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Amidation of esters with amino alcohols using organobase catalysis

A catalytic protocol for the base-mediated amidation of unactivated esters with amino alcohol derivatives is reported. Investigations into mechanistic aspects of the process indicate that the reaction involves an initial transesterification, followed by an intramolecular rearrangement. The reaction is highly general in nature and can be extended to include the synthesis of oxazolidinone systems through use of dimethyl carbonate.

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Oxazolidine | C3H389NO – PubChem

 

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Stereoselective Simmons-Smith cyclopropanation of chiral enamides

(Chemical Equation Presented) Efficient and practical access to chiral aminocyclopropanes is secured by the title reaction (see example). Both E and Z enamides undergo the cyclopropanation with high diastereoselectivity (d.r. up to > 95:5). The application of this methodology to the synthesis of biologically significant aminocyclopropanes illustrates the potential of chiral enamides as useful building blocks for stereoselective organic synthesis.

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Oxazolidine | C3H2026NO – PubChem

 

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Aminoethylation process for production of substituted ethylene diamines

A process is disclosed for producing a substituted ethylenediamine, the process comprising reacting an oxazolidinone with a secondary amine or an alkanolamine. The process includes, in one aspect, reacting precursors of the oxazolidinone in situ.

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A flexible strategy for the divergent modification of pleuromutilin

The complex antibacterial natural product, pleuromutilin, can be directly modified by the radical addition reaction of various xanthates to the unactivated terminal olefin present on C-12.

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AMINOCYCLOALKANOBENZODIOXOLES AS BETA-3 SELECTIVE ADRENERGIC AGENTS

The invention is antiobesity/antidiabetic/beta-3 agonists of the formula STR1 wherein the substituents R o, R 1, R 4, R. sub.4 ‘, R 5, R 6 or n are as defined in the specification.

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Stereoselective Synthesis of Highly Substituted Tetrahydropyrans through an Evans Aldol-Prins Strategy

A direct and general method for the synthesis of naturally occurring 2,3,4,5,6-pentasubstituted tetrahydropyrans has been developed, employing beta,gamma-unsaturated N-acyl oxazolidin-2-ones as key starting materials. The combination of the Evans aldol addition and the Prins cyclization allowed the diastereoselective and efficient generation of the desired oxacycles in two fashions: a one-pot Evans aldol-Prins protocol, in which five new sigma bonds and five contiguous stereocenters were straightforwardly generated, and a two-step version, which additionally permitted the isolation of beta,gamma-unsaturated alcohol precursors bearing an N-acyl oxazolidin-2-one in the alpha position. From these alcohols were also obtained halogenated pentasubstituted tetrahydropyrans as well as 2,3,4,5-tetrasubstituted tetrahydrofurans, shedding light on the mechanism of the process. Computational studies were consistent with the experimental findings, and this innovative Evans aldol-Prins strategy was performed for the preparation of a battery of more than 30 densely substituted tetrahydropyrans, unprecedentedly fused to a 1,3-oxazinane-2,4-dione ring, both in a racemic fashion and in an enantiomeric fashion. These novel molecules were successfully submitted to several transformations to permit simple access to a variety of differently functionalized tetrahydropyrans. Most of these unique molecules were evaluated for their antimicrobial activity against Gram-positive and Gram-negative bacteria and the yeast Candida albicans, and some structure-activity relationships were established.

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Simple exploration of 5-(Chloromethyl)oxazolidin-2-one

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Regioselective anodic alpha-methoxylation of 2-oxazolidinone on boron doped diamond in acidic methanol medium

For the first time, anodic methoxylation of 2-oxazolidinone was investigated on boron doped diamond (BDD) in CH3OHH 2SO4 medium. Voltammetric studies reveal that the 2-oxazolidinone gets oxidised at a potential of 1.5 V vs. SCE on the BDD, whereas on the graphite, the anodic oxidation takes place in the potential region of methanol oxidation. Galvanostatic electrolysis results in the formation of 4-methoxy-2-oxazolidinone (MOD) as a single product in high yield on the BDD and multiple products, along with MOD on the graphite. Generation of methoxy radical on the BDD was confirmed by Electron Spin Resonance (ESR) spectroscopy.

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As cell necrosis inhibitors of the indole compounds (by machine translation)

The invention relates to chemical formula (1) indole compounds, or its pharmaceutically acceptable salt or isomer, and in containing the same as the characteristic, as an active ingredient for the prevention or treatment of cell necrosis and its associated disease composition and method of manufacturing. (by machine translation)

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Photolysis of olefinic N-chloropyrrolidinones, N-chlorosuccinimides and N-chloro-oxazolidinones: Reactivity of cyclic carboxamidyl, imidyl and carbamyl radicals in intramolecular reactions

N-Chloro-alkenylpyrrolidinones, an N-chloro-alkenylsuccinimide and N- chloro-alkenyloxazolidinones were prepared as precursors of olefinic cyclic carboxamidyl, imidyl and carbamyl radicals constrained to undergo intramolecular reactions uniquely via their planar or slightly twisted (30- 35) Pi(N) state (1,5-transfer of an allylic hydrogen, 5-exo or 6-exo cyclization to give bicyclo[2.2.1]azaheptane and bicyclo[3.2.1]azaoctane skeletons respectively), those intramolecular reactions being unaccessible to the planar SigmaN state. Their photolysis gave products arising uniquely from intermolecular reactions of those nitrogen radicals (addition to an external olefin, hydrogen abstraction from the solvent, allylic hydrogen abstraction). An intramolecular reaction leading to bicyclo[3.3.0]azaoctane derivatives via 5-exo cyclization was observed with an N-chloro-alkenylpyrrolidinone and an N-chloro-alkenyloxazolidinone. In these two cases, both the Pi(N) and the Sigma(N) states of the cyclic amidyl radical allow orbital overlap for 5-exo cyclization.

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A framework for the environmental, health and safety hazard assessment for amine-based post combustion CO2capture

Given the environmental concerns driving process developments and considering the size and scale of potential application of post combustion capture (PCC), it is important to fully understand process hazards. In this work we present an environmental, health and safety (EHS) hazard assessment framework for screening and comparing amine based PCC options. A multi-criteria assessment compares the performance of 7 m Monoethanolamine (MEA), 4 m Diethanolamine (DEA), 10 m Diglycolamine (DGA), 8 m Piperazine (PZ) and a blend of 7 m Methyldiethanolamine (MDEA) with 2 m PZ under a set of different process conditions. The EHS assessment takes into account varying circulating volumes, process conditions and potential for solvent degradation. The EHS assessment is also compared with operating costs and life cycle assessment (LCA) metrics. The EHS assessment is carried out on two levels. The first is less data intensive and provides a unified score that can be used to compare and screen process alternatives, while the second level studies the contribution of individual degradation products to different EHS hazard categories in detail. Results of the parametric study show that lean loading is an influential factor in determining first level EHS scores, process costs and environmental impacts and a trade-off is observed between EHS and LCA scores for some of the solvents. In the second level EHS assessment, the parent amine heavily influences most mass dependent hazard categories such as the fire/explosion, acute toxicity and air mediated effects category. Heat stable salts affect the solid waste category. Most degradation products are considered corrosive or irritant and therefore feature strongly in that category in addition to the parent amine. The second level EHS assessment is complemented with workplace exposure analysis to ensure the compliance with workplace threshold limits. Nitrosamines stand out for acute and chronic toxicity effects and are therefore used as an example to demonstrate the workplace exposure. Workplace amines and nitrosamine concentrations are estimated to assess long and potential short term worker exposure as a result of gas leakages and spills respectively. Indoor ventilation rates are inadequate to keep workplace amine and nitrosamine concentrations below the recommended guidelines. To reduce short term exposure effects, a steady state liquid nitrosamine concentration lower than 13.7 mM is required. The results of the parametric study show that changing process conditions can lower nitrosamine concentrations, but can also shift the contribution of the parent amine and degradation products of the other hazard categories and affect LCA metrics. The sensitivity of the EHS and LCA results to model assumptions and conditions are tested by varying inlet NOx, expected aerosols and solvent degradation levels. Low NOx levels in the flue gas are required for PZ and MDEA-PZ systems to meet the nitrosamine concentration thresholds for environmental and health concerns. This study also highlights the need to consider hazard effects during early process design phases, identifies degradation related data gaps and critical process parameters towards more environmentally benign PCC design.

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