Cyclohexene, hydroxylation with hydrogen peroxide

C. Hydroxylation of Cyclohexene with Hydrogen Peroxide-Formic Acid 8, 9)... 

The preparation of Pans-1,2-cyclohexanediol by oxidation of cyclohexene with peroxyformic acid and subsequent hydrolysis of the diol monoformate has been described, and other methods for the preparation of both cis- and trans-l,2-cyclohexanediols were cited. Subsequently the trans diol has been prepared by oxidation of cyclohexene with various peroxy acids, with hydrogen peroxide and selenium dioxide, and with iodine and silver acetate by the Prevost reaction. Alternative methods for preparing the trans isomer are hydroboration of various enol derivatives of cyclohexanone and reduction of Pans-2-cyclohexen-l-ol epoxide with lithium aluminum hydride. cis-1,2-Cyclohexanediol has been prepared by cis hydroxylation of cyclohexene with various reagents or catalysts derived from osmium tetroxide, by solvolysis of Pans-2-halocyclohexanol esters in a manner similar to the Woodward-Prevost reaction, by reduction of cis-2-cyclohexen-l-ol epoxide with lithium aluminum hydride, and by oxymercuration of 2-cyclohexen-l-ol with mercury(II) trifluoro-acetate in the presence of ehloral and subsequent reduction. ... 

Alternatively and more conveniently this ds-hydroxylation process can be effected using only catalytic amounts of osmium tetroxide together with hydrogen peroxide, which cleaves the first formed osmate ester to the diol and regenerates the osmium tetroxide. The reaction is carried out in t-butyl alcohol and is illustrated by the conversion of cyclohexene into ds-cyclohexane-l,2-diol (Expt 5.47). 

Another kind of anti hydroxylation is the reaction of alkenes with hydrogen peroxide in the presence of vanadium pentoxide, molybdenum trioxide, selenium dioxide, and especially tungsten trioxide (tungstic acid) [131, 144]. Cyclohexene is thus converted into DL-/rarts-l,2-cyclohex-anediol [131],... 

Additional examples of the bismuth-promoted oxidation include the bismuth phthalocyanine catalyzed hydroxylation of phenol to hydroquinone and catechol with hydrogen peroxide [91SSSC(66)455], and bismuth acetate-mediated oxidation (modified Prevost reaction) of cyclohexenes to 1,2-cyclo-hexandiol derivatives (Scheme 5.14) [89CC407]. 

Then, pseudo-p-DL-gulopyranose (14) was synthesized by hydroxylation of 2,5-di-hydroxy-3-cyclohexene-l-methanol triacetate (12), which was prepared by Diels-Alder cycloaddition of 1,4-diacetoxy- 1,3-butadiene (10) and allyl acetate (11), with osmium tetroxide and hydrogen peroxide and successive acetylation as the pentaacetate (13). Analogous hydrolysis of 13 in ethanolic hydrochloric acid afforded the free pseudosugar 14 in 33% yield from 12 [2] (Scheme 7). 

Payne and Smith59 studied the hydroxylation of cyclohexene with a mixture of 34% hydrogen peroxide and a little tungstic acid in acetone. In addition to trans-1,2-cyclohexanediol, they obtained a 25% yield of 3,3-dimethyl -1,2,4-trioxaacetone derivative of the intermediate hydroxyhydroperoxide. Hydrogenation of 71 leads to tm w-cyclo-hexane-l,2-diol. 

UTD-1 may have catalytic properties such as those observed with the commercially sucsessfiil titanium silicahte TS-1 catalyst which is effective for alkane and alkene o ddation as well as phenol hydroxylation in the presence of hydrogen peroxide [8]. The large pore nature of Ti-UTD-1 should allow the reaction of large substrates such as 2,6-di-tert-butylphenol as well as the use of oxidants such as tert-butylhydroperoxide (t-BHP) which are too large for the medium pore TS-1 zeolite. Ti-UTD-1 offers an opportunity to examine reactivity in pore space greater than Ti-beta but less than the mesoporous Ti-MCM-41 type molecular sieves. In the present study results for the peroxide based oxidation of cyclohexane, cyclohexene and 2,6-di-tert-butylphenol will be presented. 

---