N. A. Anisimova

Conformational Analysis of 2-Substituted 1-Nitro- and 1-Bromo-1-nitroethenes

Conformational analysis of 2-trichloromethyl(ethoxycarbonyl)-1-nitro-and 2-trichloromethyl-(ethoxycarbonyl)-1-bromo-1-nitroethenes was performed using the dipole moment method, IR spectroscopy, and DFT quantum-chemical calculations (B3LYP/6-31G*). The nitro and ester (or trichloromethyl) groups in the molecules of these compounds were found to occupy trans positions with respect to the double C=C bond, i.e., the nitroalkenes have E, and their bromine-containing analogs, Z configuration; the compounds having an ethoxycarbonyl group are characterized by s-cis orientation of the C=C and C=O bonds.

3,3,3-Tribromo-1-nitropropene: Synthesis and structure

Abstract3,3,3-Tribromo-1-nitropropene and its precursors such as 2-hydroxy- and 2-acetoxy-1,1,1-tribromo-1-nitropropanes were prepared and characterized by IR, UV, 1H, 13C, HMQC, and HMBC NMR spectroscopy methods. Structure of tribromomethylnitroalkene was studied by X-ray diffraction.

Nitro- and Trichloromethyl-Functionalized Norbornenes

Electron-deficient conjugated nitroalkenes are active dienophiles in the Diels–Alder reactions [1–3]. The introduction of the second electron-withdrawing substituent [CO2R, P(O)(OR)2, SO3R, NO2] into the nitroalkene molecule not only enhances the reactivity of the double bond C=C, but also extends the synthetic potential of the adducts due to the possibility of transforming the substituents into the pharmacophore groups [СООН, SO3H, P(O)(OH)2, NH2] [4, 5]. Therefore functionalized adducts of diene synthesis are successfully used as intermediates in the synthesis of natural compounds (epibatidine, efanofin, estrogenic hormones) [1, 6, 7] and drugs (e.g., antiviral preparation, morphine) [8, 9].

Synthesis and structure of oxanorbornenes functionalized by nitro- and trichloromethyl groups

The reactions of furan and 2-methylfuran with 3,3,3-trichloro-1-nitro- and 1-bromo-3,3,3-trichloro-1-nitropropenes were studied to show that furan reacts by the diene condensation pathway, whereas the reactions with 2-methylfuran take two pathways: the diene synthesis and electrophilic substitution by C5.

Reaction of 3-nitro-and 3-bromo-3-nitroacrylates with sodium azide

Reactions of 3-nitro-and 3-bromo-3-nitroacrylates with sodium azide proceed as 1,3-dipolar cycloaddition and lead to the formation of triazolyl-and nitrotriazolylcarboxylates, and also of azido-and azidonitropropenoates.

3-nitro- and 3-bromo-3-nitroacrylates in reactions with phenyl azide

Abstract1,3-Dipolar cycloaddition of alkyl 3-nitro-and 3-bromo-3-nitroacrylates to phenyl azide gives regioisomeric alkyl 5(4)-nitro-1-phenyl-4,5-dihydro-1H-1,2,3-triazole-4(5)-carboxylates, the corresponding triazoles both with and without nitro group, and alkyl 3-nitro-1-phenylaziridine-2-carboxylates. Nitrotriazolecarboxylates were found to lose the ester moiety during chromatographic separation of the products on aluminum oxide. The structure of the products was determined on the basis of IR, 1H NMR, and X-ray diffraction data.

Reaction of bis(2-chloroethyl)-2-nitroethynylphosphonate with diazoacetic ester

Reactions of 1,3-dipolar cycloaddition of bis(2-chloroethyl)-2-nitroethenylphosphonate to methyl and ethyl diazoacetates proceed with the formation of a mixture of regioisomers of phosphorylated nitropyrazoline carboxylates that under the reaction conditions undergo isomeric transformations and denitration and afford a mixture of Δ1- and Δ2-pyrazoline- and pyrazolecarboxylates. Structures of the synthesized substances are studied by the methods of IR and 1H, 31P NMR spectroscopy and partially by X-ray structural analysis.

Bis(2-chloroethyl) ethenylphosphonate in the diels-alder reaction

The diene synthesis reactions of bis(2-chloroethyl) ethenylphosphonate with 3-methyl-3-thiolene 1,1-dioxide that generates isoprene under the reaction conditions, as well as with 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene, cyclopentadiene, furan, and anthracene are studied. A series of cycloalkenyl-and heterylphosphonates derived from cyclohexene, bicyclooctene, norbornene, oxanorbornene, and 9,10-dihydro-9,10-ethanoanthracene are synthesized.

Synthesis and structure of phosphorylated nitrocyclohexenes

Diene condensations of 2-nitro-and 2-bromo-2-nitroethenylphosphonates with 2,3-dimethyl-1,3-butadiene, as well as with 2,4-dihydro-and 3-methyl-2,4-dihydrothiophene 1,1-dioxides that generate 1,3-butadiene and isoprene under the reaction conditions were effected. (6-Nitrocyclohex-3-en-1-yl)phosphonates and their dehydrogenation and/or dehydrohalogenation products, namely nitrocyclohexadienyl-and nitrophenylphosphonates were prepared. The structure of the obtained compounds was proved by IR and 1H and 31P NMR spectroscopy, and independent synthesis.

Synthesis of Cyclopropane Derivatives of Aspartic Acid by Thermal Decomposition of Substituted Pyrazolines

Thermal decomposition of substituted Δ1- and Δ2-pyrazolines was used to obtain cyclopropane derivatives of aspartic and adipic acids.