Copper acetate, nitrate

The bridged annulene 5,10-epoxy[10]annulene behaves as an aromatic 1 Ore-system rather than an oxepin and reacts with copper(II) nitrate in acetic anhydride to give a 1 1 mixture of 1-and 2-nitro-5,10-epoxy[10]annulene 2 and 3.154... 

Attempts to brominate cyclopent[/>]azepine (10) with bromine failed, as did nitration with copper(II) nitrate in acetic anhydride 2 however, with one equivalent of A -bromosuccinimide in acetic acid a separable mixture of the unstable 8-bromo 11 and 6-bromo 12 derivatives, along with the stable 6,8-dibromo derivative 13, is formed. An excess of brominating agent yields the dibromo compound as the sole product. 

The 1/7-1,2-benzodiazepines 6 react with lead(IV) acetate to give 3-acetoxy-3//-l, 2-benzo-diazepines 5 with mcthanolic copper(II) nitrate, the 3-methoxy-3//-l,2-benzodiazepines 7 arc formed.123... 

Metal nitrates and acetic anhydride are particularly dangerous nitrating reagents if mixtures are made according to certain proportions. The danger also depends on the nature of the salt. Thus, with copper (II) nitrate or calcium nitrate, the mixture is always explosive whatever the proportions. 

Use of mixtures of metal nitrates with acetic anhydride as a nitrating agent may be hazardous, depending on the proportions of reactants and on the cation copper nitrate or sodium nitrate usually cause violent reactions [ 1], An improved procedure for the use of the anhydride-copper(II) nitration mixture [2] has been further modified [3] to improve safety aspects. 

Metal ions play an important role in several of these oxidative reactions as well as in biological dioxygen metabolism. As an example, copper(II) acetate and hydrogen peroxide have been used to produce a stable oxidizing agent, hydroperoxy copper(II) compound. The same oxidation system is also obtained from copper(II) nitrate and hydrogen peroxide (Eq. 1) [103] but requires the neutralization of ensuing nitric acid by potassium bicarbonate to maintain a pH 5. 

To elevate p-selectivity in nitration of toluene is another important task. Commercial production of p-nitrotoluene up to now leads with twofold amount to the unwanted o-isomer. This stems from the statistical percentage of o m p nitration (63 3 34). Delaude et al. (1993) enumerate such a relative distribution of the unpaired electron densities in the toluene cation-radical—ipso 1/3, ortho 1/12, meta 1/12, and para 1/3. As seen, the para position is the one favored for nitration by the attack of NO (or NO2 ) radical. A procednre was described (Delande et al. 1993) that used montmorillonite clay supported copper (cupric) nitrate (claycop) in the presence of acetic anhydride (to remove excess humidity) and with carbon tetrachloride as a medinm, at room temperature. Nitrotoluene was isolated almost quantitatively with 23 1 76 ratio of ortho/meta/para mononitrotoluene. 

The nitrate salt prepared by this method is hydrated. It cannot be dehydrated fully without decomposition. Anhydrous CuNOs may be prepared by dissolving copper metal in a solution of dinitrogen tetroxide, N2O4, in ethyl acetate. Upon crystaUization, an N2O4 adduct of Cu(N03)2 that probably has the composition [NO [Cu(N03)3] is obtained. This adduct, on heating at 90°C, yields blue anhydrous copper(II) nitrate which can be sublimed in vacuum at 150°C and coUected. 

Copper(ll) nitrate, being an oxidizing agent, can undergo violent reactions with readily oxidizahle substances. Reaction with acetic anhydride is violent, and heating with potassium or ammonium ferrocyanide at 220°C may cause an explosion. It can ignite paper on prolonged contact. 

Cumene Hydroperoxide Copper Acetate Copper Arsenite Copper Bromide Copper Chloride Copper Fluoioborate Copper Arsenite Copper Cyanide Copper Nitrate Copper Oxalate Copper Sulfate... 

Synonym Neatsfoot Oil Necatorina Nechexane Neutral Ahhonium Pluoride Neutral Anhydrous Calcium Hypochlorite Neutral Lead Acetate Neutral Nicotine Sulfate Neutral Potassium Chromate Neutral Sodium Chromatetanhydrous Neutral Verdigris Nickel Acetate Nickel Acetate Tetrahyorate Nickel Ammonium Sulfate Nickel Ammonium Sulfate Hexahydrate Nickel Bromide Nickel Bromide Trihydrate Nickel Carbonyl Nickel Chloride Nickel Chloride Nickel Cyanide Nickel Iiu Fluoborate Nickel Fluoroborate Solution Nickel Fluoroborate Nickel Formate Nickel Formate Dihyorate Nickel Nitrate Nickel Nitrate Hexahydrate Nickel Sulfate Nickel Tetracarbokyl Nickelous Acetate Nickelous Sulfate Nicotine Nicotine Sulfate Nifos Nitralin Nitram O-Nitraniline P-Nitraniline Nitric Acid Nitric Acid, Aluminum Salt Nitric Acid, Iron (111) Salt Compound Name Oil Neatsfoot Carbon Tetrachloride Neohexane Ammonium Fluoride Calcium Hypochlorite Lead Acetate Nicotine Sulfate Potassium Chromate Sodium Chromate Copper Acetate Nickel Acetate Nickel Acetate Nickel Ammonium Sulfate Nickel Ammonium Sulfate Nickel Bromide Nickel Bromide Nickel Carbonyl Nickel Chloride Nickel Chloride Nickel Cyanide Nickel Fluoroborate Nickel Fluoroborate Nickel Fluoroborate Nickel Formate Nickel Formate Nickel Nitrate Nickel Nitrate Nickel Sulfate Nickel Carbonyl Nickel Acetate Nickel Sulfate Nicotine Nicotine Sulfate Tetraethyl Pyrophosphate Nitralin Ammonium Nitrate 2-Nitroaniline 4-Nitroaniline Nitric Acid Aluminum Nitrate Ferric Nitrate... 

Electrophilic substitution of the cyclazine diester 2b gave 4- and/or 6-substituted derivatives typical examples are the two aldehydes (2h and 2i) obtained by Vilsmeier formylation and the 4- and 6-nitro derivatives (2j and 2k) resulting from a brief treatment of 2b with copper(II) nitrate in acetic anhydride. 

Direct nitration of thiophene, using a mild nitrating system at low temperature, gives 2-nitrothiophene in excellent yield. Acetyl nitrate, benzoyl nitrate or copper(I) nitrate in acetic anhydride or acetic acid is commonly used, and only traces of 3-nitrothiophene and 2,5-dinitrothiophene are formed. Slow addition of thiophene dissolved in acetic anhydride to a solution of nitric acid in glacial acetic acid, maintaining the temperature at 10°C, is reported to be the optimum procedure (Section 3.14.2.4.8). 

Most of the reports in the literature discuss electrophilic substitution of 1,3,6-triazacycl[3.3.3]azine (80) and the 2-methyl, 4-cyano and 4-ethoxycarbonyl derivatives. Electrophilic bromination occurs preferentially at the 4-position (if available), and subsequently at the 9- and 7-positions. These data support the electron charge density calculations (see Section 2.20.2) (73ACS3264). Nitrations are carried out using copper(II) nitrate and acetic anhydride. The central nitrogen is completely non-basic, and in the triazacycl-azines protonation occurs initially at position 6 (80) (77ACS(B)239). Ceder and Vernmark have reported that piperidine reacts with (81) via the aryne intermediate the A-E cine-substitution mechanism is an attractive alternative (equation 40). 

Aromatic nitrations performed in the presence of KIO montmori11onite lead to increased para selectivity. With toluene as test molecule, the proportion of para-nitrotoluene reaches 79% when using clay-supported copper(II) nitrate ("claycop") in the presence of acetic anhydride under high dilution conditions in CC1 (ref. 

Nitrodehalogenation can be effected, as for halobenzenes, but the reaction is only moderately effective even for the most reactive iodo compounds (equation 59).281 The reaction conditions of copper(II) nitrate and acetic anhydride are the most suitable for the general nitration of chelated... 

Figure 5-7. The direct nitration of a co-ordinated 2,4-diketonate ligand. The 2,4-diketonate complexes are not usually stable to nitric acid and the nitration is effected by milder reagents, such as a mixture of copper(n) nitrate and acetic anhydride (which generates N204). When tris(diketonate) complexes, such as [Co(acac)3] are nitrated, mixtures of mono-, bis- and tris- substituted products are obtained.

Copper acetate (0.125moll-1) has been used to displace metals sorbed on organic matter and on oxyhydroxides of iron (Soon and Bates, 1982), while 0.05moll-1 lead nitrate released specifically bound copper (Miller et al., 1986a, b). 

The rate of nitration is greatly increased under microwave irradiation. While 8-hydroxyquinoline is nitrated in 3.5 h using copper(ll) nitrate and glacial acetic acid, the same reaction is effected in 1 min under microwave irradiation in a conventional microwave oven to give the 5-nitro-8-hydroxyquinoline in 70% yield < 1997IJB1071 >. 

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