Carbon monoxide, and alcohols

Nitric acid oxidation is used where carbohydrates, ethylene glycol, and propylene are the starting materials. The diaLkyl oxalate process is the newest, where diaLkyl oxalate is synthesized from carbon monoxide and alcohol, then hydrolyzed to oxahc acid. This process has been developed by UBE Industries in Japan as a CO coupling technology in the course of exploring C-1 chemistry. 

This reaction involves the two reactants carbon monoxide and alcohol and produces esters, or lactones. The starting material, which will be considered here, is an alkene or an alkyne but it is also possible to start from activated halides (aryl- or allyl- iodides and bromides) to produce the same kind of organic products. 

The carboxytelomerization, a variant to the usual telomerization, is the carbonylation-dimerization of butadiene, carbon monoxide and alcohols. 

The combined effect of carbon monoxide and alcohol on odor sensitivity. Environment International 12,207-210. 

Platinum(II) halides react with cyanate salts to give cyanato complexes. Reacting the compounds Pt(NCO)4 with triphenylphosphine gives Pt(NCO)2(PPh3)2.1628 These platinum(II) complexes are N-bonded. Treatment with carbon monoxide and alcohol yields the complex (172 equation 476).1629... 

REPPE PROCESS. Any of several processes involving reaction of acetylene (1) with formaldehyde to produce 2-butync-l,4-diol which can be converted to butadiene (2) with formaldehyde under different conditions to produce propargyl alcohol and, form this, allyl alcohol (3) with hydrogen cyanide to yield acrylonitrile (4) with alcohols to give vinyl ethers (5) with amines or phenols to give vinyl derivatives (6) with carbon monoxide and alcohols to give esters of acrylic acid (7) by polymerization to produce cyclooctatetraene and (8) with phenols to make resins. The use of catalysis, pressures up to 30 atm, and special techniques to avoid or contain explosions are important factors in these processes. 

In this review the synthetic aspects of asymmetric hydroformylation will be discussed first the experimental data relevant to attempt a rationalization of the results will then be considered. The closely related synthesis of optically active aldehydes by hydroformylation of optically active olefinic substrates in the presence of achiral catalysts7,8 and the different asymmetric hydrocarbonylation reactions, such as the synthesis of esters from olefins, carbon monoxide and alcohols in the presence of optically active catalysts9 , are beyond the scope of this review and will not be discussed here. 

Potential applications of superconducting cuprates in electronics and other technologies are commonly known. These cuprates also exhibit significant catalytic activity. Thus, YBa2Cu307 3 and related cuprates act as catalysts in oxidation or dehydrogenation reactions (Hansen et al. 1988 Halasz 1989 Mizuno et al. 1988). Carbon monoxide and alcohol are readily oxidized over the cuprates. NH3 is oxidized to N2 and H20 on these surfaces. Ammoxidation of toluene to benzonitrile has been found to occur on YBa2Cu307 (Hansen et al. 1990). 

In Secs. 5-10 we present a series of selected examples of the use of the external reflectance technique to investigate some electrochemical systems of interest. Results from the electrochemical literature on the adsorption of hydrogen, carbon monoxide and alcohols are discussed and compared with the data from UHV measurements (Secs. 5-7). 

It is decomposed by hydrochloric acid into ethyl hydrazodicarboxyl-ate, mercuric chloride, carbon monoxide, and alcohol by piperidine into ethyl hydrazodiearboxylate, mercury, and piperylurethane by bromine into ctliyl azodicarboxylate, mercuric bromide, and ethyl bromoforni ate. 

Catalysts having a very acid nature such as metaphosphoric acid, arsenious acid, boric acid, or salts of these acids have been proposed. The addition of copper as such or as the formate serves to promote the reaction.190 Reaction chambers extremely resistant to corrosion must be tised. Catalysts such as zinc arsenite. or zinc or chromium metaphosphatc having a highly acidic nature are claimed to be effective in the formation of organic acids from carbon monoxide and alcohols at temperatures of about 300° C. and a pressure of 200 atmospheres. Even with such acidic catalysts considerable quantities of esters are stated to be formed.101... 

Processes involving the addition of carbon monoxide and alcohol to acetylene, to produce acrylates, are derived from the Reppe reaction, in which nickel carbonyl, used in stoichiometric amounts, produces the CO required by itself. In these variants, the nickel carbonyl is used in semi catalytic proportions (Rohm and Haas process) or in effective catalytic proportions (BASF process). 

Base-catalysed loss of carbon monoxide has occasionally been observed as well as the acid-catalysed decarbonylation. Such reactions include the decomposition of formic esters to carbon monoxide and alcohols under the influence of alkali alkoxides,61 e.g. ... 

The synthesis of acrylates from acetylene, carbon monoxide, and alcohols is presented as an example of a reaction that is catalyzed by the carbonyls of nickel 25), cobalt 26), and iron 26)-. 

In spite of the differences in the electronic configuration of iron, cobalt, and nickel, the manner in which their respective carbonyls function as catalysts is essentially the same, differing only in detail. Under the proper conditions, for example, any of these metal carbonyls catalyze the reaction of acetylene, carbon monoxide, and alcohols to form acrylates. An iron complex, XI, in which most of the terminal carbonyls have been replaced by cyclopentadienyl groups, has been found to function, hke dicobalt octa-carbonyl, as a homogeneous hydrogenation catalyst 16) ... 

This paper deals with the synthesis of propionic acid by the reaction of carbon monoxide, ethylene, and water and with the synthesis of iso-butyric acid and 2-methylbutyric acid, respectively, by the reaction of carbon monoxide with n-propyl alcohol and ra-butyl alcohol. Using equimolar amounts of carbon monoxide and ethylene in the presence of a nickel-kieselguhr (30 70) catalyst, a yield of 40.5% of propionic acid was obtained after two hours at 180° and 3500-psig. pressure. With a nickel iodide-silica gel (Ni Si02 = 50 50) catalyst for the reactions of carbon monoxide and alcohols, conversions up to 82.4% in the case of n-propyl alcohol and 92.8% in the case of n-butyl alcohol were obtained. The effect of the different operating variables on the reactions and the peculiarities of the catalysts have been studied and are discussed. 

Thus, the peculiarities associated with the nickel iodide-silica gel catalyst in the reactions of carbon monoxide and alcohols appeared to be rather general and quite independent of the nature of the alcohol used in the system. It is thought that the activity of the nickel iodide-silica gel catalyst may be connected with a surface complex the formation of which requires the presence of traces of water. 

Following our first report on the palladium-catalyzed reaction of vinyl triflates with olefins (Heck-type reaction), oxidative insertion of palladium(O) into the carbon-oxygen bond of easily available vinyl triflates has proved to be a general method for the generation of o-vinyl palladium intermediates which can react directly with a variety of olefinic systems, carbon monoxide and alcohols or amines,or 1-alkynes, to give conjugated... 

Phase-transfer hydrocarboxylation of terminal acetylenes 254 (R = Bu, pentyl, Ph or PhCH2CH2) with carbon monoxide, catalysed by nickel(II) cyanide, affords the alkenoic acids 255 Similarly, phenylacetylene reacts with carbon monoxide and alcohols in the presence of palladium(dibenzylideneacetone)2 to give esters of unsaturated acids, e.g. 256192. 

Competition between carbonyl and hydrocarbon ligands, though difficult to predict, is another key issue in catalytic reactions. For example, the products of the Pd-catalyzed reaction of alkenes with carbon monoxide and alcohol with the aid of an oxidant depended on whether a base was present or not, where the base played a key role to determine the site of the initial nucleophilic attack of the alcohol as shown in Scheme 8.3 [7]. Thus, with some bases added, the first step of the catalysis was thought to be formation of Pd-COOR intermediate by the attack... 

The second example concerns the possibihty of obtaining information on the aliphatic compounds present in an utban environment. The problem then consists of removing the effects of the carbon monoxide and alcohol vapors, which constitute the most significant organic and volatile compounds interfering with the ahphatic compounds and especially with methane. 

Platinum is an oxidizing catalyst which can solve this kind of problem. Tests carried out in a laboratory, conducted in conditions close to those of the targeted applications, show the efficiency of such a material in the transformation of carbon monoxide and alcohol into carbon dioxide (see Figure 9.58), without degrading the methane. 

The tests realized on this kind of sensor (see Figure 9.59) show the selective character of the device towards hydrogen, at least in the presence of methane, carbon monoxide and alcohol in air. 

Butadiene reacts with carbon monoxide and alcohols - or amines to form 3,8-nonadienoic acid derivatives. A variety of alcohols, even relatively bulky ones, can be used. For example, reaction of butadiene with CO (50 atm) in tm-butyl alcohol (Pd(OAc)2/4 Ph3P, 110 °C, 16 h) affords the /3,y-unsaturated tm-butyl ester 141 in 92% yield (Scheme 45). CO pressures greater than 50 atm slow the reaction as do Ph3P/Pd ratios greater than or less than 4 1. 

Many industrial preparations start with acetylene, carbon monoxide, and alcohol or water ... 

Geuther found that the sodium compound of athylen-dimethylen-carbonsaure (acetoacetic ester) is formed from acetic ether and sodium ethoxide, whilst formic ether gives carbon monoxide and alcohol. He represented the action of sodium ethoxide on ethyl acetate by the equation ... 

In addition, reductive elimination of palladium and nickel complexes to form esters (Equations 8.67 and 8.68), amides, and tiiioesters has been reported. -" The reductive eliminations of esters and amides were observed during mechanistic studies on the palladium-catalyzed formation of esters and amides from aryl halides, carbon monoxide, and alcohols or amines. This catalytic process is presented in Qiapter 17 (carbonylation processes). The reductive elimination of thioesters from nickel complexes were studied, in part, to understand the C-S bond-forming process of acetyl coenzyme A synthase. Prior to this work, an iron-mediated synthesis of p-lactams had been reported that appears to occur by reductive elimination to form the amide C-N bond of the lactam. ... 

The reactions of benzylic halides with carbon monoxide and alcohols form esters in good yields. However, the reactions of alkyl halides are more limited for two reasons. First, the oxidative addition of alkyl halides occurs less readily to palladium complexes than the oxidative addition of aryl halides. This difference was noted in Chapter 7. Second, the intermediate alkylpalladium halide can undergo P-hydrogen elimination. As noted in Chapters 9 and 10, these hurdles have been overcome in some cases, and cross-coupling... 

These results indicate that we can introduce various substituents onto the carbonyl carbon using a palladium catalyst. Thus, aryl triflates were converted into aryl esters or amides (Scheme 17, Table 6), and enol triflates could be converted into a,/3-unsatu-rated esters or amides by a Pd-catalyzed reaction with carbon monoxide and alcohols or amines (Eq. 

Acrylic ester synthesis from acetylene, carbon monoxide, and alcohols with the aid of nickel carbonyl is known as the Reppe synthesis and is very important in industrial applications (Reppe, 1953). This carboxylation re-... 

Butadiene reacts in the presence of Pd(0) catalyst to afford the dimer easily and in the presence of carbon monoxide and alcohol to afford the esters as shown in eq. (20.71) [223]. 

If the same reaction is carried out at temperatures between 250-270 °C and slightly increased CO-partial pressure, succinic acid is obtained as the main product [384]. High acetylene partial pressure in the acrylic ester synthesis from acetylene, carbon monoxide and alcohol in the presence of... 

If the reaction of acetylene, carbon monoxide and alcohol in the presence of Ni(CO)4 is carried out in strong acid medium with only a low CO-partial pressure, the main reaction products are unsaturated dicarb-oxylic acid esters of the type ROOC-(CH=CH)n-COOR, n being mainly 3 or 4 [386, 387]. 

The reaction of olefins and their functional derivatives with carbon monoxide and alcohols to saturated carboxylic add esters generally proceeds at a lower velocity than the formation of the free acids as illustrated in the last chapter [504]. In the presence of nickel halogenide catalysts, reaction temperatures between 180-200 °C and pressures from 100 to 200 atm are required. Yields are in the range of 90 %. With cobalt catalysts reaction temperatures between 140 to 170 °C are recommended [505]. 

Besides nickel and cobalt, almost all of the catalysts discussed in the last chapter which were suited for the formation of free acids can be applied, e. g. rhodium, palladium and, with certain restrictions, iron. Cobalt hydrocarbonyl catalyzes the stoichiometric ester synthesis at mild reaction conditions [35, 121]. The initially formed acylcobalt carbonyls react rapidly with alcohols even at 50 °C and, in the presence of Na-alcoholate, even at 0 °C to give esters [121]. Dienes with isolated double bonds react with carbon monoxide and alcohols at mild reaction conditions in the presence of Pd/HCl to give unsaturated monocarboxylic acid esters and at more severe conditions to give saturated dicarboxylic acid esters [508]. 

AUene reacts in presence of PtClg/ZnClg [498] as well as Ru2(CO)9 [512] with carbon monoxide and alcohols to give methacrylic acid esters. Yields obtained are between 40 and 50% [497]. 

Actual operating capacities of Reppe carbonylation processes are difficult to estimate since only a few data are available in the literature. However, it is known that some of the syntheses are carried out on an industrial scale, e. g. the synthesis of acrylates from acetylene, carbon monoxide and alcohols (BASF) [1004, 1005], the acetic acid synthesis from methanol and carbon monoxide and the synthesis of higher molecular weight saturated carboxylic acids from olefins, carbon monoxide and water. Propionic acid (30,000 tons/year) and to a smaller extent heptadecanoic dicarboxylic acid are manufactured via the carbonylation route at BASF. Butanol is made from propylene in Japan [1003, 1004]. 

Recently the economic aspects of the acrylate synthesis from acetylene, carbon monoxide and alcohols were reviewed in European Chemical News [583]. The technology of the acrylate synthesis was reviewed in detail by M. Sittig [584]. 

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