Cobalt Hydrocarbonyl Research Articles

Kinetic and thermodynamic analysis of the hydroformylation of isobutylene catalyzed by cobalt hydrocarbonyl

The values of the variable component of chemical affinity (A-A0) are calculated and the relation between W (a kinetic parameter) and A-A0 (a thermodynamic parameter) are established on the basis of experimental data on rates of the hydroformylation reaction (W) of isobutylene catalyzed by cobalt hydrocarbonyl, and of data on compositions of the gas and liquid phases of the reaction mixture. The linear phenomenological relations of nonequilibrium thermodynamics are found to describe the dependence of W on A-A0 quite well at a conversion level of isobutylene of ≥50%.

Unexpected Cis,Cis to Trans,Trans Isomerization of a Disilanyl Analogue of 1,5-Cyclooctadiene

Unexpected Cis,Cis to Trans,Trans Isomerization of a Disilanyl Analogue of 1,5-Cyclooctadiene

ChemInform Abstract: Hydroformylation of Olefins in the Presence of Heterogeneous Cobalt Carbonyl Catalysts.

1. The introduction of silica gel into a homogeneous catalytic system for the hydroformylation of olefins containing hydrocarbonyltributylphosphinecobalt leads to the partial deactivation of the catalyst and a decrease in the selectivity due to binding of cobalt and the ligand by the surface hydroxyl groups. 2. The chemical binding of the silica gel OH group by the bidentate silylphosphine ligands permits modification of cobalt hydrocarbonyl to give a heterogeneous selective and stable catalyst for the hydroformylation of propylene.

Hydroformylation of olefins in the presence of heterogeneous cobalt carbonyl catalysts

1. The introduction of silica gel into a homogeneous catalytic system for the hydroformylation of olefins containing hydrocarbonyltributylphosphinecobalt leads to the partial deactivation of the catalyst and a decrease in the selectivity due to binding of cobalt and the ligand by the surface hydroxyl groups. 2. The chemical binding of the silica gel OH group by the bidentate silylphosphine ligands permits modification of cobalt hydrocarbonyl to give a heterogeneous selective and stable catalyst for the hydroformylation of propylene.

The Reaction of Cobalt Hydrocarbonyl with Vinyl Ethers, Vinyl Esters and N-Vinyl Compounds, and Oxo Reaction of Them

The substituent effects on the carbonylation reaction of cobalt hydrocarbonyl with polar olefins such as ethyl vinyl ether, vinyl acetate and N-vinyl compounds (N-vinylcarbazole, N-vinylindole, N-vinylpyrrole and N-vinylpyrrolidone) were studied. These olefins were carbonylated selectively on the α-carbon to give the branched-chain acyl complexes, though the α-carbon is more sterically hindered than the β-one. The branched-chain acyl complexes formed did not isomerize into the straight-chain one, though it is known that acylcobalt complexes easily undergo such a skeletal rearrangement. The branched-chain acyl complexes derived from ethyl vinyl ether, vinyl acetate, N-vinylindole and N-vinylpyrrole showed the great tendency to be reduced by cobalt hydrocarbonyl and to be transformed into the corresponding aldehydes.The oxo reactions of these olefins as well as phenyl vinyl ether were also studied with dicobalt octacarbonyl as the catalyst. The branched-chain aldehyde (and/or the corresponding alcohol) was produced with high selectivity from each olefin used. The effects of the reaction conditions (reaction temperature, partial pressure of carbon monoxide or hydrogen) on the distribution of the products (the straight or the branched-chain one) were very little. From these results, it was concluded that the distribution of the products in the oxo reaction of those olefins with electron-donative substituents such as alkoxy, acyloxy, and N-carbazolyl is mainly decided by the direction of the addition of cobalt hydrocarbonyl to the carbon-carbon double bond, and that the attack of cobalt occurs on the α-carbon from the substituent to give the products of the branched-chain structure.

Hydrogenation of 9,10-dimethylanthracene with cobalt hydrocarbonyl

Hydrogenation of 9,10-dimethylanthracene with cobalt hydrocarbonyl

Vapor-phase olefin isomerization with cobalt hydrocarbonyl and the mechanism of the hydroformation reaction

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTVapor-phase olefin isomerization with cobalt hydrocarbonyl and the mechanism of the hydroformation reactionPaul Taylor and Milton OrchinCite this: J. Am. Chem. Soc. 1971, 93, 24, 6504–6506Publication Date (Print):December 1, 1971Publication History Published online1 May 2002Published inissue 1 December 1971https://doi.org/10.1021/ja00753a028RIGHTS & PERMISSIONSArticle Views156Altmetric-Citations34LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (358 KB) Get e-Alerts Get e-Alerts

Mechanism of the hydrogenation of butadiene with cobalt hydrocarbonyl

Mechanism of the hydrogenation of butadiene with cobalt hydrocarbonyl

The isomerization and hydrogenation of the maleate-fumarate system by cobalt hydrocarbonyl

Treatment of dimethyl maleate with DCo(CO) 4 gives deuterated dimethyl fumarate and dimethyl succinate but no deuterium incorporation in the recovered maleate. The hydrogenation of dimethyl maleate to succinate proceeds via the fumarate. For the isomerization reaction, the results are best rationalized on the basis of a 1,2- cis-addition-elimination of DCo(CO) 4 while the hydrogenation probably involves 1,4-addition to the fumarate.

The Reaction of Cobalt Hydrocarbonyl with Vinylacetate, Crotonate, Styrene, and Acrylates

Abstract Ethyl vinylacetate and ethyl crotonate reacted with cobalt hydrocarbonyl at 25°C to give three isomeric acylcobalt carbonyls, α- and γ-carbethoxy-butyrylcobalt carbonyls and β-carbethoxy-iso-butyrylcobalt carbonyl. The distribution of these complexes depends greatly on the reaction time (0.5–20 hr). In both cases the β-isomer predominates at shorter reaction times (0.5–1.5 hr), while the γ-isomer predominates at longer reaction times. This shows that isomerization occurs among the complexes and that the equilibrium is very favorable to the γ-isomer. Acrylates and styrene react with cobalt hydrocarbonyl to give two isomeric acylcobalt carbonyls. The isomerization of the acylcobalt complex with a branched structure to that with a straight-chain structure is much promoted by the phenyl and ester groups. The promoting effect of the ester groups is the highest in benzyl, followed by allyl, and ethyl, isopropyl, butyl, and cyclohexyl. Such a promoting effect can reasonably be attributed to the −I effect of these groups.

Studies of the Organic Reactions of Metal Carbonyls. XVI. Solvent Effects on the Hydroformylation of Propylene and on the Reaction of Cobalt Hydrocarbonyl with 1-Pentene

Abstract In the reaction of cobalt hydrocarbonyl with 1-pentene at 10°C, solvents have a great effect on the distribution of the products, caproylcobalt carbonyl (I) and α-methylvalerylcobalt carbonyl (II). The I-to-II ratio is 72 : 28 in toluene, in toluene-dioxane (1 : 1 in volume), and in tolueneethyl acetate. The percentage of II increases to 40–66% in toluene-diethyl ether, -tetrahydrofuran, -acetone, -ethyl alcohol, and -acetonitrile. In the hydroformylation of propylene, the distribution of the products, n- and isobutyraldehyde, is also affected by the solvents. In toluene, the n-to-iso ratio is about 75 : 25, while in dioxane and in butyl acetate the percentage of the n-aldehyde increases to 79–83%. In methyl alcohol, dimethyl acetals of the aldehydes and n- and isobutyrate are formed. The n-to-iso ratio is the highest in the esters (3.2–8.5), followed by the acetals (0.7–1.6) and the aldehydes (0.4).

The Reaction Products of the Hydroformylation of Acrolein Acetals and Acetates

Abstract The hydroformylation reactions of acrolein acetals and acetates were carried out in order to discuss the side reactions and any subsequent reactions. Acrolein cyclic acetals reacted with carbon monoxide and hydrogen in the presence of a dicobalt octacarbonyl catalyst to give n- and iso-aldehydes in a 2:1 ratio; they gave no further reaction products. Acrolein diethylacetal underwent hydroformylation using a rhodium catalyst to give n- and iso-aldehydes in a 1:2 ratio. In the presence of a cobalt catalyst, however, various products were obtained. As a result of the acidity of cobalt hydrocarbonyl and a high reaction temperature, n-aldehyde, first formed in benzene, underwent change to 2,5-diethoxytetrahydrofuran and 1,1,4-triethoxybutane. In ethanol, n- and iso-aldehydes gave the corresponding acetals. In the hydroformylation of acrolein acetate, only n-aldehyde was obtained. Iso-aldehyde seemed to be converted into 2-methyl-3-acetoxyacrolein by deacetylation. In ethanol, besides n-acetal, iso-acetal and propionaldehyde acetate, 2,5-diethoxytetrahydrofuran and 2-methyl-3-ethoxyacrolein were recognized. The former seemed to be formed from n-aldehyde by ring closure and ethanolysis. The latter seemed to be formed by the ethanolysis of 2-methyl-3-acetoxyacrolein. In ethyl orthoformate, no side reaction was observed and the yield of the main product, 1,1-diacetoxy-4,4-diethoxybutane, amounted to 80%.

Stereochemistry of the addition of cobalt hydrocarbonyl to 1,2-diphenylcyclobut-1-ene

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStereochemistry of the addition of cobalt hydrocarbonyl to 1,2-diphenylcyclobut-1-eneWilliam L. Fichteman and Milton OrchinCite this: J. Org. Chem. 1968, 33, 3, 1281–1282Publication Date (Print):March 1, 1968Publication History Published online1 May 2002Published inissue 1 March 1968https://doi.org/10.1021/jo01267a091RIGHTS & PERMISSIONSArticle Views35Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (327 KB) Get e-Alerts Get e-Alerts

Studies of the Organic Reaction of Metal Carbonyl. X. The Oxo Reaction of Ethyl Acrylate—The Effects of the Reaction Conditions on the Distribution of the Products

Abstract The ratio between the α- and β-carbethoxypropionaldehyde formed in the oxo reaction of ethyl acrylate is affected by various reaction conditions; the proportion of β-carbethoxypropionaldehyde increases with an increase in the reaction temperature, but decreases with an increase in the partial pressure of carbon monoxide or hydrogen. These effects can be explained on the basis of the reaction mechanism between cobalt hydrocarbonyl and ethyl acrylate (Y. Takegami et al., This Bulletin, 37, 1190 (1964)): in the first step of the reaction, ethyl acrylate reacts with cobalt hydrocarbonyl to give, selectively, α-carbethoxypropionylcobalt carbonyl (I), and then I isomerizes to β-carbethoxypropionylcobalt carbonyl (II). Accordingly, the rates of two competitive reactions, the isomerization of I to II and the reduction of I to the corresponding aldehyde, may be the factors determining the distribution of the oxo reaction products. Under the oxo reaction conditions, the isomerization of I to II seems to occur more easily at a relatively high temperature and to be prohibited by a high pressure of carbon monoxide. On the other hand, a relatively high pressure of hydrogen seems to be favorable to the reduction of I to the aldehyde.

Studies of the Organic Reaction of Metal Carbonyl. IX. The Formation of o-Toluylcobalt Carbonyl in the Reaction of Benzyl Chloride with Potassium Cobalt Carbonylate

Abstract The reaction between benzyl halide and potassium cobalt carbonylate has been studied. o-Toluylcobalt carbonyl is found among the reaction products. This carbonyl seems to be formed by the isomerization of benzyl cobalt carbonyl via phenylacetylcobalt tricarbonyl or o-tolylcobalt carbonyl. This isomerization occurs only at relatively high temperatures (30–50°C). At 0°C, only phenylacetyl cobalt carbonyl is formed in a good yield. The isomerization is highly promoted by the addition of cobalt hydrocarbonyl. The reaction atmosphere (carbon monoxide and nitrogen) also has a great effect on the isomerization. Such additives as oxalic acid, p-toluenesulfonic acid, trichloroacetic acid, and ethyl alcohol-hydrogen chloride have no promoting effect on the isomerization.

Studies of the Organic Reaction of Metal Carbonyl. VII. The Acceleration Effect of the Addition of Inorganic Compounds on the Reaction of Olefin Oxide with Cobalt Hydrocarbonyl

Abstract The reaction of olefin oxide with cobalt hydrocarbonyl in the presence of inorganic (and organic) additives has been investigated. 1) The addition of relatively small amounts of various compounds of copper and silver promote the carbonylation of propylene oxide. The order of the promoting effect of these compounds is Cu2O, 70>CuO, 6O>(AlCl3, 30) >Ag2O, 27>CuCl2, CuCl and Cul, 20>CuCN, 15>AgCl, 9>Cu powder, 4>None, 1 (the numbers indicating the relative rates of the gas absorption at the early stage of the reaction). Among these, cuprous oxide has the largest effect. The amount of cuprous oxide necessary for this effect is only about 0.005 mol./mol. HCo(CO)4. β-Hydroxy-/n-butyrate has been the main reaction product obtained. On the other hand, chlorides of zinc, nickel, ferric, potassium, magnesium, palladium and titanium have no promoting effect on the reaction. 2) The combination of cuprous halide (and oxide) with various organic additives, which also have a promoting effect, has a synergistic effect on the reaction of propylene oxide. 3) The reaction of epichlorohydrin is also promoted by the addition of cuprous oxide. However, in this case cuprous oxide combined with ethyl alcohol has a retardation effect.

Studies of the Organic Reaction of Metal Carbonyl. V. The Reaction of Cobalt Hydrocarbonyl with Olefin—The Effects of the Reaction Conditions and of the Structure of Olefin

Abstract It has been observed that the reaction of 1-olefin with cobalt hydrocarbonyl is remarkably affected by the reaction conditions and by the structure of olefln. Some functional groups, such as the ester, n-butoxy and phenyl groups, adjacent to a C= C bond increase the reactivity of the C=C bond; the order of the reactivity is n-butyl vinyl ether, 103>styrene, 20>ethyl acrylate, 5>pentene-1. (The numbers indicate the relative reactivities, which have been roughly calculated from the gas absorption curve.) At a relatively low temperature (below 0°C), the α-carbon atom of the C=C bond of all these olefins except pentene-1 is selectively carbonylated; the reaction scheme may be considered to be as follows; suggesting that cobalt hydrocarbonyl is acting as an acid: (Remark: Graphics omitted.) However, these acylcobalt carbonyls with the branched structure isomerize to those with the straight one: (Remark: Graphics omitted.) A relatively high temperature (25°C) and a nitrogen atmosphere promote this isomerization considerably. The reverse isomerization seems to occur only with difficulty. On the other hand, these olefins mainly give the β-carbon carbonylated product at 25 °C, the formation of which seems to result from the two successive reactions, the carbonylation of the α-carbon atom and the isomerization of the corresponding acylcobalt carbonyl. However, the distribution of the products from pentene-1 is not affected by the reaction temperature. A relatively high pressure of carbon monoxide is advantageous for this reaction. Under a nitrogen atmosphere, some reaction other than the carbonylation seems to occur very rapidly, consuming a large part of the cobalt hydrocarbonyl used; a nitrogen atmosphere has an inhibitory effect on the carbonylation.

Studies of the Organic Reactions of Metal Carbonyl. IV. The Acceleration Effect of the Addition of Organic Compounds on the Reaction of Olefin Oxide with Cobalt Hydrocarbonyl and on the Hydroformylation of Olefin Oxide

Abstract It has been observed that organic compounds with various kinds of functional groups have an accelerating effect on the reaction of olefin oxide with cobalt hydrocarbonyl and on the hydroformylation of olefin oxide. 1) The addition of a relatively small amount of ethyl alcohol promotes the carbonylation of propylene oxide with cobalt hydrocarbonyl until it is about 120 times faster than that of the standard run, carried out without alcohol. The amount of the alcohol necessary for this effect is about 2.0 mol./mol. HCo(CO)4. As the reaction products, only compounds with a β-hydroxy-n-butyryl structure (ester and aldehyde) have been obtained. 2) The compounds other than ethyl alcohol, such as n- and t-butyl alcohol, ethylene chlorohydrin, acetone, tetrahydrofuran, ether, acetal, benzaldehyde, ethyl acetate and acetonitrile, also have the same effect on this reaction. Among these compounds, ethyl and butyl alcohols have the largest effect. On the other hand, phenol has no effect. The accelerating effect is considered to be due to the basicity of these compounds. 3) The reactions of styrene oxide and epichlorohydrin with cobalt hydrocarbonyl are also promoted by the addition of ethyl alcohol.A relatively small amount of the alcohol accelerates selectively, the carbonylation of styrene oxide which is comparatively readily hydrogenated with cobalt hydrocarbonyl.2) For epichlorohydrin, the following relationship was observed to exist at an early stage of the reaction: rate of the gas absorption=k[epichlorohydrin] [ethyl alcohol]. 4) The hydroformylation of ethylene oxide seems to be selectively promoted by the addition of ethyl alcohol, which gives β-hydroxypropionaldehyde, in a low yield.

Studies of the Organic Reactions of Metal Carbonyl. II. The Reaction of Olefin Oxide with Cobalt Hydrocarbonyl

Abstract The reactions of olefin oxides with cobalt hydrocarbonyl have been studied. The effect of the reaction conditions on the nature of the reaction, especially that of propylene oxide, has been examined in detail. Propylene oxide gave only the products with β-hydroxy-n-butyryl structure under these reaction conditions: temperature, 25∼45°C; atmosphere; nitrogen or carbon monoxide; and mole ratio of propylene oxide, 1.4∼6.2. The inhibitory effect of a nitrogen atmosphere on the formation of carbonylated products (ester and aldehyde) has been observed ; under nitrogen, some side reaction was highly promoted, and the formation of carbonylated products was thereby prevented. The reactions of ethylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin have also been studied. In the reactions of styrene oxide, the mole ratio of styrene oxide had a significant effect on the nature of the reaction; at a relatively small mole ratio, the reduction gave, mainly two isomeric alcohols, but as the mole ratio increased, the carboxylation reaction seemed to increase. Epichlorohydrin gave a product with a γ-chloro-β-hydroxy-n-butyryl structure, which corresponds to that which propylene oxide gave. The order of the reactivity of these olefin oxides is as follows: cyclohexene oxide (about 5) and styrene oxide>propylene oxide (1)>ethylene oxide>>epichlorohydrin (1⁄20∼40) ; (the numbers indicate the relative reactivities). This fact seems to indicate that, in general, internal (and conjugated) olefin oxides are more reactive than terminal olefin oxides. By analogy with the relative reactivity of propylene oxide and epichlorohydrin with cobalt hydrocarbonyl, perchloric acid and ammonia, it may reasonably be considered that cobalt hydrocarbonyl reacts as an acid. Pentene-1 appeared to be less reactive than propylene oxide.

The Reaction of Cobalt Hydrocarbonyl with α,β-Unsaturated Aldehydes and Ketones

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Reaction of Cobalt Hydrocarbonyl with α,β-Unsaturated Aldehydes and KetonesRichard W. Goetz and Milton. OrchinCite this: J. Am. Chem. Soc. 1963, 85, 18, 2782–2784Publication Date (Print):September 1, 1963Publication History Published online1 May 2002Published inissue 1 September 1963https://doi.org/10.1021/ja00901a024RIGHTS & PERMISSIONSArticle Views191Altmetric-Citations54LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (419 KB) Get e-Alerts Get e-Alerts