Oxidation, aluminium isopropoxide

Oxathiine derivatives lb 301,304 Oxathizine fungicides la 44 Oxazepam la 364 Oxazolidinthione derivatives lb 301 Oxeladine citrate lb 327 Oxidation, aluminium isopropoxide la 59 -, atmospheric oxygen la 60 -, chromic acid la 59, 60 -, hydrogen peroxide la 59 -, iodine la 60... 

The isomerization reaction is also encountered in chemical manipulations of steroids. Thus, many natural steroids contain a 5-en-3-ol combination of functionalities, e.g. cholesterol. Treatment of cholesterol with an oxidizing agent (aluminium isopropoxide is particularly suitable) leads to cholest -en-3-one, the tautomerism occurring spontaneously under the reaction conditions. 

This alcohol is oxidized using an Oppenauer reaction under typical conditions with aluminium isopropoxide and cyclohexanone in boiling toluene. 

The alcohol in this sensitive indole could be oxidized to the desired ketone by heating with cyclohexanone and aluminium isopropoxide. A very similar substrate could no be oxidized efficiently after trying a wide variety of reagents.47... 

A very mild Oppenauer oxidation using acetone and aluminium isopropoxide allows the obtention of the desired ketone, while pyridine-chromic acid or manganese dioxide produce, aromatization of the ring on the left. 

The first report on the coordination polymerisation of epoxide, leading to a stereoregular (isotactic) polymer, concerned the polymerisation of propylene oxide in the presence of a ferric chloride-propylene oxide catalyst the respective patent appeared in 1955 [13]. In this catalyst, which is referred to as the Pruitt Baggett adduct of the general formula Cl(C3H60)vFe(Cl)(0C3H6),CI, two substituents of the alcoholate type formed by the addition of propylene oxide to Fe Cl bonds and one chlorine atom at the iron atom are present [14]. A few years later, various types of catalyst effective for stereoselective polymerisation of propylene oxide were found and developed aluminium isopropoxide-zinc chloride [15], dialkylzinc-water [16], dialkylzinc alcohol [16], trialkylalumi-nium water [17] and trialkylaluminium-water acetylacetone [18] and trialkyla-luminium lanthanide triacetylacetonate H20 [19]. Other important catalysts for the stereoselective polymerisation of propylene oxide, such as bimetallic /1-oxoalkoxides of the [(R0)2A10]2Zn type, were obtained by condensation of zinc acetate with aluminium isopropoxide in a 1 2 molar ratio of reactants [20-22]. 

The crystalline fraction was found to be formed via a cleavage of the C1g-0(CH2—O) bond in the monomer molecule and proved many years ago to be an isotactic polymer (with regular head-to-tail linkages) (Figure 9.1) [42]. The structure of the amorphous fraction, on the other hand, varies depending on the kind of catalyst. Some amorphous polypropylene oxide)s prepared with catalysts such as diethylzinc-methanol [43] or aluminium isopropoxide-zinc chloride [44] consist of regular head-to-tail linked units, but they are atactic (the mole fraction of isotactic diads is less than 0.6) [43]. Some other amorphous polypropylene oxide)s obtained with catalysts derived from reactions in the diethylzinc-water [44,45], and triethylaluminium-water [46] systems, and with aluminium isopropoxide [44], have been found to be irregular, i.e. to contain head-to-head and tail-to-tail enchained monomer units. 

One can note, in this connection, that styrene oxide undergoes polymerisation in the presence of aluminium isopropoxide which involves a selective cleavage of the Ca-0[CH(Ph)—O] bond [47]. On the other hand, polymerisation of styrene oxide with the diethylzinc-water catalyst was found to proceed via 0,8-0(0142—0) bond scission [48],... 

The cyclic vinyl ether (182),170 postulated last year as an intermediate in the 21-acetoxylation of the hemiacetal (183), can be prepared in good yield by heating the hemiacetal with aluminium isopropoxide in toluene under argon, followed by direct chromatography on basic alumina.171 The vinyl ether was converted into the 20,21-diol (184) either by reaction with osmium tetroxide or by acetoxylation with lead tetra-acetate, followed by hydrolysis. The hypoiodite reaction, followed by oxidation, allows direct conversion of a 21-acetoxypregnan-20/3-ol (185) into the 18-iodo-20-ketone (186), which is solvolysed in the presence of silver acetate to provide a new route to the 21-acetate of 18-hydroxydeoxycorticosterone hemiacetal (187).171... 

The secondary alcohols are oxidized to ketones by refluxing with aluminium isopropoxide, A1[0CH(CH3)2]3 [or Al(0-iPr)3], or potassium t-butoxide, KOC(CH3)3 [or KO-t-Bu]. A ketone such as acetone used in the reaction as refluxing agent is reduced to alcohol, 2-propanol. The reaction is known as the Oppenauer oxidation. The reverse reaction known as the Meerwein-Ponndorf-Verly reduction is the reduction of ketones to alcohols in the presence of alcohol such as 2-propanol. Potassium fert-butoxide can be used for the oxidation of primary alcohols. Aluminium isopropoxide in acetone is particularly used for... 

Meerwein-Ponndorf-Verley The reduction of a ketone to a secondary alcohol using isopropanol and aluminium isopropoxide. The opposite of the Oppenauer oxidation. 

Liquid-phase MPVO reactions were performed in 25 ml isopropanol (reductions) or 25 ml 2-butanone (oxidations) at 85 °C using 2.5 mmol of the appropriate substrate 4-r-butylcyclohexanone (4-Bu-ONE), 4-methylcyclohexanone (4-Me-ONE) or 4-t-butylcyclohexanol (4-Bu-OL, cis/trans mixture) 0.5 g zeolite or 0.25 mmol aluminium isopropoxide as the catalyst and 1,3,5-tri-f-butylbenzene as the internal standard. Samples were taken at regular intervals and analyzed by GC on a Carbowax CP-52 column and GC/MS. 

Sol-gel chemistry offers flexible methods for the preparation of porous metal oxides such as the transition aluminas used as catalyst supports. The physical properties of sol-gel materials depend on the nature of the reactants, the rate of mixing and the conditions of drying. High surface area aluminas have been prepared from various alkoxide and salt solutions and their textures have been examined extensively. The interest in the use of these chemically prepared materials is largely for catalyst and absorbent applications [1]. The first user of alkoxide precursor was Teichner who prepared pure aluminas by the water vapour action on aluminimn methoxide [2] and reported materials with surface area of 200 m /g. Harris and Sing [3] reported gels prepared from aluminium isopropoxide with water and... 

Aluminium isopropoxide is a Lewis acid and it is also a good catalyst for the Oppenauer oxidation and Meerwein-Ponndorf-Verley reduction reactions. In the presence of a ketone, it will oxidise d-isomenthol to d-isomenthone (Oppenauer oxidation). The hydrogen atom on C-4 is now enolisable and therefore epimerisation can occur, catalysed by the aluminium isopropoxide acting as a Lewis acid. This will give /-menthone. This can now be reduced (Meerwein-Ponndorf-Verley reduction) to /-menthol by an alcohol and aluminium isopropoxide. The ketone and alcohol for the redox reactions could be the menthols/ menthones themselves or traces of acetone/isopropanol in the aluminium isopropoxide. Obviously, the reactions shown in Figure 4.28 are all reversible. The equilibrium will eventually be driven over completely to /-menthol since the latter is the most thermodynamically favoured of all of the isomeric components in the system. 

Meerwein-Ponndorf-Verley reduction and Oppenauer oxidation (disproportionation of a ketone/ isopropyl alcohol or alcohol/acetone mixture respectively in the presence of aluminium isopropoxide). OH o... 

Fig. 8.36. As the asymmetric center of citronellal is unaffected by the reactions, all of the isopulegol and menthol isomers formed have the correct stereochemistry at Cl of the /i-menthane skeleton. There are therefore two strategies for recycling unwanted isomers. The first is to purify the ( )-isopulegol (172) by crystallization and recycle (178-180) back to citronellal by pyrolysis [221, 223, 224]. The second is to hydrogenate the mixture, separate the (—)-menthol by crystallization and treat the remainder with aluminium isopropoxide, which converts all of them, by Oppenauer oxidation, enoliza-tion, reketonization and Meerwein-Ponndorf-Verley reduction, to (—)-menthol, which is the thermodynamically most stable isomer (225).

Whereas a mononuclear alkoxide complex of aluminium which incorporates azaindole ligands has been noted [116], so azaindoles have been reported to bridge Al-centres in oxides [23, 41, 42]. This is also true of an oxide-alkoxide which incorporates the bis(trifluoromethyl)isopropoxide ligand [42]. In the case of dinuclear aggregate [[(F3C)2C(H)]0 2Al[/r-0C(H)(CF3)2]-... 

Oppenauer oxidation, using alkoxides other than aluminium, operates via a hydride transfer mechanism similar to the one depicted in the above Equation, although a complexation of the metal with the carbonyl group may not be present.22d Evidence for a radical mechanism was put forward in the case of the interaction between lithium isopropoxide and benzophenone.24... 

Rehydrated Mg/Al-OH catalysts have been found to be inactive in the MPV reduction of 4-ferf-butylcyclohexanone by isopropanol, whereas the bifunctional character of the Mg(Al)0 mixed oxides made them highly active in this reaction. The aluminium alkoxidc intermediate of the MPV reaction indeed involves a cooperation between basic and acidic sites. On mixed oxides, the abstraction of a proton from isopropanol on O2 sites gives isopropoxide anions, which are then stabilized on Al3+ and form intermediates with the aldehyde. The high activity of mixed oxide comes from the synergetic effect of strong Lewis basicity and mild acidity. 

In this context it is worth remembering that despite the many advantages offered by the standard Oppenauer oxidation such as the utilisation of inexpensive and nontoxic reagents like aluminium tri-tert-butoxide and aluminium tri-isopropoxide and a high functional group compatibility, this reaction has still not reached the level of the MPV reduction, as far as the... 

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