pyruvamide oxime. Furthermore, the study of structurereactivity relationships in the hydration of aliphatic and aromatic monofunctional nitriles and α-aminonitriles showed that the reactivity of the substrates towards hydroperoxide onion, which mostly depends on inductive effects of the substituents, is sufficiently enhanced to allow hydration of tertiary α-aminonitriles with low steric hindrance and regioselective hydration of dissymmetric α-aminodinitriles. Eisevier,.
- Taillades, Jacques
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- The Nature of the Transition State in Amides Pyrolysis. The Rates of Pyrolysis of N-benzoyl and N-acetylpropanamide, N-benzoyl and N-acetyl-2-methylpropanamide, and N-thioacetylpropanamide
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The rates of gas-phase elimination reactions of N-benzoyl and N-acetyl-propanamide and N-benzoyl and N-acetyl-2-methylpropanamide are measured and discussed.They undergo unimolecular first-order elimination reactions.The reactivities of N-benzoylamides have been compared with each other and with those of N-acetylamides.The kinetic data together with the product analysis reveals that, the statistical factor of the availability of β-hydrogen atoms for elimination as well as steric factor are obscured by polar factor in gas-phase elimination reactions of N-benzoylamides while the statistical factor rather than electronic effect operates in each of N-acetylamides.
- Al-Awadi, Nouria A.,Al-Omran, Fatima A.,Mathew, Tommy
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- The Acid-Catalyzed and Uncatalyzed Hydrolysis of Nitriles on Unactivated Alumina
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Nitriles are selectively converted into amides on unactivated alumina, with the surface hydroxyl groups serving as the source of water.
- Wilgus, Catherine Pala,Downing, Susan,Molitor, Erich,Bains, Satinder,Pagni, Richard M.,Kabalka, George W.
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p. 3469 - 3472
(2007/10/02)
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- Thermodynamics of Substituted Hydrazone and Its Fe(3+), UO2(2+), Cu(2+) and Zn(2+) Complexes. Potentiometric and Voltammetric Studies
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Complex equilibria of o-hydroxyacetophenone isobutyroyl hydrazone (H2AIBuH) with proton and Fe(3+), UO2(2+), Cu(2+) and Zn(2+) have been investigated potentiometrically in 0.1 M KCl and 20percent (v/v) ethanol-water media.The order of stability constants has been found to be Fe(3+) > UO2(2+) > Cu(2+) > Zn(2+).The dissociation of H2AIBuH and the stability constants of its Cu(2+) complexes have been found to increase with decreasing ionic strength of the medium and increasing organic content of the aquo-organic solvent.The Gibbs free enthalpy of transfer from water to ethanol-water solvents was found to be positive and increases with increasing ethanol content.The formation of the metal complexes has been found to be spontaneous, exothermic and entropically favoured as indicated from the derived thermodynamic functions (ΔG, ΔH, ΔS).Polarographic and cyclic voltammetric behaviours of H2AIBuH have been investigated in Britton-Robinson buffers of pH 2 - 12.The mechanism of the reaction process has been postulated.Moreover, the kinetic and the thermodynamic parameters for the electrode process have been evaluated. - Keywords: Gibbs free enthalpy of transfer / Potentiometry / Cyclic voltammetry / Polarography / Transition metal ions
- Shehatta, Ibrahim
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p. 109 - 122
(2007/10/02)
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- 3-AMIDOINDOLYL DERIVATIVES AND PHARMACEUTICAL COMPOSITIONS THEREOF
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The present invention is directed to a new class of 3-amido and 3-sulfamido-indolyl NMDA antagonists and their use in the treatment of a number of disease states.
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- 7-oxabicycloheptyl substituted heterocyclic amide or ester prostaglandin analogs useful in the treatment of thrombotic and vasospastic disease
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7-Oxabicycloheptane substituted prostaglandin analogs useful in treating thrombotic and vasopastic disease have the structural formula STR1 wherein m is 1, 2 or 3; n is 1, 2, 3 or 4; Z is --(CH2)2 --, --CH=CH-- or STR2 wherein Y is O, a single bond or vinyl, with the proviso that when n is 0, if Z is STR3 then Y cannot be O, and Z is --CH=CH--, n is 1, 2, 3 or 4; and when Y=vinyl, n=0; R is CO2 H, CO2 lower alkyl, CH2 OH, CO2 alkali metal, CONHSOR3, CONHR3a or --CH2 --5-tetrazolyl, X is O, S or NH; and where R1, R2, R3 and R3a are as defined herein.
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- A comparative study of the liquid-phase reduction of acrylamide and methacrylamide with cyclohexene and with molecular hydrogen over sepiolite-supported catalysts
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This paper deals with the optimization of the variables involved in the synthesis of Pd/sepiolite catalysts used in the individual and competitive reduction of acrylamide and methacrylamide with molecular hydrogen and by hydrogen transfer with cyclohexene as donor.From the reaction profiles of the acrylamide/methacrylamide pair were determined the relative reactivities and relative coefficients of adsorption corresponding to the competitive liquid-phase reductions with molecular hydrogen obtained for different catalysts, solvents, and temperatures.A similar study on the competitive hydrogen transfer reduction of both amides was rendered unfeasible by the fact that acrylamide was strongly adsorbed on the same types of sites as cyclohexene.This completely hindered cyclohexene adsorption and, as a result, inhibited the reaction altogether.
- Aramendia, M. A.,Borau, V.,Jimenez, C.,Marinas, J. M.,Sempere, M. E.,Urbano, F. J.
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- REACTION OF PHOSPHORUS THIOACID CHLORIDES WITH ETHYL ISOBUTYRIMIDATE HYDROCHLORIDE, PROPERTIES OF PHOSPHORYL THIOIMIDATES
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Phosphorus thioacid chlorides react with ethyl isobutyrimidate with the formation of 1-ethoxy-1-methylpropylideneamidothiophosphates, which can be hydrolyzed at both C=N and P-N bonds.
- Krongauz, Yu. I.,Potapova, V. V.,Sandakov, V. B.,Koroleva, T. N.,Bogomolova, L. M.
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p. 345 - 348
(2007/10/02)
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- Carbonylation (hydroformylation and hydrocarbalkoxylation) and enantioselective carbonylation of some methacrylic acid derivatives
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The hydroformylation of methyl methacrylate (1) or t-butyl methacrylate (2) takes place with fair to good chemoselectivity, the regioselectivity depending on the catalyst precursor used.By contrast, methacrylonitrile (3), methacrylamide (4), and N-benzyl-methacrylamide (5) undergo hydroformylation followed by subsequent reactions.The formyl product formed is reduced to the corresponding 2-cyano-2-methylpropan-1-ol in the case of 3, and undergoes cyclization to 2-methyl-2,3-dehydrobutyrolactames for 4 and 5.Under conditions of hydrocarbalkoxylation in the presence of palladium catalysts, 4 gives 3-methylsuccinimide.In the enantioselective reactions, extents of asymmetric induction of about 20-50percent have been obtained.
- Consiglio, Giambattista,Kollar, Laszlo,Koelliker, Robert
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p. 375 - 383
(2007/10/02)
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- β-cyclodextrin and hydripentacyanocobaltate catalyzed selective hydrogenation of α,β,-unsaturated acids and their derivatives
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Hydrogenation of the double bond of α,β-unsaturated acids, esters, anhydrides, amides, and nitriles occurs in good to excellent yields using in situ generated HCo(CN)5-3, and β-cyclodextrin as the phase transfer catalyst. Hydrolysis of the acid derivative usually accompanies double bond reduction.
- Lee,Alper
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p. 1941 - 1942
(2007/10/02)
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- Nor-statine and nor-cyclostatine polypeptides
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Polypeptides and derivatives thereof containing nor-statine and nor-cyclostatine are useful for inhibiting the angiotensinogen-cleaving action of the enzyme renin.
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- STUDY OF THE REACTIVITY OF AMMONIUM CARBOXYLATES IN THE SYNTHESIS OF AMIDES UNDER HIGH-PRESSURE DEFORMATION CONDITIONS
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On deformation under pressures up to 10 GPa the ammonium salts of aliphatic and aromatic acids, as well as mixtures of a free carboxylic acid with the ammonium salts of strong mineral acids, are converted into the corresponding amides.The amide yields increase with pressure, the magnitude of shearing deformation, and temperature.The temperature and pressure coefficients for amide formation are low and have values of 2.5-4 kJ/mole and -1 to -2 cm3/mole, respectively.The reactivity of ammonium salts in the synthesis of amides alternates in the homologous series of aliphatic acids in a similar way to the shear stress of these salts.The reactivity of the ammonium salts of aliphatic acids increases when the reaction is conducted in a matrix of an ammonium salt which possesses plasticity and a high shear stress.
- Christotina, N. P.,Zharov, A. A.
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p. 2103 - 2106
(2007/10/02)
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- Silicon Hydrides and Molybdenum(O) Catalyst: A Novel Approach for Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds
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A novel reducing system comprised of phenylsilane and catalytic amounts of Mo(CO)6 in refluxing THF efficiently effects conjugate reduction of Michael acceptors, including α,β-unsaturated ketones, carboxylic acids, carboxylic esters, amides, and nitriles.The process involves molybdenum-catalyzed hydrosilation, followed by hydrolysis of the intermediate silyl enol ether.Hydride is regioselectively transferred from the hydridosilane to the β-carbon of the substrate, and a proton from water is incorporated into the α-carbon.
- Keinan, Ehud,Perez, Daniel
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p. 2576 - 2580
(2007/10/02)
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- Process for the preparation of formamide compounds
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This invention relates to preparing formamide compounds in a process which comprises reacting an amine with a formylalkanolamine in the presence of carbon monoxide in which the mole ratio of amine to formylalkanolamine ranges from 0.2:1 to 5:1. The reaction is conducted at a temperature ranging from about 50° to 300° C. and a pressure ranging from about 100 to 10,000 psig. The amine employed in the reaction has the formula: STR1 wherein R' is hydrogen, an alkyl group of 1 to 10 carbon atoms, cyclohexyl, or --R"--O--R'", wherein R" is a divalent alkylene group of 2 to 4 carbon atoms and R'" is an alkyl group of 1 to 3 carbon atoms; and R is hydrogen or an alkyl group of 1 to 10 carbon atoms. The formylalkanolamine employed in the reaction has the formula: STR2 wherein R is an alkylene group of 1 to 3 carbon atoms, z is 0 or 1 and y is 1 or 2 and the sum of y and z is 2.
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- Ring-chain Tautomerism in Some 2-Piperidinone Derivatives
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The course of reactions between some imides and phenyllithium has been examined and structures of the products together with observed tautomerization are discussed.
- Czarnocki, Zbigniew,Wrobel, Jerzy T.
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p. 335 - 338
(2007/10/02)
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- Mechanism of the Reaction of Nitriles with Alkaline Hydrogen Peroxide. Reactivity of Peroxycarboximidic Acid and Application to Superoxide Ion Reaction
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Formation of peroxycarboximidic acid (1) is not rate-determining in the reaction of nitrile with alkaline hydrogen peroxide to form amide and oxygen; the yield of amide based on H2O2 varies from 20 to 60percent.When dimethyl sulfoxide (DMSO), a reactive substrate, is added, the rate is independent of and governed in turn by a rate-determining addition of HOO- to nitrile.This reaction gives a reliable α-value of kHOO-/kHO-, which is 10000 for benzonitrile.A facile conversion of nitrile to amide may be achieved by the reaction in the presence of DMSO, unacco mpanied by side reactions such as the epoxyamide formation from α,β-unsaturated nitrile.Kinetics and product analysis suggest that a predominant reaction is not a non-radical oxidation of H2O2 with 1 but a radical decomposition of H2O2 which is induced by the homolysis of anion of 1 (1A).No singlet oxygen could be trapped chemically.The reaction of superoxide ion, O2-., with acetonitrile is shown to be analogous to that of HOO-; the decomposition of O2-. is fast in the presence of MeCN and DMSO in benzene, affording acetamide and dimethyl sulfone.
- Sawaki, Yasuhiko,Ogata, Yoshiro
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p. 793 - 799
(2007/10/02)
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- Sulfur Nitride in Organic Chemistry. 9. The Reaction of Tetrasulfur Tetranitride with Benzyl Ketones. Preparation of 3,4-Disubstituted-1,2,5-thiadiazoles
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The reaction of tetrasulfur tetranitride (1) with various aryl and benzyl ketones (2a-o), oxindole (11), benzyl α-pyridyl ketone (12) and α-phenacylpyridine (13) afforded the corresponding 1,2,5-thiadiazoles (3a-n, 11 and 14).The scope and limitations of the above reaction were investigated and the evidences suggesting the radical anion mechanism are presented.
- Mataka, Shuntaro,Hosoki, Akira,Takahashi, Kazufumi,Tashiro, Masashi
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p. 1681 - 1685
(2007/10/02)
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