Catalytic synthesis of organic compounds by the carbonylation of unsaturated hydrocarbons and alcohols
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Abstract:
The methods of synthesis of organic compounds by the carbonylation of acetylene, diene, and alkene hydrocarbons as well as alcohols in the presence of homogeneous and heterogeneous catalysts based on Group VIII metals and acid catalysts are examined. Data are presented on the synthesis of unsaturated and saturated mono- and di-carboxylic acids and their esters, lactones, and ketones from hydrocarbons and alcohols as well as the activities, selectivities, and stabilities of the catalytic systems in the carbonylation reaction. The bibliography includes 256 references.Keywords:
Carbonylation
Alkene
Acetylene
Homogeneous Catalysis
Diene
Homogeneous carboamination, carboalkoxylation and carbolactonization of terminal alkenes are realized via oxidative gold catalysis, providing expedient access to various substituted N- or O-heterocycles. Deuterium-labeling studies established the anti nature of the alkene functionalization and the indispensible role of Au(I)/Au(III) catalysis. This study constitutes the first example of catalytically converting C(sp(3))-Au bonds into C(sp(3))--C(sp(2)) bonds in a cross-coupling manner and opens new opportunities to study gold alkene catalysis where alkylgold intermediates can be readily functionalized intermolecularly.
Alkene
Homogeneous Catalysis
Surface Modification
Oxidative addition
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An infrared study of adsorbed acetylenes has revealed several features of the nature and orientation of the adsorbed species. Acetylene, deuteroacetylene, methyl acetylene, and dimethyl acetylene are strongly chemisorbed at room temperature on alumina. Weak chemisorption also occurs with acetylene, deuteroacetylene, and methyl acetylene. The strongly held acetylene is held normal to the surface, while the weakly held acetylene is held parallel to the surface. Similar effects occur with methyl acetylene, all of the strongly held molecules being attached to the surface by the acetylenic end. Both the strongly and weakly adsorbed dimethyl acetylene is adsorbed parallel to the surface. The sites responsible for the strong chemisorption of dimethyl acetylene are different from those active in the strong chemisorption of acetylene. With silica, no strong chemisorption occurred at room temperature for either acetylene or dimethyl acetylene. For both adsorbents, the interaction between the OD (and OH) groups of the surface and the adsorbates has been studied. Exchange takes place between the highest frequency OH groups on alumina and the strongly adsorbed C2D2. An OD group at the expected frequency was observed after the exchange had taken place. The remaining two types of OH groups on alumina did not appear to interact with the strongly held species, but only with the weakly held species. With dimethyl acetylene, the silica OD groups interacted to much the same degree as did the two lower frequency alumina OD groups.
Acetylene
Chemisorption
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Alkene
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Abstract This article reviews homogeneously catalyzed carbonylation reactions with particular emphasis on catalytic hydroformylation using cobalt, rhodium, platinum, and palladium complexes. The carbonylation of methanol based on rhodium and iridium complexes (Monsanto and Cativa ™ processes, respectively) is also discussed. Examples of the utility of carbonylation in the synthesis of complex molecules are given.
Carbonylation
Homogeneous Catalysis
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Carbonylation
Homogeneous Catalysis
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A pilot plant was launched and the modes of acetylene hydrogenation on cobalt catalysts were worked out. It has been found that the modified 7% Co/ SiAl cobalt catalyst is active in the process of hydrogenating acetylene into ethylene. Optimal conditions of acetylene hydrogenation on 7% Co/ SiAl catalyst were determined. The effects of temperature, space velocity and the ratio of initial components in the hydrogenation of acetylene to ethylene were investigated. The textural characteristics of cobalt catalysts before and after the hydrogenation of acetylene were investigated by the SEM method. The structure of cobalt catalysts after the hydrogenation of acetylene does not lose catalytic activity and selectivity. It has been found that catalyst samples have channels of different sizes, flaky particles and fibers located in the gaps between large aggregates are also present on the surface. The optimum temperature was 180 ° C in the hydrogenation of acetylene into ethylene at conversion 73.0%. Conversion of acetylene increases to 81.2% when temperature rises to 200°C, acetylene conversion decreases to 68% with further temperature exceeding to 220°C. Acetylene conversion again increases from 68 to 73.6% at 140°C in the ratio of acetylene to hydrogen 1:2. The selectivity of the catalyst 7%Co/SiAl to ethylene was studied depending on the temperature in the acetylene hydrogenation reaction. The selectivity to ethylene decreases with increasing temperature, since an increase in temperature activates side reactions.
Acetylene
Space velocity
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Abstract This article reviews homogeneously catalyzed carbonylation reactions with particular emphasis on catalytic hydroformylation using cobalt, rhodium, platinum, and palladium complexes. The carbonylation of methanol based on rhodium and iridium complexes (Monsanto and Cativa ™ processes, respectively) is also discussed. Examples of the utility of carbonylation in the synthesis of complex molecules are given.
Carbonylation
Homogeneous Catalysis
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Alkene
Coupling reaction
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A radical-mediated approach to alkene hydration is described. The present strategy capitalizes on the unique radical reactivity of hydroxamic acids, which are capable of functioning as both synthetically useful oxygen-centered radical species and suitable hydrogen atom-based donors. This reaction manifold has been applied to both alkene hydrations and tandem alkene–alkene carbocyclization processes.
Alkene
Reactivity
Hydrogen atom
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The experimentally determined rate law for the addition of ICl to 22 alkenes in CCl 4 at 25 °C under conditions of (alkene) 0 [Formula: see text] (ICl) 0 is −d(ICl)/dt = k exp (alkene) 0 (ICl) 3 /{1 + C 2 (alkene) 0 } 3 . The constant C 2 is shown to be equal to K app which is a measure of the formation constant or constants of the molecular complexes in this system. Under the experimental conditions used, C 2 is a good approximation of the formation constant of the 1:1 alkene–ICl molecular complex. Thus the values of C 2 obtained allow an estimate of the effect of alkene structure on the formation constant of the first molecular complex involved in this addition reaction. The contribution of the effect of substituents on C 2 is estimated to be approximately 24% of the overall change in rate due to change in the alkene structure.
Alkene
Constant (computer programming)
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