Cupric acetate alcohols

Method 2. Place 0-2 g. of cupric acetate, 10 g. of ammonium nitrate, 21 2 g. of benzoin and 70 ml. of an 80 per cent, by volume acetic acid -water solution in a 250 ml. flask fitted with a reflux condenser. Heat the mixture with occasional shaking (1). When solution occurs, a vigorous evolution of nitrogen is observed. Reflux for 90 minutes, cool the solution, seed the solution with a crystal of benzil (2), and allow to stand for 1 hour. Filter at the pump and keep the mother liquor (3) wash well with water and dry (preferably in an oven at 60°). The resulting benzil has m.p. 94-95° and the m.p. is unaffected by recrystallisation from alcohol or from carbon tetrachloride (2 ml. per gram). Dilution of the mother liquor with the aqueous washings gives a further 1 Og. of benzil (4). 

Add I c.c. of a saturated alcoholic solution of cupric acetate to a few drops of the ester, a bluish-green crystalline precipitate of copper acetoacetic ester, (CoH903), Cu, is formed. See Appendix, p. 248. i . ... 

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

In order to shorten the reaction time, various heavy metal salts (zinc, lead, and manganese acetates) of weak organic acids, zinc or cobalt and tin chlorides are added to the reaction mixture [11]. For example, refluxing an uncatalyzed mixture of 3 moles of isobutyl alcohol and urea for 150 hr at 108°-126°C gives a 49% yield of the carbamate. Adding lead acetate or cobalt chloride to the same reaction lowers the reaction time to 75 hr, at which point an 88-92 % yield is obtained. In another example, ethylene glycol (1 mole) and urea (2 moles) are heated for 3 hr at 135°-155°C with Mn(OAc)2 to give a 78% yield of the diurethane [11]. The commercial production of butyl carbamate uses catalytic quantities of cupric acetate [12]. 

Cupric Acetate. CutCjHiO HT), sp gr 1.88, mp I I5°C, decomposes at 240°C. dark-brown powder, slightly soluble in cold HjO and alcohol moderately soluble in hot H 0 and ether. Used as a fungicide, insecticide, as a catalyst, and in pigments. 

The reaction may be assumed to go as above. The copper derivative of acetoacetic ester is formed by adding a saturated alcoholic solution of cupric acetate to the ester a bluish-green crystalline precipitate (C6H903)2 Cu is produced (cf. p. 98.)... 

Acyloins have also been employed extensively as starting materials for the synthesis of imidazoles, usually in the presence of added aldehyde (or acid) and using ammoniacal cupric acetate to oxidize the acyloin to the corresponding a-dicarbonyl compound.24 Alicyclic and aromatic ketols and ketol acetates in an alcoholic solution of cupric acetate and ammonia undergo ring closure to the corresponding 2-imidazoyl ketones. Hence, benzoyl carbinol refluxed for 1 hour in... 

These additions to the conjugated system are catalyzed by bases such as sodium hydroxide, sodium methoxide, tertiary amines, piperidine, and quaternary ammonium hydroxides. Cupric acetate catalyst is used in the conversion of acrolein to /S-methylmercaptopropionaldehyde, CHjSCHjCHjCHO (84%). The addition of mercaptans is analogous to the addition of alcohols to these systems (method 121). However, the thiol group is more active than the hydroxyl group, as is shown by... 

Aldehydes have been formed from alcohols by the use of other oxidizing agents. Dihydroxyacetone has been oxidized with excess cupric acetate to hydroxypyruvic aldehyde in 87% yield. p-Cyanobenzyl alcohol treated at 0° with a chloroform solution of nitrogen tetroxide gives practically pure p-cyanobenzaldehyde (90%). Aromatic alcohols containing nitro groups have been oxidized to the corresponding nitro aldehydes with concentrated nitric acid, e.g., o- and p-nitrobenzaldehydes (80-85%). m-Nitrobenzenesulfonic acid in basic media has been used for the oxidation of substituted benzyl alcohols, most satisfactorily for the water-soluble phenolic benzyl alcohols. Selenium dioxide, or less effectively tellurium dioxide, oxidizes benzyl alcohol slowly to benzaldehyde. ... 

Most Williamson reactions proceed by the 8 2 mechanism, but there is evidence (see p. 446) that in some cases the SET mechanism can take place, especially with alkyl iodides. Secondary alcohols have been converted to the corresponding methyl ether by reaction with methanol in the presence of ferric nitrate nonahy-drate. Vinyl ethers have been formed by coupling tetravinyl tin with phenols, in the presence of cupric acetate and oxygen. " The palladium-catalyzed coupling of vinyl triflates and phenols has also been reported. ... 

A very suitable oxidant for the conversion of acyloins into a-diketones is ammonium nitrate in the presence of catalytic amounts of cupric acetate. This reagent converts benzoin into benzil in 90% yield [476], The same result is obtained with bismuth sesquioxide 481] and sodium bromate 740 (equation 450). On the other hand, ceric ammonium nitrate does not give benzil but cleaves the bond between the alcoholic and the keto groups and cleaves benzoin into benzaldehyde and benzoic acid [425]. 

The complex then reacts with the alcohol in a manner similar to that postulated by the Baker mechanism for the base-catalyzed reaction. The kinetics involving this square root law is not valid for the cupric acetate-or zinc naphthenate-catalyzed reaction of these tertiary isocyanates. It seems that metal salts of strong acids and of weak acids conform to different mechanisms. 

The amino alcohol (Scheme 3) has two substituents, R and R. The R comes from the amino acid and R comes from the Grignard reagent. The amino alcohol was reacted with salicylaldehyde to give a Schiff base, whose treatment with cupric acetate followed by alkaline work-up afforded a copper(II) complex, in which the Schiff base was incorporated as a tridentate ligand [29,30]. 

In a related study, pentaphenylantimony (21) was found to decompose at room temperature in toluene and in the presence of catalytic amounts of cupric acetate to form triphenylantimony and a 4 1 ratio of diphenyl to benzene , jn butyl alcohol as solvent, however, the products were triphenylantimony (0.43 mole), benzene (1.67 mole), ethanoic acid (0.07 mole) and butyl phenyl ether (0.44 mole) together with Sb(0Ac)3 and cuprous acetate. The mechanisms of these reactions were not discussed. 

Aqueous alcohol (followed by cupric acetate and then sulfuric acid) was reported by Ponzio to produce 3-benzoylamino-4-phenylfuroxan from 4-phenylfuroxan.380 Clearly, an extensive degradation has taken place of one of the two molecules of the furoxan involved in the product. 

Cupric Stearate. Octadecanoic acid copper salt. C HwCu04 mol wt 630.46. C 68.58%, H 11.19%, Cu 1008%, O 1015%. (C1,Hj5COO)2Cu. Prepd by metathesis of alcohol cupric acetate with an alcohol soln of stearic acid Martin, Waterman, J. Chem Soc. 1957, 2545 Rai, Mehrotra, J. Inorg. Nucl. Chem. 21, 311 0 961). 

CycHzation of methyl farnesate. Reaction of methyl irons,trans-fasiKsa.Vo (1) with NBS and cupric acetate in r-butyl alcohol-HOAc yields the cyclic product (2) in 12% yield. The product was transformed into snyderol (3), a sesquiterpene in Laurencia snyderae. ... 

Arylation of a wide range of NH/OH/SH substrates by oxidative cross-coupling with boronic acids in the presence of catalytic cupric acetate and either triethyl-amine or pyridine at room temperature in air. The reaction works for amides, amines, anilines, azides, hydantoins, hydrazines, imides, imines, nitroso, pyrazi-nones, pyridones, purines, pyrimidines, sulfonamides, sulfinates, sulfoximines, ureas, alcohols, phenols, and thiols. It is also the mildest method for NIO-vinylation. The boronic acids can be replaced with siloxanes or starmanes. The mild condition of this reaction is an advantage over Buchwald-Hartwig s Pd-catalyzed cross-coupling. The Chan-Lam C-X bond cross-coupling reaction is complementary to Suzuki-Miyaura s C-C bond cross-coupling reaction. 

Catalytic oxidation of sugars and alcohols is a more direct method. Hydrogen peroxide and iron salts were used originally (see under Hydrogen peroxide oxidations). However, much better yields have been obtained by the direct oxidation with cupric salts 159). The action of a limited excess of cupric acetate for a short time on methanol solutions of L-sorbose or l-xylose has given a 60 % yield of the osone. 

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). ... 

The oxidation of secondary alcohols to ketones in good yields is effected by sulfuric-chromic acid mixtures. For water-soluble alcohols the reaction is carried out in aqueous solution at 20°-40°C. Insoluble aromatic alcohols are oxidized in an acetic acid solvent. Some other oxidation reagents that have been used are nitric acid, copper sulfate in pyridine, cupric acetate in 70% acetic acid, ferric chloride... 

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