Benzoyl Nitrate Research Articles

Geometric and electronic structures of benzoyl nitrite and benzoyl nitrate

The electronic structures of benzoyl nitrite (C 6H 5C(O)ONO) and benzoyl nitrate (C 6H 5C(O)ONO 2) have been studied by HeI photoelectron spectroscopy (PES) and quantum chemical calculations. The photoelectron spectra are assigned with the help of the outer valence Green’s function (OVGF) calculations. The first vertical ionization energies of C 6H 5C(O)ONO and C 6H 5C(O)ONO 2 are determined to be 9.20 and 9.54 eV, respectively. According to the results of theoretical calculations, it can be concluded that a planar C C(O) O N O skeleton in C 6H 5C(O)ONO and a planar C C(O) O N skeleton in C 6H 5C(O)ONO 2 are the stable structures in the gas phase.

ChemInform Abstract: para-Selective Mononitration of Alkylbenzenes Under Mild Conditions by Use of Benzoyl Nitrate in the Presence of a Zeolite Catalyst.

Toluene and other alkylbenzenes are mononitrated in essentially quantitative yield at ambient temperature by benzoyl nitrate in the presence of aluminium/proton exchanged large port mordenite; the reaction is highly para-selective. The use of benzoyl nitrate in combination with an acidic zeolite catalyst provides a convenient method for high yielding and para-selective nitration of alkylbenzenes.

Para-selective mononitration of alkylbenzenes under mild conditions by use of benzoyl nitrate in the presence of a zeolite catalyst

Toluene and other alkylbenzenes are mononitrated in essentially quantitative yield at ambient temperature by benzoyl nitrate in the presence of aluminium/proton exchanged large port mordenite; the reaction is highly para -selective.

Aroyl peroxides. Part VI. Reactions of aroyl peroxides with nitrogen dioxide

The products of the decomposition of benzoyl peroxide in carbon tetrachloride in the presence of nitrogen dioxide have been investigated quantitatively, and the mechanism previously suggested has been confirmed. The reaction of benzoyl peroxide with nitrogen dioxide in the absence of solvent has been found to be similar, but less complex. The formation of benzoyl nitrate was indicated by the isolation of a nitration product from reactions in the presence of p-xylene. The decomposition of a series of aroyl peroxides in the presence of nitrogen dioxide gave the corresponding nitro-compounds.

Benzoyl nitrate reduction with halide ions

Benzoyl nitrate reduction with halide ions

The reactions of some indole derivatives with benzoyl nitrate. Novel oxidative coupling reactions of 2-methylindoles

Indole derivatives with a free position 3 are converted by benzoyl nitrate into the corresponding 3-nitro-derivatives. Under the same conditions, 3-methylindole gives 3-methyl-2-nitroindole, and 2,3-diphenylindole yields a mixture containing 3,3-diphenyloxindole and 6-nitro-2,3-diphenylindole. 2,3-Dimethylindole is oxidized by benzoyl nitrate to 3-methylindole-2-carbaldehyde, and under somewhat different conditions to two compounds, which, on the basis of spectral and chemical evidence, are identified as 5a,10b,12-trimethyl-5a,6,10b,11-tetrahydropyrrolo[1,2-a:5,4-b′]di-indole and the corresponding 6-nitroso-derivative. 3-Ethyl- and 3-phenyl-2-methylindole give similar products.

Reactions of organometallic complexes with carbon monoxide. Part I. Carbonylation and reduction of arylmercury(II) complexes and some related reactions of ethylene

The reactions of phenylmercury(II) complexes with carbon monoxide have been investigated to establish whether ‘carbonylation’ reactions take place. The basic nitrate, (HgPh)2(OH,NO3), is the only complex that yields useful amounts of benzoic acid derivatives. The pattern of reactivity of the complexes, HgPhX is reminiscent of that of mercury(II) salts and follows the ‘hardness’ of X. In aqueous solution, oxyanion complexes are reduced either to diphenylmercury and mercury or to mercury alone; this is consistent with attack of HgPh+ or H+ on a mercurated formic acid derivative. Similar reactions occur in benzene but the reduction of nitric acid by carbon monoxide as it is formed has a buffer effect which prevents reductive cleavage of (HgPh)2(OH,NO3). Benzoato(phenyl)-mercury is formed together with decomposition products from the reaction intermediate, benzoyl nitrate. This decomposition is very pressure sensitive, yielding benzoic anhydride at high pressure and biphenyl derivatives at low pressure. Carbonylation of (HgPh)2(OH,ClO4) also gives a small yield of benzoic acid. In methanol solution HgPh(CO·OMe) is formed by addition reactions of carbon monoxide when X = OH– or AcO–. The basic nitrate yields, also, some diphenylmercury but mainly methyl benzoate and methyl benzoylformate. Phenylmercury(II) complexes also add ethylene forming HgPh(CH2CH2OMe).

The free radical decomposition of benzoyl nitrate and its pressure dependence

The free radical decomposition of benzoyl nitrate is benzene and toluene to give products resulting from the formation of phenyl and benzoyloxy radicals is described. These products include biphenyl from reactions in benzene and benzyl benzoate and methylbiphenyls from reactions in toluene. The yields of radical decomposition products are comparable to yields of the non-radical decomposition products of benzoyl nitrate, benzoic anhydride and benzoic acid. The marked effect of applied pressure in inhibiting the radical mode of decomposition is also described.

Medium-Sized Cyclophanes. III. The Nitration Reaction of [2.2]Metacyclophane with Benzoyl Nitrate

Abstract The nitration reaction of [2.2]metacyclophane was carried out using dilute nitric acid or benzoyl nitrate under various conditions. Dilute nitric acid afforded 2-nitro-4, 5, 9, 10-tetrahydro-pyrene as the sole product, confirming Allinger’s original experiments, whereas benzoyl nitrate furnished a complex mixture consisting of 4, 5, 9, 10-tetrahydropyrene, 4, 5-dihydropyrene and pyrene, together with the nitration product. A series of experiments established that 4, 5, 9, 10-tetrahydropyrene, which was formed by the 1, 4-elimination reaction of Allinger’s intermediate, was the initial product of the reaction. Two competitive reactions, nitration and dehydrogenation reactions of the tetrahydropyrene, were assumed to be occurring, thus accounting for the experimental results.

Studies on cinnolines. IV. On nitration of cinnoline 2-oxide.

Cinnoline 2-oxide (I) gave 5-, 6-and 8-nitrocinnoline 2-oxides (II, III, and IV) on warming with nitric and sulfuric acids or potassium nitrate in sulfuric acid. The nitration of I with benzoyl nitrate afforded II. 5-, 6- and 8-Aminocinnolines (V, VI, VII), 6-and 8-aminocinnoline 2-oxides (VIII and IX), and 5-aminodihydrocinnoline (X) were synthesized for the determination of the structures of II, III and IV. The effect of 2-N-oxide of I in this reaction was affected by the concentration of sulfuric acid and the reaction temperature.

POTENTIAL ANTI-CANCER AGENTS. XIV. REACTION OF 3-SUBSTITUTED PYRIDAZINE 1-OXIDE WITH BENZOYL NITRATE.

POTENTIAL ANTI-CANCER AGENTS. XIV. REACTION OF 3-SUBSTITUTED PYRIDAZINE 1-OXIDE WITH BENZOYL NITRATE.

STUDIES ON CINNOLINES. II. ON NITRATION OF CINNOLINE 1-OXIDE.

Cinnoline 1-oxide (1) gave 4-nitrocinnoline 1-oxide (II) and a small amount of 5-nitrocinnoline 1-oxide (V) on warming with nitric and sulfuric acids, and gave 4, 5-dinitrocinnoline 1-oxide (IV) by using fuming nitric acid in sulfuric acid. The nitration of I with benzoyl nitrate afforded 3-nitrocinnoline 1-oxid (VI). I was converted into 4-chlorocinnoline (VIII) on the treatment with phosphoryl chloride.

Studies on nitration of 7-tosyloxy-, 7-methoxy-, 5-tosyloxy-, and 5-methoxyquinoline 1-oxide with benzoyl nitrate

Studies on nitration of 7-tosyloxy-, 7-methoxy-, 5-tosyloxy-, and 5-methoxyquinoline 1-oxide with benzoyl nitrate

芳香環状異項環の分極 第133報

As the final product of nitration of quinoline 1-oxide and its derivatives with benzoyl nitrate, benzoates of 2-hydroxyquinoline 1-oxide (III)-system was obtained. Therefore, infrared absorption spectra of 2-hydroxyquinoline 1-oxide (III), 4-hydroxy-quinoline 1-oxide (IV), 2, 4-dihydroxyquinoline (V), and their nitro and acyl derivatives were examined. It was revealed by this examination that compounds of (III)- and (IV)-system take the N-hydroxyquinolone type (IIIb) and the betaine type (IVc), respectively. The acylated derivatives of (III)-and (IV)-systems exhibit absorption of C=O stretching vibration due to N-acyloxyl group at a shorter wave-length region than the acyloxyl group in ordinary phenols and this was found to be helpful in discriminating them from acylated derivatives of 2, 4-dihydroxyquinoline (V)-system.

ヒノリン系アミノN-オキシドのニトロ化に関する研究

Reaction of benzoyl nitrate with 2, 4-dimethylquinoline 1-oxide and lepidine 1-oxide in chloroform solution at room temperature was examined. The products obtained from the quinoline compound were 3-benzoyloxy-2, 4-dimethylquinoline (syrup; picrate of needles, m.p. 235-237°), 2-benzoyloxylepidine (prismatic crystals, m.p. 80-82°; picrate of prisms, m.p. 146-148°), and a small amount of yellow needles, m.p. 185-187°, C22H16 O2N4 (assumed to be a glyoxime superoxide-type compound), besides recovery of 27% of the starting material (Chart 1, II). Lepidine 1-oxide produced 3-benzoyloxylepidine (needles, m.p. 18-20°; picrate of microneedles, m.p. 214-215°) besides recovery of 40% of the oxide (Chart 1, III). In both cases, a large amount of the starting material was recovered and the compounds formed by this reaction were those expected to be produced by the action of benzoic anhydride and not the 3-nitro derviatives. This supports the assumed mechanism (Chart 1, I) forwarded by Ochiai and Kaneko for the formation of 3-nitroquinoline 1-oxide from quinoline 1-oxide by the action of benzoyl nitrate.Quinoline 1-oxide forms a stable complex of m.p. 157.5-158.5° with boron trifluoride. Its nitration with benzoyl nitrate under the same conditions as above afforded 4-nitroquinoline 1-oxide in 54% yield and the reaction mechanism shown in Chart 1 was forwarded. Nitration of the boron trifluoride-complex with acid mixture at 15-20° chiefly produces 5- and 8-nitro derivatives, with a small amount of 4-nitro compound as a by-product.

496. Kinetics and mechanism of aromatic nitration. Part V. Nitration by acyl nitrates, particularly by benzoyl nitrate

496. Kinetics and mechanism of aromatic nitration. Part V. Nitration by acyl nitrates, particularly by benzoyl nitrate

Preparation and Properties of Benzoyl Nitrate

Preparation and Properties of Benzoyl Nitrate

I.—The preparation and reactions of benzoyl nitrate

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