Ammonium-directed epoxidation

The epoxidation method developed by Noyori was subsequently applied to the direct formation of dicarboxylic acids from olefins [55], Cyclohexene was oxidized to adipic acid in 93% yield with the tungstate/ammonium bisulfate system and 4 equivalents of hydrogen peroxide. The selectivity problem associated with the Noyori method was circumvented to a certain degree by the improvements introduced by Jacobs and coworkers [56]. Additional amounts of (aminomethyl)phos-phonic acid and Na2W04 were introduced into the standard catalytic mixture, and the pH of the reaction media was adjusted to 4.2-5 with aqueous NaOH. These changes allowed for the formation of epoxides from ot-pinene, 1 -phenyl- 1-cyclohex-ene, and indene, with high levels of conversion and good selectivity (Scheme 6.3). 

The copolymerization mechanisms show that the propagation reactions are bimolecular in two alternating steps and that the rate-determining step is the slower propagation reaction. In our case, the slower reaction is the addition of the epoxide (Eqs. (38), (43), (47), (52), (59), (67), and (71) in the respective schemes) 99) as has also been found for the initiation by ammonium salts56). Since the tertiary amine does not directly take part in growth reactions (cf. 3.3.3), a more suitable expression for the copolymerization rate is Eq. (84) where the tertiary amine should be replaced by an active centre. 

Thiiranes can be prepared directly from alkenes using specialized reagents. Thiourea with a tin catalyst gives the thiirane, for example. " Interestingly, internal alkynes were converted to 1,2-dichorothiiranes by reaction with S2CI2 (sulfur monochloride).It is noted that epoxides are converted to thiiranes with ammonium thiocyanate and a cerium complex. " A trans-thiiration reaction occurs with a molybdenum catalyst, in which an alkene reacts with styrene thiirane to give the new thiirane. 

Epoxides can be converted directly to episulfides by treatment with NH4SCN and ceric ammonium nitrate.Diazoalkanes, treated with sulfur, give episulfides.It is likely that R2C=S is an intermediate, which is attacked by another molecule of diazoalkane, in a process similar to that shown in 16-46. Thioketones do react with diazoalkanes to give episulfides.Thioketones have also been converted to episulfides with sulfur ylids.Carbenes, such as the dichlorocarbene from CHCI3 and base, react with thioketones to give an... 

The extract is washed with ammonium sulfate solution, dried, and hitered. The solution is used directly for an epoxidation or other reaction. The yield cited is based upon iodimetric titration. 

Key Words Direct propylene epoxidation. Propylene oxide, Gold, Titanium, Propene, Au/Ti catalysts. Catalysis by gold. Titanium silicalite, TS-1, Gold/TS-1, Hydrogen peroxide, Kinetics, Design of experiments, Deposition-precipitation, Ammonium nitrate, Selective oxidation, Alkene epoxidation, Density functional theory, DFT calculations, QM/MM calculations. 2008 Elsevier B.v. 

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