Synthesis and Crystal Structure of 3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)- pyrrol-2-yl)pentane·2CH_3OH

3,3＇-Bis（5-（N-（4-hydroxylphenyl）imidomethyl）pyrrol-2-yl）pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·（CH3OH）2, belongs to the orthorhombic system, space group Pccn with a = 18.094（2）, b = 11.6890（16）, c = 13.3629（19） , V = 2826.3（7） 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F（000） = 1080 and μ（MoKα） = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ（I）, and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.

Chloroaluminate ionic liquid catalyzed isomerization of n-pentane in the presence of product distribution improver

The ionic liquid Et3NHC1-2AIC13 can catalyze the isomerization of n-pentane. This paper investigates the ionic liquid catalyzed isomerization performance of n-pentane with several product distribution improvers in an autoclave. The product distribution of n-pentane isomerization could be improved by such improvers as benzene, cyelohexane, and methyl cyclohexane at the expense of conversion of n-pentane. The optimal product distribution improver was determined to be cyclohexane. The yield of isomerate and the selectivity of liquid isoalkanes increased, whereas the conversion of n-pentane decreased, with increasing cyclohexane amount. At the same conversion of n-pentane, the research octane number （RON） of liquid product, with cyclohexane amount of 0.5 wt%, was about 1.3 higher than that without cyclohexane. At the same reaction conditions, the presence of cyclohexane enhanced the yield of isomerate, the selectivity of liquid isoalkanes, and the RON of the liquid product, but reduced the conversion of n-pentane.

Preparation of VPO Catalysts and Effect of Zirconium Promoter on the Selective Oxidation of Pentane

This study focuses on the effects of reducing solvents used in the preparation of vanadyl pyrophosphate （VPO）, and ZrO2 and （ZrO）2P2O7 promoters on the structure and catalytic performance of VPO catalysts. The VPO catalysts were prepared by the following steps： 1） Formation of vanadium phosphate by the reaction of V2O5 and H3PO4, 2） Synthesis of VPO precursor through the reduction of vanadium phosphate by reducing solvents, and 3） Activation of the precursor. For Zr promoted VPO, Zr was added to the precursor before activation. The P/V atomic ratios of different VPO catalysts, which were prepared by using different reducing solvents, were different. The precursor prepared by using isobutanol or isobutanol-benzyl alcohol contained VO（H2PO4）2 and VOHPO4·0.5H2O. The precursor prepared by using hexanol also contained VO（H2PO4）2 and VOHPO4·0.5H2O crystal phases, but the amount of VOHPO4·0.5H2O was much less than that of VO（H2PO4）2. After activation, all the VPO catalysts, prepared by using different reducing solvents, contained only the （VO）2P2O7 crystal phase. The VPO prepared by using isobutanol-petroleum ether as reducing solvent was the most active, while the VPO prepared by using hexanol had the lowest activity. Nevertheless, their total selectivity to phthalic and maleic anhydrides was almost the same. Both ZrO2 and （ZrO）2P2O7 promoters increased the activity and selectivity of VPO, but ZrO2 promoter increased the activity of VPO more drastically than （ZrO）2P2O7 promoter.

Increased breath ethane and pentane concentrations in currently unmedicated patients with schizophrenia

Schizophrenia is a common and debilitating mental illness. The disorder is thought to be developmental in origin, with oxidative stress being implicated as possible pathophysiological mechanism. Breath alkanes provide a non-invasive means to assess oxidative stress, with ethane levels reportedly increased in medicated patients with schizophrenia. It is possible, however, that the psychotropic medications used to treat the disorder result in elevated breath ethane levels. We have therefore measured the concentration of ethane and pentane, markers of oxidative stress, in the breath of currently unmedicated patients with schizophrenia. Alveolar breath samples were collected, applied to thermal desorption tubes, and analyzed using a combination of two-stage thermal de-sorption, gas chromatography and mass spectrometry. Compared to healthy controls ethane and pentane levels were found to be elevated in patients with schizophrenia, while levels of butane were normal. Our data support the notion that oxidative stress is increased in schizophrenia and that this is unlikely to be a consequence of antipsychotic medications. In addition, breath alkane analysis may represent a rapid and non-invasive means to monitor oxidative stress occurring in schizophrenia.

Syntheses and Characterization of Two Novel Copper(II) Malonate Complexes Functionalized with 3,3’-Bis(pyrazolyl)pentane and 4,4’-Trimethylenedipyridine

Two novel copper complexes (1,2) with N,O-donor ligands were synthesized by reaction of copper(II) malonates with 3,3’-bis(pyrazolyl)pentane and 4,4’-trimethylenedipyridine in methanol at moderate temperature. These compounds were characterized by elemental analysis, UV-VIS, IR spectroscopies and powder X-ray diffraction analyses. Compound (1) melts at higher temperature (202°C) than compound (2) (100°C). The IR spectra showed typical vibrations related to C=N and C=C, characteristic of pyrazolyl and pyridine ligands.

A practical access to fluoroalkylthio(seleno)-functionalized bicyclo[1.1.1]pentanes

Rational design of new bioisosteres through introduction of high-value functional groups to bicyclo[1.1.1]pentane(BCP)is of particular use for drug discovery.Disclosed herein is the first access to valuable fluoroalkylthio(seleno)-functionalized BCPs.A range of SCF3,SCF2H,SCFH2,SeCF3,SeC4F9,and SeC8F17 groups are readily incorporated to BCPs under mild conditions.Concomitant installation of a sulfone provides a platform for incorporation of the BCP motif to bioactive molecules.This practical protocol features novel BCP scaffolds,broad substrate scope,excellent atom-economy,simple operation,and gramscale preparation.

Separation and Characterization of Nitrogen-Rich Components in Coker Gas Oils from Athabasca Bitumen

It is well known that gas oils from oilsands bitumen are difficult to hydrotreat. In order to develop the most appropriate flow sheet and operating conditions, a thorough knowledge of the molecular structure and behaviour of bitumen and its gas oil products is needed. In this work, the gas oil samples are fractionated in an attempt to isolate and identify the problematic molecular species for hydrotreating. It is found that the major nitrogen sources in coker gas oils are associated with relatively small pentane insoluble species and an even smaller, highly polar, hexane insoluble species. Structural information obtained for these fractions indicates that they are formed during the cracking of resin molecules. Nitrogen speciation shows that the pyrroles are the primary nitrogen type, with pyridines also being an important species. Both nitrogen species are undesirable in the hydrotreating process. Pyrroles in particular are subject to polymerisation, producing gums and sediments that foul filters and other equipment while pyridines can directly deactivate the hydrotreating catalyst.

Synthesis of Novel Electron Donors and Their Application to Propylene Polymerization

A series of electron donors,including 1,1-cyclopentanecarboxylic acid diethyl ester (CPCADEE),1,1cyclopentanedimethanol acetic diester (CPDMAD),1,1-biethoxymethyl pentane (BEMP),2,2-diethyl diethylmalonate (DEDEM)and 2,2-diethyl-1,3-propanediol acetic diester (DEPDADE),were synthesized by diethyl malonate (DEM).The purities and structures of the above products were characterized by gas chromatography (GC) and gas chromatography-mass spectrometer (GC-MS),respectively.Furthermore,the possible optimal three-dimensional structures of these donors were simulated by means of Gaussian 03 and Chem 3D.Then these electron donors were coordinated with tetrachloro titanium (TiCl 4) and chloride magnesium (MgCl 2)to obtain the catalysts for the polymerization of propylene.The catalytic activities and properties of polypropylene are greatly improved by adding external donor(ED) when CPCADEE or DEPDADE is used as internal donor(ID).However,when BEMP was used as ID,the highest catalytic activity is obtained without adding ED,which can reduce production costs and simplify catalytic synthesis.The experiments indicate that BEMP has the shortest distance of oxygen atoms and the highest electronegativity.

Photoinduced generation of alkyl and phthalimide nitrogen radicals from N-hydroxyphthalimide esters for the synthesis of benzophenone-type bioisosteres

N-Hydroxyphthalimide(NHPI)esters have emerged as powerful sources of alkyl radicals generated by single-electron transfer,but homolysis of NHPI ester to produce an alkyl radical and a phthalimide nitrogen radical is still in its infancy.In this study,we developed a light-induced method for generation of alkyl and phthalimide nitrogen radicals from NHPI esters and subsequent reactions of the radicals with[1.1.1]propellane and aryl aldehydes for rapid generation of bicycle[1.1.1]pentane ketones.This method does not require metals or photosensitizers,features a broad substrate scope(90 examples)and excellent functional group tolerance,and can be used for the functionalization of structurally complex natural products and drugs.Mechanistic investigations indicate that the reaction involves photoinduced homolytic cleavage of the Cs_(2)CO_(3)-NHPI ester complex to produce alkyl and phthalimide nitrogen radicals and subsequent hydrogen atom transfer between the phthalimide nitrogen radical and the aldehyde to generate an acyl radical.

Iodopentafluorosulfanylation of [1.1.1]propellane and further functionalizations

Pentafluorosulfanylated(SF_(5^(-))) aromatics have shown great potential in drugs, and the bioisosteric replacement of aromatic ring with bicyclo[1.1.1]pentane(BCP) unit has attracted considerable attention recently. Consequently, pentafluorosulfanylated bicyclo[1.1.1]pentanes(SF_(5^(-))BCPs) should have application in the realm of drug discovery. In this study, a one-pot iodopentafluorosulfanylation of [1.1.1]propellane with SF_(5)Cl and CH_(2)I_(2)for the practical synthesis of iodopentafluorosulfanylated bicyclo[1.1.1]pentane(SF_(5^(-))BCP-I) was developed. SF_(5^(-))BCP-I was the first example of SF_(5^(-))BCPs that could be transformed. The first general method to access SF_(5^(-))substituted bicyclo[1.1.1]pentane derivatives was demonstrated through photoredox-catalyzed radical addition of SF_(5^(-))BCP-I to alkenes and alkynes.

Deterioration in Heat Transfer of Endothermal Hydrocarbon Fuel

Numerical studies under supercritical pressure are carried out to study the heat transfer characteristics in a single-root coolant channel of the active regenerative cooling system of the scramjet engine, using actual physical properties of pentane. The relationships between wall temperature and inlet temperature, mass flow rate, wall heat flux, inlet pressure, as well as center stream temperature are obtained. The results suggest that the heat transfer deterioration occurs when the fuel temperature approaches the pseudo-critical temperature, and the wall temperature increases rapidly and heat transfer coefficient decreases sharply. The decrease of wall heat flux, as well as the increase of mass flow rate and inlet pressure makes the starting point of the heat transfer deterioration and the peak point of the wall temperature move backward. The wall temperature increment induced by heat transfer deterioration decreases, which could reduce the severity of the heat transfer deterioration. The relational expression of the heat transfer deterioration critical heat flux derives from the relationship of the mass flow rate and the inlet pressure.

NOVEL BIOMARKERS FOUND IN SOUTH FLORIDA BASIN

Some 11 novel series of biological markers, aryl isoprenoids, have been found in Sunniland sedimentary organic matter (both oil and its source rock) of the South Florida Basin (USA). All of them have the same homologous key ions m/z 91+14n (n=0—10). In this paper, only one of these homologous series, 2, 3, 6-trimethylphenylisoprenoids, will be discussed organic-geochemically. Two new maturity indicators, ΣHⅠ/ΣHⅡ and ΣHB/ΣHA, have been put forward, and it is suggested that these novel biomarker compounds can be used as indicators of organic facies and maturity of sedimentary organic matter.

Recent advances in the applications of[1.1.1]propellane in organic synthesis

As a highly strained small molecule,[1.1.1]propellane has been widely used in various synthetic transformations owing to the exceptional reactivity of the central bond between the two bridgehead carbons.Utilizing strain-release approaches,the rapid development of strategies for the construction of bicyclo[1.1.1]pentane(BCP)and cyclobutane derivatives using[1.1.1]propellane as the starting material has been witnessed in the past few years.In this review,we highlight the most recent advances in this field.Accordingly,the reactivity of[1.1.1]p ropellane can be divided into three pathways,including radical,anionic and transition metal-catalyzed pathways under appropriate conditions.