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71.
Methyl oleate (18∶1) and linoleate (18∶2) were readily transformed to the correspondinggem-dichlorocyclopropane derivatives in high yield, using triethylbenzylammonium chloride as the phase-transfer catalyst in the
presence of aqueous NaOH and CHCl3. Reaction of dichlorocarbene with methyl 12-hydroxystearate furnished methyl 12-chlorostearate (49%) and 12-O-formylstearate (19%). The hydroxy group in methyl ricinoleate was protected (O-tetrahydropyran-2′-yl) prior to dichlorocyclopropanation of the ethylenic bond. Removal of the protecting group allowed the
hydroxy group to be converted to a chloride,O-acetyl, azido orO-formyl function. Treatment of methyl ricinoleate with thionyl chloride, followed by the reaction with dichlorocarbene gave
the corresponding 12-chloro-dichlorocyclopropane derivative. The dichlorocyclopropane derivative of oleic acid was transformed
to a C19 allenic fatty acid when treated witht-butyl lithium. However, the remaining dichlorocyclopropane derivatives, containing an additional functional group in the
alkyl chain, failed to yield the corresponding allenic derivatives. All derivatives were characterized by a combination of
spectroscopic and chromatographic techniques, including infrared,1H nuclear magnetic resonance (NMR), and13C NMR spectroscopy. 相似文献
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The use and impacts of accelerated weathering of limestone (AWL; reaction: CO2+H2O+CaCO3→Ca2++2(HCO3−) is explored as a CO2 capture and sequestration method. It is shown that significant limestone resources are relatively close to a majority of CO2-emitting power plants along the coastal US, a favored siting location for AWL. Waste fines, representing more than 20% of current US crushed limestone production (>109 tonnes/yr), could provide an inexpensive or free source of AWL carbonate. With limestone transportation then as the dominant cost variable, CO2 mitigation costs of $3-$4/tonne appear to be possible in certain locations. Perhaps 10–20% of US point–source CO2 emissions could be mitigated in this fashion. It is experimentally shown that CO2 sequestration rates of 10−6 to 10−5 moles/sec per m2 of limestone surface area are achievable, with reaction densities on the order of 10−2 tonnes CO2 m−3day−1, highly dependent on limestone particle size, solution turbulence and flow, and CO2 concentration. Modeling shows that AWL would allow carbon storage in the ocean with significantly reduced impacts to seawater pH relative to direct CO2 disposal into the atmosphere or sea. The addition of AWL-derived alkalinity to the ocean may itself be beneficial for marine biota. 相似文献
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A spherical acoustic resonator was developed for measuring sound velocities in the gaseous phase and ideal-gas specific heats for new refrigerants. The radius of the spherical resonator, being about 5 cm, was determined by measuring sound velocities in gaseous argon at temperatures from 273 to 348 K and pressures up to 240 kPa. The measurements of 23 sound velocities in gaseous HFC-134a (1,1,1,2-tetrafluoroethane) at temperatures of 273 and 298 K and pressures from 10 to 250 kPa agree well with the measurements of Goodwin and Moldover. In addition, 92 sound velocities in gaseous HFC-152a (1,1-difluoroethane) with an accuracy of ±0.01% were measured at temperatures from 273 to 348 K and pressures up to 250 kPa. The ideal-gas specific heats as well as the second acoustic virial coefficients have been obtained for both these important alternative refrigerants. The second virial coefficients for HFC-152a derived from the present sound velocity measurements agree extremely well with the reported second virial coefficient values obtained with a Burnett apparatus.Paper dedicated to Professor Joseph Kestin. 相似文献
79.
N Cho Y Nara M Harada T Sugo Y Masuda A Abe K Kusumoto Y Itoh T Ohtaki T Watanabe S Furuya 《Canadian Metallurgical Quarterly》1998,46(11):1724-1737
On the basis of structural information for the cyclic hexapeptide endothelin (ET) receptor antagonist, TAK-044, a series of thieno[2,3-d]pyrimidine-2,4-dione derivatives bearing a carboxyl group and aromatic rings that were important for receptor binding were designed, synthesized, and evaluated for ET receptor binding affinities and inhibitory activities against ET-induced vasoconstriction. Optimization of each substituent in the thieno[2,3-d]pyrimidine ring led to the discovery of a novel and potent nonpeptide ET receptor antagonist, 6-(4-methoxymethoxyphenyl)-5-methylsulfonylaminomethyl-1-(2- methylthiobenzyl)-2,4-dioxo-1,2,3,4-tetrahydrothieno[2,3-d]p yrimidine-3- acetic acid (32 g), which binded to human ETA and ETB receptor subtypes with affinities (IC50) of 7.6 and 100 nM, respectively. Compound 32 g effectively antagonized ET-induced vasoconstriction and the inhibitory effect mediated by the ETB receptor was more potent than that of bosentan, while the inhibitory effect mediated by the ETA receptor was slightly less potent than that of bosentan. 相似文献
80.
M Watanabe M Nakamura K Sato M Kano MI Simon Y Inoue 《Canadian Metallurgical Quarterly》1998,10(6):2016-2025
Ligand binding to neurotransmitter and hormone receptors which couple to the Gq subclass of GTP-binding protein leads to the activation of phospholipase Cbeta (PLCbeta) which hydrolyses phosphatidyl-inositol 4,5-bisphosphate, yielding a pair of second messengers, diacylglycerol and inositol 1,4,5-trisphosphate (IP3). The expression of PLCbeta1-4 mRNAs was comparatively examined by in situ hybridization in the mouse brain. In adults, PLCbeta1 mRNA was expressed predominantly in the telencephalon, including the cerebral cortex, hippocampus, amygdala, lateral septum and olfactory bulb, with little expression in most thalamic nuclei. PLCbeta2 mRNA was distributed in the white matter, suggesting its expression in non-neuronal cells, most likely oligodendrocytes. PLCbeta3 mRNA was specifically expressed in cerebellar Purkinje cells. The highest levels of PLCbeta4 mRNA were detected in Purkinje cells. High levels of PLCbeta4 mRNA were also found in the thalamus and medial septum, whereas weak signals were detected in most telencephalic regions, thus showing an expression pattern almost reciprocal to that of PLCbeta1 mRNA. During development, such characteristic regional expression of PLCbeta1 and PLCbeta4 were observed starting in late foetal stages, while specific expression of PLCbeta2 and PLCbeta3 appeared in early postnatal stages. We conclude that despite the existence of four PLCbeta isoforms, only one or two of them is expressed in individual neurons and glial cells. The distinct expression of PLCbetas provides a molecular basis for analysing the nature of the specific signal transduction pathway leading to the production of diacylglycerol and IP3 in distinct cell types and in different regions of the brain. 相似文献