The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process. 相似文献
The cover picture shows that sequential 1,1‐dihydrosilylation of terminal aliphatic alkynes with primary silanes enabled by one earth‐abundant cobalt catalyst has been developed. This protocol is operationally simple using readily available aliphatic alkynes, including simple acetylene and complex drug derivative, for efficient access to valuable gem‐bis(dihydrosilyl)alkanes in highly regioselective and atom‐economic manners. Corresponding asymmetric transformations are achieved with excellent enantioselectivities. More details are discussed in the article by Lu et al. on page 457–461.
Highly dispersed α-Fe_2O_3/NaY,NiO/NaY,and CuO/NaY catalyst systems were pre-pared by impregnation method.Dispersion thresholds of the transition metal oxides on NaY" zeolitewere determined by XRD phase analysis.The dispersion capacities of the transition metal oxides on NaYzeolite are much lower than that estimated on the basis of a closed packed monolayer in the micropores.The catalytic activity and selectivity of the highly dispersed oxide catalyst systems for ethylben-zene and cyclohexane dehydrogenation reactions were reported. 相似文献
The thermal conductivities of several nanofluids (dispersions of alumina nanoparticles in ethylene glycol) were measured at temperatures ranging from 298 to 411 K using a liquid metal transient hot wire apparatus. Our measurements span the widest range of temperatures that have been investigated to date for any nanofluid. A maximum in the thermal conductivity versus temperature behavior was observed at all mass fractions of nanoparticles, closely following the behavior of the base fluid (ethylene glycol). Our results confirm that additional temperature contributions inherent in Brownian motion models are not necessary to describe the temperature dependence of the thermal conductivity of nanofluids. Our results also show that the effect of mass or volume fraction of nanoparticles on the thermal conductivity of nanofluids can be correlated using the Hamilton and Crosser or Yu and Choi models with one adjustable parameter (the shape factor in the Hamilton and Crosser model, or the ordered liquid layer thickness in the Yu and Choi model). 相似文献
Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD3OD/(D6)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents. 相似文献
[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base. 相似文献