Aluminum alkoxide oxide

The widely used Moifatt-Pfltzner oxidation works with in situ formed adducts of dimethyl sulfoxide with dehydrating agents, e.g. DCC, AcjO, SO], P4O10, CCXTl] (K.E, Pfitzner, 1965 A.H. Fenselau, 1966 K.T. Joseph, 1967 J.G. Moffatt, 1971 D. Martin, 1971) or oxalyl dichloride (Swem oxidation M. Nakatsuka, 1990). A classical procedure is the Oppenauer oxidation with ketones and aluminum alkoxide catalysts (C. Djerassi, 1951 H. Lehmann, 1975). All of these reagents also oxidize secondary alcohols to ketones but do not attack C = C double bonds or activated C —H bonds. 

Manufacture. Hydroxypivalyl hydroxypivalate may be produced by the esterification of hydroxypivaUc acid with neopentyl glycol or by the intermolecular oxidation—reduction (Tishchenko reaction) of hydroxypivaldehyde using an aluminum alkoxide catalyst (100,101). 

This reaction is important in the manufacture of long-chain alcohols by means of hydrolysis of the aluminum alkoxide. Examples of oxidation of metal alkoxides (40,42) include ... 

The oxidation of a hydroxyl group by an aluminum alkoxide-catalyzed hydrogen exchange with a receptor carbonyl compound is known as the Oppenauer oxidation. For oxidation of steroidal alcohols the reaction is generally... 

The reduction of ketones to secondary alcohols and of aldehydes to primary alcohols using aluminum alkoxides is called the Meerw>ein-Ponndorf-Verley reduction. The reverse reaction also is of synthetic value, and is called the Oppenauer oxidation. ... 

There are also reactions in which hydride is transferred from carbon. The carbon-hydrogen bond has little intrinsic tendency to act as a hydride donor, so especially favorable circumstances are required to promote this reactivity. Frequently these reactions proceed through a cyclic TS in which a new C—H bond is formed simultaneously with the C-H cleavage. Hydride transfer is facilitated by high electron density at the carbon atom. Aluminum alkoxides catalyze transfer of hydride from an alcohol to a ketone. This is generally an equilibrium process and the reaction can be driven to completion if the ketone is removed from the system, by, e.g., distillation, in a process known as the Meerwein-Pondorff-Verley reduction,189 The reverse reaction in which the ketone is used in excess is called the Oppenauer oxidation. 

Alfol Also called the Conoco process and the Muhlheim process. The same name is used for the products as well. A process for making linear primary alcohols, from C2 to C28, from ethylene. The ethylene is reacted with triethyl aluminum, yielding higher alkyl aluminums These are oxidized with atmospheric oxygen under mild conditions to aluminum alkoxides, which are then hydrolyzed by water to the corresponding alcohols ... 

FIGURE 1.2. Formation of nanoparticles of metal oxide by reverse micelle method. A solution of inverse micelles is first formed by adding a long-chain alkylamine to a toluene solution. A small amount of water is trapped in the reverse micelle core. Mixing the reverse micelle solution with an aluminum alkoxy amine adduct results in hydrolysis of the aluminum alkoxide adduct and formation of nano-sized particles of aluminum oxyhydroxide after drying. These particles are shown in the SEM picture above. 

A variation of this method was used to control the surface properties of aluminum oxide particles, particularly the surface density of Lewis acid sites. Instead of using a long-chain amine surfactant, the solution of aluminum alkoxide precursor was mixed with a small amine to convert the alkoxide dimer (or oligomer in general) into monomeric alkoxide-amine adduct. Controlled hydrolysis of this adduct produces an aluminum oxyhydroxide in which the surface A1 ions are coordinated to amine... 

A number of reagents containing oxide components are used in zeolite manufacture [19]. Silica is provided by addihon of sodium or other alkali silicate solutions, precipitated, colloidal, or fumed silica, or tetraalkylorthosihcate (alkyl = methyl, ethyl) and certain mineral silicates such as clays and kaolin. Alumina is provided as sodium aluminate, aluminum sulfate soluhon, hydrous aluminum oxides such as pseudo boehmite, aluminum nitrate, or aluminum alkoxides. Additional alkali is added as hydroxide or as halide salts, while organic amines and/or... 

Considerable effort has been carried out by different groups in the preparation of amphiphihc block copolymers based on polyfethylene oxide) PEO and an ahphatic polyester. A common approach relies upon the use of preformed co- hydroxy PEO as macroinitiator precursors [51, 70]. Actually, the anionic ROP of ethylene oxide is readily initiated by alcohol molecules activated by potassium hydroxide in catalytic amounts. The equimolar reaction of the PEO hydroxy end group (s) with triethyl aluminum yields a macroinitiator that, according to the coordination-insertion mechanism previously discussed (see Sect. 2.1), is highly active in the eCL and LA polymerization. This strategy allows one to prepare di- or triblock copolymers depending on the functionality of the PEO macroinitiator (Scheme 13a,b). Diblock copolymers have also been successfully prepared by sequential addition of the cyclic ether (EO) and lactone monomers using tetraphenylporphynato aluminum alkoxides or chloride as the initiator [69]. 

Hydrogen transfer reactions from an alcohol to a ketone (typically acetone) to produce a carbonyl compound (the so-caUed Oppenauer-type oxidation ) can be performed under mild and low-toxicity conditions, and with high selectivity when compared to conventional methods for oxidation using chromium and manganese reagents. While the traditional Oppenauer oxidation using aluminum alkoxide is accompanied by various side reactions, several transition-metal-catalyzed Oppenauer-type oxidations have been reported recently [27-29]. However, most of these are limited to the oxidation of secondary alcohols to ketones. 

The reversible reduction of aldehydes or ketones to the corresponding alcohols using aluminum alkoxides such as aluminum isopropoxide (Al[OCH(CH3)2]3), the reducing alcohol usually being isopropyl alcohol (Le., RCOR + CH3CH(0H)CH3 RCH(OH)R + CH3C0CH3). The reaction is facilitated by the removal of acetone by distillation". This reaction has served as a model for metal-ion-dependent hydride transfer reactions catalyzed by certain enzymes. The reverse reaction is known as the Oppenauer oxidation . ... 

Catalytic reduction of codeine gives dihydrocodeine and Oppenauer oxidation (a ketone such as acetone and an aluminum alkoxide, the ketone being reduced to an alcohol) gives hydrocodone. Hydrocodone can also be prepared directly from codeine with a metal catalyst, which isomerizes the allylic alcohol to a ketone. Codeine is prepared by methylation of morphine, which is isolated from the opium poppy. Hydrocodone is more potent than codeine. Acetaminophen is a mild analgesic and is discussed in Section 8. 

Cationic polymerization of alkylene oxides generally produces low molecular weight polymers, although some work [26] seems to indicate that this difficulty can be overcome by the presence of an alcohol (Fig. 1.3). Higher molecular weight polyethylene oxides can be prepared by a coordinated nucleophilic mechanism that employs such catalysts as alkoxides, oxides, carbonates, and carboxylates, or chelates of alkaline earth metals (Fig. 1.4). An aluminum-porphyrin complex is claimed to generate immortal polymers from alkylene oxides that are totally free from termination reaction [27]. 

Aluminum methoxide Al(OMe)3 is a solid which sublimes at 240 °C in vacuum. Aluminum isopropoxide melts in the range 120-140 °C to a viscous liquid which readily supercools. When first prepared, spectroscopic and X-ray evidence indicates a trimeric structure which slowly transforms to a tetramer in which the central Al is octahedrally coordinated and the three peripheral units are tetrahedral.162,153 Intramolecular exchange of terminal and bridging groups, which is rapid in the trimeric form, becomes very slow in the tetramer. There is MS and other evidence that the tetramer maintains its identity in the vapour phase.164 Al[OCH(CF3)2]3 is more volatile than Al[OCH(Me)2]3 and the vapour consists of monomers.165 Aluminum alkoxides, particularly Al(OPr )3, have useful catalytic applications in the synthetic chemistry of aldehydes, ketones and acetals, e.g. in the Tishchenko reaction of aldehydes, in Meerwein-Pondorf-Verley reduction and in Oppenauer oxidation. The mechanism is believed to involve hydride transfer between RjHCO ligands and coordinated R2C=0— A1 groups on the same Al atom.1... 

Instead of the displacement reaction, aluminum alkyls may be oxidized with dry air to produce aluminum alkoxides that, after hydrolysis with dilute sulfuric acid or water, yield linear primary alcohols with an even number of carbon atoms (fatty... 

Oppenauer oxidations.5 Oppenauer oxidations and Meerwein-Ponndorf-Ver-ley reductions are usually carried out in the presence of aluminum alkoxides in at least stoichiometric amounts. Kagan et al. report that both reactions can be carried... 

Reduction then proceeds by successive transfers of hydride ion, H e, from aluminum to carbon. The first such transfer reduces the acid salt to the oxidation level of the aldehyde reduction does not stop at this point, however, but continues rapidly to the alcohol. Insufficient information is available to permit very specific structures to be written for the intermediates in the lithium aluminum hydride reduction of carboxylic acids. However, the product is a complex aluminum alkoxide, from which the alcohol is freed by hydrolysis ... 

Organic primers formulated with corrosion inhibitors are typically applied to pretreated metal surfaces to protect the surfaces prior to adhesive bonding and during environmental exposure. Pike [7-11] found that inorganic primers, such as sec-butyl aluminum alkoxide, improved the durability of aluminum-epoxy bonds when applied to both porous and nonporous aluminum oxide surfaces. It was shown that the effective thickness of the inorganic primer was directly related to the degree of oxide porosity and the depth of the porous oxide layer resulting from the normally used pretreatments for aluminum [10,11]. 

There is an apparent optimum relative humidity level required to achieve good adhesion and durability. Priming the steel adherends at 18% RH caused failure in the wedge samples within the steel (oxide) layer. Adherends primed at 34% RH failed within the alkoxide primer layer, whereas at 51% RH failure occurred primarily within the adhesive layer. This change in locus of failure with humidity was not evident using the wedge crack test when the adherends were primed with aluminum alkoxides. A peel-type test would probably be more sensitive in detecting these shifts in failure mode. 

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