Nitration of some 2-substituted thionaphthenes

A study is made of the nitration of thionaphthene-2-aldehyde, its diacetate, and of 2-(-nitrovinyl)thionaphthene. UV and IR spectroscopy show that nitration of thionaphthene-2-aldehyde in acetic anhydride gives a mixture of 3-nitrothionaphthen-2-aldehyde diacetate, 4-nitrothionaphthene-2-aldehyde diacetate, and 6-nitrothionaphthene-2-aldehyde diacetate in the ratios 106624, while nitration of thionaphthene-2-aldehyde diacetate gives a mixture of 3-nitrothionaphthene-2-aldehyde diacetate, 4-nitrothionaphthene-2-aldehyde diacetate, and 6-nitrothionaphthene-2-aldehyde diacetate in the ratios 363826. Nitration of 2-(-nitrovinyl)thionaphthene gives 4-nitro-2-(-nitrovinyl)thionaphthene.     

Orientation in the nitration of 2-pyridones

The ratio of 3- and 5-nitro isomers formed in the nitration of 2-pyridones with nitric acid is determined by the reaction temperature but is independent of the concentration of the nitrating agent. The presence of a phenyl group in the 6 position of the -pyridone ring hinders incorporation of a nitro group in the 5 position.Translated from Khimiya Geterotsikicheskikh Soedinenii, No. 1, pp. 72–75, January, 1978.     

Nitro derivatives of the thiophene series. 4. Nitration of thiophene derivatives with metal nitrates in acetic anhydride

The nitration of 2-formylthiophene, 2-acetothienone, and unsaturated ketones of the thiophene series with copper and aluminum nitrates in acetic anhydride at various temperatures was studied. At low temperatures 2-acetothienone gives a mixture of 4- and 5-nitro isomers, while 2-formylthipphene gives only a 5-nitro-substituted compound in the diacetate form; ,-unsaturated ketones are not nitrated under these conditions. When the reaction is carried out at 70–90 °C, one can obtain mixtures of nitro ketones in the case of unsaturated ketones; 2-formylthiophene is oxidized to thiophene-2-carboxylic acid, while 2-acetothienone gives a substance, the structure of which could not be established. The reaction of copper and aluminum nitrates with acetic anhydride was investigated by means of thermal and x-ray diffraction analysis. It is shown that the reaction is accompanied by the formation of free nitric acid, and the nitrating agent in these mixtures is consequently the nitronium cation.See [1] for communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 913–916, July, 1981.     

Nitration of phenol in 1,4-dioxane

The nitration of phenol with excess nitric acid in aqueous dioxane, in contrast to the nitration in aqueous ethanol, yields exclusively 2,4-dintrophenol, whereas at equimolar ratio of phenol and nitric acid the major reaction products are mononitrophenols (99%), among which the p-isomer prevails.     

Mononitro-β-carbolines

By the direct nitration of harmane and 1,3-dimethyl-, 1-ethyl-, 1-n-propyl-, and 1-isopropyl--carbolines with concentrated nitric acid or a mixture of nitric and acetic acids, 6- and 8-nitro-1-alkyl--carbolines have been obtained. A chromatographic method for separating the nitration products on alumina is proposed.     

Effect of Industrial Detonation Nanodiamonds on the Ratio of Mononitrotoluene Isomers in Nitration of Toluene with a Sulfuric-Nitric Acid Mixture

A qualitative and quantitative influence exerted by addition of detonation nanodiamonds on the formation selectivity of mononitrotoluene isomers in the heterophase nitration of toluene with a sulfuric-nitric acid mixture having low nitration activity was found. It is shown that the isomer ratio of the ortho-/paramononitrotoluenes can be varied within the range 1.00–2.7 at a temperature of 50°C by changing the stirring intensity within the range 300–5000 rpm. It was found that the strongest influence on the ortho-/para-ratio of the mononitrotoluene isomers is exerted by nanodiamonds having surface chemically modified via oxidation with a mixture of concentrated nitric and sulfuric acids.     

Nitration of 3-methyl-1<Emphasis Type="Italic">H</Emphasis>-1,2-diazaphenalene and its n-substituted derivatives

1-Substituted 1H-1,2-diazaphenalenes (1H-benzo[de]cinnolines) undergo nitration with nitric acid leading to the formation of di- and trinitro derivatives. The yield of nitration products depends on nitric acid concentration.     

Nitro derivatives of the thiophene series. 2. Nitration of thienyl-substituted unsaturated methyl ketones

The nitration of 4-(5-R-2-thienyl)-3-buten-2-ones with nitric acid in acetic anhydride is accompanied by the formation of a mixture of nitro isomers, whereas nitration with nitric acid and copper and aluminum nitrates in carbon tetrachloride, dichloroethane, and acetonitrile leads to the production of only the -nitro ketone. The results of quantum-chemical calculations of the reactivity indexes within the CNDO/2 approximation are in agreement with the experimental data on electrophilic substitution of these compounds in the basic and protonated forms.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 325–328, March, 1981.     

Nitration of 3-Methylaceperidazines with a Large Excess of Fuming Nitric Acid

Nitration of N-acetyl-3-methylaceperidazine with a 2–3-fold excess of nitric acid (d 1.36, 1.48) in glacial acetic acid results in the exclusive formation of mono- and dinitroderivatives. The nitration of 3-methylaceperidazine and its N-alkyl- and N-acetyl-substituted derivatives with a 6–9-fold excess of fuming nitric acid (d 1.54) in the same conditions results in the formation of both the expected products of mono- and dinitration and a product of the electrophilic addition of nitric acid to a double bond of acenaphthene scaffold of the molecule of nitration product.     

Nitro derivatives of 3-hydroxyquinoline

The nitration of 3-hydroxyquinoline with concentrated nitric acid in sulfuric acid at ?30 to +30°C gives 5-nitro-3-hydroxyquinoline (85–92%) and 7-nitro-3-hydroxyquinoline (7–12%). 4-Nitro-3-hydroxyquinoline is formed in 70% yield by nitration in acetic acid. 4,5-Dinitro-3-hydroxyquinoline is formed by further nitration of 4- and 5-nitro-3-hydroxyquinolines.     

Nitration of polyhaloalkenes by mixtures of nitric and sulfuric acids

Conclusions The nitration of polyhaloalkenes was carried out under conditions for the complete conversion of nitric acid to the nitronium cation. Butyl esters of -nitrocarboxylic acids were obtained by esterification of the nitration products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2814–2815, December, 1985.     

N,N′-dialkyl-N,N′-dinitrosulfodiamides

N,N-dinitrosulfodiamides are formed in the nitration of sulfodiamides with concentrated nitric acid or nitronium borofluoride, and also on substitutional nitration of the corresponding N,N-di-tert.-butyl derivatives with those reagents. Sulfuryl chloride reacts with the disodium salt of ethylene N,N-dinitramine to produce 2,5-dinitro-1,2,5-thiadiazolidine-1,1-dioxide. The corresponding N-nitrosulfamides are formed when nitramine salts react with methane sulfochloride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1812–1815, August, 1989.     

Nitration of 2,3′-bithienyl

The nitration of 2,3′-bithienyl ( 1 ) with fuming nitric acid in acetic anhydride at 0° gives a mixture of 3-nitro- ( 2 ), 2′ -nitro- ( 3 ) and 5-nitro-2,3′-bithienyl ( 4 ) with relative percentages of 38.7%, 34.8% and 26.5%. When the nitration of 1 was carried out with fuming nitric acid in acetic acid at 20°, the same compounds 2, 3 and 4 were obtained, but with different relative percentages: 20.4%, 36.5% and 43.1% respectively. The results of the mononitration of 1 are compared with those obtained in other electrophilic substitutions and with the theoretical predictions. The further nitrations of 2, 3 and 4 with nitric acid in acetic anhydride at room temperature lead to the formation of five dinitro-2,3′-bithienyl isomers. Compound 2 gives a mixture of 2′,3-dinitro- ( 5 ) and 3,5′-dinitro-2,3′-bithienyl ( 6 ); compound 3 gives a mixture of 5 , 2′,5-dinitro- ( 7 ) and 2′,4-dinitro-2,3′-bithienyl ( 8 ); compound 4 gives 7 and 5,5′-dinitro-2,3′-bithienyl ( 9 ). The possible reasons of the formation of the various dinitro-2,3′-bithienyl isomers are discussed.     

The action of a nitrating mixture on benzo-1,5-diazepine

It has been shown that the action of a mixture of nitric and sulfuric acids on 2,4-dimethylbenzo-1, 5-diazepine leads to processes of nitration, hydrolytic cleavage, and oxidation with simultaneous isomerization, with the formation of N,N-diacetyl-4-nitro-1,2-phenylenediamines, benzotriazole, and 2-acetyl-3-methylquinoxaline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1133–1134, August, 1970.     

Synthesis of α-functional nitro compounds by the nitration of activated carbonyl compounds in a two-phase system

2-Nitro-1,3-dicarbonyl and -nitromonocarbonyl compounds were synthesized in the yields varying from moderate (30 %) to nearly quantitative by the nitration of -dicarbonyl compounds in a two-phase system: sulfuric/nitric acid mixture-chloroform at - 10÷10 °C. The use of phase transfer conditions made it possible to avoid the formation of furoxans as by-products and to simplify the isolation of products. This method is quite common for preparing various -functional nitro compounds including those containing a CF₃-group. Key words: nitration, -functional nitro compounds.Translated fromIzvestiya Akademn Nauk. Seriya Khimicheskaya, No. 1, pp. 76–79, January, 1994.     

Radiation-induced nitration of organic compounds in aqueous solutions

Radiation-induced nitration of organic compounds in aqueous solutions was studied. It was found that γ-irradiation of solutions containing acetic and nitric acid and/or their salts gives nitromethane. Dependences of the product yield on the absorbed dose and the contents of components were established. The mechanism of radiation nitration involving radicals is discussed.     

Nitration of 8-substituted 2,3-dihydro-1H-1,5-benzodiazepin-2-ones

The nitration of a number of 8-R-4-R-2,3-dihydro-1H-1,5-benzodiazepin-2-ones with substituents in the diazepin (4-R=CH₃, C₆H₅, and C₆H₄OCH₃-p) and benzene (8-R=Cl, Br) rings takes place in the 7 position. The presence in the benzene ring of a strong electron-donor substituent (methoxy group), by determining the direction of electrophilic substitution in the ortho position with respect to it, leads to the formation of 7- and 9-nitro isomers in a ratio of 43.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 551–554, April, 1978.     

Nitration of 3-methyl-6,7-dihydro-1<Emphasis Type="Italic">H</Emphasis>-indeno[6,7,1-<Emphasis Type="Italic">def</Emphasis>]cinnoline and its <Emphasis Type="Italic">N</Emphasis>-substituted derivatives

The nitration of 3-methylaceperidazine (3-methyl-6,7-dihydro-1H-indeno[6,7,1-def]cinnoline) and its N-substituted derivatives with nitric acid of different concentrations requires harsh conditions and is accompanied by dehydrogenation and dimerization of the initial compound.     

Synthesis of a new potential antiviral agent — 9-allyloxymethylguanine

A convenient method has been developed for the synthesis of 9-allyloxymethylguanine. The direct alkylation of the trimethylsilyl derivative of guanine allyloxymethyl chloride gives a 64% yield of 9- and 7-allyloxymethylguanine (31). A mixture of 9- and 7-allyloxymethyl-N-acetylguanine (74) can be obtained in 56% yield by the condensation of diacetylguanine with allyloxymethyl acetate in dimethyl sulfoxide in the presences of p-toluenesulfonic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1113, August, 1993.     

Electrophilic substitution reactions of acylated 2-aminoindole derivatives

The bromination, nitration, and acylation reactions of various acyl derivatives belonging to the 2-aminoindole series of compounds have been investigated. It has been found that substitution occurs both at the -carbon atom as well as at the 5- and 6-positions of the benzene ring. The ratio of reaction products depends upon the nature of the electrophile as well as on the degree of substitution of the 2-aminoindole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 941–945, July, 1985.