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Conformation analysis and computation of energy barrier to rotation about CN bond in para-methylphenyl carbamate and its solvent dependence in comparison with tertiary carbamates and tertiary amides

Barrier to rotation about conjugated CN bond in p-Methyl phenyl carbamate (PMPC) was computed 14-16 kcal/mol at three levels of HF, B3LYP and MP2 using 6-311++G? ? basis set. The solvent effect and energy barriers about CN bond in PMPC were compared to the case of tertiary carbamates and tertiary amides. Moreover, it is shown that in primary carbamates such as PMPC and tertiary amides isomerisation process passes through TS2 and TS1 respectively, while in tertiary carbamates goes through a combination of both TSs. Furthermore, X-ray analysis which is reported for the first time for primary aryl carbamates demonstrated that the inclusive plane of carbamate functional group is perpendicular to the plane of phenyl ring. The results of computations are completely in agreement with the X-ray data.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H827NO – PubChem

 

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Electrolytic partial fluorination of organic compounds. Part 78: Regioselective anodic fluorination of 2-oxazolidinones

Various 2-oxazolidinones were galvanostatically electrooxidized in the presence of various fluoride salts. It was found that a fluorine atom was introduced to the alpha-position of the nitrogen atom of N-acyl- and N-alkoxycarbonyl-2-oxazolidinones to provide the corresponding alpha-fluorinated products in moderate to good yields. In the case of N-phenoxycarbonyl derivative, fluorination took place on the phenyl group selectively.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H396NO – PubChem

 

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SUBSTITUTED BRIDGED UREA ANALOGS AS SIRTUIN MODULATORS

The present invention relates to novel substituted bridged urea analog compounds of Formula (I) or pharmaceutically acceptable salts thereof, corresponding pharmaceutical compositions, processes for making and use of such compounds, alone or in combination with other therapeutic agents, as Sirtuin Modulators useful for increasing lifespan of a cell, and for use in treating and/or preventing a wide variety of diseases and disorders, which include, but are not limited to, for example, diseases or disorders related to aging or stress, diabetes, obesity, neurodegenerative diseases, cardiovascular disease, blood clotting disorders, inflammation, cancer, and/or flushing as well as diseases or disorders that would benefit from increased mitochondrial activity.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H85NO – PubChem

 

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Understanding the mechanism of procedure-controlled enantioselectivity switch in cinchona alkaloid thiourea catalyzed [3+2] cycloaddition: H-bonds controlled enantioselectivity

Density functional theory has been applied to the novel procedure-controlled enantioselectivity switch in the synthesis of chiral 2-oxazolidinone (3) through [3+2] cycloaddition between gamma-hydroxy-alpha,beta-unsaturated carbonyl compound (1) and isocyanate (2) catalyzed by a cinchona-alkaloid based aminothiourea catalyst. The study shows that three stages are involved in the whole process. In stage one, for Procedure A, 1 reacts with 2 to give carbamate intermediate. Then catalyst 4 is added. For Procedure B, catalyst 4 first activates 2 via quinuclidine N attacking isocyanate C. Then 1 is involved. In stage two, hydrogen is transferred from carbamate N to Ts O atom which is different from the quinuclidine N protonation mechanism. The last step is ring closure in which carbamate N attacks C atom of CC bond. From free energy profiles, the enantioselectivities of the reaction are determined by stage two. Further analysis shows that H-bond is the key in the procedure-controlled enantioselectivity switch. Different H-bonds (NAHA?OAC and NBHB?OAC in Procedure A vs NAHA?OAC and NBHB?OBS in Procedure B) lead to different relationships between thiourea and carbamate planes (vertical or parallel). In Procedure A, CC listing above carbamate plane is the favorable pathway to give R-3. However, in Procedure B, CC listing behind carbamate plane is more favorable to generate S-3.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H603NO – PubChem

 

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One pot microwave-assisted synthesis of 3-benzyl-5-hydroxymethyl-1, 3-oxazolidin-2-one

Oxazolidinone is a five-member heterocyclic ring used as a privileged structure for the synthesis of ligands for different biological targets. Many synthetic approaches have been made available for oxazolidinone, however, they were found to be either time/energy consuming or multistep process. One of the approach is a one-pot method to synthesize 3-benzyl-5-hydroxymethyl-oxazolidin-2-one using reflux overnight (>12 h). The aim of the present work was to develop an improved method by the use of microwave irradiation to make 3-benzyl-5-hydroxymethyl-oxazolidin-2-one. Benzyl amine was reacted with the various carbonate salts and epichlorohydrin, in presence of bases and solvent and the reaction was carried out under open and sealed-vessel conditions. Various factors including the use of carbonate salts, base, solvent, time, temperature and power were optimized. Microwave-assisted synthesis of 3-benzyl-5-hydroxymethyl-1,3-oxazolidin-2-one gave yields of 69.59% and 77.0% in an open vessel and a closed vessel, respectively with reduction in reaction time from overnight (>12 h) to 1 h in the open vessel and to 30 min in closed vessel.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H884NO – PubChem

 

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Ethylene carbonate production by cyclocondensation of ethylene glycol and urea in the presence of metal oxides and metal acetylacetonates

A promising method for the production of ethylene carbonate is the cyclocondensation of ethylene glycol and urea in the presence of a catalyst. In this study, the catalytic effect of oxides and acetylacetonates of various metals on the occurrence of this reaction has been examined. It has been shown that cobalt acetylacetonate is the most effective catalyst. The effect of reaction conditions (temperature, pressure, contact time, and catalyst concentration) on the main parameters of catalytic conversion has been studied.

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Catalytic asymmetric synthesis of trisubstituted aziridines

A method is described which provides for the direct asymmetric catalytic synthesis of trisubstituted aziridines from imines and diazo compounds. While unactivated imines were not reactive to alpha-diazo carbonyl compounds in which the diazo carbon was disubstituted, N-Boc imines react with both alpha-diazo esters and alpha-diazo-N-acyloxazolidinones to give trisubstituted aziridines with excellent diastereo- and enantioselectivities.

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Fluorine in fragrances: Exploring the difluoromethylene (CF2) group as a conformational constraint in macrocyclic musk lactones

The CF2 group is incorporated into specific positions within the lactone ring of the natural musk lactone, (12R)-(+)-12-methyl-13-tridecanolide, a constituent of Angelica root oil, Angelica archangelica L. The approach is taken as it was anticipated that CF2 groups would dictate corner locations in the macrocycle and limit the conformational space available to the lactone. Three fluorine containing lactones are prepared by organic synthesis. One (8) has CF2 groups located at the C-6 and C-9 positions, another (9) with CF2 groups at the C-5 and C-9 positions, and a third (10) with a CF2 group at C-8. Two of the fluorine containing lactones (8 and 10) were sufficiently crystalline to obtain X-ray crystal structures which revealed that the CF2 groups do adopt corner locations. All three lactones were subject to computational analysis at the B3LYP-D3/6-311+G?? level to assess the relative energies of different conformers. In all cases, the global minima and most of the lowest energy minima have squared/rectangular geometries and located the CF2 groups at the corners. The lowest energy structures for 8 and 10 closely approximated the observed X-ray structures, suggesting good convergence of theory and experiment in determining relevant low energy conformations. All three compounds retained a pleasant odour suggesting the rings retained sufficient conformational flexibility to access relevant olfactory conformations.

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Oxazolidine – Wikipedia,
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Inhibitors of the glycine transporter type-2 (GlyT-2): synthesis and biological activity of benzoylpiperidine derivatives.

A series of benzoylpiperidine analogs related to 4a was prepared, and their ability to inhibit the uptake of [(14)C]-glycine in COS7 cells transfected with human glycine transporter type-2 (GlyT-2) was evaluated. Small structural changes to the benzoylpiperidine region of the molecule led to a significant decrease in GlyT-2 inhibitory activity. In contrast, the distal aryl ring was more tolerant to functional group modifications and could accommodate a variety of substitutes at the C-2 or C-3 positions. Comparable activities to 4a were obtained by replacing the anilino nitrogen with an ether linkage 27 or by exchanging the isopropoxy ether moiety with an isopropyl amino group 15. A distinct preference for a 2-carbon tether (n=1) was observed relative to the corresponding 3-carbon homolog (n=2).

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Oxazolidine – Wikipedia,
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Chapter 2 The heterocyclic chemistry associated with the herbicide glyphosate

The search for alternative new aminoalkyl phosphonates or phosphinates with similar or dramatically improved biological activity versus glyphosate has stimulated an enormous research effort in exploratory phosphorus and heterocyclic chemistry. Many new synthetic methods have been developed over the last two decades to prepare a variety of structural analogs of glyphosate containing a modified skeleton. Despite the large numbers of compounds evaluated, none has surpassed the overall biological properties of glyphosate itself, either on the enzymatic level or under field conditions. Consequently, the search for a second-generation, glyphosate-like herbicide continues (2).

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Oxazolidine – Wikipedia,
Oxazolidine | C3H1002NO – PubChem