- A solvent-free and formalin-free Eschweiler-Clarke methylation for amines
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Primary and secondary amines are N-methylated by a mixture of paraformaldehyde and oxalic acid dihydrate in good to excellent yields. The reaction proceeds without involvement of organic solvents and toxic formalin. Reaction temperatures of 100°C are required for the decomposition of oxalic acid into the intermediate formic acid which acts as the actual reductant. The reaction conditions have been optimized, and the mechanism has been elucidated by means of deuteration experiments.
- Rosenau, Thomas,Potthast, Antje,Roehrling, Juergen,Hofinger, Andreas,Sixta, Herbert,Kosma, Paul
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Read Online
- Development and scale-up of an aqueous ethanolamine scrubber for methyl bromide removal
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A scrubber system was developed specifically to remove methyl bromide liberated during a demethylation process. On-line mass spectrometry (MS) was implemented and developed as a tool to monitor and quantify the methyl bromide scrubber efficiency during the demethylation reaction for laboratory and pilot-plant campaign runs. The MS technique is relatively simple to interface to existing equipment, requires no direct sample contact, and allows for the sampling from multiple ports. Results of the MS on-line monitoring using ethanolamine for both the laboratory and pilot plant showed scrubber removal efficiency of >99%. In addition to MS, ion chromatography and other gravimetric methods were implemented to confirm the level of methyl bromide consumed by the scrubber.
- Hettenbach, Kevin,Am Ende, David J.,Leeman, Kyle,Dias, Eric,Kasthurikrishnan, Narasimhan,Brenek, Steven J.,Ahlijanian, Paul
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Read Online
- Syntheses of 1,2-di-O -palmitoyl-sn -glycero-3-phosphocholine (DPPC) and analogs with 13C- and 2H-labeled choline head groups
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The syntheses of four head group labeled analogs of 1,2-di-O-palmitoyl-sn-glycero-3-phosphoc (DPPC) (6) by a general method from 1,2-di-O-palmitoyl-sn -glycero-3-phosphatidic acid (5) have been performed. The syntheses of 1,2-di-O-palmitoyl-sn-glycero-3-phospho[α-13C]choline (6a) and 1,2-di-O-palmitoyl-sn-glycero-3-phospho[β13C]choline (6b) were performed from labeled [l-13C]glycine (1a) in 52% overall yield and from [2-13C]glycine (1b) in 56% overall yield, respectively. 1,2-Di-O-palmitoyl-sn-glycero-3-phosphol[N(C2H3)3]choline (9) was prepared from 2-aminoethanol in 39% overall yield. 1,2-Di- O-palmitoyl-sn-glycero-3-phospho[α-C2H2]choline (12) was prepared from N,N-dimethylglycine ethyl ester in 50% overall yield.
- Lin, Sonyuan,Duclos Jr., Richard I.,Makriyannis, Alexandros
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Read Online
- Kinetics of hydroxyethylation of dimethylamine
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The kinetics of hydroxyethylation of dimethylamine with oxirane was studied in the temperature interval 20-50°C at the oxirane : dimethylamine molar ratio of 1:3. The influence exerted on the reaction rate by the reaction product, dimethylethanolamine, was examined.
- Danov,Kolesnikov,Efremov,Mezhenin
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Read Online
- Preparation method N-N -dimethyl monoethanolamine
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The invention provides N-N - dimethyl monoethanolamine preparation method which comprises the following steps: Pd, N dimethyl formamide and methanol undergo addition reaction under the action of a supported N - catalyst, and a reduction reaction is carried out in a hydrogen atmosphere to generate N-N - dimethyl monoethanolamine. The method has the advantages of reacting N, N - dimethyl formamide and methanol to prepare N, N - dimethyl monoethanolamine, avoiding the use of ethylene oxide, high activity of supported Pd catalyst, uneasy loss of catalyst, simple operation and good economic benefit.
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Paragraph 0062-0063
(2021/10/05)
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- PROCESS FOR PREPARING N-SUBSTITUTED ALKANOLAMINES AND/OR N-SUBSTITUTED DIAMINES FROM GLYCOLALDEHYDE
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A process for preparing a N-substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde is provided, which comprises reacting glycolaldehyde with an aminating agent of formula (III) in a solvent comprising at least one C1-C3 alkanol and/or tetrahydrofuran in the presence of hydrogen and a supported noble metal catalyst, wherein in formulas (I) - (III) : R and R', independently from each other, represent hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-C30 alkoxyalkyl, or C3-30 dialkylaminoalkyl, provided that at least one of R and R' is not hydrogen.
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Page/Page column 9
(2021/06/22)
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- RET INHIBITORS, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
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Provided herein are a RET inhibitor, a pharmaceutical composition thereof and uses thereof. In particular, provided is a compound having Formula (I) or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof. Provided is a pharmaceutical composition comprising the compound, and uses of the compound and pharmaceutical composition thereof for the preparation of a medicament, in particular for treatment and prevention of RET-related diseases and conditions, including cancer, irritable bowel syndrome, and/or pain associated with irritable bowel syndrome.
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Paragraph 00230; 00409; 00657
(2020/07/05)
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- General and Phosphine-Free Cobalt-Catalyzed Hydrogenation of Esters to Alcohols
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Catalytic hydrogenation of esters is essential for the sustainable production of alcohols in organic synthesis and chemical industry. Herein, we describe the first non-noble metal catalytic system that enables an efficient hydrogenation of non-activated esters to alcohols in the absence of phosphine ligands (with a maximum turnover number of 2391). The general applicability of this protocol was demonstrated by the high-yielding hydrogenation of 39 ester substrates including aromatic/aliphatic esters, lactones, polyesters and various pharmaceutical molecules.
- Shao, Zhihui,Zhong, Rui,Ferraccioli, Raffaella,Li, Yibiao,Liu, Qiang
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supporting information
p. 1125 - 1130
(2019/10/22)
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- Integrated preparation method of DMAE and DMAEE in microtubule reactor
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The invention discloses an integrated preparation method of DMAE and DMAEE in a microtubule reactor. The method comprises respectively feeding ethylene oxide and an aqueous solution of dimethylamine and water as a catalyst into a micro-tube reactor through a pump according to a mole ratio of ethylene oxide to dimethylamine oo 1-2: 1, setting a reaction temperature in the micro-tube reactor to 60-90 DEG C and pressure to 1.3+/-0.2 Pa and controlling standing time of the materials in the micro-tube reactor in 15-90s, wherein the efflux from the micro-tube reactor is an aqueous solution of DMAE and DMAEE. The method has the advantages of high atomic economy, good reaction selectivity, mild reaction conditions, short reaction time, simple catalyst and simple product separation.
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Paragraph 0035-0036; 0042
(2018/03/23)
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- Low-Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis
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Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process—reductive aminolysis—was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.
- Pelckmans, Michiel,Vermandel, Walter,Van Waes, Frederik,Moonen, Kristof,Sels, Bert F.
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p. 14540 - 14544
(2017/10/23)
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- Salt, a resist pattern of photoresist composition and method of manufacture
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PROBLEM TO BE SOLVED: To provide salt and a resist composition capable of forming a pattern having an excellent focus margin (DOF).SOLUTION: The salt is represented by formula (I) (wherein, Qand Qeach independently represent a fluorine atom or 1C-6C perfluoroalkyl group; Lrepresents a bivalent 2C-17C saturated hydrocarbon group, in which a methylene group contained in the bivalent saturated hydrocarbon group may be replaced with an oxy group or a carbonyl group; Rand Reach independently represent a 1C-12C hydrocarbon group: and Zrepresents an organic counter ion).
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Paragraph 0329
(2017/02/28)
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- Design, Synthesis, and Biological Evaluation of Scutellarein Derivatives Based on Scutellarin Metabolic Mechanism in Vivo
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Three series of scutellarein derivatives have been designed and synthesized based on metabolic mechanism of scutellarin (1) in vivo. Their thrombin inhibition activities were tested through the analyzation of prothrombin time (PT), activated partial thromboplastin time (APTT), thrombin time (TT), and fibrinogen (FIB). The antioxidant activities of these target products were assessed by 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) assay and the ability to protect PC12 cells against H2O2-induced cytotoxicity, and their solubilities were evaluated by ultraviolet (UV) spectrophotometer. The results showed that the two isopropyl groups substituted derivative (18c) demonstrated stronger anticoagulant activity, better water solubility, and good antioxidant activity compared with scutellarein (2), which warrants further development of 18c as a promising agent for ischemic cerebrovascular disease treatment. Three series of scutellarein derivatives have been designed and synthesized based on metabolic mechanism of scutellarin (1) in vivo. The results of the biological evaluation showed that the two isopropyl groups substituted derivative (18c) demonstrated stronger anticoagulant activity, better water solubility, and good antioxidant activity compared with scutellarein (2), which warrants further development of 18c as a promising agent for ischemic cerebrovascular disease treatment.
- Dong, Ze-Xi,Shi, Zhi-Hao,Li, Nian-Guang,Zhang, Wei,Gu, Ting,Zhang, Peng-Xuan,Wu, Wen-Yu,Tang, Yu-Ping,Fang, Fang,Xue, Xin,Li, He-Min,Cheng, Hai-Bo,Yang, Jian-Ping,Duan, Jin-Ao
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p. 946 - 957
(2016/05/24)
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- High color stability, N, N-dialkylethanolamine manufacturing method
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A process for preparing an N,N-dialkylethanolamine of the formula (I) having high colour stability where R1 and R2 are each independently a C1- to C8-alkyl group, by reacting ethylene oxide (EO) with a corresponding dialkylamine (R1R2NH) in the presence of water, wherein the reaction is effected continuously in a reactor, the reaction temperature is in the range from 90 to 180°C and the residence time (RT) in the reactor is in the range from 1 to 7 min, the reactor output is treated thermally at a temperature in the range from 80 to 160°C over a period in the range from 20 to 1000 min, and then the N,N-dialkylethanolamine is removed by distillation.
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Paragraph 0045
(2017/02/23)
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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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- Free-radical polymerization of itaconic acid in the presence of choline salts: Mechanism of persulfate decomposition
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Kinetics of decomposition of persulfate activated by choline in aqueous solution has been studied. Additionally, the products of choline degradation were analyzed by 1H NMR spectroscopy, and betaine aldehyde was identified as the main oxidation product. Thus, radical-chain redox mechanism is postulated to explain experimental results. The mechanism was successfully verified using kinetic modeling approach. Moreover, it was found that due to formation of complex of itaconic acid and choline chloride, the salt solubility of the acid in water was increased. Finally, free-radical polymerization of itaconic acid initiated by persulfate in aqueous solution of the choline salt yielded poly(itaconic acid) with higher molecular weight and increased polydispersity.
- Bednarz, Szczepan,B?aszczyk, Alicja,B?azejewska, Diana,Bogda?, Dariusz
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p. 297 - 304
(2015/02/19)
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- RANEY nickel-catalyzed reductive N-methylation of amines with paraformaldehyde: Theoretical and experimental study
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RANEY Ni-catalyzed reductive N-methylation of amines with paraformaldehyde has been investigated. This reaction proceeds in high yield with water as a byproduct. RANEY Ni can be easily recovered and reused with a slight decrease of the yield. Using density functional theory (DFT), the mechanism of RANEY Ni-catalyzed reductive N-methylation is discussed in detail. The reaction pathway involves the addition of amine with formaldehyde, dehydration to form the imine and hydrogenation. In the transition state of hemiaminal dehydration, the C-O bond cleavage of the aromatic amine is more difficult than that of the aliphatic amine. For the aromatic amine, a higher energy barrier must be overcome, which results in a relatively low yield. After addition of amine with formaldehyde and dehydration, imine is obtained and preferred to adsorb on the bridge site of the Ni(111) surface. The preferential pathways of imine hydrogenation involve the pre-adsorbed hydrogen atom attacking the nitrogen atom of the imine. The energy barrier of hydrogenation is much lower than that of addition and dehydration. Thus, the hydrogenation of imine is a relatively rapid reaction step. In the reductive N-methylation of secondary amine, the possible dehydration pathway is different from the one of the primary amine. In the dehydration of the secondary amine, the intermediate hemiaminal is initially adsorbed on the bridge site of the Ni(111) surface, then undergoes C-O bond cleavage, and eventually the hydroxyl is located in the bridge site. With the final hydrogenation, the product is obtained by adsorption on the top site of the Ni(111) surface.
- Ge, Xin,Luo, Chenxi,Qian, Chao,Yu, Zhiping,Chen, Xinzhi
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p. 43195 - 43203
(2015/02/19)
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- PROCESS FOR PREPARING AN N,N-DIALKY-ETHANOLAMINE HAVING HIGH COLOR STABILITY
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A process for preparing an N,N-dialkylethanolamine of the formula I having high color stability where R1 and R2 are each independently a C1- to C8-alkyl group, by reacting ethylene oxide (EO) with a corresponding dialkylamine (R1R2NH) in the presence of water, wherein the reaction is effected continuously in a reactor, the reaction temperature is in the range from 90 to 180° C. and the residence time (RT) in the reactor is in the range from 1 to 7 min, the reactor output is treated thermally at a temperature in the range from 80 to 160° C. over a period in the range from 20 to 1000 min, and then the N,N-dialkylethanolamine is removed by distillation.
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(2012/06/30)
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- 15N magnetic resonance hyperpolarization via the reaction of parahydrogen with 15N-Propargylcholine
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15N-Propargylcholine has been synthesized and hydrogenated with para-H2. Through the application of a field cycling procedure, parahydrogen spin order is transferred to the 15N resonance. Among the different isomers formed upon hydrogenation of 15N- propargylcholine, only the nontransposed derivative contributes to the observed N-15 enhanced emission signal. The parahydrogen-induced polarization factor is about 3000. The precise identification of the isomer responsible for the observed 15N enhancement has been attained through a retro-INEPT (15N-1H) experiment. T1 of the hyperpolarized 15N resonance has been estimated to be ca. 150 s, i.e., similar to that reported for the parent propargylcholine (144 s). Experimental results are accompanied by theoretical calculations that stress the role of scalar coupling constants (JHN and JHH) and of the field dependence in the formation of the observed 15N polarized signal. Insights into the good cellular uptake of the compound have been gained.
- Reineri, Francesca,Viale, Alessandra,Ellena, Silvano,Alberti, Diego,Boi, Tommaso,Giovenzana, Giovanni Battista,Gobetto, Roberto,Premkumar, Samuel S. D.,Aime, Silvio
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supporting information; experimental part
p. 11146 - 11152
(2012/08/28)
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- PROCESS FOR THE PRODUCTION OF ETHYLENE GLYCOL AND RELATED COMPOUNDS
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The present invention provide a process for the production of compounds of general formula (I), Y-CH2CH2-Z (I) wherein Y and Z are functional groups independently selected from the group consisting of a hydroxyl group and R1R2N and wherein R1 and R2 may be the same or different and are functional groups selected from the group consisting of hydrogen and substituted or non- substituited alkyl groups comprising 1 to 8 carbon atoms, or R1R2N is a cyclic compound selected from the group of aromatic and non-aromatic cyclic compounds optionally comprising one or more heteroatoms in addition to the nitrogen atom, said process comprising the steps of: (i) reacting carbon monoxide and an amine in the presence of oxygen to provide a compound of general formula (II) wherein R1 and R2 or R1R2N are as defined above and X is selected from the group consisting of R1R2N and R3O, wherein R3 is selected from alkyl groups comprising 1 to 8 carbon atoms; and (ii) converting the compound of general formula (II) into a compound of general formula (I) by a process that comprises a hydrogenation reaction.
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Page/Page column 10-12
(2010/12/17)
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- Cavitands with introverted functionality stabilize tetrahedral intermediates
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The synthesis and characterization of two deepened cavitand hosts with introverted functionality - f unctional groups directed into the cavity - is described. Two functions can be introverted, alcohol and aldehyde, and they show the formation of hemiacetals and hemiketals on binding small guests with complementary functional groups. The structures of the bound hemiacetals are determined by 1D and 2D NMR studies. The arrangements of the guests in the cavitands enhance the equilibrium constants of carbonyl additions, K/K ctrl, between 13- and 105-fold, compared to their counterparts in solution. The stabilization of the addition products is due to the prior complexation of the guests and the organized solvation provided to the tetrahedral intermediates by a network of secondary amides at the cavitand rim.
- Hooley, Richard J.,Restorp, Per,Iwasawa, Tetsuo,Rebek Jr., Julius
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p. 15639 - 15643
(2008/09/19)
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- Process for producing alkanolamines
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A process for producing an alkanolamine includes supplying a reactive distillation apparatus having an inner contacting surface which simultaneously facilitates a reaction process and a distillation process, feeding a first reactant including an amine represented by R′3-XNHX, wherein R′ is a hydrocarbon group, and X is 1, 2, or 3, feeding a second reactant including an akylene oxide represented by R″O, wherein R″ is a C2-C10-alkylene, feeding a catalyst in an amount from 0% to about 15% by weight of a mixture of the first reactant, the second reactant and the catalyst; recycling an overhead output from an overhead portion including an unreacted portion of the amine and the catalyst to achieve a substantially total reflux of the amine and the catalyst, and collecting a product output including an alkanolamine, the alkanolamine being a member selected from the group consisting of a monoalkanolamine, a dialkanolamine, and a trialkanolamine.
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- Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts
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The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH3OH) promoted by the conventional solid acids (H-mordenite, β-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and γ-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH 3OH in the reaction of 2-aminoethanol with methanol (amine/CH 3OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 °C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P2O5/SiO2 and Cs/SiO2, respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO2. The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.
- Oku, Tomoharu,Arita, Yoshitaka,Tsuneki, Hideaki,Ikariya, Takao
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p. 7368 - 7377
(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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- Reaction of 1-(R-sulfonyl)indoles with N,N-dibenzyl-β-amino alcohols
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The reaction of 1-(methylsulfonyl)- and 1-(phenylsulfonyl)indoles with N,N-dibenzylamino alcohols leads to the formation of a mixture of isomeric 1-(β-aminoethyl)indoles.
- Kurkin,Karchava,Yurovskaya
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p. 1141 - 1148
(2007/10/03)
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- Synthesis of 2-(dimethylamino)ethanol by the hydrogenolysis of tris(2-hydroxyethyl)amine
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A new reaction for the selective hydrogenolysis of tris(2-hydroxyethyl)amine into 2-(dimethylamino)ethanol by molecular hydrogen over metallic palladium catalyst is disclosed.
- Kiyoura, Tadamitsu,Muraishi, Teruo
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p. 1829 - 1829
(2007/10/03)
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- EFFICIENT AND/OR SELECTIVE METHYLATION BY DIAZOMETHANE OF ALCOHOLS, HALO ALCOHOLS, GLYCOLS, AMINO ALCOHOLS AND MERCAPTO ALCOHOLS WITH THE USE OF A PROTON-EXCHANGED X-TYPE ZEOLITE AS AN ACID-BASE BIFUNCTIONAL CATALYST
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Reactions of diazomethane with butanol, allyl alcohol and β- and γ-halo alcohols led to efficient methylation (giving the corresponding methyl ethers) with the use of a proton-excahnged X-type zeolite compared with H2SO4.The reactions with propylene and isobutylene glycols using the zeolite provided regioselective methylation of the primary OH rather than the secondary or tertiary OH, whereas regioselectivity was not observed in the reactions using H2SO4.The reactions with 2-aminoethanol and 2-mercaptoethanol showed high chemoselective S-methylation and N-monomethylation, respectively, in the presence of the zeolite instead of H2SO4.The mechanism for the reactions is proposed to involve acid-base bifunctional catalysis of the zeolite in which the acidic site reacts with diazomethane to form its conjugate acid, and the nucleophilicity of OH and SH groups is enhanced by the interaction of the basic site with the proton of the groups.
- Takeuchi, Hiroshi,Kishioka, Hiroaki,Kitajima, Kunio
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p. 121 - 126
(2007/10/02)
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- Linear dicarbonylation of difunctionalized butenes
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Difunctional butenes are linearly dicarbonylated into 3-hexene-1,6-dioic acid or alkyl diesters thereof, well suited for the ultimate production of, e.g., adipic acid, by reacting such difunctional butene with carbon monoxide and, if appropriate, an alcohol, at an elevated temperature under superatmospheric pressure, in the presence of at least one source of hydrogen chloride and a catalytically effective amount of palladium, at least a portion of which palladium being in the zero oxidation state, as well as a quaternary onium chloride of nitrogen or phosphorus, the nitrogen or phosphorus atom being tetracoordinated to carbon atoms, with the proviso that the nitrogen atom may be coordinated to two pentavalent phosphorus atoms.
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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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- Processes for the preparation of aminoethers
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A process for preparing aminoethers, particularly bis[2-(N,N-dialkylamino)alkyl]ethers, which comprises contacting a carboxylated aminoether with a metal oxide catalyst under conditions effective to produce the aminoether. Many of these aminoethers are useful as catalysts in the production of polyurethanes, especially cellular polyurethanes.
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- DEHYDROGENATION OF SUBSTITUTED ALCOHOLS TO ALDEHYDES ON ZINC OXIDE-CHROMIUM OXIDE CATALYSTS
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Sixteen primary alcohols of the structure RCH2OH (R = CH3, C2H5, (CH3)2CH, (CH3)3CCH2, HOCH2, CH3OCH2, C6H5, C6H5CH2, C6H5OCH2, ClCH2, BrCH2, F3C, CNCH2, (CH3)2NCH2, (C2H5)2NCH2 and tetrahydrofurfuryl) were explored for the possibility of obtaining the corresponding aldehydes by dehydrogenation on solid catalysts.Various catalysts were tested and two zinc oxide-chromium oxide catalysts were selected for further work because their activity and selectivity was satisfactory; moreover, the selectivity could be improved by addition of sodium into the catalysts and of water into the feed.The reaction was performed in the temperature range 250 - 450 deg C and at atmospheric pressure. 2-Chloroethanol, 2-bromoethanol, ethylene glycol, 2-cyanoethanol and 2-(N,N-diethylamino)ethanol decomposed and deactivated the catalyst.The other alcohols were studied from the point of kinetics of dehydrogenation, which was described by a Langmuir-Hinshelwood type rate equation (3), and of substituent effects on rate, which were correlated by Taft equation (1) with the slope ρ* = -1.46.The preparative value of catalytic dehydrogenation for obtaining substituted aldehydes was confirmed by prolonged runs and isolation of the aldehydic product by distillation using as the feeds 2-methoxyethanol and 2-(N,N-dimethylamino)ethanol, respectively.
- Gulkova, Daniela,Kraus, Milos
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p. 2215 - 2226
(2007/10/02)
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- Temperature and Pressure Effects on the Reversible Reaction of a Parent Phenol (GH) Corresponding to Galvinoxyl with Aliphatic Amines
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The effects of temperature and pressure on the reversible reaction between GH and aliphatic amines in acetonitrile have been studied spectrophotometrically.The formation of the free ions rather than that of ion pairs has been confirmed by the modified Benesi-Hildebrand (B-H) plot.From the plot the equilibrium constants were estimated.From the temperature dependence of the equilibrium constant (K), the heat and entropy of reactions were estimated to be: (ΔH0)av=-44.5 kJ mol-1, and (ΔS0)av=-193 J K-1 mol-1.From the pressure dependence of K the reaction volume (ΔV0)av was estimated to be -40 dm3 mol-1.When unbranched primary amines were used, a side reaction took place for which an explanation has been given.
- Nishimura, Norio,Iga, Siroh,Satoh, Masahiro,Yamamoto, Shunzo
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p. 2437 - 2441
(2007/10/02)
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- Antihypertensive 1,4-dihydropyridines having a conjugated ester
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1,4-dihydropyridine derivatives represented by the following general formula, STR1 in which R3 is a combination of an unsaturated straight chain hydrocarbon group or derivative thereof connected by a single bond with an unsaturated hydrocarbon group or derivative thereof so that the unsaturated carbon atoms of the two groups are in conjugated relationship. These compounds have a hypotensive action the effective time of which is long, which makes the blood pressure descend slowly, and the toxicity of which is low.
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- Method of making boron analogues
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A method of synthesizing boron analogues of choline and choline related mrials is disclosed. The method comprises reacting N,N dimethylethanolamine with hydrogen chloride or an acid chloride to form an ester hydrochloride. The resulting aminoalcohol hydrochloride or ester hydrochloride is further reacted with tetraethyl NBH4. Also disclosed are pharamaceutically interesting compounds of acetylcholine.
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- Homogeneously Catalyzed Synthesis of β-Amino Alcohols ans Vicinal Diamines from Ethylene Glycol and 1,2-Propanediol
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Disubstituted β-amino alcohols and tetrasubstituted vicinal alkanediamines have been synthesized in high yield and at mild temperatures by the selective amination of ethylene glycol and 1,2-propanediol catalyzed by ruthenium or iridium complexes.
- Marsella, John A.
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p. 467 - 468
(2007/10/02)
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- Catalysts for alkoxylation reactions
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Catalysts producing a sharply peaked alkoxylation distribution during the alkoxylation of organic materials comprise mixtures of BF3 and metal alkyls or metal alkoxides, SiF4 and metal alkyls or metal alkoxides, or mixtures of these catalysts.
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- Methods of alkoxylation
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Catalysts comprising mixtures of HF and metal alkoxides and mixed metal alkoxides produce a sharply peaked alkoxylation distribution during the alkoxylation of organic materials.
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- Catalysts for alkoxylation reactions
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Catalysts and a method of using said catalysts for the alkoxylation of a variety of materials is disclosed. Catalysts so described produce alkoxylates having a very sharp alkoxylate distribution. The catalysts are supported and unsupported dialkoxy and dialkyl metal fluorides and halides and alkyl metal difluorides and dihalides.
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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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- PREPARATION DE SELS D'AMINOALKYLPHOSPHONIUMS
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Three synthetic methods have been applied to prepare amino phosphonium salts: (C6H5)3P+-(CH2)n-N-.The best ways have been determined for different n values and different substituents on the nitrogen atom.In all cases, yields are better with n=3, but no intramolecular stabilization has been detected.
- Dantas, T. N. de Castro,Laval, J. P.,Lattes, A.
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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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- Extremely low viscosity adducts of lactams with alcohols
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Adducts useful as solvents are prepared from lactams and an aliphatic, cycloaliphatic or araliphatic alcohol or thioalcohol. Solutions of the adducts in the lactam, alcohol or thioalcohol are also disclosed as well as a process for preparing the adducts and solutions thereof.
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