Acetals from alkoxides

The usual products from alkoxides and acids are dialkoxytitanium diacylates (130,131). The third acyl group, but not the fourth, can often be iatroduced by a2eotropiag the lower alcohol with ben2ene (132). Using acetic anhydride, the same hexaacetoxydititanoxane is prepared from the chloride forms. 

D. Cahard, P. Duhamel, Alkoxide-Mediated Preparation of Enolates from Silyl Enol Ethers and Enol Acetates - From Discovery to Synthetic Applications, Eur. J. Org. Chem. 2001, 1023-1031. 

Diastereoselective Acetal Fission Followed by Benzylation (Step 2). Upon treatment with KHMDS and 18-crown-6 in THF at —78 °C, the acetal from the (/f,/ )-bis-sulfoxide is rapidly converted into the alkoxide having the (lS,2f ) configuration. The counter cation of the base is very important for high selectivity. Diastereoselectivity was seen to increase in the order LiHMDS (8% de) 96% de). 

Chemical decomposition is usually observed in solid reactions, such as carbonate, hydroxides, nitrate, acetate, oxalates, alkoxides and so on, when they are heated at a certain temperature. The decomposition leads to the formation of a new solid product, together with one or more gaseous phases, which is usually used to produce powders of simple oxides in most cases and complex oxides sometimes. Although this method has not been widely reported for the synthesis of transparent ceramic powders, it could be a potential technique for such a purpose, due to its various advantages, such as simple processing, inexpensive raw materials, and capability of large scale production. In fact, the calcination step involved in most wet-chemical processing routes, especially chemical precipitation or co-precipita-tion, is chemical decomposition, either from carbonates or hydroxides, as discussed later. 

In the two other techniques, the cation (Zr, Y) sources from alkoxides or alkoxide/acetates were dissolved in organics like butanol and propanol the solutions thus produced were dispersed in suitable oil phases like toluene or heptane, and water added into the dispersion, so as to induce gelation of the cation precursors through hydrolysis-polycondensation. The median particle size after calcination was around 50 pm. 

Chemical decomposition reactions, in which a solid reactant is heated to produce a new solid plus a gas, are commonly used for the production of powders of simple oxides from carbonates, hydroxides, nitrates, sulfates, acetates, oxalates, alkoxides, and other metal salts. An example is the decomposition of calcium carbonate (calcite) to produce calcium oxide and carbon dioxide gas ... 

Reactions that proceed under neutral conditions are highly desirable. An important event in TT-allylpalladium chemistry is the introduction of highly reactive allylic carbonates (Sect. V.2.1.3), Their reactions can be carried out under mild neutral conditions. " Also, reactions of allylic carbamates, " allyl aryl ethers, and vinyl epoxides proceed without addition of bases. As shown by the mechanism in Scheme 6, the oxidative addition of allyl methyl carbonates is followed by decarboxylation as an irreversible process to afford TT-allylpalladium methoxide, and the generated methoxide picks up a proton from pronucleophiles (NuH), such as active methylene compounds. This in situ formation of the alkoxide is the reason why the reaction of aUyl carbonates can be carried out without addition of bases from outside. Alkoxides are rather poor nucleophiles, and alkyl allyl ethers are not formed from them. In addition, formation of TT-allylpalladium complexes from allylic carbonates involving decarboxylation is irreversible. In contrast, the formation of TT-allylpalladium acetate from allyl acetate is reversible. 

Powders from Alkoxides and Salts. Two solutions were prepared individually for the synthesis of lead titanate (PbTiOs) particles by Tartaj et al. (2001) (i) titanium tetra-butoxide in 2-propanol, and (ii) lead acetate in glacial acetic acid. The solutions were mixed under stirring, and a water-2-propanol mixture added to this for the initiation of hydrolysis. As in some other cases, crystalline seeds of the target compound, suspended in 2-propanol, were added (10 wt%) to the transparent sol already obtained. The gels obtained through this process were dried and ground to small particles and calcined at 400°C for 20 h for use in the preparation of sintered bodies. X-ray diffractometry of the calcined sample showed it to be fully crystallized to phase-pure PbTiOs, while an unseeded sample did not crystallize under the same conditions. 

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... 

Hydrolysis of TEOS in various solvents is such that for a particular system increases directiy with the concentration of H" or H O" in acidic media and with the concentration of OH in basic media. The dominant factor in controlling the hydrolysis rate is pH (21). However, the nature of the acid plays an important role, so that a small addition of HCl induces a 1500-fold increase in whereas acetic acid has Httie effect. Hydrolysis is also temperature-dependent. The reaction rate increases 10-fold when the temperature is varied from 20 to 45°C. Nmr experiments show that varies in different solvents as foUows acetonitrile > methanol > dimethylformamide > dioxane > formamide, where the k in acetonitrile is about 20 times larger than the k in formamide. The nature of the alkoxy groups on the siHcon atom also influences the rate constant. The longer and the bulkier the alkoxide group, the lower the (3). 

Besides direct hydrolysis, heterometaHic oxoalkoxides may be produced by ester elimination from a mixture of a metal alkoxide and the acetate of another metal. In addition to their use in the preparation of ceramic materials, bimetallic oxoalkoxides having the general formula (RO) MOM OM(OR) where M is Ti or Al, is a bivalent metal (such as Mn, Co, Ni, and Zn), is 3 or 4, and R is Pr or Bu, are being evaluated as catalysts for polymerization of heterocychc monomers, such as lactones, oxiranes, and epoxides. An excellent review of metal oxoalkoxides has been pubUshed (571). 

PZN-PT, and YBa2Cug02 g. For the preparation of PZT thin films, the most frequently used precursors have been lead acetate and 2irconium and titanium alkoxides, especially the propoxides. Short-chain alcohols, such as methanol and propanol, have been used most often as solvents, although there have been several successful investigations of the preparation of PZT films from the methoxyethanol solvent system. The use of acetic acid as a solvent and chemical modifier has also been reported. Whereas PZT thin films with exceUent ferroelectric properties have been prepared by sol-gel deposition, there has been relatively Httle effort directed toward understanding solution chemistry effects on thin-film properties. 

The vapor-phase esterification of ethanol has also been studied extensively (363,364), but it is not used commercially. The reaction can be catalyzed by siUca gel (365,366), thoria on siUca or alumina (367), zirconium dioxide (368), and by xerogels and aerogels (369). Above 300°C the dehydration of ethanol becomes appreciable. Ethyl acetate can also be produced from acetaldehyde by the Tischenko reaction (370—372) using an aluminum alkoxide catalyst and, with some difficulty, by the boron trifluoride-catalyzed direct esterification of ethylene with organic acids (373). 

Azirines react with alcohols in the presence of alkoxides to give alkoxyaziridines (67JA4456). Further treatment with alcohol and alkoxide results in the formation of amino ketone acetals. Alkoxyaziridines are not isolated in general from the acid-catalyzed addition of methanol to azirines. Azirines are also known to react with amines (66JOC1423). Frequently the initially produced adducts undergo subsequent transformations. 

An isolated acetoxyl function would be expected to be converted into the alkoxide of the corresponding steroidal alcohol in the course of a metal-ammonia reduction. Curiously, this conversion is not complete, even in the presence of excess metal. When a completely deacetylated product is desired, the crude reduction product is commonly hydrolyzed with alkali. This incomplete reduction of an acetoxyl function does not appear to interfere with a desired reduction elsewhere in a molecule, but the amount of metal to be consumed by the ester must be known in order to calculate the quantity of reducing agent to be used. In several cases, an isolated acetoxyl group appears to consume approximately 2 g-atoms of lithium, even though a portion of the acetate remains unreduced. Presumably, the unchanged acetate escapes reduction because of precipitation of the steroid from solution or because of conversion of the acetate function to its lithium enolate by lithium amide. 

Alkali metal alkoxides, r-butyl acetate neat, 45°, 30 min, 98% yield of r-butyl ester from methyl benzoate. The rate constant for the reaction increases with increasing ionic radius of the metal and with decreasing polarity of the solvent. Equilibrium for the reaction is achieved in <10 sec. Other examples eire presented. " ... 

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