Nitrobutadienes and their halogen derivatives: synthesis and reactions

Kaberdin, R. V.; Поткин, В. И.; Zapol’skii, V. A.

doi:10.1070/rc1997v066n10abeh000310

Cited by 52 publications

(42 citation statements)

References 22 publications

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“…Starting from 2-nitroperchlorobutadiene (1), 7 4-nitrothiophenes 3a-c are accessible in very good yields (90-95%). 6 Ipso-formylation of 3a-c under Vilsmeier-Haack conditions give the 4-nitrothiophene-2-carbaldehydes (4a-c) in good yields (70-79%).…”

Section: Resultsmentioning

confidence: 99%

ChemInform Abstract: Chemistry of Polyhalogenated Nitrobutadienes. Part 12. Synthesis of Novel, Highly Substituted Bi‐ and Tricyclic 5,6,7,8‐Tetrahydro‐4H‐chromen‐5‐ones.

et al. 2013

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-Knoevenagel condensation of 3,4-push-pull-substituted thiophene-2-carbaldehydes 4 with malononitrile gives the gem-dicyanovinylthiophenes 5, followed by a Michael addition of dimedone and a subsequent cyclization to 4-(2-thienyl)-5,6,7,8-tetrahydro-4H-chromen-5-ones 6. Protonolysis of the latter in methanol led to a mixture of four heterocycles 7-10, the main product being the novel tricyclic 9-(2-thienyl)-6,7-dihydro-5H-thieno[3,2-b]chromen-8(9H)-one derivative 7. A mechanism of the protonolysis reaction is proposed, the structures of the two products 7a/8a have been confirmed by X-ray analysis.

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Section: Resultsmentioning

confidence: 99%

ChemInform Abstract: Chemistry of Polyhalogenated Nitrobutadienes. Part 12. Synthesis of Novel, Highly Substituted Bi‐ and Tricyclic 5,6,7,8‐Tetrahydro‐4H‐chromen‐5‐ones.

et al. 2013

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“…4-(2-Naphthyl)pyrazole (IV) synthesized was brought into reaction with an active electrophile, 2-nitropentachloro-1,3-butadiene (VI), highly reactive in the processes of nucleophilic vinyl chlorine substitution [6]. It turned out that pyrazole IV was less active in the reaction with nitrodiene VI than its isomer V which readily reacted with the nitrodiene at room temperature [2].…”

Section: Z-3-(2-naphthyl)-3-chloro-2-propen-1-al (I) Easilymentioning

confidence: 99%

Uncommon Heterocyclization into a Pyrazole System of Z-3-(2-Naphthyl)-3-chloro-2-propenal Semicarbazone and Thiosemicarbazone

2005

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By reaction of Z-3-(2-naphthyl)-3-chloro-2-propenal with semicarbazide hydrochloride and thiosemicarbazide the corresponding semicarbazone and thiosemicarbazone were obtained that underwent a heterocyclization into a pyrazole system with elimination of amide moieties and with migration of the naphthyl fragment into the position 4 of the pyrazole ring. The alkylation of 4-(2-naphthyl)pyrazole synthesized with 2-nitropentachloro-1,3-butadiene afforded 1,1-bis[4-(2-naphthyl)-pyrazol-1-yl]-2-nitrotrichloro-1,3-butadiene.Z-3-(2-Naphthyl)-3-chloro-2-propen-1-al (I) easily prepared from 2-acetonaphthone by VilsmeierHaack reaction [1] contains two reactive sites (C=O and =CCl) that permits an effective application of the compound to building up versatile heterocyclic systems including a naphthalene fragment: benzodiazepine, isoxazole, pyrimidine [2], and quinoline [3]. We formerly demonstrated that the reaction between chloropropenal I and hydrazine hydrate was a convenient procedure for preparation of 5-(2-naphthyl)pyrazole [2].The goal of this study was preparation of chloropropenal I semicarbazone and thiosemicarbazone and the attempt at their heterocyclization into a pyrazole system containing a naphthalene fragment and amide or thioamide groups respectively.Semicarbazone II and thiosemicarbazone III of chloropropenal we obtained in 8082% yield by reacting chloropropenal I with semicarbazide hydrochloride and thiosemicarbazide respectively. The IR spectra of compounds II and III obtained lacked the absorption bands of the aldehyde group and contained the bands from C=N bonds vibrations at 1563 (compound II) and 1597 cm 1 (compound III). Vibrations of the NH 2 groups of compounds II and III are characterized by absorption bands at 3473 and 3432 cm 1 respectively, and vibrations of the NH groups appeared as broadened bands in the region 32063283 cm 1 . In the 1 H NMR spectra of compounds II and III alongside the resonances from the protons of the naphthyl groups and exocyclic =CH broadened singlets were observed with the chemical shifts d 9.410.5 and 6.356.45 ppm belonging to the protons of the NH and NH 2 groups respectively.The heterocyclization of compounds II and III into a pyrazole system was effected by boiling in the glacial acetic acid. We expected to obtain pyrazole with a naphthyl fragment attached to position 5 of the ring and amide or thioamide group in position 1. However the process occurred differently and involved a loss of amide groups and a migration of the naphthyl fragment into position 4 of the pyrazole ring. Thus in both cases the same product was obtained that based on elemental analysis, 1 H NMR, IR, and mass spectra was assigned a structure of 4-(2-naphthyl)pyrazole (IV).In the mass spectrum of compound IV the molecular ion peak is present with m/z 194 and relative abundance 100%, and the elemental analysis corresponds to an empirical formula C 13 H 10 N 2 . The IR and 1 H NMR spectra of compound IV essentially differ from the spectra of 5-(2-naphthyl)-pyrazole (V) we have synthesized p...

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“…Compound 2 gave 6 and 8 with morpholine (5) and thiomorpholine (8), respectively (Scheme 1). The structure of these novel compounds 2 and 3a-h were determined by microanalysis and spectroscopic data.…”

mentioning

confidence: 98%

The Novel N, S-Substituted Halonitrodienes from the Reactions of Thiosubstituted Nitrodiene with Piperazine and Morpholine

Ibis¹,

Onul²

2005

Phosphorus, Sulfur, and Silicon and the Related Elements

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The substituted 1,2-dibromomethanethio nitrodiene 2 was obtained from the addition of bromine to S-substituted nitrodien 1 in carbon tetrachloride. N,S-substituted compounds 4a-h were synthesized from the reactions of compound 2 with several substituted piperazine derivatives 3a-h in dichloromethane. N,S-substituted compounds 6 and 8 were synthesized from the reaction of 2 with morpholine (5) and thiomorpholine (7) in dichloromethane, respectively. Dibutadienyl piperazines 10, 12, and 14 were synthesized from the reactions of 2 with homopiperazine (9), piperazine (11), and 2,5-dimethylpiperazine (13), respectively.

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Nitrobutadienes and their halogen derivatives: synthesis and reactions

Cited by 52 publications

References 22 publications

ChemInform Abstract: Chemistry of Polyhalogenated Nitrobutadienes. Part 12. Synthesis of Novel, Highly Substituted Bi‐ and Tricyclic 5,6,7,8‐Tetrahydro‐4H‐chromen‐5‐ones.

ChemInform Abstract: Chemistry of Polyhalogenated Nitrobutadienes. Part 12. Synthesis of Novel, Highly Substituted Bi‐ and Tricyclic 5,6,7,8‐Tetrahydro‐4H‐chromen‐5‐ones.

Uncommon Heterocyclization into a Pyrazole System of Z-3-(2-Naphthyl)-3-chloro-2-propenal Semicarbazone and Thiosemicarbazone

The Novel N, S-Substituted Halonitrodienes from the Reactions of Thiosubstituted Nitrodiene with Piperazine and Morpholine

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