Anions alkylation

The reactions of these nucleophilic processes are usually S 2 rather than S l. The reaction rate is methyl > ethyl > isopropyl, as with the alkyl hahdes. As the species to be alkylated becomes more nucleophilic, alkylation becomes faster, eg, a sulfur-containing anion alkylates more quickly than a phenohc anion. 

Side-chain anionic alkylation reactions with aromatic compounds take place when cataly2ed with strong basic catalysts, like Na—K (228). The yield is 83% when o-xylene reacts with butadiene... 

Thus the reactions of cyclic or acyclic enamines with acrylic esters or acrylonitrile can be directed to the exclusive formation of monoalkylated ketones (3,294-301). The corresponding enolate anion alkylations lead preferentially to di- or higher-alkylation products. However, by proper choice of reaction conditions, enamines can also be used for the preferential formation of higher alkylation products, if these are desired. Such reactions are valuable in the a substitution of aldehydes, which undergo self-condensation in base-catalyzed reactions (117,118). Monoalkylation products are favored in nonhydroxylic solvents such as benzene or dioxane, whereas dialkylation products can be obtained in hydroxylic solvents such as methanol. The difference in products can be ascribed to the differing fates of an initially formed zwitterionic intermediate. Collapse to a cyclobutane takes place in a nonprotonic solvent, whereas protonation on the newly introduced substitutent and deprotonation of the imonium salt, in alcohol, leads to a new enamine available for further substitution. 

All of the reactions described above use anionic alkyl metal complexes as stoichiometric reductants. Cationic zirconium catalyst 58 was shown to re-ductively cyclize a variety of 1,5-dienes to give both mono- and bicyclic silane products when H3SiPh was employed as the stoichiometric reductant (Scheme 10) [32]. Poor yields due to competing polymerization processes were observed when less substituted dienes were employed. It is likely that... 

Other methods that use 55 anions as precursor for the synthesis of fullerene-derivatives usually involve chemical formation of the anion. Alkylation of 55 has been accomplished, e.g. by reduction with propanethiol and potassium carbonate in DMF [91,92], sodium methanethiolate in acetonitrile [93], the naphthalene radical anion in benzonitrile[94], potassium naphthalide [95] or simply with zinc [96]. 

Intramolecular methanesulfonamide anion alkylation and aldol condensation reactions have been employed for the synthesis of 2,1-benzothiazine 2,2-dioxides. For instance, Blondet and Pascal have utilized such a process for the formation of compounds 225 and 226 from ortV o-substituted aldehyde 227 and alkyl chloride 228, respectively (Scheme 30) <1994TL2911>. 

Detergent In relationship to fuel technology, a detergent is an oil-soluble surfactant added to fuel aiding in the prevention and removal of deposits. Examples include anionic alkyl aryl sulfonates, cationic fatty acid amides, or nonionic polyol condensates. 

This evidence supports the concept that the Ziegler polymerization of styrene is by catalysts with cationicities which lie between the cationic Friedel-Crafts system and the anionic alkyl sodium system. Its character can be shifted depending on the ratio of the aluminum to titanium. 

How does the anionic alkyl of the original trialkylaluminum or of the dialkylaiuminum chloride, which has sufficient anionic character to undergo anionic hydride exchange or CH3OT reaction, form a catalyst which becomes cationic under certain polymerization conditions No studies of this have been reported. One possibility is an internal oxidation-reduction reaction that converts an anionic alkyltitanium trichloride to a cationic alkyltitanium trichloride (Equation 10). Basic and electrophilic catalyst components would determine the relative contributions of the anionic and cationic forms. This type of equilibrium or resonance structures could also explain the color in transition metal compounds such as methyltitanium trichloride (73). 

We have recently observed that anionic alkyl and aryl derivatives of the group 6B metal carbonyls undergo insertion reactions with carbon dioxide to afford the corresponding carboxylates, e.g., as depicted in Eq. (25) (44, 72). An ORTEP representation of one such product of C02... 

Other Carbon Stabilized Anions Alkylations of Enolate Anions (page 871)... 

Komblum, in his investigations of the factors that control the course of ambident anion alkylation reactions [64, 65], found a new type of radical chain substitution reaction that involves anion-radicals and free radical intermediates. When... 

Alkylate Anions. Alkyls or aryls that are coordinately unsaturated can combine with additional alkylate anions to give anions such as [Co(C6F5)4]2, [ThMe7]3", and [CpLuMe3]2. These are often obtained by using lithium alkyls in the presence of tmen and crystallize as [Li tmen]+ salts. The alkylate anions of copper are extensively used in organic syntheses. 

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