Carbon dioxide three-component reactions

Two-component methods represent the most widely applied principles in sulfone syntheses, including C—S bond formation between carbon and RSOz species of nucleophilic, radical or electrophilic character as well as oxidations of thioethers or sulfoxides, and cheletropic reactions of sulfur dioxide. Three-component methods use sulfur dioxide as a binding link in order to connect two carbons by a radical or polar route, or use sulfur trioxide as an electrophilic condensation agent to combine two hydrocarbon moieties by a sulfonyl bridge with elimination of water. 

The three-component reaction between isatin 432a, a-aminoacids 433 (proline and thioproline) and dipolarophiles in methanol/water medium was carried out by heating at 90 °C to afford the pyrrolidine-2-spiro-3 -(2-oxindoles) 51. The first step of the reaction is the formation of oxazlidinones 448. Loss of carbon dioxide from oxazolidinone proceeds via a stereospecific 1,3-cycloreversion to produce the formation of oxazolidinones almost exclusively with /razw-stereoselectivity. This /f-azomethine ylide undergo 1,3-dipolar cycloaddition with dipolarophiles to yield the pyrrohdinc-2-r/ V -3-(2-oxindolcs) 51. (Scheme 101) <2004EJ0413>. 

The three-component reaction of indole (2) with sugar hydroxyaldehyde 281 and Meldrum s acid 282, with a catalytic amount of D,L-proline, afforded the 3-substitution product 283 as a single isomer [203]. The substituent possesses the czs-fused furo [ 3,2- b ] pyranonc skeleton. The proline catalyzes the Knoevenagel condensation of the sugar aldehyde 281 and Meldrum s acid 282 to provide the alkylidene derivative 284 of Meldrum s acid. Then a diastereo-selective Michael addition of indole and an intramolecular cyclization of this adduct 285 with evolution of carbon dioxide and elimination of acetone furnish the furopyranone in one-pot (Scheme 62). 

To a flame-dried, three-neck, 1-1 flask were added, in order, p-xylene (107 g, 1.0 mol), phosphorus trichloride (412 g, 3.0 mol), and anhydrous aluminum chloride (160 g, 1.2 mol). The reaction mixture was slowly heated to reflux with stirring. After 2.5 h at reflux, the reaction was allowed to cool to room temperature and the volatile components distilled at reduced pressure. The residual oil was slowly added to cold water (1 1) with stirring, and a white solid formed. The solid was removed by filtration, washed with water, and air dried. The solid was suspended in water (1 1) to which was added 50% sodium hydroxide solution (90 ml) to cause dissolution. The solution was saturated with carbon dioxide and filtered through Celite . The basic solution was washed with methylene chloride (200 ml) and acidified with concentrated hydrochloric acid (200 ml). The white solid that separated was isolated by extraction with methylene chloride (3 x 250 ml). The extracts were dried over magnesium sulfate, filtered, and evaporated under reduced pressure to give the pure 2,5-dimethylbenzenephosphinic acid (99 g, 60%) as an oil, which slowly crystallized to a solid of mp 77-79°C. 

The concept of employing three components, all of which contribute one carbon atom to the final allene unit (see Scheme 5.4), is illustrated in its purest form by the reaction of carbon dioxide (165) with 2 equiv. of an alkylidenetriphenylphosphorane 166, the process very likely involving the generation in the first step of a ketene intermediate 167, which subsequently reacts with further 166 to yield the allene product 168 (Scheme 5.25) [66]. 

Since the insertion of carbon dioxide apparently involves a sequence of reactions, it is instructive to consider the available pathways that can lead to insertion. A simple picture of the available mechanisms for C02 insertion is outlined schematically in (52). There are three components the metal center, the ligand, and the inserting molecule, C02. Any two of these components may be bound together initially. 

An efficient and convenient methodology for the aerobic oxidation of alcohols catalysed by sol-gel trapped perruthenate and promoted by an encapsulated ionic liquid in supercritical carbon dioxide solution has been reported. The reaction is highly selective and useful for substrates otherwise difficult to oxidize.263 A four-component system consisting of acetamido-TEMPO-Cu(C104)2-TMDP-DABCO has been developed for aerobic alcohol oxidation at room temperature. The catalytic system shows excellent selectivity towards the oxidation of benzylic and allylic alcohols and is not deactivated by heteroatom-containing (S, N) compounds. The use of DMSO as the reaction medium allows the catalysts to be recycled and reused for three runs with no significant loss of catalytic activity.264... 

The transport rates of carbon dioxide and hydrogen sulfide through these carbonate membranes can be significantly increased by adding catalysts to increase the rates of the slow reactions of Equations (11.21) and (11.22). A variety of materials can be used, but the anions of the weak acids such as arsenite, selenite and hypochlorite have been found to be the most effective. Small concentrations of these components increase permeation rates three- to five-fold. 

Ammonium carbamates are readily and reversibly produced on reaction of secondary amines with carbon dioxide. In the presence of a ruthenium catalyst precursors such as Ru3(CO)12 [3], (arene)RuCl2(PR3) [4] or Ru(methallyl)2(dppe) [5] (dppe=bis(diphenylphosphino)ethane) complexes, the three-component combination of a secondary amine, a terminal alkyne, and carbon dioxide selectively provides vinylcarbamates resulting from addition of carbamate to the terminal carbon of the triple bond (Scheme 2). 

Figure 11.1 shows the eleven basic unit operations in the reaction section of the vinyl acetate process. Three raw materials, ethylene (C2H4), oxygen (O,), and acetic acid (HAc), are converted into the vinyl acetate (VAc) product. Water (H,0) and carbon dioxide (CO,) are byproducts. We assume that an inert component, ethane (C2H6), enters with the fresh ethylene feed stream. We consider the following two reactions ... 

The cold-finger condenser is rather different from the above three. It is cooled by either solid carbon dioxide / acetone (-78°C) or liquid nitrogen (-196°C). The coolant is placed in the top of the condenser and more coolant is added as required. This results in an extremely cold surface on the inside of the condenser. Condensers of this type are usually employed for reactions that involve solvents or components that boil at or below room temperature (e.g. liquid ammonia, b.p. -33 C), although they can be used for higher boiling materials as well. 

Until the 1920s, a-amino acids 5 were synthesized by the hydrolysis of the a-anoino-sub-stituted alkyl cyanides but subsequently the a-amino acids were produced industrially by hydrolyzing the hydantoin derivatives 4 (Scheme 1). The latter can be prepared by the Bucherer-Bergs four-component reaction (BB-4CR),f an MCR of type II that forms 4 from carbon dioxide and the three components of the S-3CR. The a-amino acids thus prepared are obtained in much higher yields than by the S-3CR. 

Synthesis of most commercial silicon carbide whiskers is a result of the reaction of carbon with silicon dioxide so that the three-component... 

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