- Hydrogenation of Esters by Manganese Catalysts
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The hydrogenation of esters catalyzed by a manganese complex of phosphine-aminopyridine ligand was developed. Using this protocol, a variety of (hetero)aromatic and aliphatic carboxylates including biomass-derived esters and lactones were hydrogenated to primary alcohols with 63–98% yields. The manganese catalyst was found to be active for the hydrogenation of methyl benzoate, providing benzyl alcohol with turnover numbers (TON) as high as 45,000. Investigation of catalyst intermediates indicated that the amido manganese complex was the active catalyst species for the reaction. (Figure presented.).
- Li, Fu,Li, Xiao-Gen,Xiao, Li-Jun,Xie, Jian-Hua,Xu, Yue,Zhou, Qi-Lin
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- REDUCTIVE PREPARATION OF TERTIARY DIMETHYLAMINES FROM NITRILES
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This disclosure describes a low temperature process for the preparation of dimethyl amines from nitriles via reductive amination. In some embodiments, the process proceeds under mild conditions with aqeuous dimethylamine and show an unexpected rate acceleration by the inclusion of an acid addition salt of the dimethylamine.
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Paragraph 0039
(2017/04/04)
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- Reductive amination of nitriles using transfer hydrogenation
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This disclosure describes a low temperature process for the preparation of tertiary amines from nitriles and secondary amines via reductive amination using transfer hydrogenation. The process can use a nitrile and a dialkylamine and proceeds under surprisingly mild conditions using a palladium catalyst and the corresponding dialkylammonium formate as the hydrogen donor, and show a pronounced acceleration in the presence of water.
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Paragraph 5; 6; 7; 8
(2016/11/09)
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- Nanopalladium-catalyzed conjugate reduction of Michael acceptors-application in flow
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A continuous-flow approach towards the selective nanopalladium-catalyzed hydrogenation of the olefinic bond in various Michael acceptors, which could lead to a greener and more sustainable process, has been developed. The nanopalladium is supported on aminofunctionalized mesocellular foam. Both aromatic and aliphatic substrates, covering a variation of functional groups such as acids, aldehydes, esters, ketones, and nitriles were selectively hydrogenated in high to excellent yields using two different flow-devices (H-Cube and Vapourtec). The catalyst was able to hydrogenate cinnamaldehyde continuously for 24 h (in total hydrogenating 19 g cinnanmaldehyde using 70 mg of catalyst in the H-cube) without showing any significant decrease in activity or selectivity. Furthermore, the metal leaching of the catalyst was found to be very low (ppb amounts) in the two flow devices.
- Nagendiran, Anuja,S?rensen, Henrik,Johansson, Magnus J.,Tai, Cheuk-Wai,B?ckvall, Jan-E.
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supporting information
p. 2632 - 2637
(2016/05/24)
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- Improved Second Generation Iron Pincer Complexes for Effective Ester Hydrogenation
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Hydrogenation of esters to alcohols with a well-defined iron iPr2PNP pincer complex has been recently reported by us and other groups. We now introduce a novel and sterically less hindered Et2PNP congener that provides superior catalytic activity in the hydrogenation of various carboxylic acid esters and lactones compared to the known complex. Successful hydrogenation proceeds under relatively mild conditions (60°C) with lower catalyst loadings.
- Elangovan, Saravanakumar,Wendt, Bianca,Topf, Christoph,Bachmann, Stephan,Scalone, Michelangelo,Spannenberg, Anke,Jiao, Haijun,Baumann, Wolfgang,Junge, Kathrin,Beller, Matthias
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supporting information
p. 820 - 825
(2016/03/09)
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- Synthesis of scutellarein derivatives to increase biological activity and water solubility
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In order to improve the biological activity and water solubility of scutellarin (1), some derivatives of its main metabolite (scutellarein) were designed and synthesized. All the compounds were tested for their thrombin inhibition activity through the analyzation of thrombin time (TT), activated partial thromboplastin time (APTT), prothrombin time (PT) and fibrinogen (FIB). Their antioxidant activities were assessed by measuring their scavenging capacities toward 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and the ability to protect PC12 cells against H2O2-induced cytotoxicity, their water solubility were also assessed by ultraviolet (UV) spectrophotometer. The results showed that compound 8b demonstrated stronger anticoagulant and antioxidant activity, better water solubility compared with scutellarein (2), which warrants it as a promising agent for the treatment of ischemic cerebrovascular disease.
- Shi, Zhi-Hao,Li, Nian-Guang,Shi, Qian-Ping,Zhang, Wei,Dong, Ze-Xi,Tang, Yu-Ping,Zhang, Peng-Xuan,Gu, Ting,Wu, Wen-Yu,Fang, Fang,Xin-Xue,Li, He-Min,Yang, Jian-Ping,Duan, Jin-Ao
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p. 6875 - 6884
(2015/11/11)
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- Catalytic hydrogenation of esters. Development of an efficient catalyst and processes for synthesising (R)-1,2-propanediol and 2-(l-Menthoxy)ethanol
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A ruthenium catalyst for the reduction of esters by hydrogenation has been developed. Processes for the hydrogenation of esters have also been developed for (R)-1,2-propanediol and 2-(l-menthoxy)ethanol. The catalyst shows good catalytic activity for the hydrogenation of esters in methanol. Methyl lactate was reduced at 30 °C and gave turnover numbers (TON) up to 4000. The optical purity of the (R)-1,2-propanediol made by the hydrogenation of methyl (R)-lactate was higher than that via the asymmetric hydrogenation of hydroxyacetone. A hydrogenation process to replace the lithium aluminum hydride (LAH) reduction used in the production of 2-(l-menthoxy)ethanol was developed.
- Kuriyama, Wataru,Matsumoto, Takaji,Ogata, Osamu,Ino, Yasunori,Aoki, Kunimori,Tanaka, Shigeru,Ishida, Kenya,Kobayashi, Tohru,Sayo, Noboru,Saito, Takao
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experimental part
p. 166 - 171
(2012/05/20)
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- METHOD FOR PRODUCING N,N-SUBSTITUTED-3-AMINOPROPAN-1-OLS
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The present invention relates to a process for preparing N,N-substituted 3-aminopropan-1-ols by a) reacting secondary amine with acrolein at a temperature of (?50) to 100° C. and a pressure of 0.01 to 300 bar, and b) reacting the reaction mixture obtained in stage a) with hydrogen and ammonia in the presence of a hydrogenation catalyst at a pressure of 1 to 400 bar, wherein the molar ratio of secondary amine to acrolein in stage a) is 1:1 or more and the temperature in stage b) is in the range from (?50) to 70° C. In a preferred embodiment, acrolein which has been obtained from glycerol based on renewable raw materials is used. The invention further relates to the use of an N,N-dimethyl-3-aminopropan-1-ol (DMAPOL) based on renewable raw materials as a catalyst for polyurethane preparation, as a scrubbing fluid in gas scrubbing, in the electronics chemicals and electroplating sectors, as a feedstock in organic synthesis, and as an intermediate in the production of pharmaceuticals and crop protection compositions.
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Page/Page column 9
(2011/12/12)
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- METHOD FOR PRODUCING N,N-SUBSTITUTED-1,3-PROPANDIAMINES
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The present invention relates to a process for preparing N,N-substituted 1,3-propanediamine by a) reacting secondary amine with acrolein at a temperature of from (?50) to 100° C. and a pressure of from 0.01 to 300 bar, andb) reacting the reaction mixture obtained in stage a) with hydrogen and ammonia in the presence of a hydrogenation catalyst at a temperature of from 40 to 400° C. and a pressure of from 1 to 400 bar, wherein the molar ratio of secondary amine to acrolein in stage a) is 2:1 or more and the hydrogenation catalyst used in stage b) comprises cobalt. In a preferred embodiment, acrolein which has been obtained from glycerol based on renewable raw materials is used. The invention further relates to the use of N,N-dimethyl-1,3-propanediamine (DMAPA) based on renewable raw materials as a feedstock for lubricant soaps and other detergents, coagulants, polymers and comb polymers. In a further preferred embodiment, stage b) is performed in the presence of water.
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Page/Page column 8
(2011/04/18)
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- ALCOHOL PRODUCTION METHOD BY REDUCING ESTER OF LACTONE WITH HYDROGEN
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Provided is an alcohol production method comprising the step of reducing an ester or a lactone with hydrogen to produce a corresponding alcohol without addition of a base compound by using, as a catalyst, a ruthenium complex represented by the following general formula (1): [in-line-formulae]RuH(X)(L1)(L2)n ??(1)[/in-line-formulae] wherein X represents a monovalent anionic ligand,L1 represents a tetradentate ligand having at least one coordinating phosphino group and at least one coordinating amino group or a bidentate aminophosphine ligand having one coordinating phosphino group and one coordinating amino group, andL2 represents a bidentate aminophosphine ligand having one coordinating phosphino group and one coordinating amino group, provided thatn is 0 when L1 is the tetradentate ligand, and n is 1 when L1 is the bidentate aminophosphine ligand.
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Page/Page column 14
(2010/04/23)
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- Construction of an Artificial Glutathione Peroxidase Active Site on Copolymer Vesicles
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To construct an efficient GPx mimic, a novel method for preparing polymer-based vesicles carrying GPx-active sites was developed. A series of block copolymers loaded with recognition and catalytic sites were synthesized based on polystyrene-block-poly[tri(ethylene glycol) methyl ether acrylate]s (PS-PMEO3MAs). By altering the molar ratio of the functional copolymers, vesicles with GPx activity were obtained by self-assembly of these functional copolymers through blending. The optimum GPx mimic constructed by the blending process exhibited high catalytic activity and acted as a real catalyst with typical saturation kinetics behavior. The method may be of benefit for designing other enzyme mimics and may cast a light on constructing other biologically related functional nanoparticles.Self-assembly of functional copolymers through blending is a novel and simple method to construct efficient glutathione peroxidase(GPx) mimics. The optimum blended GPx mimic is obtained by optimizing the structure of the functional block copolymers and altering the ratio of the functional block copolymers. The blended GPx mimic exhibits remarkable catalytic activity and acts as a real catalyst with typical saturation kinetics behavior.
- Yin, Yanzhen,Huang, Xin,Lv, Chunyan,Wang, Liang,Yu, Shuangjiang,Luo, Quan,Xu, Jiayun,Liu, Junqiu
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experimental part
p. 1505 - 1516
(2011/10/09)
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- 2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION
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The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.
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- Detritylation Procedure under Non-Acidic Conditions: Naphthalene Catalysed Reductive Cleavage of Trityl Ethers
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The reaction of primary, secondary, allylic and benzylic trityl ethers 1 with lithium powder and a catalytic amount of naphthalene led to reductive cleavage of the trityl-oxygen bond, affording the corresponding alcohols 2 in good to excellent yields under very mild reaction conditions. The detritylation process could successfully be extended to several hydroxy, alkoxy and amino functionalised trityl ethers. This methodology represents a new and efficient detritylation procedure under non-acidic reaction conditions.
- Yus, Miguel,Behloul, Cherif,Guijarro, David
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p. 2179 - 2184
(2007/10/03)
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- Enhanced product selectivity in continuous N-methylation of amino alcohols over solid acid-base catalysts with supercritical methanol
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The unique properties of supercritical fluids can be exploited for fine-tuning product selectivity. Under the conditions listed for the N-methylation of amino alcohols (see scheme) over solid acid-base bifunctional catalysts, the total yield and product selectivity could be improved. Enhanced product selectivity might be attributed to the milder reaction conditions possible with supercritical methanol, as well as the increased concentration of methanol on the catalyst.
- Oku, Tomoharu,Ikariya, Takao
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p. 3476 - 3479
(2007/10/03)
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- Nucleophilicity towards a Vinylic Carbon Atom: Rate Constants for the Addition of Amines to the 1-Methyl-4-vinylpyridinium Cation in Aqueous Solution
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Second-order rate constants (kNu) have been measured for the addition of 44 primary amines (including five α-effect amines), 28 secondary amines, 19 tertiary amines, ammonia and hydroxide ion to the vinyl group of the 1-methyl-4-vinylpyridinium cation (1) in aqueous solution at 25 deg C (ionic strength 0.1 mol dm-3).Nucleophilic attack is shown to be rate-determining for primary and secondary amines being generally more reactive than primary amines, with secondary amines of the same basicity.After classification of these species in terms of structure, they describe a number of Broensted-type correlations having βnuc in the range 0.35-0.54 for six structural classes of primary amine, βnuc = 0.48 for α-effect amines, and βnuc in the range 0.23-0.34 for four structural classes of secondary amine.Substitution upon the α-carbon atom reduces amine nucleophilicity of both primary and secondary amines.The presence of an unsaturated carbon atom (either sp2- or sp-hybridized) as the β-carbon atom leads to an enhanced reactivity relative to the corresponding β-sp3 species in all cases.Tertiary amines are in general less reactive than other amines of the same basicity.Broensted-type plots for tertiary amines present the appearance of random scatter which is not readily decipherable in terms of structure. β-Hydroxy and β-amino tertiary amines are unusually reactive relative to their basicity.All of these phenomena suggest that protonation of the carbanionic intermediate by a molecule of water is the rate-determining step for the addition of tertiary amines to 1.Rate constants for the attack of primary and secondary amines on 1 are shown to correlate with literature data for a variety of other reactions involving rate-determining nucleophilic attack of amines upon electrophilic carbon.These kNu for primary and secondary amines reacting with 1 are also shown to correlate with Ritchie's N+ parameters for nucleophilic attack at electrophilic sp2-carbon.N+ parameters for amine nucleophiles have not been widely available previously; the parameters that have been available for selected amines are known to be sensitive to the nature of the defining electrophile.The minimal steric hindrance at the electrophilic centre in nucleophilic attack upon 1 suggests that this species is an appropriate electrophile for the definition of N+ parameters for amine nucleophiles; these parameters are evaluated for 70 primary and secondary amines and ammonia and are suggested to provide an appropriate data base for future investigations of the reactivity and selectivity of amine attack upon sp2-carbon electrophiles in aqueous solution.
- Heo, Christina K. M.,Bunting, John W.
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p. 2279 - 2290
(2007/10/02)
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- Omega-quaternary ammonium alkyl esters and thioesters of acidic nonsteroidal antiinflammatory drugs
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Quaternary ammonium alkyl esters and thioesters of acidic nonsteroidal anti-inflammatory drugs (NSAIDs) are disclosed. These esters and thioesters display the anti--inflammatory profile of the parent NSAIDs with greatly reduced gastrointestinal irritancy, providing a more favorable separation of therapeutic activity and toxicological side effects than the parent NSAIDs.
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- The influence of a base on the methylation of aminoalchols
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A selective methylation towards N and O atoms on aminoalcohols was observed using metal hydride reagents as the base, and the predominant factors for the selectivity were investigated in detail.
- Kashima, Choji,Harada, Kazuo,Omote, Yoshimori
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p. 288 - 290
(2007/10/02)
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- CLEAVAGE OF N-METHOXYMETHYLAMMONIUM SALTS. III. TRANSFORMATION OF AMMONIUM SALT DERIVATIVES OF ALIPHATIC AMINO ALCOHOLS IN DIMETHYL SULFOXIDE
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The dealkylation of methoxymethyl quaternary ammonium salts of some aliphatic amino alcohols in DMSO leads to the simultaneous formation of the hydrohalides of methyl(aminoalkyl)formals and the corresponding amino alcohols.The formals are formed by an intermolecular mechanism.
- Bystrova, L. P.,Kuznetsov, S. G.,Chigareva, S. M.
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p. 1549 - 1553
(2007/10/02)
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- HYDROBORATION D'AMINES ALLYLIQUES. REACTIVITE DES ORGANOBORANES
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Hydroboration of differently substituted allylic amines has been studied systematically.It was possible to demonstrate the importance of the hydroboration agent on the formation of aminoboranes.Oxidation of aminoboranes by hydrogen peroxyde in basic medium has ben examined and has led, with good yields, to primary aminoalcohols or a mixture of isomeric aminoalcohols.The influence of steric hindrance on the double bond and that of substitution of the nitrogen atom have been shown.
- Baboulene, Michel,Torregrosa, Jean-Luc,Speziale, Vincent,Lattes, Armand
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p. 565 - 570
(2007/10/02)
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- 2'-(4,6-Disubstituted)-s-triazin-2-yl)amino-6'-dialkylamino flurans
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Fluorans useful as color precursors, particularly in the art of carbonless duplicating are normally colorless and are represented by the structural formula STR1 wherein R represents non-tertiary alkyl of one to four carbon atoms; R1 and R2 represent hydrogen or non-tertiary alkyl of one to four carbon atoms; R3 and R4 represent chlorine, NH2 or one of the groups --NR5 -(lower-alkylene)-N(R6)(R7), --NR5 -(lower-alkylene-N(R8)(R9)(R10) An, -NR5 -(lower-alkylene)-OH, -NR5 -(lower-alkylene) STR2 --NR5 -(HSO3 -C6 H4) or --O-(lower-alkylene)-N(R8)(R9) in which R5, R6 and R7 represent hydrogen or non-tertiary alkyl of one to four carbon atoms; R8 and R9 represent non-tertiary alkyl of one to four carbon atoms; R10 represents non-tertiary alkyl of one to four carbon atoms, benzyl or benzyl substituted in the benzene ring by one or two of halo or alkyl of one to three carbon atoms; and An represents an anion.
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