Cupric nitrate-Acetic anhydride

Nitration Acetone cyanohydrin nitrate. Acetyl nitrate. /-Amyl nitrate. Cupric nitrate-Acetic anhydride. Dinitrogen pentoxide. Dinitrogen tetroxide. Dinitrogen tetroxide-Boron trifluoride. Nitronium tetrafluoroborate. Nitryl chloride. Polyphosphoric acid-Nitric acid. Potassium f-butoxide-Amyl nitrate. Tetranitromethane. 

Cupric nitrate-Acetic anhydride [bottom of 1,163J. 

Aromatic substitution Cupric nitrate-acetic anhydride. Triethyl orthoformatc. Autoxidation Potassium /-butoxide. Salcomine. 

Cupric nltrate-Acetic anhydride. For nitration, probably via acetyl nitrate. In the examples formulated -" cupric nitrate was added, either as a solid or suspended in acetic anhydride, to a solution of the substrate in acetic anhydride. 

Nitration of thiophene with cupric nitrate in acetic anhydride or acetic acid is considered to be milder than nitric acid in the same solvents and has been used successfully with thiophene derivatives which decomposed on conventional nitration/ ... 

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. 

Nitration of 1-hydroxyquinolizinium nitrate affords only a 31% yield of the betaine nitrated at the 2-position (64JCS3030). With quinolizin-4-one (14), which may be regarded as the betaine of 4-hydroxyquinolizinium ion, nitration in acetic acid at room temperature gives a 43% yield of 1,3-dinitroquinolizone. Only by use of cupric nitrate in acetic anhydride is there some mononitration (a mixture of 1- and 3-isomers), but here again the major product is the dinitro compound (64T1051). 

The nitration of ethyl 4/f-thieno[3,2- ]pyrrole-5-carboxylate (68 R = C02Et) has been carried out <84JHC215> using cupric nitrate in acetic anhydride with low yields obtained after purification by column chromatography (69 R = C02Et) 34%, (70 R = C02Et) 42%, (71 R = C02Et) 3%. 

Acyl nitrates, usually produced from nitric acid or cupric nitrate in acetic anhydride. 

OXIDATION, REAGENTS Dimethylsulf-oxide-Acetic anhydride. 1-Amyl hydroperoxide. N-Bromosuccinimide. Ceric ammonium nitrate. Chloramine. o-Chlo-ranil. 1-Chlorobenzotriazole. N-Chloro-succinimide-Dimethyl Sulfide. Chromic acid. Chromic anhydride. Chromyl chloride. Cobalt(ll) acetate. Cupric acetate monohydrate. Cupric nitrate-Pyridhic complex. 2,3-Dichloro-5,6-dicyano-l, 4-benzoquinonc. Dicyclohcxyl-18-crown-... 

Sondheimer el al. have used this reagent to effect electrophilic substitution of annulenes. Thus l,8-bisdehydro[14]annulene (1) on nitration with cupric nitrate in acetic anhydride at room temperature was attacked at the position adjacent to the triple bond to yield the 3-mononitro compound (2) as black needles which on heating... 

Laszlo and coworkers [13] developed a one-pot nitration method based on the use of claycop , cupric nitrate-impregnated acidic montmorillonite clay K-10. Nitration was conducted in the liquid phase under Menke conditions in the presence of acetic anhydride as water-trapping agent regioselectivity was high for p-NT. In a further development, the one-pot polynitration of mainly activated aromatic compounds and in particular toluene was examined using the same catalyst... 

CUPRIC NITRATE (3251-23-8) A strong oxidizer. Violent reaction with reducing agents, combustible materials, acetic anhydride, ethers, potassium ferrocyanide, finely divided tin. The aqueous solution is a medium-strong acid. Incompatible with bases, acetylene, ammonia, aliphatic amines, alkanolamines, amides, alkylene oxides, cyanides, epichlorohydrin, esters, isocyanates, organic anhydrides, vinyl acetate. Attacks metals in the presence of moisture. 

Electrophilic Substitution Reactions of Monocyclic Thiophens.— The reaction of thiophen with iV-(methylsulphonyl)hexafluoroacetoneimine gave (34) in 57% yield. Nitration of 3-(diacetoxymethyl)thiophen with acetyl nitrate or cupric nitrate in acetic anhydride gave the 5- and 2-isomers in the ratio 2.3 3.0. The product composition from the nitration of 3-methylthiophen was determined to be 3-methyl-2-nitrothiophen, 78% 3-methyl-4-nitrothiophen, 2.1% and 4-methyl-2-nitrothiophen, 20%. ... 

To a solution of 0.96 g fluorobenzene (10 mmol) in 50 mL n-hexane was added 5 g clay-supported cupric nitrate and 9.4 mL acetic anhydride (100 mmol). The mixture was stirred vigorously at room temperature for 48 h, and then filtered under reduced pressure. The filter cake was washed with -hexane, and the organic solvent was combined, dried, and evaporated. The residue was purified by silica gel column chromatography (cyclohexane/EtOAc, 9 1) to afford 53% nitrofluorobenzene, with 25 1 of orlholpara selectivity. 

PROBLEM 13.55 The molecule shown below undergoes reaction with cupric nitrate in acetic anhydride (a source of NOj) to give a high yield of the substituted product shown. Write a mechanism for this reaction. 

Cyclotriveratrylene in acetic acid added to a soln. of acetyl nitrate prepared by stirring a mixture of acetic anhydride and cupric nitrate trihydrate at room temp., then stirred 0.5 hr. at 50 4-(4,5-dimethoxy-2-nitrobenzyl)-5-(2-acetoxy-methyl-4,5-dimethoxybenzyl)-l,2-dimethoxybenzene. Y 76.5%. F. e. s. T. Sato, T. Akima, and K. Uno, Soc. Perkin I 1973, 891. 

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