Carbon monoxide Carbonylation

Under a pressure (20 bar) of carbon monoxide, carbonylative silylcarbocyclization of enyne 92 was examined in the presence of a cationic rhodium-BINAP catalyst (Scheme 31).86 Although the enantioselectivity is low, the five-membered carbocycle functionalized with an alkenylsilane moiety and a formyl group was obtained with high selectivity. 

Carbonylations of aldehydes incorporate an inexpensive source of carbon, carbon monoxide, and can convert ubiquitously available aldehydes into various synthetically useful functionalities. This chapter deals with the most prominent applications of carbonylation methodology to aldehydes and is restricted to reactions where a direct bond is formed between the carbonyl moiety of the aldehyde (C or O) and carbon monoxide. Carbonylations of aldehydes mostly involve severe structural reorganizations of both reacting... 

Keywords Carbon monoxide Carbonyl compounds Heterocycles ... 

METHANESULFONIC ACID METHYL MERCAPTAN METHYL CHLOROSILANE METHYLAMINE METHYL SILANE TETRANITROMETHANE CARBON MONOXIDE CARBONYL SULFIDE CARBON DIOXIDE CARBON DISULFIDE BROMOTRIFLUOROETHYLENE... 

CYANOGEN BROMIDE CYANOGEN CHLORIDE CYANOGEN FLUORIDE CARBON MONOXIDE CARBONYL SULFIDE CARBON OXYSELENIDE CARBON DIOXIDE CARBON DISULFIDE CARBON SELENOSULFIDE CYANOGEN... 

All the above-mentioned initiators are very sensitive towards substances with active hydrogen. Care must therefore be taken to exclude acids, water, thiols, amines, and acetylene derivatives. Oxygen, carbon dioxide, carbon monoxide, carbonyl compounds, and alkyl halides which can react with the initiator, also interfere with the reaction. Careful purification and drying of the starting materials and apparatus is, therefore, absolutely essential, especially when dealing with living polymers (see Example 3-19). 

Keywords Carbonylation Ruthenium Carbon monoxide Carbonylative cycloaddition C-H bond activation... 

Cativa A process for making acetic acid by reacting methanol with carbon monoxide (carbonylation). The catalyst contains iridium acetate with promoters. Developed joindy by BP Chemicals, Hull, UK, and the University of Sheffield. First announced in 1996 and installed between 1995 and 1999 in four plants that had been using the former Monsanto acetic acid process. The first plant designed for the process was built by BP Petronas in Malaysia in 2000. A joint venture of BP with Sinopec used the process in a plant expansion in Chongqing, China, in 2005, and planned to build another plant in Nanjing, for completion in 2007. 

In a separate study of the decomposition of sulfinic acids in the absence of solvent at 200 °C the major products were sulfur dioxide and alkenes . Minor products were water, carbon dioxide, carbon monoxide, carbonyl sulfide and sulfur. The reaction is considered to proceed by a unimolecular free radical mechanism, although kinetic evidence is lacking. Olefin formation results from transfer reactions followed by elimination and one plausible pathway is... 

Chemiluminescence is also shown with a few simple mineral compounds. Otto (21) expressed the opinion that, if ozone causes a luminescence in the presence of water, it acts upon impurities therein. Hydrogen sulfide gives rise to an ultraviolet chemiluminescence with ozone (Zabiezynski and Orlowski, 33). Several oxygen compounds of nitrogen, especially nitric oxide, show, under the action of ozone, a spectrum different from that of active nitrogen [Morren (20), Sarrasin (23), Strutt (26), Knauss and Murrey (17) ]. Solid phosphorus trixode becomes luminescent [Thorpe and Tutton (29)]] and so do carbon monoxide, carbonyl sulfide, and carbonyl chloride at 200 C. The first of these furnishes a band spectrum of 4000 to 5000 A. which corresponds to a bimolecular process [Trautz and Seidel (31) and Trautz and Haller (30)]. Siloxane too shows oxyluminescence [Kautsky and Zocher (16)] under the influence of ozone. 

The reaction of nitriles with carbon monoxide, carbonyl compounds, carboxylates, ketenes, 1-aminoal-kynes and carbenes has been reviewed recently... 

When 3,3-disubstituted cyclopropenes are treated with transition metal catalysts in the presence of carbon monoxide, carbonylated cyclodi- and cyclooligomerization products are obtained either solely or in addition to homo-cyclodi- and homo-cyclotrimers. The carbonylation products 3,3,7,7-tetramethyl-exo-tricyclo[4.1.0.0 ]heptan-5-one (2) and 4-isopropyl-6,6-dimethyl-bicyclo[3.1.0]hex-3-en-2-one (3) are formed as major products from 3,3-dimethylcyclopropene and carbon monoxide with tetracarbonylnickel as catalyst at ambient pressure and 20°C. Increasing the carbon monoxide pressure to 4.5-5.25 x 10" Torr leads to increased selectivity for the formation of 2 which is obtained in 54% yield along with a 24% yield of ketone 3. 

The photo-oxidation products of carbon disulfide in the laboratory were identified as carbon monoxide, carbonyl sulfide, sulfur dioxide, and a polymer that adhered to the sides of the reaction vessel (Heicklen et al. 1971). Although carbon disulfide absorbs light at wavelengths between 280 and 350 nm, dissociation does not occur under environmental conditions because of low molar absorptivity (Atkinson et al. 1978 Wood and Heicklen 1971) and direct photolysis of carbon disulfide in the atmosphere does not appear to be significant. EPA (1978a) stated that the information available indicated that carbon disulfide is relatively persistent in the atmosphere. For the atmospheric oxidation of carbon disulfide to sulfur dioxide, carbonyl sulfide, and carbon monoxide, the half-life was estimated to be about 12 days. 

Alkyl radicals formed via abstraction of the hydrogen atom may react with molecular oxygen present in the solution if dioxygen is replaced with carbon monoxide, carbonylation of the alkane occurs to produce an aldehyde or a ketone... 

Carbon monoxide carbonylates methane at 573-673 K in the presence of nitrous oxide on a rhodium-doped iron phosphate catalyst to produce methyl acetate [88a]. Vapor-phase carbonylation of toluene yields p-tolualdehyde, which can be easily oxidized to terephthalic acid [88b]. 

When the reaction is performed under pressurized carbon monoxide, carbonylative addition occurs, affording the (Z)-l,3-bis(arylthio)-2-alken-l-ones 5 (Scheme 1), where carbon monoxide is regioselectively incorporated at the terminal carbon of the acetylenes [7]. Higher pressure is essential to suppress the generation of the direct adduct of the disulfide 4. 

For nonpolar fluids [32, 33] (methane, ethane, propane, n-butane, w-pentane, n-hexane, n-heptane, n-octane, argon, oxygen, nitrogen, ethylene, isobutane, cyclohexane, sulfur hexafluoride, carbon monoxide, carbonyl sulfide, n-decane, hydrogen sulfide, isopentane, neopentane, isohexane, krypton, w-nonane, toluene. 

If, however, carbonyl(cyclopentadienyl)(trimethylphosphine)carbyne complexes of molybdenum and tungsten are allowed to react with carbon monoxide, carbonylation at the carbyne carbon takes place forming r l-ketenyl complexes in nearly quantitative yields [3,9]. 

Anionic hydridoiron species undergo selective addition to a, -unsaturated earbonyl compounds in methanol to give reduction products (Noyori et al., 1972c). Under an atmosphere of carbon monoxide, carbonylation takes place. Methylmalonate is selectively obtained from acrylate by treatment of the reaction mixture with alcoholic iodine (Masada et al., 1970). The organo-iron complexes are readily acylated by treatment with alkyl iodides in an aprotic solvent (Mitsudo et al., 1974). 

The carbon oxides, particularly the dioxide, have been discussed in earlier chapters, principally Chapter 11. Recall that Joseph Priestley worked with fixed air to produce soda water. The carbonation of soft drinks is still the second leading use of CO2. (The leading use is of the solid as the refrigerant dry ice .) CO2 is produced by the complete combustion of hydrocarbons (p. 286) and plays a major role in the greenhouse effect (p. 369). Earlier we discussed the role of CO and CO2 in the production of syngas (p. 259) and the gasification of coal. In Chapter 6 (p. 132) we noted the utility of carbon monoxide (carbonyl) as a ligand in the Mondprocess for the purification of nickel. 

Wittig olefination of ketone 49 with cyclopropylidenephosphorane afforded methylenecyclopropane 50. Subsequent cyclopropanation with dibromocarbene followed by debromination with zinc gave spiropentane 51. When 51 was treated with a rhodium catalyst under an atmospheric pressure of carbon monoxide, carbonylative skeletal rearrangement took place to give rise to the cyclopen-tenone 56. Mechanistically, the C4-C5 bond of spiropentane 51 adds oxidatively... 

Anthracene Arsenic trifluoride Benzyl chloride Benzyl cyanide Boron trifluoride Bromine trifluoride Butyl lithium Butyl mercaptan Calcium arsenide Carbon bisulfide Carbon monoxide Carbonyl fluoride Carbonyl sulfide Chlorine monofluoride Chlorine trifluoride Chloroacetic anhydride Chloroacetyl chloride Chloroform Chrysarobin Coal tar Cyanogen... 

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