Perruthenate, potassium

Material 1 was also treated with 3-bromopropyltrichlorosilane to yield a propyl tether with a bromo-head group (4). Substitution with either trimethylamine or triethylamine to form the corresponding quaternary ammonium species, followed by ion exchange with potassium perruthenate afforded the catalytic species (5) and (6) respectively. The black solid 5 was found to be an equally efficient catalyst for the oxidation reactions and 6 was found to be a more highly active recoverable and reusable... 

In experiments (i) and (iv), no oxidation was observed after 50 h, in toluene / oxygen at 80 °C implying that a perruthenate derived species was responsible for the catalysis and not Ru02. In experiments (i) and (iii), approximately 10% and 70% oxidation respectively, to the aldehyde was observed after 3 days under the same conditions and complete leaching of potassium perruthenate was observed in both cases. The used solid material from experiments (ii) and (iii) showed no catalytic oxidative activity when reused.. 

As expected, inorganic perruthenates, like sodium perruthenate (NaRu04) or potassium perruthenate (KRu04), are soluble in water and insoluble in apolar organic solvents. On the other hand, the perruthenate ion (Ru04) is unstable in aqueous solution because it produces the oxidation of water according to the following Equation.55... 

The difficulties associated with the chromium reagents (stoichiometric amounts required harsh conditions low selectivity) [95-97] led to the development of polymer-supported perruthenate 124 by Ley et al. [98]. These efforts were built upon a large body of experience with soluble salts of the perruthenate ion, e.g., tetra-propylammonium permthenate (TRAP) [99, 100]. The reagent 124 was prepared by prolonged exposure of anion-exchange resin (125) to an aqueous solution of potassium perruthenate 126. 

A very mild oxidative transformation of nitro compounds into ketones using tetrapropylam-monium perruthenate (TPAP) has been developed. A stoichiometric amount of TPAP in the presence of A-methylmorpholine A-oxide (NMO) and 4 A molecular sieves (MS).18a As the reaction conditions are neutral and mild, this method is compatible with the presence of other sensitive functionalities (Eq. 6.11). This transformation can be carried out with 10 mol% of TPAP and 1.5 equiv of NMO in the presence of potassium carbonate, 4 A MS, and silver acetate (Eq. 6.12).18b... 

Ac, acetyl AIBN, azobis(isobutanonitrile) All, allyl AR, aryl Bn, benzyl f-BOC, ferf-butoxycarbonyl Bu, Butyl Bz, benzoyl CAN, ceric ammonium nitrate Cbz, benzyloxycarbonyl m-CPBA, m-chloroperoxybenzoic acid DAST, diethylaminosulfur trifluoride DBU, l,8-diazabicyclo[5.4.0]undec-7-ene DCC, /V. /V - d i eye I oh e x y I c ar bo -diimide DCM, dichloromethyl DCMME, dichloromethyl methyl ether DDQ, 2,3-dichloro-5,6-dicyano-l,4-benzoquinone DEAD, diethyl azodicarboxylate l-(+)-DET, L-(+)-diethyl tartrate l-DIPT, L-diisopropyl tartrate d-DIPT, D-diisopropyl tartrate DMAP, 4-dimethylaminopyridine DME, 1,2-dimethoxyethane DMF, /V./V-dimethylformamide DMP, 2,2-dimethoxypropane Et, ethyl Im, imidazole KHMDS, potassium hexamethyldisilazane Me, methyl Me2SO, dimethyl sulfoxide MOM, methoxymethyl MOMC1, methoxymethyl chloride Ms, methylsulfonyl MS, molecular sieves NBS, N-bromosuccinimide NIS, /V-iodosuccinimide NMO, /V-methylmorpho-line N-oxide PCC, pyridinium chlorochromate Ph, phenyl PMB, / -methoxvbenzyl PPTs, pyridiniump-toluenesulfonate i-Pr, isopropyl Py, pyridine rt, room temperature TBAF, tetrabutylammonium fluoride TBS, ferf-butyl dimethylsilyl TBDMSC1, f-butylchlorodimethylsilane Tf, trifhioromethylsulfonyl Tf20, trifluoromethylsulfonic anhydride TFA, trifluoroacetic acid THF, tetrahydrofuran TMS, trimethylsilyl TPAP, tetra-n-propylammonium perruthenate / -TsOH. / -toluenesulfonic acid... 

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