Alkoxides reactivity

Oxolane [66-69], 1,4-dioxane [70] or, eventually, an excess of benzyl bromide [71] or chloride [72, 73] are the solvents of choice complementing the dipolar aprotic solvents mentioned above. A catalytic effect of tetrabutylammonium iodide has been observed [66, 69] for this reagent system 1,2 5,6-di-O-isopropylidene-ot-D-gluco-furanose needs 24 h boiling with excess benzyl bromide and sodium hydride in oxolane for complete benzylation of the hindered secondary hydroxyl group, but 165 min at 20 °C are sufficient when 0.01 equiv. of the catalyst is present. Ion-pair formation is probably responsible for the increase of the alkoxide reactivity [66]. 

Rate laws and kinetic parameters for substitution reactions at complexes Cp2TiX2 in acetonitrile solution at 298.2 K have been reported (X = halide or alkoxide). Reactivities are discussed in terms of the nature of the leaving group, the entering group, and the non-leaving Cp ligand. A volume of activation of —15 cm3 mol-1 has been determined for the reaction with thiocyanate.1124... 

Titania and Zirconia Membranes Prepared by the Polymeric Route Titanium and zirconium propoxides can be used as precursors for the preparation of nanoporous titania and zirconia membranes. To avoid the precipitation of inhomogeneous hydroxide particles during the hydrolysis step, the alkoxide reactivity can be modified with acetylacetone (acacH). This chelating agent reacts readily with transition metal alkoxides, as follows [34] ... 

Wylation under neutral conditions. Reactions which proceed under neutral conditions are highly desirable, Allylation with allylic acetates and phosphates is carried out under basic conditions. Almost no reaction of these allylic Compounds takes place in the absence of bases. The useful allylation under neutral conditions is possible with some allylic compounds. Among them, allylic carbonates 218 are the most reactive and their reactions proceed under neutral conditions[13,14,134], In the mechanism shown, the oxidative addition of the allyl carbonates 218 is followed by decarboxylation as an irreversible process to afford the 7r-allylpalladium alkoxide 219. and the generated alkoxide is sufficiently basic to pick up a proton from active methylene compounds, yielding 220. This in situ formation of the alkoxide. which is a... 

The TT-allylpalladium complexes 241 formed from the ally carbonates 240 bearing an anion-stabilizing EWG are converted into the Pd complexes of TMM (trimethylenemethane) as reactive, dipolar intermediates 242 by intramolecular deprotonation with the alkoxide anion, and undergo [3 + 2] cycloaddition to give five-membered ring compounds 244 by Michael addition to an electron-deficient double bond and subsequent intramolecular allylation of the generated carbanion 243. This cycloaddition proceeds under neutral conditions, yielding the functionalized methylenecyclopentanes 244[148], The syn-... 

As long as the nucleophilic atom is the same the more basic the nucleophile the more reactive it is An alkoxide ion (RO ) is more basic and more nucleophilic than a carboxylate ion (RC02 )... 

The imide proton N-3—H is more acidic than N-1—H and hence this position is more reactive toward electrophiles in a basic medium. Thus hydantoins can be selectively monoalkylated at N-3 by treatment with alkyl haUdes in the presence of alkoxides (2,4). The mono-A/-substituted derivatives (5) can be alkylated at N-1 under harsher conditions, involving the use of sodium hydride in dimethylform amide (35) to yield derivatives (6). Preparation of N-1 monoalkylated derivatives requires previous protection of the imide nitrogen as an aminomethyl derivative (36). Hydantoins with an increased acidity at N-1—H, such as 5-arylmethylene derivatives, can be easily monoalkylated at N-3, but dialkylation is also possible under mild conditions. 

GopolymeriZation Initiators. The copolymerization of styrene and dienes in hydrocarbon solution with alkyUithium initiators produces a tapered block copolymer stmcture because of the large differences in monomer reactivity ratios for styrene (r < 0.1) and dienes (r > 10) (1,33,34). In order to obtain random copolymers of styrene and dienes, it is necessary to either add small amounts of a Lewis base such as tetrahydrofuran or an alkaU metal alkoxide (MtOR, where Mt = Na, K, Rb, or Cs). In contrast to Lewis bases which promote formation of undesirable vinyl microstmcture in diene polymerizations (57), the addition of small amounts of an alkaU metal alkoxide such as potassium amyloxide ([ROK]/[Li] = 0.08) is sufficient to promote random copolymerization of styrene and diene without producing significant increases in the amount of vinyl microstmcture (58,59). 

Alkoxide-Type Initiators. Using the guide that an appropriate initiator should have approximately the same stmcture and reactivity as the propagating anionic species (see Table 1), alkoxide, thioalkoxide, carboxylate, and sUanolate salts would be expected to be usehil initiators for the anionic polymeri2ation of epoxides, thikanes, lactones, and sUoxanes, respectively (106—108). Thus low molecular weight poly(ethylene oxide) can be prepared... 

The very high reactivity of the P—Cl bonds in (4) forms the basis for the now well-known macromolecular substitution method, which has been used to synthesize polymers of types (1) and (2) and some polymers that are hybrids of these and (3). The method involves nucleophilic reactions of (4), and to some extent of its difluoro analogue, with alkoxides or amines. 

Partial hydrolysis of a metal alkoxide to form reactive monomers. 

Reactive halogens in various series have been removed by catalytic hydrogenation with either platinum or palladium catalysts, and other nucleophiles which have been used in chloride displacements include hydroxide ion, alkoxides, hydrosulflde, hydrazine and toluene-p-sulfonylhydrazine, and trimethyl phosphite. 

Organolithium and organomagnesium reagents are highly reactive toward most carbonyl compounds. With aldehydes and ketones, the tetrahedral adduct is stable, and alcohols are isolated after protonation of the adduct, which is an alkoxide ion. 

Detailed mechanistic studies have been carried out on aminolysis of substituted aryl acetates and aryl carbonates. Aryl esters are considerably more reactive than alkyl esters because the phenoxide ions are better leaving groups than alkoxide ions. The tetrahedral intermediate formed in aminolysis can exist in several forms which differ in extent and site of protonation ... 

Fluorme replacement m condensedpolyfluoroaromatics can be a complicated process In perfluoroanihracene the fluonne reactivity toward replacement by methoxide foQows the order 2-F > 9-F [14], whereas in perfluoropyrene, the reactivity decreases in the senes 1-F > 3-F > 6-F> 8-F [75] In decafluoro-l,4-di-hydronaphlhalene, the 6-fluorme is most easily replaced [75] (equation 10) All fluonne atoms in perfluoronaphthalene are replaced by alkoxide or aryloxide with Al, 7 -dimethylimidazolidm-2 one (DMI) as the solvent [16] (equation 11)... 

Alkyltrifluorosilanes and disubstituted difluorosilanes are themselves quite reactive with nucleophiles such as lithium amide bases [102, 103 104], alkyl-lithium reagents [1051, Gngnard reagents [105], or alkoxides [105] (equations 82 and 83)... 

Because the pK s of the aldehyde and water are similar, the solution contains significant quantities of both the aldehyde and its enolate. Moreover, their reactivities are complementary. The aldehyde is capable of undergoing nucleophilic addition to its carbonyl group, and the enolate is a nucleophile capable of adding to a carbonyl group. And as shown in Figure 18.4, this is exactly what happens. The product of this step is an alkoxide, which abstracts a proton from the solvent (usually water or ethanol) to yield a (3-hydroxy aldehyde. A compound of this type is known as an aldol because it contains both an aldehyde function and a hydroxyl group (aid + ol = aldol). The reaction is called aldol addition. 

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