Cupric salts, derivatives

Cupric salts derived from the oxide CuO are stable in contact with air and water and comprise the most used compounds of copper. Cupric ions, Cu++, are present in solutions of cupric salts. 

Metallic Derivatives, (a) Cuprous Acetylide. CujCg. Prepare an ammoniacal solution of cuprous chloride by first adding dilute ammonia to 2-3 ml. of dilute copper sulphate solution until the initial precipitate just redissolves and a clear deep-blue solution is obtained now add an aqueous solution of hydroxylamine hydrochloride drop by drop with shaking until the solution becomes first green and then completely colourless, the cupric salt being thus reduced to the cuprous derivative. 

The air oxidation of phenylacetylene and secondary amines in the presence of cupric acetate in benzene solution yields ynamines [22], This reaction requires only catalytic amounts of cupric salts and gives high conversions in less than 30 min when the Cu+2/phenylacetylene ratio is only 0.02. Only 1,4-diphenylbutadiyne is produced if the stoichiometric amount of cupric ion is used in the absence of oxygen. The yield of ynamine can be increased from 45 to 90 % if the stoichiometric amounts of a reducing agent such as hydrazine are continuously added during the course of the reaction. The use of primary amines under similar conditions yields the acetamide derivative. 

The reactions of thiocyanogen may roughly be divided into two types (1) Reactions in which the radical combines directly with metals to form the corresponding thiocyanates, and with cuprous thiocyanate to form the cupric salt. (2) Reactions in which a substitution is effected for example, with aniline, dimethylaniline and phenol, the corresponding jj-thiocyano-derivatives and thiocyanie acid are formed.1... 

Both cupric and cuprous salts act as oxidizers, the cupric derivatives being reduced to the cuprous or metallic condition, and the cuprous compounds to metallic copper. Alkaline solutions of cupric salts are employed in oxidation-processes in organic chemistry.2... 

The adducts derived from aldoximes and carbodiimides are not stable. They undergo dissociation to give nitriles 472. This reaction is a useful synthetic route to produce nitriles from aldehydes and hydroxylamine in the presence of DCC and cupric salts in one step. The reaction of of the oximes with carbodiimides is best conducted in a two phase system (methylenechloride/water) using triethylamine, and the yields are almost quantitative." ... 

Treatment of 2-Iithio-l,3-dithianes with iodine, cupric salts, 1,2-di-bromoethane, or nitro compounds effects oxidative dimerization to give the dimer 72 plus a small amount of the 2-methylene derivative 73. 

The gas-phase pyrolysis of chrysanthanyl acetate affords a mixture of acyclic unsaturated aldehydes and enol acetates, all of which are probably derived from the 1,4-biradical (625). ° Results are also discussed of the pyrolyses of chrysanthanyl alcohol and other emio-pinen-7-ols. The photochemical free radical reaction between P-pinene and t-butyl hypochlorite has been studied, and the oxidative addition of cyclopentanone to p-pinene in the presence of cupric salts has been observed. Photoaddition of iV-nitrosopiperidine to P-pinene at — 40 gave the a-piperidinium... 

The cupric salt of 5-chlorotetrazole is as sensitive as its 5-bromo deiivate (2.54 cm for 2 kg hammer). Brisance of the chloro-deiivative is about the same as bromo-derivative. They both also have about the same initiating efficiency (0.3 g for RDX) [1]. Bagal [2]... 

Early examples of enantioselective extractions are the resolution of a-aminoalco-hol salts, such as norephedrine, with lipophilic anions (hexafluorophosphate ion) [184-186] by partition between aqueous and lipophilic phases containing esters of tartaric acid [184-188]. Alkyl derivatives of proline and hydroxyproline with cupric ions showed chiral discrimination abilities for the resolution of neutral amino acid enantiomers in n-butanol/water systems [121, 178, 189-192]. On the other hand, chiral crown ethers are classical selectors utilized for enantioseparations, due to their interesting recognition abilities [171, 178]. However, the large number of steps often required for their synthesis [182] and, consequently, their cost as well as their limited loadability makes them not very suitable for preparative purposes. Examples of ligand-exchange [193] or anion-exchange selectors [183] able to discriminate amino acid derivatives have also been described. 

Thermal properties of several chlorinated phenols and derivatives were studied by differential thermal analysis and mass spectrometry and in bulk reactions. Conditions which might facilitate the formation of stable dioxins were emphasized. No two chlorinated phenols behaved alike. For a given compound the decomposition temperature and rate as well as the product distribution varied considerably with reaction conditions. The phenols themselves seem to pyro-lyze under equilibrium conditions slowly above 250°C. For their alkali salts the onset of decomposition is sharp and around 350°C. The reaction itself is exothermic. Preliminary results indicate that heavy ions such as cupric ion may decrease the decomposition temperature. 

Valine.—This amino acid is contained mixed with leucine in the fractions of the esters which boil between 6o° and 90° C. Its isolation and separation from leucine is of extreme difficulty, since these compounds, as well as their copper salts into which they are converted by boiling with freshly precipitated cupric oxide, tend to form mixed crystals. Its isolation was only effected by these means in certain cases, and its amount is really much more than the figures represent from its yield. It is best characterised by conversion into its phenylhy-dantoine derivative by treatment with phenyl isocyanate in alkaline solution. The phenylureido acid is first formed, and this loses a molecule of water, as shown by Mouneyrat, and is changed into its anhydride or phenylhydantoine by treatment with hydrochloric acid. The following reactions occur —... 

Alkyl hydroperoxides are known to be oxidized to alkylperoxy radicals by cupric, cobaltic, and manganic salts. Although CeIV has not yet been reported to oxidize hydroperoxides and although mechanisms for ionic oxidation of alkoxy derivatives have not been put forward, Reaction 1 is a possible first step. 

Copper salts, cupric or cuprous also will catalyze the carbonylation of amines. Piperidine, for example, gives a urea derivative with carbon monoxide, and it, too, is probably a metal amide—carbon monoxide insertion reaction. 

Ammino-derivatives of Cupric Sulphate.—Cupric sulphate forms with ammonia four ammino derivatives, namely, pentammino-cupric sulphate, [Cu(NII3)5]S04 tetrammino-cupric sulphate, [Cu(NH3)4]S04 diammino-cupric sulphate, [Cu(NH3)2]S04 and monammino-cuprzc sulphate, [Cu(NH3)]S04. The tetrammino salt is the best known and the one most easily obtained. It exists both in the anhydrous and in the hydrated state. 

Hydroxylamine Derivatives.—Several derivatives of cupric sulphate containing hydroxylamine in place of ammonia are known. Thus, cupric sulphate unites with hydroxylamine, giving a mono-hydroxylamino-compound Cu[NH20H]S04, a dihydroxylamino-salt, [Cu(NH20H)2]S04, and a pentahydroxylamino-salt, [Cu(NH2OIT) ]SO.j. The latter is unstable, but the two former compounds are stable in the dry state and even in solution up to 0° C. Above that temperature reduction of the salts occurs. 

Tetrammino-cupric Chloride Monohydrate, [Cu(NI-l3)4]Cl2.H20. —When ammonia is passed into a hot saturated solution of cupric chloride a dark blue solution is formed, and, on cooling, dark blue crystals are deposited. The salt crystallises in blue quadratic prisms which lose water on drying, giving the anhydrous salt described above. If heated it loses ammonia, passing into the diammino-derivative, and finally, on further heating, decomposes completely. Water attacks the substance and converts it into cupric ammonium chloride, ammonium chloride, and basic cupric chloride. 

The Ammines of Corps , Silver, and Gold—Ammino-derivatives of Cupric Sulphate—Hydroxylamine-derivatives of Cupric Sulphate—Cupro-ammino-sulphates—Ammino-salts of Cuprio Halides—Ammino-ouprous Halides— Ammino-derivatives of Silver Halides—Ammino-derivatives of Silver Nitrate —Ammino-derivatives of Gold Salts—Aurous Halides—Auric Halides— Derivatives of Auric Oxide, Auric Nitrate, Anrie Phosphate, Perohlorate— Derivatives of Mixed Salts. 

It is well known that copper salts can catalyze the photocycloaddition of dienes [56]. The reaction can be very diastereoselective and useful as an access to polycyclic molecules, especially 1 - vinyl-2-allylcyclanes [57]. The reaction of vinylglycine, cinnamyl derivatives 76, and analogs is also catalyzed by Cu(I) produced in situ by the reduction of cupric triflate. The coordination of the double bonds to the copper ion during the [2 4- 2]-photocycloaddition process increase ... 

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