A. A. Kuzhaeva

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.

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.

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 and structure of 1,3,3,3-tetrabromo-1-nitropropene

Preparation of a previously unexplored gem-bromonitroethene compound, 1,3,3,3-tetrabromo-1-nitropropene, is reported. The product structure has been confirmed by IR, UV, 1H and 13C NMR spectroscopy (including HMBC).

Synthesis and Structure of Nitrocyclohexenylcarboxylates

The diene condensation of 3-nitro- and 3-bromo-3-nitroacrylates with 2,3-dimethyl-1,3-butadiene and isoprene obtained under the reaction condition from 3-methyl-3-thiolene-1,1-dioxide was investigated. The formed 6-nitro-3-cyclohexenylcarboxylates were subjected to the intramolecular transformation (dehydration and dehydrohalogenation) to give the corresponding nitrocyclohexadienyl- and arylcarboxylates. The structure of the obtained compounds was established from the IR, 1H NMR spectra and independent synthesis.

Acrylate and its 3-nitro derivatives in reactions with anthracene

Ethyl acrylate as well as 3-nitro- and 3-bromo-3-nitroacrylates were shown to react with anthracene to form diene synthesis adducts. In the case of bromonitroacrylate the reaction proceeds with more difficulty. Firstly, alkylation products form along with cycloaddition adducts; secondly, compounds, initially formed by two directions, undergo dehydrohalogenation to give the corresponding conjugated nitroalkenes.

Synthesis of 11-amino-9,10-dihydro-9,10-(ethano)anthracen-12-ylphosphonic acid

Synthesis of a new representative of β-aminophosphonic acids and related esters, namely, 11-amino-9,10-dihydro-9,10-(ethano)anthracen-12-ylphosphonic acid and the respective bis(2-chloroethyl)-phosphonate was carried out.

Synthesis of β-aminophosphonic acids of cyclohexane, norbornane, and bicyclooctane series

New method for preparation of the previously unknown β-aminophosphonic acids of cyclohexane, norbornane, and bicyclooctane series from the corresponding nitrocycloalkenylphosphonates is developed. The structure of all compounds obtained is studied by the spectral (IR and 1H and 31P NMR) methods.

Synthesis and Structure of Cyclohexenes Functionalized by Nitro and Trifluoro(chloro)methyl Groups

Cyclohexenes functionalized by nitro and trihalomethyl groups were produced by condensation of 1-nitro- and 1-bromo-1-nitro-3,3,3-trifluoro(chloro)propenes with 2-methyl- and 2,3-dimethyl-1,3-butadienes; their structure was characterized by IR, 1H, 13C, 19F NMR spectroscopy, and X-ray diffraction method.

Reactions of 3-nitro- and 3-bromo-3-nitroacrylates with 1,3-cyclohexadiene

Nitroacrylates and their derivatives are known to be active dienophiles in the Diels–Alder reaction with acyclic [1, 2] and cyclic {cyclopentadiene [3, 4], furan [5, 6], β-furylnitroethene [7], β-(2-nitrovinyl)indole [8]} 1,3-dienes. In this work we investigate the reaction of the nitroand gem-bromonitroacrylates I, II with 1,3-cyclohexadiene. The study of these reactions is of interest for the development of convenient methods of the synthesis of functionalized bicycleoctenes, which are important intermediates in the synthesis of fragments of the natural compounds (hormones, vitamin D3, etc.) [1, 9]. Cyclopentadiene is known to react with nitroacrylate I at 0°C to give a mixture of endoand exodiastereomers of the corresponding nitronorbornene in a quantitative yield [3, 4]. In contrast to cyclopentadiene the reaction of 1,3-cyclohexadiene occurs in more rigid conditions (boiling the reaction mixture in benzene for 36 h) and results in a mixture of endoand exo-isomers of ethyl 3-nitrobicyclo[2.2.2]-5-octen2-ylcarboxylate IIIa, IIIb in 87% yield. The endoisomer IIIa was isolated in pure form by the repeated chromatography of the bicyclooctene isomers mixture. Bromonitroacrylate II reacts with cyclohexadiene under similar conditions (benzene, 80°C, 40 h) to afford a mixture of the difficultly separable products, from which by the column chromatography the endoIVa and exo-IVb isomers of ethyl 3-bromo-3-nitrobicyclo[2.2.2]-5-octen-2-ylcarboxylate in the ratio of 6:1 with an overall yield of 45%, and the products of DOI: 10.1134/S1070363212120213