Ethylene reactions with carbon dioxide

Ethylene glycol can be manufactured by the reaction of ethylene oxide with carbon dioxide to form ethylene carbonate (eq. 17) which can be hydroly2ed to ethylene glycol (eq. 18). 

The Grignard reagent from 2-thenyl chloride can be obtained by the use of the "cyclic reactor.However, rearrangement occurs in its reaction with carbon dioxide, ethyl chlorocarbonate, acetyl chloride, formaldehyde, and ethylene oxide to 3-substituted 2-methylthio-phenes, Only in the case of carbon dioxide has the normal product also been isolated. 

Telechelic polymers, containing one or more end groups with the capacity to react with other molecules, are useful for synthesizing block and other copolymers [Fontanille, 1989 Hsieh and Quirk, 1996 Nuyken and Pask, 1989 Pantazis et al., 2003 Patil et al., 1998 Quirk et al., 1989, 1996 Rempp et al., 1988]. Living anionic polymers can be terminated with a variety of electrophilic reagents to yield telechelic polymers. For example, reaction with carbon dioxide, ethylene oxide, and allyl bromide yield polymers terminated with carboxyl, hydroxyl, and allyl groups, respectively. Functionalization with hydroxyl or carboxyl groups can also be achieved by reaction with a lactone or anhydride, respectively. Polymers with amine end... 

Treatment of (127) with sodium in liquid ammonia followed by ethylene diamine gave (128), while reaction with cyclohexylamine gave the tautomeric system (129). Reaction of (129) with metal acetates gave the metal complexes (130). The -position of (127) is acidic enough to be metallated with butyllithium, and upon reaction with carbon dioxide followed by hydrolysis, (131) was obtained in... 

Carboxylation has also been seldom used especially for the constmction of various spiro-8-lactones. Rieke et al. have developed a direct synthesis of spiro-8-lactones from conjugated dienes and epoxides [114,115] (Scheme 67). Treatment of 1,2-bis (methylene)-cyclohexane-magnesium reagent derived from diene 306, with an excess of ethylene oxide, gave intermediate 307, which upon reaction with carbon dioxide and hydrolysis afforded the spiro-8-lactone 308. 

The new recycling concept was apphed to several C - C bond-forming reactions, for example, to the telomerization of butadiene with ethylene glycol or carbon dioxide, to the isomerizing hydroformylation of frans-4-octene and to the hydroamino-methylation of 1-octene with morpholine. 

The existing literature contains airpriungly few references dealing with controlled oxidation of ethylene oxides. Mention has been nuulr (see section UL1.C.) of the catalytic oxidation of ethylene oxide to carbon dioxide and water at high temperatures. This section will hi-devoted to the relatively few known publications describing niililrr oxidative reactions. 

The iodine-catalyzed reaction of aziridines with carbon dioxide leads to 2-oxazolidinones (251). Because carbon dioxide effectively polymerizes ethyleneimine, only low yields are obtained when unsubstituted ethyleneimine reacts with C02. However, direct insertion of carbon dioxide [124-58-9] into aziridines can be accomplished, with better yields, by ethoxycarbonylation of aziridines with subsequent elimination of ethylene under flash vacuum conditions (252). 1- Phenyl aziridine [696-18-4] can react with C02 under antimony [7440-56-0] catalysis to give AI-phenyl-2-oxazolidinone in good yields (253). At low temperatures and with the exclusion of atmospheric humidity, the reaction of ethyleneimine with carbon dioxide produces the unstable ethyleneiminium salt [51645-58-2] of IV-vinylcarbamic acid (254,255). 

In the field of olefin carboxylation, stoichiometric reactions have been described to occur between non-activated alkenes, CO2 and an electron-rich transition-metal complexes, such as Ni(0) [3], Ti(II) [4] or Fe(0) [5]. A Pd-catalyzed CO2 fixation occurs into methylenecyclopropane derivatives affording lactones [6]. The reaction of carbon dioxide with ethylene is difficult and its carboxylation to propionic acid, catalyzed by Rh derivatives [7], needs drastic experimental conditions. 

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