- CO2 Methanation via Amino Alcohol Relay Molecules Employing a Ruthenium Nanoparticle/Metal Organic Framework Catalyst
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Methanation of carbon dioxide (CO2) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst comprising ruthenium nanoparticles (NPs) immobilized on a Lewis acidic and robust metal–organic framework (MOF). The Ru NPs are well dispersed on the surface of the MOF crystals and have a narrow size distribution. The catalyst efficiently transforms amino alcohols to oxazolidinones (upon reaction with CO2) and then to methane (upon reaction with hydrogen), simultaneously regenerating the amino alcohol relay molecule. This protocol provides a sustainable, indirect way for CO2 methanation as the process can be repeated multiple times.
- Chidambaram, Arunraj,Cui, Xinjiang,Dyson, Paul J.,Fei, Zhaofu,Nguyen, Tu N.,Shyshkanov, Serhii,Stylianou, Kyriakos C.
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- Combining Low-Pressure CO2 Capture and Hydrogenation to Form Methanol
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This paper describes a novel approach to CO2 hydrogenation, in which CO2 capture with aminoethanols at low pressure is coupled with hydrogenation of the captured product, oxazolidinone, directly to MeOH. In particular, (2-methylamino)ethanol or valinol captures CO2 at 1-3 bar in the presence of catalytic Cs2CO3 to give the corresponding oxazolidinones in up to 65-70 and 90-95% yields, respectively. Efficient hydrogenation of oxazolidinones was achieved using PNN pincer Ru catalysts to give the corresponding aminoethanol (up to 95-100% yield) and MeOH (up to 78-92% yield). We also have shown that both CO2 capture and oxazolidinone hydrogenation can be performed in the same reaction mixture using a simple protocol that avoids intermediate isolation or purification steps. For example, CO2 can be captured by valinol at 1 bar with Cs2CO3 catalyst followed by 4-isopropyl-2-oxazolidinone hydrogenation in the presence of a bipy-based pincer Ru catalyst to produce MeOH in 50% yield after two steps.
- Khusnutdinova, Julia R.,Garg, Jai Anand,Milstein, David
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- Schiff's Bases as Intermediates in the Hydrolytic Decomposition of 2-Alkyl-3-methyl-1,3-oxazolidines in Aqueous Acid
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The kinetics for the hydrolysis of 2-alkyl-3-methyl-1,3-oxazolidines have been examined spectrophotometrically in acidic solutions.The decomposition of the substrates to 2-methylaminoethanol and the corresponding aldehydes have been shown to proceed via stable intermediates which are kinetically and u.v.-spectroscopically very similar to the acyclic cationic Schiff's base derived from isobutyraldehyde and 2-methoxyethylmethylamine.The mechanisms for the formation and breakdown of the Schiff's base intermediate are discussed on the basis of pH-rate profiles, activation parameters, salt effects, and solvent deuterium isotope effects.
- Pihlaja, Kalevi,Parkkinen, Aija,Loennberg, Harri
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- A near-IR uncaging strategy based on cyanine photochemistry
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The development of photocaging groups activated by near-IR light would enable new approaches for basic research and allow for spatial and temporal control of drug delivery. Here we report a near-IR light-initiated uncaging reaction sequence based on readily synthesized C4'-dialkylamine-substituted heptamethine cyanines. Phenol-containing small molecules are uncaged through sequential release of the C4'-amine and intramolecular cyclization. The release sequence is initiated by a previously unexploited photochemical reaction of the cyanine fluorophore scaffold. The uncaging process is compatible with biological milieu and is initiated with low intensity 690 nm light. We show that cell viability can be inhibited through light-dependent release of the estrogen receptor antagonist, 4-hydroxycyclofen. In addition, through uncaging of the same compound, gene expression is controlled with near-IR light in a ligand-dependent CreERT/LoxP-reporter cell line derived from transgenic mice. These studies provide a chemical foundation that we expect will enable specific delivery of small molecules using cytocompatible, tissue penetrant near-IR light.
- Gorka, Alexander P.,Nani, Roger R.,Zhu, Jianjian,Mackem, Susan,Schnermann, Martin J.
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- Electrochemical Reductive N-Methylation with CO2Enabled by a Molecular Catalyst
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The development of benign methylation reactions utilizing CO2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, we report the first electrochemical reductive N-methylation reaction with CO2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO2, with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO2 and nitro-compounds are reduced concurrently to yield N-methylamines with high monomethylation selectivity via the overall transfer of 12 electrons and 12 protons.
- Rooney, Conor L.,Wu, Yueshen,Tao, Zixu,Wang, Hailiang
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supporting information
p. 19983 - 19991
(2021/12/01)
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- Preparation method of N-methylmonoethanolamine
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The invention provides a preparation method of N-methyl monoethanolamine. Under the action of a supported Cu catalyst, formaldehyde, ammonia gas and ethanol react, the product is separated through vacuum distillation, and the used supported Cu catalyst is prepared from a Cu-containing compound, a ligand and a carrier. According to the catalyst, amino acid is adopted as a ligand, N and O in the amino acid are complexed with copper, the activity of an active component is improved, complexation with formaldehyde and ammonia gas is avoided, an intermediate for an addition reaction of the ammonia gas and the formaldehyde is efficiently catalyzed to generate a coupling reaction with ethanol, and the supported Cu catalyst is not prone to loss. And a secondary addition reaction in an ethylene oxide method is avoided.
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Paragraph 0047-0048; 0049-0050; 0063-0064; 0065-0066
(2021/11/03)
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- Discovery of benzimidazole analogs as a novel interleukin-5 inhibitors
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A series of novel hydroxyethylaminomethylbenzimidazole analogs 5a-y were synthesized and evaluated for their IL-5 inhibitory activity using pro-B Y16 cell line. Among them, 2-(((4-(cyclohexylmethoxy)-1H-benzo[d]imidazol-2-yl)methyl)amino)butan-1-ol (5e, 94.3% inhibition at 30 μM, IC50 = 3.5 μM, cLogP = 4.132) and 3-cyclohexyl-2-(((4-(cyclohexylmethoxy)-1H-benzo[d]imidazol-2-yl)methyl)amino) propan-1-ol (5k, 94.7% inhibition at 30 μM, IC50 = 5.0 μM, cLogP = 6.253) showed the most potent inhibitory activity. The essential feature of SAR (Fig. 5) indicated that the chromenone ring can be replaced by a benzimidazole ring to maintain the inhibitory activity. In addition, the hydroxyethylaminomethyl group was suitable for the IL-5 inhibitory activity. Moreover, the hydrophobic substituents on carbon play an important role in the IL-5 inhibitory activity of these analogs. However, N-substituted analogs did not improve inhibitory activity. In addition, MTT assay of 5e and 5k with normal B lymphoblasts revealed that they had no significant effects on cell viability.
- Boggu, Pulla Reddy,Kim, Youngsoo,Jung, Sang-Hun
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- MALDI-TOF MS investigation of the unconventional termination of living polyoxazoline with ammonia
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Poly(2-oxazoline) (POx) based materials have experienced renewed interest, due to their biocompatibility and broad functional diversity. Although research pertaining to cationic ring opening polymerization (CROP) of 2-oxazoline derivatives spans upwards of 5 decades, modern characterization techniques, specifically Matrix Assisted Laser-Desorption Ionization—Time of Flight Mass Spectrometry (MALDI-TOF MS), were not available during early studies to aid in identifying polymer end-groups. Through careful synthesis and analytical characterization, evidence supports an alternative mode of nucleophilic attack during ammonia termination, with nucleophilic attack occurring at a different site on the terminal oxazolinium than where polymer propagation occurs. Furthermore, investigations employing targeted end-group modification, in conjunction with MALDI and NMR analysis, determined the structure of the resultant terminal group was a hydroxyethylamino end group. Based on the observed data, a mechanistic explanation for the observed 2-oxazoline ring-opening termination is proposed.
- Kosakowska, Karolina A.,Dimitrov, Philip,Panambur, Gangadhar,Grayson, Scott M.
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p. 1303 - 1312
(2017/03/15)
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- N-Alkylation of Alkylolamines with Alcohols Over Mesoporous Solid Acid–Base Cs–B–Zr Catalyst
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Abstract: The mesoporous solid acid–base Cs–B–Zr mixed oxides were synthesized using the co-precipitation method followed by a subsequent thermal treatment. The catalytic activity of solid Cs–B–Zr mixed oxide was tested for solvent free acid–base catalysed direct alkylolamines with alcohols as green alkylating agent. The effects of Cs/B/Zr ratio, calcination temperature, reaction conditions, and reaction substrate on the catalytic performance of the catalysts were investigated. The XRD, N2 adsorption–desorption, ICP-OES, FT-IR and NH3/CO2-TPD results showed that the mesoporous structure and acid–base properties of the catalysts play important roles in the reaction. A suitable number of acid and basic sites on the catalyst lead to a high activity for the N-alkylation reaction. Graphical Abstract: A direct N-alkylation of amino alcohol with alcohols has been developed using mixed oxide Cs–B–Zr as an acid–base bifunctionalized catalyst.[Figure not available: see fulltext.]
- Chen, Aimin,Wang, Houyong,Liu, Rui,Bo, Yingying,Hu, Jun
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p. 1182 - 1193
(2016/07/06)
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- Preparation of ionic liquid-based vilsmier reagent from novel multi-purpose dimethyl formamide-like ionic liquid and its application
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In continuation of research to explore the applied potential of DMF-like ionic liquid, the ionic liquid version of N,N-dimethyliminiumchloride (Vilsmier reagent) has been synthesized from DMF-like ionic liquid and tested effectively for its capacity to achieve more useful organic transformations. The results show that DMF-like ionic liquid is world's first task specific ionic liquid which has catalyzed numerous diverse type of reaction and is multipurpose in its application. Thus a new term for this DMF-like ionic liquid has been coined that is DMF-like "multipurpose" ionic liquid. Copyright
- Hullio, Ahmed Ali,Mastoi
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experimental part
p. 1647 - 1657
(2012/09/21)
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- First multipurpose task specific ionic liquid: Designing and synthesis of novel dimethyl formamide-like ionic liquid and its applications as a green solvent alternative to dimethyl formamide dependent reactions
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A novel imidazole based task specific ionic liquid with dimethyl formamide (DMF) functionality has been designed and synthesized. The proposed dimethyl formamide like task specific can be used as a green alternative solvent-cum-organocatalyst for wide range of organic reactions which essentially depend on DMF. Dimethyl formamide as a solvent, due to its inherited structural features is found to affect the outcome of many reactions. Some of DMF-dependent reactions are investigated in its ionic liquid version with encouraging results. DMFlike ionic liquid acts both as a green reaction media and recyclable organocatalyst. Main advantages include easy reaction procedure, short reaction duration, easy work up and moreover the wide scope applications.
- Hullio, Ahmed Ali,Mastoi,Khan, Khalid
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experimental part
p. 5411 - 5418
(2012/06/29)
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- Therapeutic quinazoline derivatives
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A compound of formula (I) or a salt, ester, amide or prodrug thereof; where X is O, or S, S(O), S(O)2 or NR6 where R6 is hydrogen of C1-6alkyl; R5 is an optionally substituted 6-membered aromatic ring containing at least one nitrogen atom, and R1, R2, R3, R4 are independently selected from halogeno, cyano, nitro, C1-3alkylsulphanyl, —N(OH)R7— (wherein R7 is hydrogen, or C1-3alkyl), or R9X1— (wherein X1 represents a direct bond, —O—, —CH2—, —OC(O), —C(O)—, —S—, —SO—, —SO2—, —NR10C(O)—, —C(O)NR11—, —SO2NR12—, —NR13SO2— or NR14— (wherein R10, R11, R12, R13 and R14 each independently represents hydrogen, C1-3alkyl or C1-3alkoxyC2-3alkyl), and R9 is hydrogen, optionally substituted hydrocarbyl, optionally substituted heterocyclyl or optionally substituted alkoxy; provided that at least one of R2 or R3 is other than hydrogen. These compounds inhibit aurora 2 kinase and are useful in the preparation of medicaments for the treatment of proliferative disease such as cancer.
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- Pyrithione biocides enhanced by zinc metal ions and organic amines
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The present invention is directed to a stable, soluble, antimicrobial composition concentrate comprising pyrithione or a pyrithione complex in an amount of from about 0.5% to about 30 weight percent, a zinc source in an amount of from about 0.1% to about 10%, and an organic amine component in an amount of from about 30% to about 80%, said percents being based upon the total weight of the composition concentrate. The invention is also directed to methods of controlling the growth of free-living microorganisms or biofilms using the antimicrobial composition of the invention, and products made using the antimicrobial composition of the invention.
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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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- Trifluoroacetamides from amino alcohols as nucleophilic trifluoromethylating reagents
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Both non-enolizable and enolizable carbonyl compounds underwent nucleophilic trifluoromethylation by a new family of cheap and efficient trifluoroacetamide reagents derived from vic-amino alcohols (see picture). From an ecological and an economic viewpoint these represent a promising alternative to other known trifluoromethylation reagents.
- Joubert, Jerome,Roussel, Solveig,Christophe, Carole,Billard, Thierry,Langlois, Bernard R.,Vidal, Thierry
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p. 3133 - 3136
(2007/10/03)
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- Process for producing 1,3-dialkyl-2-imidazolidinone compound
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There is provided a process for preparing a 1,3-dialkyl-2-imidazolidinone by using an alkylene oxide as a first component, using at least one of (A) carbon dioxide and a monoalkylamine; (B) a carbon dioxide compound of the monoalkylamine; and (C) an 1,3-dialkylurea, reacting the first and second components by heating at 50 ° C. or higher to give 1,3-dialkyl-2-imidazolidinone, characterized in that the total molar amount of a molar feed amount of the monoalkylamine included in the component (A), a molar feed amount of the monoalkylamine part of the carbon dioxide compound of monoalkylamine, component (B), and the double of a molar feed amount of the 1,3-dialkylurea, component (C), is at least three folds of a molar feed amount of the alkylene oxide. The preparation process of this invention uses an industrially readily available alkylene oxide as a starting material and can be suitably conducted with a higher yield in an industrial scale.
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- 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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p. 407 - 415
(2013/09/06)
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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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- Control of aminophosphine chelate ring-opening in Pt(II) and Pd(II) complexes: Potential dual-mode anticancer agents
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We show that bis(aminophosphine) complexes of the type [M(R1R2N(CH2)nPPh2)2 ]2+, M = Pt(II) or Pd(II), can exist in chelate ring-closed and ring-opened forms both in the solid state and in aqueous solution. The equilibrium between them in solution can be controlled by the nature of the groups R1 and R2 (H, Me, Bz, cyclohexyl), by the bridge length n, and by the pH and Cl- concentration. X-Ray crystal structures are reported for the ring-closed complexes cis-[Pt(H2N(CH2)2PPh2-P,N)2 ]Cl2, cis-[Pt(H2N(CH2)3PPh2-P,N)2 ]Cl2, and cis-[Pt(Me(H)N(CH2)2PPh2-P,N)2][HCl 2]2, the mono-ring-opened complex cis-[Pd(Me2N(CH2)2PPh2-N,P)Cl(Me 2NH(CH2)2PPh2-P)](NO3) 2, the di-ring-opened complex cis-[Pt(Me2N(CH2)3PPh2-P)2 CL2], and, for comparison, the monochelate cis-[Pd(Me2N(CH2)3PPh2-N,P)CL2 ]. These square-planar complexes exhibit varying degrees of distortion and variable M-N bond lengths dependent not only on the trans influence of P but also on steric effects within the complex, pH-induced chelate ring-opening of cis-[Pt(Me2N(CH2)2PPh2-P,N)2 ]CL2 had an associated pK value of 6.9. In contrast, complexes with R1 and R2 = H, n = 2 or 3 or R1 = H and R2 = Me, n = 2, are more difficult to ring-open. Thus the complexes cis-[Pt(Me(H)N(CH2)2-PPh2-P,N)2]CL 2 and cis-[Pt(H2N(CH2)3PPh2-P,N)2 ]CL2, had associated pK values of 2.1 and 2.9, respectively. These aminophosphine complexes may exhibit anticancer activity by two mechanisms: by disrupting mitochondrial membrane potentials as bis-chelated (ring-closed) lipophilic cations, or by direct binding to DNA bases as ring-opened complexes.
- Habtemanam, Abraha,Watchman, Beth,Potter, Brian S.,Palmer, Rex,Parsons, Simon,Parkin, Andrew,Sadler, Peter J.
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p. 1306 - 1318
(2007/10/03)
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- Process for the continuous preparation of hydroxyalkylamides
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Process for the continuous preparation of hydroxyalkylamides Process for the continuous preparation of hydroxyalkylamides from carboxylic esters and alkanolamines, wherein the reaction of the starting materials is carried out in an extruder or intensive mixer by intensive mixing and brief reaction with supply of heat and simultaneous removal of the alcohol formed and the final product is then isolated.
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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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- Scavenger assisted combinatorial process for preparing libraries of amides, carbamates and sulfonamides
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This invention relates to a novel solution phase process for the preparation of amide, carbamate, and sulfonamide combinatorial libraries. These libraries have utility for drug discovery and are used to form wellplate components of novel assay kits.
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- Synthesis and Hydrolytic Lability of α-Phenoxyacetamides Containing Hydroxy Groups in the N-alkyl Residue
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Secondary and tertiary amides of 3,5-biscarbonyl>phenoxyacetic acid bearing hydroxy groups in positions β (β-OH) and γ (γ-OH) relative to the acetamide nitrogen atom have been synthesized.Such amides easily undergo cleavage of the acetamide bond in water at neutral pH.Hydrolysis rate constant for a series of such amides and protonation constants for the corresponding leaving amines were determined.No simple correlation between the two parameters could be found.A study of the dependence of these parameters on the structural features of the substrates, such as the presence of an N-methyl group and number of β-OH and γ-OH groups, was carried out.All these features lead to enhancement of the amide hydrolysis rate and a synergistic effect is operative when both N-methyl and β-OH groups are contained in the substrate.Presence of a methyl group increases the basicity of amines whereas β-OH and γ-OH groups have the opposite effect.Mechanistic speculations seem to indicate that the abnormal lability of the acetamide bond is due to protic-like catalysis by an intramolecular OH...N hydrogen bond.
- Anelli, Pier Lucio,Brocchetta, Marino,Canipari, Sonia,Losi, Pietro,Manfredi, Giuseppe,et al.
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p. 135 - 142
(2007/10/03)
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- Process for the preparation of polyoxyalkylated amines
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A process for the preparation of polyoxyalkylated compounds comprising at least one primary or secondary amine function is provided comprising reacting at least one amino-alcoholate (B) produced from an amino-alcohol (A) including at least one OH group and at least one primary or secondary amine function, by replacing a fraction or all the OH groups by OM groups, M being selected from sodium, potassium, rubidium and cesium, with an oxirane, a mixture of oxiranes or a sequence of oxiranes, in an aprotic and anhydrous solvent, in an anhydrous atmosphere and at a temperature of between about 0° C. and 200° C.
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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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- ORALLY ACTIVE RENIN INHIBITORS
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This invention relates to compounds of the formula STR1 wherein Q, Z, D, E, R 3, R 4, R 5 and R 6 are defined as below, and the pharmaceutically acceptable salts thereof are disclosed. The compounds are useful as antihypertensive agents.
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- A new synthetic route to macrocycles: Synthesis of large ring enaminolactones
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Macrocyclic enaminolactones 5 are prepared in three steps from commercially available chloroalcohols 1. The cyclization step is performed by intramolecular nucleophilic addition of the hydroxy group to an aminomethyleneketene generated by thermolysis.
- Jourdain,Pommelet
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p. 1545 - 1548
(2007/10/02)
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- Acid-Catalyzed Decomposition of 1-Alkyltriazolines: A Mechanistic Study
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1-Alkyltriazolines are five-membered cyclic triazenes containing the unusual Z-configuration for the triazene moiety.The hydrolytic decomposition of these compounds in aqueous or mixed acetonitrile-aqueous buffers leads predominantly to the formation of the corresponding 1-alkylaziridines and lesser amounts of 2-(alkylamino)ethanols, alkylamines, and acetaldehyde.The latter two products presumably result from hydrolysis of a rearrangement produkt, N-ethylidenealkylamine.Neither the nature of the 1-alkyl group nor the pH of the medium greatly influences the product distribution, although decomposition in purely aqueous buffers slightly reduces the aziridine yields.The rate of hydrolysis of 1-alkyltriazolines is about twice as fast as that of the analogous acyclic 1,3,3-trialkyltriazenes and varies in the order tert-butyl > isopropyl > ethyl > butyl > methyl > propyl > benzyl.The mechanism of the decomposition is specific acid-catalyzed (A1) involving rapid reversible protonation followed by rate-limiting formation of a 2-(alkylamino)ethyldiazonium ion.The slopes of the log kobs versus pH plots are near -1.0.The solvent deuterium isotope effect, kH2O/kD2O, is in all cases methyl > ethyl.
- Smith, Richard H.,Wladkowski, Brian D.,Taylor, Jesse E.,Thompson, Erin J.,Pruski, Brunon,et al.
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p. 2097 - 2103
(2007/10/02)
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- Ruthenium catalyzed reactions of ethylene glycol with primary amines: steric factors and selectivity control
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The selectivity of reactions of ethylene glycol with primary amines in the presence of RuCl2(PPh3)3 at 120 deg C is highly dependent on the steric nature of the amine.Selectivity to di-amination is favored by smaller alkyl groups on the amine while large amines cleanly yield ethanolamines.This contrasts with the results obtained with secondary amines at this temperature, in which ruthenium-triphenylphosphine catalyst systems always favor mono-amination.In the case of sec-butyl amine, where almost equal amounts of mono- and di-aminated product are obtained, the selecti vity can be shifted to mono-amination by the addition of excess triphenylphosphine.The steric effects seen in these reactions are consistent with standard steric parameters availble from the literature.
- Marsella, John A.
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- Orally active renin inhibitors
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This invention relates to compounds of the formula wherein Q, Z, D, E, R3, R?, R? and R? are defined as below, and the pharmaceutically acceptable salts thereof are disclosed. The compounds are useful as antihypertensive agents.
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- 1H NUCLEAR MAGNETIC RESONANCE SPECTRAL DETECTION OF THE INTERMEDIATES INVOLVED IN THE ACID-CATALYSED HYDROLYSIS OF 2-SUBSTITUTED 3-METHYL-1,3-OXAZOLIDINES
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The hydrolytic decomposition of 2-alkyl- and 2-aryl-substituted 3-mathyl-1,3-oxazolidines to 2-methylaminoethano9l and appropriate aldehyde has been studied by 1H n.m.r. spectroscopy in deutterioperchloric acid.The time-dependent spectra confirmed that the release of the final products is preceded by an equilibration of the starting material with three different species, viz. two geometric isomers of an acyclic cationic Schiff's base and a carbinolamine, which subsequently undergoes the rate-limiting heterolysis to the products.
- Parkkinen, Aija,Mattinen, Jorma,Loenberg, Harri,Pihlaja, Kalevi
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p. 827 - 832
(2007/10/02)
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- Intramolecular Cyclization Products from Alkanolamines and Epichlorohydrin
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Tetriary (2-hydroxyethyl)dialkylamines reacted with epichlorohydrin to form mixtures containing equal amounts of 2-(hydroxymethyl)-4,4-dialkylmorpholinium chlorides and perhydro-6-hydroxy-4,4-dialkyl-1,4-oxazepinium chlorides.Secondary (2-hydroxyethyl)alkylamines gave a 9:1 ratio of the corresponding bases in agreement with the prediction of Baldwin's rules.
- Buriks, Rudy S.,Lovett, Eva G.
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p. 5247 - 5254
(2007/10/02)
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- DEBENZYLATION OF N-BENZYLAMINO DERIVATIVES BY CATALYTIC TRANSFER HYDROGENATION WITH AMMONIUM FORMATE
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A method for deprotection of several N-benzyl derivatives of amines to the corresponding amino derivatives with ammonium formate and 10percent Pd-C is reported.
- Ram, Siya,Spicer, Leonard D.
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p. 415 - 418
(2007/10/02)
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- Catalytic Transfer Hydrogenolysis of N-Benzyl Protecting Groups
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The catalytic transfer hydrogenolysis of a number of N-benzyl compounds has been examined.Of the three hydrogen donors studied, ammonium formate and hydrazine hydrate were more effective than sodium hypophosphite.In general, debenzylation of secondary and tertiary benzylamines could be readily accomplished by refluxing the substrate with an excess of the hydrogen donor in alcoholic solvents for a few hours using catalytic amounts of 10percent palladium on carbon.The two N-benzyl heteroaromatic amines studies were stable to the above conditions.
- Adger, B. M.,O'Farrell, C.,Lewis, N. J.,Mitchell, M. B.
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- Fiber-reactive disazo brown dye having vinylsulfone-type reactive group
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A compound, or a salt thereof, represented by the following formula, STR1 wherein A is a substituted or unsubstituted phenylene or naphthylene group, B is STR2 in which R3 is a hydrogen atom or a lower alkyl, lower alkoxy, acylamino or ureido group, and R4 is a hydrogen atom or a lower alkyl or lower alkoxy group, R1 and R3 are independently a hydrogen atom or a substituted or unsubstituted lower alkyl group, X is a substituted or unsubstituted amino, lower alkoxy, substituted phenoxy or sulfo group, Y is --SO2 CH=CH2 or --SO2 CH2 CH2 Z, in which Z is a group capable of being split by the action of an alkali, and m is 2 or 3, which is useful for dyeing hydroxyl group- or amide group-containing fiber materials to give dyed products of a brown color having excellent fastness properties with good build-up property.
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- Reduction of Heterocycles with Nickel-Aluminum Alloy
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Pyrazines, pyridazines, isoxazoles, oxazole, 4-methylpyrimidine, and indole are reduced by nickel-aluminum alloy in potassium hydroxide solution.The reaction is simple to carry out and does not require special apparatus or hydrogen atmospheres.The products were the fully hydrogenated species although benzene rings were not attacked. 4-Methylpyrimidine gave 1,3-diaminobutane and oxazole gave 2-(methylamino)ethanol.It was found that the reaction frequently exhibited an induction period.
- Lunn, George
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p. 1043 - 1046
(2007/10/02)
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- OXAZOLIDINES. 1. BASIC CATALYTIC DISPROPORTIONATION OF CYCLOHEXANOSPIRO-2-OXAZOLIDINES: SYNTHESIS OF N-SUBSTITUTED 4,5,6,7-TETRAHYDROINDOLES
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It has been shown that the basic catalytic disproportionation of cyclohexanospiro-2-oxazolidines in the presence of potasium hydroxide or sodium methylate leads to N-substituted 4,5,6,7-tetrahydroindoles with a yield of up to 73percent.The influence of the character of substituents at the nitrogen atom of oxazolidine on the course of the reaction has been established.
- Kukharev, B.F.,Stankevich, V.K.,Kukhareva, V.A.
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p. 437 - 439
(2007/10/02)
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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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- Syntheses of α-C-Functionalized N-Nitrodialkylamines: Esters of methanol and 1-ethanol
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The α-acetoxynitramines 5 and 6 - important derivatives for studying the biological properties of N-nitrodialkylamines 4 - have been synthesized, and the stability of the ester bond has been investigated.The reaction of N-nitroalkylamines 7 with 1-halogenoethyl acetates 9, thought to afford 6, yielded the diazene N-oxides 10 as the main products.
- Plesch, Winfried,Wiessler, Manfred
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p. 1494 - 1503
(2007/10/02)
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- Renal dilating methods and compositions using 4-(3,4-dihydroxyphenyl)-1,2,3,4-tetrahydroisoquinolines
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4-Phenyl-1,2,3,4-tetrahydroisoquinolines whose structures have two hydroxy groups substituted at the 3,4-position on the 4-phenyl ring have been found to have renal vasodilating activity upon internal administration. The active ingredients are prepared by cyclizing N-(2-substituted benzyl)-1-(3,4-dimethoxyphenyl)-aminoethanol using either a Lewis acid or an acid cyclizing agent followed by demethylation at the 3,4-dimethoxyphenyl moiety.
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- Kinetic Analysis of the Ring Opening of an N-Alkyloxazolidine. Hydrolysis of 2-(4-Methylphenyl)-2,3-dimethyl-1,3-oxazolidine
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Hydrolysis of the title oxazolidine, III, occurs in two separate reaction stages, reversible ring opening to a cationic Schiff base, IV, followed by a considerably slower formation of hydrolysis products.The ring opening occurs in an H+-catalyzed reaction and in a pH-independent reaction, with the crossover between the two occurring at about pH 5.A general acid catalyzed pathway (α = 0.70) is also observed.The equilibrium constant (pKI(+)) for IV * III + H+ is 7.45, this number being obtained spectroscopically and in a kinetic analysis.The kinetic analysis also furnishes a dissociation constant (pKSH(+)) for the protonated oxazolidine of 6.19, the difference between pKSH(+) and pKI(+) showing that after attainment of equilibrium the conjugate acid of III is a 19:1 mixture of cationic Schiff base and protonated oxazolidine.The formation of hydrolysis products involves rate-limiting addition of water or hydroxide ion to IV, although a small percentage of a reaction via an oxocarbonium ion derived from C-N cleavage of the protonated oxazolidine cannot be ruled out.Rate constants for the water and hydroxide addition are slower than their intramolecular counterparts, this being particulary true in comparing hydroxide ion reactions.This occurs despite the fact that the ring closure is a supposedly disfavored 5-endo-trigonal process.
- McClelland, Robert A.,Somani, Riaz
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p. 4345 - 4350
(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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- 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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