Cupric acetate oxidation

The plant bufadienolide scillarenin (500) has been synthesized. The starting material was 15a-hydroxycortexone (501), which was converted into the diketone ketal (502) by cupric acetate oxidation at C(21), followed by selective ketalization and tosylate elimination. Protection at C(3) as the dienol ether, oxiran formation at C(20) with dimethylsulphonium methylide, and regeneration of the C(3)- and C(21)-oxo-groups by acid hydrolysis then provided (503). Selective reaction at C(21) with the sodium salt of diethyl methoxycarbonyl-methylphosphonate, and boron trifluoride rearrangement of the epoxide ring to the aldehydo-unsaturated ester (504), was followed by enol lactonization to the bufadienolide (505). This was converted, in turn, to scillarenin (500) via the 14,15-bromohydrin, by standard reactions. Unsubstituted bufadienolides have also been prepared by the same method. 

Lead tetraacetate cupric acetate Oxidative decarboxylation Ethylene derivs. from carboxylic acids... 

Asymmetric synthesis of acetylenic alcohols is possible by reduction of the corresponding ketones with lithium aluminium hydride complexed with sugar derivatives the optical yields are 4—1%. The trimethylether of the naturally occurring robustol (30), from the leaves of Grevillea robusta A. Cunn., has been synthesized in 55 % yield via cupric acetate oxidative cycliza-tion of the diacetylene (31). ... 

Cyclodecanedione has also been prepared by oxidation of sebacoin with chromium trioxide in acetic acid, - Cupric acetate in acetic acid has been used for oxidation of an a-hydroxyketone by Ruggli and Zeller. ... 

Oxidation of 20-keto-21-hydroxy steroids with oxygen in aqueous methanol or in anhydrous methanol in the presence of cupric acetate has been reported to give good yields of the corresponding 21-aldehydes. 

A solution of bismuth trioxide in hot glacial acetic acid provides a specific method for the oxidation of acyloins. " The reaction rate is dependent on the steric accessibility of the ketol system. A 2,3-ketol requires less than one hour for completion but an 11,12-ketol is not yet fully oxidized in thirty hours." The reaction is highly selective as a-keto acids, hydrazines and phenols are not oxidized. In a direct comparison with cupric acetate, this procedure is somewhat superior for the preparation of a 2,3-diketone from a 2-keto-3-hydroxy steroid. ... 

Cupri-. cupric, copper(II). -azetst, n. cupric acetate, copper(II) acetate, -carbonat, n. cupric carbonate, copper(II) carbonate, -chlorid, n. cupric chloride, copper(II) chloride. -hydroxyd, n. cupric hydroxide, cop-per(II) hydroxide. -ion, n. cupric ion, copper(II) ion. -ozalat, n. cupric oxalate, copper(II) oxalate, -oxyd, n. cupric oxide, copper(II) oxide. -salz, n. cupric salt, copper(II) salt, -suifat, n. cupric sulfate. copper(II) sulfate, -sulfid, n. cupric sulfide, copper(II) sulfide, -verbihdung, /. cupric compound, copper(II) compound, -wein-saure, /. cupritartaric acid. 

The homogeneous, anaerobic, oxidation of propargyl alcohol by cupric acetate in buffered pyridine solution is an example of a general reaction... 

Treatment of the complex with further amine produced the violet dyes. The importance of this complex in the mechanism is suggested by the inability of cupric acetate, nitrate or sulphate to achieve the oxidation. 

Evans, Nicoll, Strause and Waring46 oxidized D-glucose and D-fructose in aqueous solution with excess cupric acetate at 50° for the purpose of ascertaining whether the general principles underlying the mechanism of carbohydrate oxidation in alkaline solutions are sufficient to explain the course of such oxidations in acid solutions. D-Glucosone was claimed to be one of the first products of oxidation the osone was not isolated, and,... 

Weidenhagen48 further investigated this reaction he found that osone formation could become the main reaction if ethanol or methanol was used as a solvent, the cupric acetate was not in excess, and the reaction time was limited. Oxidation of D-glucose or D-fructose was reported to give a 40% yield of D-glucosone.14-46... 

In the preparation of D-glucosone by the direct oxidation of D-glucose, D-fructose, or D-mannose by such reagents as that of Fenton,37 cupric acetate,16- 46- 46 selenious acid,16-61 etc., the degree of oxidation must be carefully controlled if the osone, which is the first product, is to be the main product of the reaction. The nature and mechanism of formation of the products of further oxidation of D-glucosone are discussed on p. 68. 

Creosol, 33, 17 Crotonaldehyde, 33, IS 34, 29 diethyl acetal, 32, 5 Cupric acetate monohydrate, 36, 77 Cuprous oxide-silver oxide, 36, 36, 37 Cyanamide, 34, 67 36, 8 Cyanoacetamide, 32, 34 Cyanoacetic acid, 31, 25 Cyanoacetylurea, 37, 16 >-Cyanobenzaldehyde, 30, 100 >-Cyanobenzaldiacetate, 36, 59 3-Cyano-5,6-dimethyl-2(l)-pyridone, 32,34 N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl- -anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-m-chloroaniline, 36, 7 Cyanogen, 32, 31 Cyanogen iodide, 32, 29 Cyanogen iodide, complex with sodium iodide, 32, 31... 

The primary function of the mammalian red blood cell is to maintain aerobic metabolism while the iron atom of the heme molecule is in the ferrous (Fe+2) oxidation state however, copper is necessary for this process to occur (USEPA 1980). Excess copper within the cell oxidizes the ferrous iron to the ferric (Fe+3) state. This molecule, known as methemoglobin, is unable to bind oxygen or carbon dioxide and is not dissociable (Langlois and Calabrese 1992). Simultaneous exposure of sheep to mixtures of cupric acetate, sodium chlorite, and sodium nitrite produced a dose-dependent increase in methemoglobin formation (Calabrese et al. 1992 Langlois and Calabrese 1992). 

Oxidative addition consumes one equivalent of expensive Pd(OAc)2 in most cases. However, progress has been made towards the catalytic oxidative addition pathway. Knolker s group described one of the first oxidative cyclizations using catalytic Pd(OAc)2 in the synthesis of indoles [19]. They reoxidized Pd(0) to Pd(II) with cupric acetate similar to the Wacker reaction, making the reaction catalytic with respect to palladium [20]. 

Only two general methods have been developed for the synthesis of the macrocyclic annulenes.9 The first of these, developed by Sondheimer and co-workers, involves the oxidative coupling of a suitable terminal diacetylene to a macrocyclic polyacetylene of required ring size, using typically cupric acetate in pyridine. The cyclic compound is then transformed to a dehydroannulene, usually by prototropic rearrangement effected by potassium i-butoxide. Finally, partial catalytic hydrogenation of the triple bonds to double bonds leads to the annulene. 

Venetian red inorg chem A pigment with a true red hue contains 15-40% ferric oxide and 60-80% calcium sulfate. va nesh an red verdigris See cupric acetate. vard-a.gres ( vermiiion See mercuric sulfide. var mil-yan (... 

It is to be noted that cupric acetate has been used to oxidize other systems, for example, a-ketols, phenols, thiols, and nitro-alkanes. 

Oxidative coupling, phenylacetylene to. diphenyldiacetylene with cupric acetate, 46,39... 

Akermark et al. reported the palladium(II)-mediated intramolecular oxidative cyclization of diphenylamines 567 to carbazoles 568 (355). Many substituents are tolerated in this oxidative cyclization, which represents the best procedure for the cyclization of the diphenylamines to carbazole derivatives. However, stoichiometric amounts of palladium(II) acetate are required for the cyclization of diphenylamines containing electron-releasing or moderately electron-attracting substituents. For the cyclization of diphenylamines containing electron-attracting substituents an over-stoichiometric amount of palladium(II) acetate is required. Moreover, the cyclization is catalyzed by TFA or methanesulfonic acid (355). We demonstrated that this reaction becomes catalytic with palladium through a reoxidation of palladium(O) to palladium(II) using cupric acetate (10,544—547). Since then, several alternative palladium-catalyzed carbazole constructions have been reported (548-556) (Scheme 5.23). 

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