Titanium silicate molecular sieves oxidation reactions

Titanium silicate molecular sieves not only catalyze the oxidation of C=C double bonds but can be successfully employed for the oxidative cleavage of carbon-nitrogen double bonds as well. Tosylhydrazones and imines are oxidized to their corresponding carbonyl compounds (243) (Scheme 19). Similarly, oximes can be cleaved to their corresponding carbonyl compounds (165). The conversion of cyclic dienes into hydroxyl ketones or lactones is a novel reaction reported by Kumar et al. (165) (Scheme 20). Thus, when cyclopentadienes, 1,3-cyclohexadiene, or furan is treated with aqueous H202 in acetone at reflux temperatures for 6 h in the presence of TS-1, the corresponding hydroxyl ketone or lactone is obtained in moderate to good yields (208). 

Further interesting developments in this field are the discovery of the large pore titanium silicate molecular sieve ETS-10 [77] and the synthesis of mesoporous materids containing titanium and vanadium [78-81], Much systematic work will be required to elucidate how useful these new materials are as catalysts in selective oxidation reactions. 

In green oxidation reactions, zeolite TS-1 is the typical catalyst. Since the size of its channels ranges from 5 to 6 A, TS-1 can be used as the catalyst only for benzene and phenol conversion. However, ordered mesoporous titanium silicate materials have pores large enough for the catalytic reactions of bulkier molecules, and this is very important for the production of fine chemicals. For example, for the oxidation reaction of terpineol, Ti-MCM-41 performs much better than do microporous titanium silicate molecular sieves as a catalyst.1-291... 

The oxidation of various hydrocarbons such as n-octane, cyclohexane, toluene, xylenes and trimethyl benzenes over two vanadium silicate molecular sieves, one a medium pore VS-2 and the other, a novei, iarge pore V-NCL-1, in presence of aqueous HjOj has been studied. These reactions were carried out in batch reactors at 358-373 K using acetonitrile as the solvent. The activation of the primary carbon atoms in addition to the preferred secondary ones in n-octane oxidation and oxidation of the methyl substituents in addition to aromatic hydroxyiation of alkyl aromatics distinguish vanadium silicates from titanium silicates. The vanadium silicates are also very active in the secondary oxidation of alcohols to the respective carbonyl compounds. V-NCL-1 is active in the oxidation of bulkier hydrocarbons wherein the medium pore VS-2 shows negligible activity. Thus, vanadium silicate molecular sieves offer the advantage of catalysing selective oxidation reactions in a shape selective manner. 

The incorporation of Ti into various framework zeolite structures has been a very active research area, particularly during the last 6 years, because it leads to potentially useful catalysts in the oxidation of various organic substrates with diluted hydrogen peroxide [1-7]. The zeolite structures, where Ti incorporation has been achieved are ZSM-5 (TS-1) [1], ZSM-11 (TS-2) [2] ZSM-48 [3] and beta [4]. Recently, mesoporous titanium silicates Ti-MCM-41 and Ti-HMS have also been reported [5]. TS-1 and TS-2 were found to be highly active and selective catalysts in various oxidation reactions [6,7]. All other Ti-modified zeolites and molecular sieves had limited but interesting catalytic activities. For example, Ti-ZSM-48 was found to be inactive in the hydroxylation of phenol [8]. Ti-MCM-41 and Ti-HMS catalyzed the oxidation of very bulky substrates like 2,6-di-tert-butylphenol, norbomylene and a-terpineol [5], but they were found to be inactive in the oxidation of alkanes [9a], primary amines [9b] and the ammoximation of carbonyl compounds [9a]. As for Ti-P, it was found to be active in the epoxidation of alkenes and the oxidation of alkanes and alcohols [10], even though the conversion of alkanes was very low. Davis et al. [11,12] also reported that Ti-P had limited oxidation and epoxidation activities. In a recent investigation, we found that Ti-P had a turnover number in the oxidation of propyl amine equal to one third that of TS-1 and TS-2 [9b]. As seen, often the difference in catalytic behaviors is not attributable to Ti sites accessibility. 

E-Caprolactam (CL) is a very important monomer for the production of nylon-6, and about 4.2 million tons of CL were manufactured worldwide in 1998 [126]. Most current methods of CL production involve the conversion of cyclohexanone with hydroxylamine sulfate into cyclohexanone oxime followed by Beckmaim rearrangement by the action of oleum and then treatment with ammonia, giving CL. A serious drawback ofthis process is the co-production of a large amount of ammonium sulfate waste [126, 127]. Raja and Thomas reported a method for one-step production of cyclohexanone oxime and CL by the reaction of cyclohexanone with ammonia under high-pressure air (34.5 atm) in the presence of a bifunctional molecular sieve catalyst [128]. Hydrogen peroxide oxidation of cyclohexanone in the presence of NH3 catalyzed by titanium silicate is reported to produce CL [129]. In patent work, on the other hand, the transformation of l,l -peroxydicyclohexylamine (PDHA) to a 1 1 mixture of CL and cyclohexanone by LiBr has been reported [130]. 

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