Archives for Chemistry Experiments of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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The crystal structures of four chiral thioureas, which are normally used as organocatalysts, are reported by the first time. Each compound is assembled in the crystal in a different way according to their chiral moiety in the thiourea skeleton, being dependent on the presence or the absence of the OH group in the aminoindanol or aminoindane moiety, respectively. Thiourea 1, which contains an aminoindane group, is assembled into a zigzag chain linked via N-H···S hydrogen bonds. Thiourea 2, with an aminoindanol and a phenyl group, interacts mainly through O-H···S and N-H···S bonds in a very congested structure. Thiourea 3 disposes in a zigzag chain mainly through S···O-H bonds and in further superposed zigzag chains through N-H···S hydrogen bonds. The compound 4 is coordinated in a coplanar organization via O···H-N interactions, forming very tight dimers, which are further arranged in chain of dimers through O-H···S interactions. The general trends in the patterns of packing of these four compounds are compared to those commonly observed in the crystalline solids of other thiourea and urea structures. The different arrangements adopted by our chiral thioureas in the solid state are rationalized and discussed in terms of molecular structure, remarking the importance of the OH group in the aminoindanol scaffold in the determination of the preferred solid assembly. A comparison correlating the crystal structures, specifically the interactions in the crystal network and the configuration adopted by the thioureas, with the catalytic efficiency previously observed by the same structures, is included.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A stereodynamic chemosensor having a parallel arrangement of a substrate-binding salicylaldehyde unit and an adjacent pyridyl N-oxide fluorophore undergoes rapid condensation with chiral amino alcohols and subsequent asymmetric transformation of the first kind toward a single rotamer. Crystallographic analysis shows that the concomitant central-to-axial chirality imprinting is controlled by minimization of steric repulsion and by intramolecular hydrogen bonding between the bound amino alcohol and the proximate N-oxide group. The substrate binding event results in strong CD effects and characteristic fluorescence changes which can be used for instantaneous in situ determination of the absolute configuration, enantiomeric composition and total concentration of a variety of chiral amino alcohols. This chemosensing approach avoids time-consuming workup and purification steps, and it is applicable to minute sample amounts which reduces the use of solvents and limits waste production.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Boron enolates obtained from optically active oxazolidinone derivative of cis-1-amino-2-hydroxyindan are reacted with various aldehydes to provide highly enantioselective aldol products in good yields.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The degradation of 2-amino-2-methyl-1-propanol (AMP) has been investigated in the presence of oxygen. AMP was not stable and the overall degradation rate of AMP was close to that of Nmethyldiethanolamine (MDEA) under identical conditions. The primary degradation products identified by GC-MS were acetone, 2,4-lutidine and 4,4-dimethyl-2-oxazolidinone. The oxidative degradation rates of AMP strongly depended upon oxygen partial pressure. The effect of temperature on the overall degradation rates was also measured. No significant catalytic effect was observed when 0.1mM ferrous oxalate (Fe C2O4) and 0.1mM copper sulphate (CuSO4) were added into the AMP solutions, respectively, and the degradation rates of AMP show a weak dependence on a radical initiator. Carbon dioxide (CO2) was found to speed up the overall degradation rate of AMP.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Compounds of formula I, Ia or Ib and pharmaceutically acceptable salts thereof, useful in the treatment of neuropsychiatric disorders such as psychoses; pharmaceutical compositions comprising a compound of formula I and a pharmaceutically acceptable diluent or carrier; and methods of treating neuropschiatric disorders comprising administering to a mammal (including man) in need of such treatment an effective amount of a compound of formula I, or a pharmaceutically acceptable salt thereof; STR1

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The spotlighted dual functions of pyridine as a denaturant and as a stabilizer for duplex DNA are thoroughly investigated using spherical nucleic acids (SNAs). At neutral pH, pyridine destabilizes the duplex interconnects of assembled SNAs, resulting in a gradual decrease in their melting temperature (Tm) as a function of the pyridine concentration. This result is in good agreement with the conventional role of pyridine as a powerful denaturant for free duplex DNA. On the contrary, the addition of pyridine dramatically increases the Tm of hybridized SNAs under acidic conditions, which could be a striking result of pyridine’s stabilizing effect for DNA duplex as previously suggested on the basis of the pyridine-nucleobase interactions. After comprehensive and quantitative investigation based on the analysis of the sharp melting transitions of SNAs, however, we report that, in fact, the pH increase induced by pyridine is also an essential parameter accounting for pyridine’s DNA-stabilizing effects under acidic conditions. Importantly, we prove that pyridine, particularly at a low concentration, does not increase the Tm of hybridized SNAs even under acidic conditions, if the pH increase by pyridine is corrected to maintain the same initial pH.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A two-step process for the conversion of a trans-1-amino-2-hydroxycycloalkane stereoselectively to a cis-1-amino-2-hydroxycycloalkane is disclosed. The novel step, a one-step hydrolysis with formal inversion, can be used to convert an amide of a trans-1-amino-2-hydroxycycloalkane to a cis-1-amino-2-hydroxycycloalkane. Methods for obtaining the trans-1-amino-2-hydroxycycloalkanes and their amides from alkenes are also disclosed, as are the novel, substantially optically pure 1-amino-2-indanols and 1-amido-2-indanols obtained thereby. A preferred process converts indene to cis-1-amino-2-indanol.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The diesel engine generally achieves the highest fuel, energy, and thermal efficiency due to its very high compression/expansion ratio (14:1 to 25:1). Diesel engines can have a thermal efficiency that exceeds 50%. The main problem is that they emit more pollution like fine black soot particulates (C8H to C10H) and nitrogen oxides (NOX). These pollutants have been causing serious problems for human health and the global environment and also impacts on the engine. There are many types of catalysts investigated for simultaneous control of these two pollutants, i.e., platinum group metals (PGM; Pt, Pd, Rh, and Ir) based, spinel-type oxides, hydrotalcite, rare earth metal oxides, mixed transient metal oxides, etc. The high raw material cost of PGM catalysts has become a significant issue, so developing non-PGM catalysts are one of the promising challenges. There are no extra reductants required because soot catalytically oxidizes itself in the presence of NOX at a faster rate than molecular oxygen and simultaneously NOX is reduced to nitrogen. The order of oxidation potential of NOX to oxidized soot in comparison to molecular oxygen is as follows: NO2 > NO > O2. To meet the very strict EPA US 2010 and Euro VI regulations of particulate matter (PM) and NOX for heavy-duty and light-duty vehicular stringent emission, it is very important to apply the integrated catalytic systems to significantly remove PM and NOX simultaneously. Many papers related to simultaneous control of soot and NOX over different catalysts have been published but till now some of effective catalysts showing high conversion at low temperatures (possibly within the range typical of diesel exhaust: 150?450C) have not been reviewed. Thus, this article provides a summary of published information regarding the effective catalysts, their preparation methods, properties, and application for simultaneous control of diesel soot and NOX.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Cyclic and acyclic polyethers have been analysed by atmospheric pressure ion mobility spectrometry (IMS). The reduced mobilities of gas-phase cyclic polyether ions may be distinguished from their acyclic analogues as a consequence of differences in the collision cross-sections of their adopted conformations. Peaks attributed to polyether/protonated amine complexes are formed when polyethers are introduced in the presence of N-ethylmethylamine, n-propylamine and benzylamine vapour. Variations in the reduced mobilities for the polyether complexes containing isomeric N-ethylmethylamine and n-propylamine guests are associated with small conformational differences for these ions. SYBYL molecular modelling software was used to confirm structural characteristics inferred from the experimental mobility data.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The use of cavitation in advanced oxidation processes (AOPs) to treat acidic effluents and process water has become a promising trend in the area of environmental protection. The pH value of effluents ? often acidified using an inorganic acid, is one of the key parameters of optimization process. However, in the majority of cases the effect of kind of inorganic acid on the effectiveness of degradation is not studied. The present study describes the results of investigations on the use of hydrodynamic cavitation (HC) for the treatment of a model effluent containing 20 organic compounds, representing various groups of industrial pollutants. The effluent was acidified using three different mineral acids. It was demonstrated that the kind of acid used strongly affects the effectiveness of radical processes of oxidation of organic contaminants as well as formation of harmful secondary pollutants. One of important examples is a risk of formation of p-nitrotolune. Sulfuric acid was the only chemical used for acidification which caused effective treatment with lack of formation of monitored type of secondary pollutants. The best treatment effectiveness ? during a 6-hour cavitation process – in most cases much above 80% along with 90% TOC removal was obtained in the case of sulfuric acid. Nitric acid provided lower effectiveness (above 60% for most of the compounds). The worst performance are reported for hydrochloric acid ? below 50% of degradation for most of the compounds.

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Reference:
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis—I. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis