1-vinyl Derivatives Research Articles

Synthesis and Unexpected Transformation of 5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-1H-pyrrol-2-amine into 5-{[2-(2-Hydroxyethoxy)ethenyl]sulfanyl}-1H-pyrrol-2-amine in the Presence of a Superbase

Successive one-pot reactions of monolithiated N,N-diethylprop-2-yn-1-amine with 2-(ethenyloxy)­ethyl isothiocyanate and 2-(bromomethyl)-1,3-dioxolane afforded 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]-1[2-(ethenyloxy)ethyl]-N,N-diethyl-1H-pyrrol-2-amine in 91% yield. In the system t-BuOK–DMSO at room tem­perature (1 h), the product was converted to 1-[2-(ethenyloxy)ethyl]-N,N-diethyl-5-{[2-(2-hydroxyethoxy)­ethenyl]­sulfanyl}-1H-pyrrol-2-amine (yield 68%) instead of expected 1-vinyl derivative.

The “one pot” synthesis of 4,5-dihydrobenzo[g]indole and its 1-vinyl derivative from 1-tetralone, hydroxylamine, and dichloroethane in the system KOH-DMSO

4,5-Dihydrobenzo[g]indole and its 1-vinyl derivative were obtained from 1-tetralone, hydroxylamine, and dichloroethane in the superbasic system KOH-DMSO (140 °C, 3 h) in a total yield of 88%. The proposed method provides a fire-safe and explosion-proof approach to indole derivatives in demand.

Expedient Synthesis of 1‐Vinylpyrrole‐2‐carbaldehydes.

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Expedient synthesis of 1-vinylpyrrole-2-carbaldehydes

1-Vinylpyrrole-2-carbaldehydes and 1-vinyl-4,5-dihydrobenzo[ g]indole-2-carbaldehyde were synthesized in 56–91% yields from their 1-vinyl derivatives by a modified Vilsmeier–Haack reaction. A low temperature (−78 °C) is required to avoid removal of the N-vinyl group, whereas at elevated temperature (reflux in 1,2-dichloroethane) the latter process leads to direct conversion of 1-vinylpyrroles to pyrrole-2-carbaldehydes.

Inhibition of catechol- O-methyltransferase by 1-vinyl derivatives of nitrocatechols and nitroguaiacols : Kinetics of the irreversible inhibition by 3-(3-hydroxy-4-methoxy-5-nitro benzylidene)-2,4-pentanedione

It is well known that activated alkene derivatives react with thiol groups according to a Michael's addition reaction. On the basis of the presence of at least one thiol group essential for the activity of catechol- O-methyltransferase (COMT), several 1-vinyl derivatives of nitrocatechol and nitroguaiacol were synthesized and tested as potential irreversible active site-directed inhibitors of COMT. All the synthesized products were potent inhibitors of partially purified pig liver COMT. However, the inhibition was reversible in most cases, with the exception of 3-(3-hydroxy-4-methoxy-5-nitrobenzylidene)-2,4-pentanedione (compound 2) which inhibited COMT in an irreversible manner. When the inhibition of COMT was measured as a function of the length of time of pre-incubation with 2, biphasic kinetics were observed, suggesting the modification of at least two thiol groups which are essential for COMT activity. The analysis of the two parts of the inhibition curve as a function of the inhibitor concentration showed that compound 2 modified the more reactive group in a non-specific manner, while it behaved as an active site-directed inhibitor on the second slow-reacting thiol group. Importantly, a saturating concentration of S- adenosyl- L-methionine (AdoMet) in the pre-incubation mixture gave pseudo-first order kinetics, suggesting total protection of one thiol group. Magnesium ions had no effect on the protection of COMT by AdoMet. In the presence of 3,5-dinitrocatechol (DNC) slight protection of COMT was observed; when the inactivation of both groups was analysed independently, protection of the specifically modified group was detected, while the reaction with the other group was faster in the presence of DNC. When both AdoMet and DNC were present, inactivation of COMT by 2 was not observed, suggesting that both reacting groups are located at or near the active site.

Synthesis of 2-(2-selenienyl)pyrrole from methyl-2-selenienylketoxime and acetylene

The reaction of methyl-2-selenienylketoxime with acetylene in KOH-DMSO gives 2-(2-selenienyl)pyrrole and its 1-vinyl derivative.

Pyrroles from ketoximes and acetylene. 44. Methyl aryl ketoximes with reactive substituents

The Trofimov reaction was extended to methyl aryl ketoximes with substituents in the benzene ring that are unstable with respect to the action of a strongly basic medium. The corresponding pyrroles and their 1-vinyl derivatives were obtained. 4-Nitroacetophenone oxime, from which only 2-phenyl- and 1-vinyl-2-phenylpyrrole were obtained, and 4-bromoacetophenone oxime, the reaction of which leads to the formation of 1-vinyl-2-(4-vinyloxyphenyl)pyrrole in addition to the principal 2-(4-bromophenyl)pyrrole, constituted exceptions.

Pyrroles from ketoximes and acetylene. 43. 1,2-Dihaloalkanes and vinyl chloride in the synthesis of 2-(4-alkylthiophenyl)pyrroles

2-(4-Alkylthiophenyl)-3- and 2-(4-alkylthiophenyl)-5-methylpyrroles and their 1-vinyl derivatives were synthesized by the reaction of alkyl(4-alkylthiophenyl)ketoximes with dihaloalkanes or vinyl chloride in the KOH-DMSO system at 120–140‡C and atmospheric pressure.

Molecular structure, orbital structure, and relative stability of conformational isomers of 2-phenyl-5-trifluoroacetylpyrrole and its 1-vinyl derivative, according to data obtained by MNDO and MINDO/3 methods

According to quantum-chemical calculations and IR spectra, the molecule of 1-vinyl-2-phenyl-5-trifluoroacetylpyrrole has two spectroscopically different rotational isomers. Both forms are characterized by a practically orthogonal position of the phenyl substituent and a substantially nonplanar position of the vinyl and trifluoroacetyl substituent s relative to the central pyrrole fragment. The unsubstituted 2-phenyl-5-trifluoroacetylpyrrole exists primarily in a single form with a planar position of the trifluoroacetyl substituent and an orthogonal position of the phenyl substituent.

ChemInform Abstract: Pyrroles from Ketoximes and Acetylene. Part 35. Synthesis of 2‐(4‐Alkylthiophenyl)pyrroles and Their 1‐Vinyl Derivatives.

ChemInform Abstract: Pyrroles from Ketoximes and Acetylene. Part 35. Synthesis of 2‐(4‐Alkylthiophenyl)pyrroles and Their 1‐Vinyl Derivatives.

Pyrroles from ketoximes and acetylene. No. 36. 4,4,6,6-Tetramethyl-4,5,6,7-tetrahydro-5-azaindole, its nitroxyl and vinyl derivatives, and spin-labelled copolymer

An oxime containing a nitroxyl functional group site, 2,2,6,6-tetramethyl-1-nitroxyl-4-hydroxyiminopiperidine, has been shown for the first time to engage in productive pyrrole synthesis via reaction with acetylene in KOH-DMSO. The behavior of 2,2,6,6-tetramethyl-4-piperidone oxime and its 1-hydroxy derivative in this reaction has also been investigated. The corresponding 5-azaindole and its 5-nitroxyl and 1-vinyl derivatives have been synthesized in this manner. 1-Hydroxy-4-piperidone oxime reacts at 50–60‡C under the general reaction conditions undergoing oxidative conversion to 5-azaindole, while at 105‡C in the presence of excess acetylene reduction of the hydroxy group also takes place. The formation of a pyrrole ring does not involve radical chains, although vinylation of the resulting pyrroles apparently involves one-electron transfer. 1-Vinyl-4,4,6,6-tetramethyl-4,5,6,7-tetrahydro-5-azaindole has been used for the preparation of a spin-labelled polyvinyl alcohol copolymer.

Pyrroles from ketoximes and acetylene. 35. Synthesis of 2-(4-alkylthiophenyl)pyrroles and their 1-vinyl derivatives

2-(4-Alkylthiophenyl)- and 2-(4-phenylthiophenyl)pyrroles and their 1-vinyl derivatives were synthesized by the reaction of 4-alkylthio- and 4-phenyl-thioacetophenone oximes with vinyl chloride in a KOH-DMSO system at 120 and 130‡C and at atmospheric pressure.

Pyridonecarboxylic acids as antibacterial agents. 9. Synthesis and antibacterial activity of 1-substituted 6-fluoro-1,4-dihydro-4-oxo-7-(4-pyridyl)-1,8-naphthyridine-3- carboxylic acids.

The title compounds (7a-e) with ethyl, 2-fluoroethyl, 2-hydroxyethyl, vinyl, or cyclopropyl groups, respectively, at C-1 were prepared by the method involving the Balz-Schiemann reaction of 2-(4-pyridyl)pyridine- and 7-(4-pyridyl)-1,8-naphthyridinediazonium tetrafluoroborates (15 and 27). The 1-ethyl, 1-(2-fluoroethyl), and 1-vinyl derivatives showed in vitro activities as potent as the corresponding 7-(1-piperazinyl) analogues against Staphylococcus aureus 209P JC-1 and Escherichia coli NIHJ JC-2 but were less active against Pseudomonas aeruginosa 12. Among the 7-(4-pyridyl) derivatives having the different C-1 substituent, 1-cyclopropyl derivative 7e was found to be the most active. In vivo efficacy of 7e was superior to that of enoxacin against experimental infections due to S. aureus 50774. Some aspects of structure-activity relationships associated with the C-1, C-6, and C-7 substituents were discussed.

ChemInform Abstract: Pyrroles from Ketoximes and Acetylene. Part 23. 2‐(1‐Naphthyl)‐ and 2‐(2‐Naphthyl)‐pyrroles, and Their 1‐Vinyl Derivatives.

AbstractDie Oxime von 1‐ und 2‐Acetylnaph4 thalin (I) werden in Gegenwart von Kalium‐ und Lithiumhydroxid in Dimethylsulfoxid als Lösungsmittel mit Acetylen (II) zu Naphthylpyrrolen (III) und deren N‐Vinylderivaten (IV) umgesetzt.

ChemInform Abstract: SINGLE-STAGE SYNTHESIS OF 4,5-DIHYDROBENZ(G)INDOLE AND ITS 1-VINYL DERIVATIVE FROM α-TETRALONE OXIME AND VINYL CHLORIDE

Chemischer InformationsdienstVolume 14, Issue 8 Heterocyclic Compounds ChemInform Abstract: SINGLE-STAGE SYNTHESIS OF 4,5-DIHYDROBENZ(G)INDOLE AND ITS 1-VINYL DERIVATIVE FROM α-TETRALONE OXIME AND VINYL CHLORIDE A. I. MIKHALEVA, A. I. MIKHALEVASearch for more papers by this authorI. A. ALIEV, I. A. ALIEVSearch for more papers by this authorR. N. NESTERENKO, R. N. NESTERENKOSearch for more papers by this authorG. A. KALABIN, G. A. KALABINSearch for more papers by this author A. I. MIKHALEVA, A. I. MIKHALEVASearch for more papers by this authorI. A. ALIEV, I. A. ALIEVSearch for more papers by this authorR. N. NESTERENKO, R. N. NESTERENKOSearch for more papers by this authorG. A. KALABIN, G. A. KALABINSearch for more papers by this author First published: February 22, 1983 https://doi.org/10.1002/chin.198308188Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume14, Issue8February 22, 1983 RelatedInformation

Pyrroles from ketoximes and acetylene. 23. 2-(1-naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives

2-(1-Naphthyl)- and 2-(2-naphthyl)pyrroles and their 1-vinyl derivatives were synthesized in 22–64% yields by the reaction of 1- and 2-acetylnaphthalene oximes with acetylene at both atmospheric pressure and elevated pressures in an alkali metal hydroxide-dimethyl sulfoxide system.

Pyrroles from ketoximes and acetylene. 22. Dihaloethanes in place of acetylene in reactions with cyclohexanone oxime

4,5,6,7-Tetrahydroindole and its 1-vinyl derivative were obtained in overall yields of 30–60% by the reaction of cyclohexanone oxime with 1,2-dichloro- and 1,2-dibromoethane in the MOH-dimethyl sulfoxide (DMSO) superbase system (M = K, Na, Li). Nucleophilic substitution of the halogen in the dihaloethanes by the oximate anion to give the corresponding ethylene glycol bis (imido ether) is a side reaction. The effect of the reaction conditions on the yields of products and the selectivity of the process was examined.

Electron-excited state of azoles and their 1-vinyl and 1-ethyl derivatives

Electron-excited state of azoles and their 1-vinyl and 1-ethyl derivatives

Pyrroles from ketoximes and acetylene 8. Synthesis of 4,5,6,7-tetrahydroindole and its 1-vinyl derivative

4,5,6,7-Tetrahydroindole or 1-vinyl-4,5,6,7-tetrahydroindole was obtained in 81 and 93% yields, respectively, by reaction of cyclohexanone oxime with acetylene at 90–140‡C in the presence of alkali metal hydroxides or alkoxides in dimethyl sulfoxide (DMSO) or mixtures of DMSO with low-polarity or nonpolar solvents. The reaction is effective both in an autoclave (initial pressure 8–16 gage atm) and at atmospheric pressure.

Chromium(III) heterocomplexes—IV Isothiocyanato-complexes of chromium(III) with some monodentate imidazoles

Inner complexes of the general formulae, [Cr L 3(NCS) 3] and [Cr L 3(NCS)(OH) 2] ( L = imidazole, and its 1-methyl, 1-ethyl and 1-vinyl derivatives), have been prepared by substitution in K 3[Cr(NCS) 6] and characterised. The 2-alkyl (methyl, ethyl and isopropyl) imidazoles from complexes of the types [Cr L 3(NCS) 3] and [Cr L 2(NCS) 3H 2O] by similar substitutions. The room-temperature magnetic moments (3.64–3.94 B.M.) are characteristic of chromium(III) in octahedral site symmetry. The N-bonding of thiocyanate has been suggested on the basis of v-CN (2130-2105 cm −1), v-CS (865-795 cm −1) and δ-NCS (495-485 cm −1). The electronic spectral bands have been analysed to determine the parameters, 10Dq, B and β, on the bases of which the relative positions of the ligands have been suggested in the spectrochemical and nephelauxetic series.