Sodium periodate with catalysts

A number of other reagents have been used to cleave C=N bonds, especially those not easily hydrolyzable with acidic or basic catalysts or which contain other functional groups that are attacked under these conditions. In particular, oximes have been converted to the corresponding aldehyde or ketone by treatment with, among other reagents, microwave irradiation on clay (Clayan), on wet sodium periodate... 

Oxidative cleavage of alkenes using sodium periodate proceeds effectively in a monophasic solution of acetic acid, water, and THF with very low osmium content or osmium-free. The orders of reactivity of alkenes are as follows monosubstituted trisubstituted >1,2 disub-stituted > 1,1-disubstituted > tetrasubstituted alkynes.100 Cleavage with polymer-supported OSO4 catalyst combined with NaI04 allows the reuse of the catalyst.101... 

The most widely used of the methods involving a reduction of periodate, only, to iodate employs the arsenite ion4 as reductant, in a solution maintained at neutrality with sodium bicarbonate, with iodide ion as catalyst. 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

In conjunction with a ruthenium oxide co-catalyst, sodium periodate has been used as a mild oxidizing agent in the presence of benzyltriethylammonium chloride... 

End and Pfalz have reported that chiral ruthenium-bisamide (26) complex is a useful catalyst for epoxidation of E-olefins with sodium periodate as a terminal oxidant, although enantiose-lectivity is moderate (Scheme 6B.25) [70]. It is noteworthy that tranT-(I-mcthylstyrene is a better substrate than m-P-methylstyrene for this reaction in terms of enantioselectivity. Competitive... 

Two tandem alkene metathesis-oxidation procedures using Grubb s second-generation ruthenium catalyst resulted in unique functional group transformations. Use of sodium periodate and cerium(III) chloride, in acetonitrile-water, furnished cis-diols. Oxidation with Oxone, in the presence of sodium hydrogencarbonate, yielded a-hydroxy ketones.296 Secondary alcohols are oxidized to ketones by a hydrogen... 

Catalytic conversions were experimentally studied in Russia toward the end of the nineteenth century, and especially in the twentieth century, and regularities were empirically established in a number of cases. The work of A. M. Butlerov (1878) on polymerization of olefins with sulfuric acid and boron trifluoride, hydration of acetylene to acetaldehyde over mercury salts by M. G. Kucherov (1881) and a number of catalytic reactions described by V. N. Ipatieff beginning with the turn of the century (139b) are widely known examples. S. V. Lebedev studied hydrogenation of olefins and polymerization of diolefins during the period 1908-13. Soon after World War I he developed a process for the conversion of ethanol to butadiene which is commercially used in Russia. This process has been cited as the first example of commercial application of a double catalyst. Lebedev also developed a method for the polymerization of butadiene to synthetic rubber over sodium as a catalyst. Other Russian chemists (I. A. Kondakov I. Ostromyslenskif) were previously or simultaneously active in rubber synthesis. Lebedev s students are now continuing research on catalytic formation of dienes. 

MET-CAMO was prepared from 5/ -methylthebaine (57) [109,110] via 14/ -amino-7,8-dihydro-5/ -methylcodeinone (59) which was obtained by the Kirby-McLean procedure [111]. Thus, oxidation of 2,2,2-trichloroethyl A-hydroxycarbamate with sodium periodate in the presence of 5/ -methylthebaine gave the adduct (58). Catalytic hydrogenation using a Pd/C catalyst in methanol in the presence of sodium acetate-acetic acid buffer yielded amine (59). Reaction with 4-nitrocinnamoyl chloride furnished amide (60) and ether cleavage using boron tribromide yielded MET-... 

Al203, and Nal with an iron catalyst. Sodium periodate and iodine was... 

The results of some oxidations with potassium permanganate differ depending on the pH of the reaction. For example, stearolic acid gives 9,10-diketostearic acid at pH 7-7.5 (achieved with carbon dioxide) and azelaic acid on treatment at pH 12 [864]. In some reactions, potassium permanganate is used as a catalyst for oxidation with other oxidants, such as sodium periodate. Thus alkenes are cleaved to carbonyl compounds or acids via vicinal diols obtained by hydroxylation with potassium permanganate, followed by cleavage by sodium periodate [763, 552]. 

The catalyst was prepared by 72-hour treatment of 100 gm of Linde sodium sieve with 1700 ml of 22.1 wt % ammonium nitrate. During this period the slurry was occasionally stirred. The slurry was filtered, and after working the solid several times with water, it was dried at room temperature. The amount of sodium ion replaced by ammonium ion was determined by analyzing the filtrate for sodium using the magnesium uranyl acetate reagent. The extent of replacement was found to be 52% and this compared favorably with the results of Turkevich and Ciborowski (3), who found, using the same method of preparation but a different method of analysis, a 56% replacement. 

V. Mirkhani, M. Moghadam, S. Tangestaninejad, B. Bahramian, Polystyrene-bound imidazole as a heterogeneous axial ligand for Mn(salophen)Cl and its use as biomimetic alkene epoxidation and alkane hydroxylation catalyst with sodium periodate, Appl. Catal. A 311 (2006) 43. 

Benzyl phenyl sulphide, norbornene, cw-cyclooctene, and 4-vinyl-1-cyclohexene were obtained from Aldrich and (IS)-(-)-a-pinene from Fluka. Phenyl sulphide was prepared from benzene and sulphur chloride following the literature procedure[9]. Reference samples of sulphoxides and sulphones were prepared by oxidation of sulphides with sodium periodate[10] and hydrogen peroxide[ll] respectively. Reference samples of epoxides were made by following Kaneda et al.[ 2 procedure. Metal phthalocyanines[13] were prepared from appropriate metal salt, 1,2-dicyanobenzene with ammonium molybdate as catalyst and were characterized by elemental analysis. 

Attention was confined to carbon catalysts, since preliminary experiments with silica gel and with metal catalysts gave negative results. Various grades of animal and vegetable charcoal were used they were pretreated in a standard way, by shaking for a prolonged period with concentrated hydrochloric acid, followed by dilute sodium hydroxide solution. After being washed free from electrolyte and dried, the charcoal was refluxed for several hours with absolute alcohol and then with benzene. Finally, the charcoal was heated to 200° and maintained at a pressure of less than 10 mm. for several hours. Within experimental error, the catalytic effects of similar areas of different charcoals were the same. The materials used for most of this work had areas of the order of W cm.Vg. 

Titania with alumina, zirconia, or stannic oxide produces a steady increase in the yield of sodium sulfate with increasing time of reaction. Stannic oxide with either zirconia, alumina, or thoria has fairly high initial activity but is quickly quenched with very little conversion occurring after a few hours. Thoria with zirconia shows a definite initial inhibition with a fair increase in activity after the induction period. Zinc oxide inhibits the activity of titania. Likewise, the combination of thoria with alumina shows very little promise as a catalyst towards the Hargreaves reaction. 

To a 1-liter, three-necked, round-bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer, and propylene oxide feed inlet are added 94 gm (1.0 mole) of phenol and 5 gm (0.13 mole) of sodium hydroxide. The reaction mixture is heated to 125°C and 590 gm (10.2 mole) of propylene oxide is added to the reaction mixture over a 54-hr period. The catalyst is neutralized with sulfuric acid and then filtered from the salts. The residue is stripped under reduced pressure at room temperature to remove any remaining volatiles. The product weighs 684 gm and has a MW of 495 (by OH number), which corresponds to about 7 moles of propylene oxide-phenol molecule. 

Whilst the Sharpless epoxidation with titanium catalysts and the Jacobsen-Katsuki epoxidation with manganese(salen) complexes are at the forefront of enantioselec-tive epoxidation with metal catalysts, there are alternative systems available. Ruthenium pyridinebisoxazoline (PYBOX) complexes have been independently reported, using either phenyliodinium diacetate or sodium periodate as... 

---