123-38-6Relevant articles and documents
Kinetic study of the oxidation of propan-1-ol by alkaline hexacyanoferrate(III) catalyzed by ruthenium trichloride
Mucientes,Poblete,Rodriguez,Santiago
, p. 662 - 668 (1997)
The oxidation kinetics of propan-1-ol by alkaline hexacyanoferrate(III) catalyzed by ruthenium trichloride were studied spectrophotometrically. The initial rate method was used for kinetic analysis. The reaction rate shows a fractional order in [oxidant] and [substrate] and a first-order dependence on [RuCl3]. The dependence on [OH-] is complicated. A reaction mechanism involving two active catalytic species is proposed. Each one of these species forms an intermediate complex with the substrate. The attack of these complexes by hexacyanoferrate(III) in rate-determining step produces a radical species which is further oxidized in the subsequent step.
Molecular Hydrogen Complexes in Catalysis: Highly Efficient Hydrogen Production from Alcoholic Substrates catalysed by Ruthenium Complexes.
Morton, David,Cole-Hamilton, David J.
, p. 1154 - 1156 (1988)
The complex catalyses the thermal production of hydrogen from a range of different alcoholic substrates with rates corresponding to up to >1000 catalyst turnover h-1; the mechanism of the reaction is discussed and possible reasons for the high efficiency of this catalyst including the fact that loss of hydrogen occurs from a molecular hydrogen complex, are explored.
Bulky monophosphite ligands for ethene hydroformylation
Tricas, Hugo,Diebolt, Olivier,Van Leeuwen, Piet W.N.M.
, p. 198 - 205 (2013)
A wide range of monophosphite ligands was investigated in rhodium-catalyzed ethene hydroformylation. A stoichiometric gas mixture CO/H2/ethene 1:1:1 was used, the reaction being thus 100% atom economic. The reaction was found to be very selective and only propanal was formed under the reaction conditions studied. The most efficient catalytic system was L1-modified rhodium, and reaction parameters were optimized for this ligand. Under optimized catalytic conditions, reaction rates 10-15 times higher than those of the triphenylphosphine-modified system were obtained, demonstrating the high suitability of π-accepting ligands for this reaction. Stability tests, resistance toward water and acids in particular, showed the good stability of the selected phosphite L1. Notably, L1 was more stable than cyclic phosphites L6 and L13.
Formation of C3H6 from the Reaction C3H7 + O2 and C2H3Cl from C2H4Cl + O2 at 297 K
Kaiser, E. W.,Wallington, T. J.
, p. 18770 - 18774 (1996)
The generation of conjugate olefins from the reactions of propyl (reaction 1) or chloroethyl (reaction 2) radicals with O2 has been investigated as a function of total pressure (0.4-700 Torr) at 297 +/- 2 K.The experiments were carried out by UV irradiation of mixtures of propane (or ethyl chloride), Cl2, and O2 to generate alkyl radicals.Propylene from reaction 1 was measured by FTIR spectroscopy, while vinyl chloride from reaction 2 was monitored by both FTIR and gas chromatographic analysis.At pressures where the formation of propylperoxy radicals is near the high-pressure limit, the propylene yield from reaction 1 was inversely dependent on total pressure (YC3H6 P-0.68+/-0.03), proving that it is formed via rearrangement of an excited propylperoxy adduct that can also be stabilized by collision.The vinyl chloride yield decreased from 0.3 + /- 0.1 percent at 1 Torr to 0.1 percent at 10 Torr.Because the formation of chloroethylperoxy radicals is in the fall-off region over this pressure range, the vinyl chloride yield cannot be ascribed unambiguously to an addition-elimination process.The propylene yield from reaction 1 is 2-4 times smaller than the ethylene yield from C2H5 + O2 over the pressure range 0.4-100 Torr, while the vinyl chloride yield from reaction 2 is 40 times smaller between 1 and 10 Torr.This is consistent with more efficient stabilization of the excited propylperoxy relative to the ethylperoxy adduct caused by the presence of additional vibrational modes.The markedly smaller ambient temperature vinyl chloride yield from reaction 2 may result from a combination of more efficient stabilization resulting from the lower frequency of the C-Cl bond and reduction of the C-H bond reactivity upon Cl substitution.
The Photochemical Reaction of Benzocinnoline. IV. Comments on the Mechanism of 2,2'-Diaminobiphenyl Formation
Inoue, Hiroyasu,Hiroshima, Yukimi,Sakai, Toshihiko,Sakurai, Tadamitsu,Fukuda, Norio
, p. 2829 - 2830 (1981)
In order to determine the mechanism of 2,2'-diaminobiphenyl formation from benzocinnoline, effect of aldehyde on the reaction was examined.It is proposed that ethanal, which was generated from ethanol in the initial photoreduction, formed an adduct with 5,6-dihydrobenzocinnoline, and that the resulting adduct participated in the subsequent photo-induced 2,2'-diaminobiphenyl formation.
A sensitive cataluminescence-based sensor using a SrCO3/graphene composite for n-propanol
Zhang, Qianchun,Meng, Feifei,Zha, Lin,Wang, Xingyi,Zhang, Guoyi
, p. 57482 - 57489 (2015)
In this paper, we developed a cataluminescence-based sensor using SrCO3/graphene for sensitive and selective detection of n-propanol. The composite was characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and gas adsorption. The sensor was coupled with a miniature vaporizing device to detect n-propanol in liquid samples. The experimental results revealed that the SrCO3/graphene sensor exhibited a sensitivity for n-propanol 5.8 times higher than that of pure SrCO3, indicating that the sensitivity of the SrCO3/graphene sensor was increased by adding graphene to SrCO3. The linear range of the sensor was 0.2 to 32 mg L-1 (r = 0.9987) with a limit of detection of 0.08 mg L-1. The sensor showed a rapid response of 2 s and a recovery time of 20 s, respectively. The sensor was used to analyze samples spiked with known concentrations of n-propanol. The concentrations of n-propanol in all samples were well quantified with satisfactory recoveries, indicating that the SrCO3/graphene sensor is a promising candidate for fast, sensitive, selective detection of n-propanol. We also discuss the possible mechanism based on the reaction products.
Dehydration of 1,3-butanediol over rare earth oxides
Gotoh, Hiroshi,Yamada, Yasuhiro,Sato, Satoshi
, p. 92 - 98 (2010)
Vapor-phase catalytic dehydration of 1,3-butanediol was investigated over rare earth oxides (REOs) calcined at different temperatures. In the dehydration of 1,3-butanediol over REOs such as Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Lu2O3, and Y2O3, 3-buten-2-ol and 2-buten-1-ol were preferentially produced. REOs exhibited different catalytic activities in the dehydration of 1,3-butanediol depending on their crystal structures. CeO2 showed the highest formation rate with the highest selectivity to the unsaturated alcohols among the REOs. Cubic REOs also selectively produced the unsaturated alcohols: cubic Er2O3, Yb2O3, and Lu2O3 showed high formation rate of the unsaturated alcohols. Since the formation rates of the unsaturated alcohols over Er2O3 and CeO2 were suppressed in CO2 and NH3 carrier gas flows more than in H2 flow, it is probable that the acid-base sites play a major role of the formation of the unsaturated alcohols.
Hydrolysis of Aldal Acetals
Su Min Oon,Kubler, Donald G.
, p. 1166 - 1171 (1982)
Eleven aldal acetals were synthesized, and the kinetics of their hydrolyses in water and in water-acetonitrile were studied as model systems for the hydrolysis of sucrose. α,α'-Diethoxypropyl ether (an aldal acetal) hydrolyzes in water without hemiacetal buildup.The reaction is not subject to general acid catalysis and the value of kD3O(+)/kH3O(+) = 2.44, both results being characteristic of an A1 mechanism.The energy of activation for the hydrolysis of α,α'-diethoxydipropyl ether was 84.98 kJ mol -1 in water and showed no temperature dependency over the range of 15 - 35 deg C.The structural effects for the hydrolysis of aldal acetals parallel those for acetal hydrolysis.
Thermolysis of Dioxetanes: 3,3-Diethyl-1,2-dioxetane and 3,3-Dimethyl-4-ethyl-1,2-dioxetane
Baumstark, Alfons L.,Dunams, Tambra
, p. 3754 - 3756 (1982)
3,3-Diethyl-1,2-dioxetane (1) and 3,3-dimethyl-4-ethyl-1,2-dioxetane (2) were synthesized in 10percent yield by closure of the corresponding bromo hydroperoxides with base.Thermal decomposition of 1 and 2 produced only the expected cleavage products.Dioxetanes 1 and 2 directly produced high yields of triplet carbonyl products upon thermal decomposition similar to those reported for other alkyl-substituted dioxetanes.The activation parameters of the thermal decomposition of 1 and 2 were determined from Arrhenius plots (for 1, Ea = 24.9 kcal/mol, log A = 13.1, k60 deg C = 6.5*1E-4 s-1, ΔSexcit. = -0.8 eu; for 2, Ea = 24.7 kcal/mol, log A = 12.8, k60 deg C = 3.4*1E-4 s-1, ΔSexcit. = -2.3 eu).Also, trimethyl-1,2-dioxetane (3) and 3,3-dimethyl-1,2-dioxetane (4) were prepared and the activation parameters redetermined (for 3, Ea = 24.9 kcal/mol, log A = 13.0, k60 deg C = 4.5*1E-4 s-1, ΔSexcit. = -1.4 eu; for 4, Ea = 23.4, log A = 12.5, k60 deg C = 1.4*1E-4 s-1, ΔSexcit. = -3.6 eu).The results suggest that a major substituent effect on alkyldioxetane thermolysis is due to 3,3 steric interactions as opposed to 3,4 steric interactions.
Regioselective rhodium-diphosphine ligand catalyzed hydroformylation of vinyl acetate
Liang, Haoran,Zhang, Lin,Zheng, Xueli,Fu, Haiyan,Yuan, Maolin,Li, Ruixiang,Chen, Hua
, p. 977 - 981 (2012)
Rhodium-catalyzed hydroformylation of vinyl acetate with the use of diphosphine ligands was studied. A high regioselectivity (branched:linear of 99:1) and activity (TOF: 4000 h-1) under optimum conditions were achieved by using a 2,2'-bis(diphenylphosphino methyl)-1,1'-biphenyl ligand. The high turnover number (9200) obtained under mild conditions and stability of the catalyst indicates that it would be useful for industrial vinyl acetate hydroformylation.
