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1.
Fluoro-substituted aliphatic nitriles are shown to undergo the Houben-Hoesch reactions with arenes in CF3SO3H to give fluoro-substituted ketones in good yields. The fluorine substituents appear to enhance the reactivities of the nitriles (and the nitrilium ion intermediates) compared to similar aliphatic nitriles. Fluoro-substituted ketones are also shown to be accessible through the reactions of organometallic reagents and fluoro-substituted nitriles. 相似文献
2.
Irene Ortín 《Tetrahedron》2009,65(48):9944-6277
To avoid the epimerization of the C(11a)-stereocenter previously observed in 6,11a-cis-pyrazino[1,2-b]isoquinolin-1,4-diones, we present in this paper the C(3)-alkylation of 1-methoxy-pyrazino[1,2-b]isoquinolin-4-ones to obtain all-cis derivatives through a very reliable protocol. The success of the acid-promoted cyclization to get pentacyclic (R3=arylmethyl) or tetracyclic (R3=2-bromo-2-propenyl) compounds is dependent on the nature of the C(3)-unsaturated chain and of the N-substituent, but these limitations have been overcome by using trifluoromethanesulfonic as a superacid catalyst. The C-(3)-alkylation of pyrazino[1,2-b]isoquinolin-4-one is also studied. 相似文献
3.
Ang Li 《Tetrahedron letters》2009,50(17):1924-9
The triflic acid (CF3SO3H) promoted cyclizations of 2-styrylbiaryls are found to be useful for the synthesis of polycyclic aromatic compounds, including functionalized derivatives of polycyclic aromatic compounds and heterocyclic systems. The reaction involves cationic cyclization followed by an elimination of benzene from the intermediate product. 相似文献
4.
In superacids HSO3F and CF3SO3H, it has been found that 3-arylindenones are very stable and exist as a doubly protonated species. NMR showed protonation both at the oxygen of the carbonyl group and at the C2 carbon of the indenone system. 3-Arylindenones proved however very sensitive to heat and light. Their [2+2] photodimerization under daylight has been studied. 相似文献
5.
A two step process for converting ketone or aldehyde via 1,1-dichloro-1-alkenes to the corresponding 1,1,1-trifluoroderivatives is described, based on HF addition and chlorine-fluorine exchange under superacidic conditions. 相似文献
6.
固体超强酸(SO4^2-/ZrO2)的异丁烷/1-丁烯烷基化反应性能和失活研究 总被引:3,自引:0,他引:3
研究了固体超强酸(SO4^2-/ZrO2)催化剂的酸性及异丁烷-1-丁烯烷基化反应性能,结果表明,固体超强酸的酸性与焙烧温度有关,适当提高焙烧温度有利于样品酸强度的提高,但焙烧温度过高会导致脱硫,使样品酸强度和酸量降低,固体超强酸的异丁烷/1-丁烯烷基化催化反应活性与其酸性相对应,酸性强,反应活性高,但催化剂的活性衰减很快,这是催化剂表面的快速积炭所致。 相似文献
7.
Agnieszka Grzelka Marek Cypryk Peter C. Hupfield 《Journal of organometallic chemistry》2004,689(4):705-713
Kinetics studies of the condensation of model hydroxyl-terminated oligosiloxanes, pentamethyldisiloxane-1-ol (MDH) and heptamethyltrisiloxane-1-ol (MD2H), catalysed by protic complex of tetrakis(pentafluorophenyl)borate in the toluene solution were performed. The dominating reaction was condensation, which was accompanied by disproportionation of oligosiloxanols. Water released in the condensation forms separate dispersed phase, but the phase separation and the presence of water does not affect the rate of the polycondensation. Both processes, condensation and disproportionation, show analogous kinetic laws being first order in silanol and half order in catalyst. They exhibit also similar values of activation parameters. The kinetics are explained by the formation of a reactive protic complex of silanol with borate being in fast preequilibrium with an unreactive complex including two borate molecules and the silanol molecules. The equilibrium lies to the side of the unreactive borate complex. 相似文献
8.
以硅溶胶和氧氯化锆为硅源和锆源,采用水热合成的方法制得具有ZSM-5结构的Zr-Si分子筛;用0.5mol/L的硫酸处理该分子筛,并在550℃焙烧,制得具有ZSM-5结构的SO4^2-/ZrO2-SiO2分子筛型的固体超强酸。采用XRD、SEM、TG、IR、NH3-PHD和指示剂法对其结构和酸性进行表征。结果表明,该SO4^2-/ZrO2-SiO2具有ZSM-5结构和超强酸性,其酸强度大于-13.75,且具有良好的热稳定性。 相似文献
9.
10.
New process to control hydrolysis step during sol-gel preparation of sulfated zirconia catalysts 总被引:2,自引:0,他引:2
Sulfated zirconia catalysts were prepared by sol-gel process using a new method allowing the control of the hydrolysis step
of zirconium alkoxides. Prepared samples were characterized by N2 adsorption (desorption) at 77 K, XRD, chemical analysis of total sulfur and XPS. Catalytic properties have been evaluated
in n-butane and n-hexane isomerization reactions. Obtained results show that time necessary for gelation is significant and
depends considerably on the nature of the zirconium precursor. Concerning the properties of the solids obtained by this method,
it has been noted that the use of the zirconium propoxide led to a better retention of the sulfate species, which improves
activity during isomerization reactions. It has been found also that an initial S/Zr molar ratio equal to 0.5 allowed to obtain
an optimal sulfur content and a high specific surface area. 相似文献