Carbon monoxide catalyzed reactions

Kolbel et al. (K16) examined the conversion of carbon monoxide and hydrogen to methane catalyzed by a nickel-magnesium oxide catalyst suspended in a paraffinic hydrocarbon, as well as the oxidation of carbon monoxide catalyzed by a manganese-cupric oxide catalyst suspended in a silicone oil. The results are interpreted in terms of the theoretical model referred to in Section IV,B, in which gas-liquid mass transfer and chemical reaction are assumed to be rate-determining process steps. Conversion data for technical and pilot-scale reactors are also presented. 

Having greater resemblance to natural fatty acids are the products of the coordination-catalyzed hydrocarboxylation of olefins with water and carbon monoxide (Reppe reaction) [58] ... 

Figure C shows carbon monoxide insertion reactions. There are a number of reduction reactions of carbon monoxide catalyzed by transition metals, and these, I believe, all involve an insertion of carbon monoxide into a metal hydride as an initial step. Cobalt hydrocarbonyl reacts with carbon monoxide to give formate derivatives. This is probably an insertion reaction also.

Copper salts, cupric or cuprous also will catalyze the carbonylation of amines. Piperidine, for example, gives a urea derivative with carbon monoxide, and it, too, is probably a metal amide—carbon monoxide insertion reaction. 

Susuki and Tsuji reported the first Kharasch addition/carbonylation reactions of olefins 126 with CCI4 and carbon monoxide catalyzed by [CpMo(CO)3]2 127 and proposed a carbometalation mechanism (Fig. 37) [229]. A kinetic study disproved... 

Susuki and Tsuji reported the first Kharasch addition/carbonylation sequences to synthesize halogenated acid chlorides from olefins, carbon tetrachloride, and carbon monoxide catalyzed by [CpFe(CO)2]2 [101]. Its activity is comparable to or better than that of the corresponding molybdenum complex (see Part 1, Sect. 7). Davis and coworkers determined later that the reaction does not involve homolysis of the dimer to a metal-centered radical, which reduces the organic halide, but that radical generation occurs from the dimeric catalyst after initial dissociation of a CO ligand and subsequent SET [102]. The reaction proceeds otherwise as a typical metal-catalyzed atom transfer process (cf. Part 1, Fig. 37, Part 2, Fig. 7). 

Catalytic reactions with hydrosilanes and carbon monoxide. The reactions of olefins, cyclic ethers, and aldehydes with a hydrosilane and carbon monoxide catalyzed by Co2(CO)k or Ru or Rh complexes have been reviewed (48... 

In this more interesting case, each monomer adds only to an end unit of the other kind (k = 0, km - 0). In the polymer, units MA and M then alternate. Coordination copolymerization of olefins and carbon monoxide, catalyzed by complex hydrides of Pd(II) or Rh(I) in the presence of an alcohol co-solvent to yield polyketo esters, provides an example [133,134] Olefin and carbon monoxide are added altematingly, and reaction with alcohol terminates the kinetic chain and restores the catalyst. For ethene as the olefin ... 

Examples of catalysts in combustion reaction include the effect of H2O on the carbon monoxide oxidation reaction CO H- 2 C02- Nitric oxide also catalyzes CO oxidation through the mechanism 2 NO 4-O2 2NO2 (overall) and NO2 -f CO NO H- CO2. In both of these examples, an intermediate compound (for example, NO2) is formed and then destroyed. The addition of a small amount of NO2 to an H2 — O2 mixture leads to a branched-chain explosion by introducing the relatively rapid initiation step NO2 H- X NO H- O H- X, with the O atoms so produced generating the usual H2 — O2 chain. The NO2 also participates in the efficient termination step NO2 H- O NO H- O2, which is sufficiently important at large concentrations of NO2 to cause a slow reaction to be... 

However, palladium and nickel catalyzed versions promise, at the moment, an even wider range of possibilities. The need to maintain the catalytic cycle by continuous regeneration of the zerovalent metal catalyst limits, nevertheless, the functionalizability of the metallated center in the cyclized intermediate. For the same reason, the readily accessible starting materials may contain various functional groups which are compatible with the reaction conditions and which may be of value for the syntheses of complex heterocycles such as alkaloids. Carbon monoxide insertion reactions of the cyclized a-metal intermediates were shown to afford monocyclic methyl carboxylates and/or annulated cyclopentanones (cyclopentenones) with concomitant stereocontrolled formation of up to four carbon-carbm bonds. 

An organometallic equivalent that opens epoxides is a hydrosilane, for example, MeaSiH, and carbon monoxide, catalyzed by dicobalt octacarbonyl See 10-55 for other coupling reactions with organosilanes. Silyl enol ethers react with epoxides in a related reaction, but a Lewis acid, such as TiCl4, is required. ... 

Alkyl formates were prepared in insertion reactions of alcohols with carbon monoxide, catalyzed by a mixture of DBU and an epoxide (84EUP104875). 

The hydroformylation of alkenes is commonly run using soluble metal carbonyl complexes as catalysts but there are some reports of heterogeneously catalyzed reactions of olefins with hydrogen and carbon monoxide. Almost all of these are vapor phase reactions of ethylene or propylene with hydrogen and carbon monoxide catalyzed by rhodium, " 20 ruthenium,nickel, 22,123 cobalt, 23,124 and cobalt-molybdenum 23 catalysts as well as various sulfided metal catalysts. 23,125,126... 

Carbon monoxide insertion reactions in hydrocarbyl complexes of group VIII are particularly relevant because several industrial processes involving carbonylation of an organic substrate are catalyzed by metals belonging to this group. In the subsections that follow, reference to catalytic processes is made on each specific occasion. 

To enhance understanding of the CO-olefin copolymerization reaction catalyzed by nickel organometallic complexes (for the similar copolymerization reaction catalyzed by palladium compounds, see below), consider the carbon monoxide insertion reaction with nickel(II) compounds containing the bidentate P, O donor B ... 

Few examples of stereoselective transition metal catalyzed carbonylative multicomponent cycloadditions leading to other than five-membered rings have been reported1 72. Typical is the reaction of 3,3-dimethylcyclopropene with carbon monoxide, catalyzed by a palladium(O) complex, to stereoselectively form hexamcthyltrishomotropone as a tetracyclic adduct l73. 

Attention now turned to the installation of the carbonyl moiety. First, carbon-ylation of iodide 45 with bis(triphenylphosphine)palladium(II) dichloride and hydrazine at 60 °C was investigated (Entry 1, Table 4). After 30 min, the starting material had been fully consumed, furnishing a low yield of an unidentifiable product, and potentially formed via reaction of hydrazine with the carbonyl moiety. In contrast, application of high temperature carboalkoxylation conditions was successful (Entry 2). Carboalkoxylation with carbon monoxide catalyzed by palladium tetrakis(triphenylphosphine) with... 

Ortar and Morera have published a concise methodology for the synthesis of photoactive ketones [60]. More specifically, 4-aroyl-L-phenylalanines were used to study peptide protein interactions. They were synthesized by palladium-catalyzed coupling of 4-iodo-L-phenylalanines with organostannanes and carbon monoxide. The reaction proceeds under mild conditions with a PdCl2/PPh3 system in the presence of 1 bar CO at 90 °C in DMF. 

Albanesi, G., and M. Tovaglieri Reactions between Acetylenic Hydrocarbons and Carbon Monoxide catalyzed by Cobalt Carbonyls. 1. Octatrienediolides. Chim. e. ind. (Milan) 41, 189 (1959). Chem. Abstr. 53, 19872d (1959). 

Conjugated dienes can be selectively hydrated to ketones in the presence of cationic ruthenium complexes with bipyridyl ligands. The role of ruthenium is to catalyze the isomerization of allylic alcohols formed by the addition of water to diene. This method allows one to convert butadiene to methyl ethyl ketone in high yield [187]. Hydration of triple bonds is one of the oldest catalytic processes of organic chemistry. Though this reaction has no industrial value, it can serve as a tool of fine organic synthesis. The hydration can be catalyzed by rhodium salts under phase-transfer conditions [188]. The more exotic process of the hydrolysis of phenylacetylene to toluene and carbon monoxide catalyzed by ruthenium complex should also be mentioned [189] ... 

Despite the fragmentary results known to date, the dediazotation of diazoalkanes coupled with the carbene-carbon monoxide trapping reaction seems to be a promising synthetic path for the preparation of various carboxylic acid derivatives through the ketene intermediate product. Especially the highly effective and selective cobalt-catalyzed examples of the reactions are worth to explore in more detail. 

SCHEME 6.83 Palladium-catalyzed cascade carbon monoxide insertion reaction. 

When the transition-metal-catalyzed hydrothiolation of unsaturated compounds is performed in the presence of carbon monoxide, carbonylation reactions may proceed with the introduction of sulfanyl groups. In fact, a series of carbonylative thiolation reactions of alkynes and allenes are reported. These reactions provide useful tools to synthetically important organosulfur compounds [104, 105]. For example, the rhodium-catalyzed reaction of alkynes with thiols and CO provides the corresponding thioformylation products regioselectively [106, 107]. Switching the catalyst from rhodium complex to platinum complex leads to a sharp reversal of regioselectivity of CO introduction [108, 109] (Scheme 32). 

Under high pressures and temperatures, iodine reacts with oxygen to form iodine pentoxide [12029-98-0] (44). The reaction of iodine with carbon monoxide under acidic conditions is catalyzed by palladium salts (45). Phosphorous vapor and iodine react to form phosphoms trHodide [13455-01 -17, PI (46). 

Other important uses of stannic oxide are as a putty powder for polishing marble, granite, glass, and plastic lenses and as a catalyst. The most widely used heterogeneous tin catalysts are those based on binary oxide systems with stannic oxide for use in organic oxidation reactions. The tin—antimony oxide system is particularly selective in the oxidation and ammoxidation of propylene to acrolein, acryHc acid, and acrylonitrile. Research has been conducted for many years on the catalytic properties of stannic oxide and its effectiveness in catalyzing the oxidation of carbon monoxide at below 150°C has been described (25). 

Oxidation. Carbon monoxide can be oxidized without a catalyst or at a controlled rate with a catalyst (eq. 4) (26). Carbon monoxide oxidation proceeds explosively if the gases are mixed stoichiometticaHy and then ignited. Surface burning will continue at temperatures above 1173 K, but the reaction is slow below 923 K without a catalyst. HopcaUte, a mixture of manganese and copper oxides, catalyzes carbon monoxide oxidation at room temperature it was used in gas masks during World War I to destroy low levels of carbon monoxide. Catalysts prepared from platinum and palladium are particularly effective for carbon monoxide oxidation at 323 K and at space velocities of 50 to 10, 000 h . Such catalysts are used in catalytic converters on automobiles (27) (see Exhaust CONTHOL, automotive). 

Phosgene. The reaction between carbon monoxide and chlorine is catalyzed by activated carbon and gives phosgene [75-44-5] in neatly quantitative yield (eq. 6) (25). 

CO Oxidation Catalyzed by Palladium. One of the best understood catalytic reactions occurring on a metal surface is the oxidation of carbon monoxide on palladium ... 

Examples of perfluoroalkyl iodide addition to the triple bond include free radical addition of perfluoropropyl iodide to 1 -heptyne [28] (equation 21), thermal and free radical-initiated addition of lodoperfluoroalkanesulfonyl fluorides to acetylene [29] (equation 22), thermal addition of perfluoropropyl iodide to hexa-fluoro 2 butyne [30] (equation 23), and palladium-catalyzed addition of per-fluorobutyl iodide to phenylacetylene [31] (equation 24) The E isomers predominate in these reactions Photochemical addition of tnfluoromethyl iodide to vinylacetylene gives predominantly the 1 4 adduct by addition to the double bond [32] Platinum catalyzed addition of perfluorooctyl iodide to l-hexyne in the presence of potassium carbonate, carbon monoxide, and ethanol gives ethyl () per fluorooctyl-a-butylpropenoate [JJ] (equation 25)... 

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