Pyrroline Derivatives Research Articles

Recyclization of ?-hydroximino-?-oxo-3-imidazoline and 3-imidazoline-3-oxide derivatives to pyrrolines

Reaction of α-hydroximino-β-oxo-3-imidazoline and 3-imidazoline-3-oxide derivatives with hydroxylamine results in recyclization leading to the formation of pyrroline derivatives, namely dioxines or nitrosooximes. Oxidation of dioximinopyrroline gives a pyrrolofuroxane.

Cyclisation of imine radicals derived from sulphenylimines: A simple access to Δ 1-pyrrolines.

Treatment of various sulphenylimines containing a γ,δ—double bond with tri-n-butylstannane affords the corresponding pyrroline derivatives in good yield.

Stable vinylnitroxyl radicals, pyrroline derivatives

The first representatives of stable vinyl nitroxides,viz., radicals of the pyrroline series, were synthesized.

Multiple radical additions starting with iminyl radicals derived from sulphenylimines.

Iminyl radicals obtained by tri-n-butylstannane induced cleavage of S-phenyl sulphenylimines readily cyclise onto suitably located double bonds. The intermediate carbon centered radical can be trapped by a variety of electron-poor olefins thus providing an entry into synthetically useful pyrroline derivatives.

ChemInform Abstract: Transformation of N‐Tosyl‐2‐(1,3‐butadienyl)aziridine into N‐Tosyl‐2‐ethenyl‐3‐pyrroline.

AbstractButadienyl‐aziridines such as (I) or ‐azetidines such as (III) activated by N‐tosyl groups rearrange smoothly to vinyl pyrroline derivatives such as (II) or vinylpiperidines such as (IV) in the presence of a catalytic amount of Pd(PPh3)4.

Synthesis of 1-Benzoylpyrroline Derivative and Related Compounds

Several new pyrroline derivatives were prepared from 4-amino-1-benzoyl-3-benzylidene-4-pyrroline- 2-one (4).

On the crossed-aldol reaction of cyclohexane-1,2-dione with acetone, and the preparation of pyrroline derivatives from the product

Acetone reacts with cyclohexane-1,2-dione, on refluxing in the presence of potassium carbonate, to give the crossed-aldol product, 2-hydroxy-2-acetonylcyclohexanone, 2 (R=CH3). Other methyl ketones react similarly with cyclohexane-1,2-dione. This is believed to be a consequence of unfavorable dipole interaction in the 1,2-dione. The product, on reaction with liquid ammonia, afforded the 5-amino-4-hydroxy-1-pyrroline derivative, 5, which was reduced with lithium aluminum hydride to the 3-hydroxy-1-pyrroline, 7.

ChemInform Abstract: New Antiarrhythmic Agents. 2,2,5,5‐Tetramethyl‐3‐pyrroline‐3‐carboxamides and 2,2,5,5‐Tetramethylpyrrolidine‐3‐carboxamides.

AbstractAus dem Dibrompiperidon (I) erhält man durch Reaktion mit den Aminen (II) bzw. (IV) in einer Favorski‐Umlagerung die Pyrroline (IIIa) bis (IIIg) und (V).

New antiarrhythmic agents. 2,2,5,5-Tetramethyl-3-pyrroline-3-carboxamides and 2,2,5,5-tetramethylpyrrolidine-3-carboxamides.

N-(omega-Aminoalkyl)-2,2,5,5-tetramethyl-3-pyrroline- or -pyrrolidine-3-carboxamides were acylated on the primary amino group of the side chain by means of reactive acid derivatives (acid chlorides, activated esters, phthalic anhydrides, phthalimide, 2-alkyl-4H-3,1-benzoxazin-4-ones) or they were alkylated by forming the Schiff bases and subsequent sodium borohydride reduction. Other tetramethyl-3-pyrrolinecarboxamide compounds were synthesized by acylating the aminoalkyl compounds with 2,2,6,6-tetramethyl-3,5-dibromo-4-piperidinone in a reaction involving Favorskii rearrangement. Saturation of the double bond of some pyrroline derivatives furnished the pyrrolidinecarboxamides. The new compounds of each type were active against aconitine-induced arrhythmia and several of them had higher activity and better chemotherapeutic index than quinidine. A few selected examples from each type of the active new compounds showed strong activity against ouabain-induced arrhythmia; for comparison known drugs such as lidocaine, mexiletine, and tocainide were selected. The most potent compounds were oxidized to the paramagnetic nitroxides and the latter were reduced to the N-hydroxy derivatives; these products had no or only decreased antiarrhythmic effect.

1,3‐Dipolare Addition von 2‐Benzonitrilio‐2‐propanid an 7‐Methylthieno[2,3‐c]pyridin‐1,1‐dioxid und Folgereaktionen

1,3‐Dipolar Addition of 2‐Benzonitrilio‐2‐propanid to 7‐Methylthieno[2,3‐c]pyridine 1,1‐Dioxide and Subsequent ReactionsThe addition of dipole 2, generated photochemically from 2,2‐dimethyl‐3‐phenyl‐2H‐azirine (1), to 7‐methylthieno[2,3‐c]pyridine 1,1‐dioxide yields the pyrroline derivative 4 as a major product and regioisomer 5 in low yield. Compound 4 can be transformed into the pyrrolidine derivative 11 by ring opening, loss of SO2 and hydrogenation. Bromopyrroline derivative 14 gives either by dehydrohalogenation compound 18 or, by substitution, nitrile 17 or ethoxy derivative 19. Substitution of 14 and ring opening yields methoxypyrrole derivative 20, which gives access to the unstable hydroxypyrrole and hydroxypyrrolidine derivative 28 resp. 30. The vinylsulfone 18 is the starting material for addition‐ring‐cleavage reactions. Oxidation of pyrroline derivative 4 gives epoxy‐substituted N‐oxide 39 and di‐N‐oxide 40; and oxidative transformation of pyrrolidine derivative 11 yields the (hydroxymethyl)pyridylpyrrolidine derivative 45.

Photochemistry of 9-[2-(N-Substituted Aminotnethyl)-1-naphthyl]phenanthrenes. Intramolecular Addition of Amines to Excited State of Phenanthrene in Conformationally Rigid System

Abstract Irradiation of benzene solutions of 9-[2-(N-substituted aminomethyl)-1-naphthyl]phenahthrenes (3a–d) gave pyrroline derivatives by the attack of the NH group on the C-9 carbon atom of the phenanthrene ring. The reactions were highly selective in regio- and stereochemical senses, and occurred through exciplexes formed by intramolecular interaction between the ammo group and the excited phenanthrene moiety in 3a–d. Mechanistic features of these photoreactions are discussed on the basis of chemical and photochemical properties of substrates and products.

Reactions of diphenylbutadiyne with carbodiimides in the presence of iron carbonyls

Reactions of diphenylbutadiyne with diarylcarbodiimides in the presence of iron carbonyls produce three types of pyrroline derivative, 1-aryl-3-phenyl-4-phenyl-ethynyl-5-aryliminopyrrolin-2-one, 1-aryl-4-phenyl-3-phenylethynyl-2,5-bis(arylimino)pyrroline and 1,1′-diaryl-3,3′-diphenyl-2′,5,5′-tris(arylimino)-4,4′-bipyrrolin-2-one (Ar = phenyl, p-tolyl and p-chlorophenyl). A similar reaction using dicyclohexylcarbodiimide gives 1-cyclohexyl-3-phenyl-4-phenylethynyl-5-cyclohexyliminopyrrolin-2-one as the sole product. Acid hydrolysis of the above phenylethynyl-pyrrolinones and -pyrrolines affords the corresponding phenylethynylpyrroline-2,5-diones. The bipyrrolines have been similarly hydrolyzed to the bipyrroline-2,2′,5,5′-tetrone derivatives. The reaction of the phenylethynylpyrrolinone (Ar = phenyl) with diphenyl or di- p-tolyl carbodiimide in the presence of Fe(CO) 5 gives the bipyrroline derivative as the isocyanide insertion product. The arylisocyanide iron carbonyl complexes Fe(CO) 5 − m (CNAr) m are considered to be the active species for the formation of phenylethynyl bis(imino)pyrrolines and bis(imino)pyrroline rings in bipyrrolines.

Reaction of 1-Nitro-2, 2-bis(methylthio)ethylene. II. Synthesis of 2-Hydroxyimino-3-methylthio-5-oxopyrroline Derivatives

Methyl 1-cyano-2-methylthio-3-nitrocrotonate, 1-phenyl-2-methylthio-3-nitrocrotonitrile, and 1-cyano-2-methylthio-3-nitrocrotonamide, which contain cyano and nitro group at 1-and 3-position, were refluxed in MeOH or EtOH to give 2-hydroxy-3-methylthio-5-oxopyrroline derivatives, with ring closure between cyano and nitro group. The reaction of methyl 1-cyano-2-methylthio-3-nitrocrotonate with equimolar amount of amine gave methyl 2-hydroxy-3-amino-5-oxopyrroline-4-carobxylate which was replaced methylthio with amino group and with ring closure. However, with excess amine gave amine salt of nitro group, and also replaced with methylthio group. The raction of pyrroline derivatives with active methylene compounds gave the corresponding substituted compounds.

Synthesis of Pyrrole Nucleosides by the Photo-dehydrogenation of Δ3-Pyrroline Derivatives

Abstract 1-(β-d-Glucopyranosyl)pyrrole (VI) was prepared by the photo-dehydrogenation of 1-(2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl)-Δ3-pyrroline (IV) in the presence of oxygen and benzophenone, followed by deacetylation. The nucleoside (VI) was also derived directly from 1-(d-glucosyl)-Δ3-pyrroline (III) by photochemical means. The synthesis of 1-(α-d-ribofuranosyl)-pyrrole (XI), its β-anomer (XII), and 1-(β-d-ribopyranosyl)pyrrole (XIII) was accomplished by photodehydrogenation of 1-(2′,3′-O-isopropylidene-d-ribosyl)-Δ3-pyrroline, followed by the removal of the protecting group. The treatment of 1-(2′,3′-O-isopropylidene-α-d-ribofuranosyl)pyrrole (VIII) with 80% aqueous acetic acid afforded a novel α-cyclonucleoside, 1-(2-C,2′-O-isopropylidene-α-d-ribofuranosyl)pyrrole (XIV), besides XI–XIII. The formation of pyrrole by the photodehydrogenation of Δ3-pyrroline (II) itself was confirmed by gas chromatography.

Synthesis of Pyrrole Nucleosides by Photodehydrogenation of a Δ3-Pyrroline Derivative

Synthesis of Pyrrole Nucleosides by Photodehydrogenation of a <i>Δ</i>3-Pyrroline Derivative

Enamine chemistry—X : The reaction of enamines with α-chloroacrylonitrile

Addition of α-chloroacrylonitrile to aldehyde enamines has been shown to give cyclobutanes, whereas addition to enamines derived from cyclic ketones produces quaternary salts. It is proposed that these salts result from an intramolecular reaction of initially formed alkylation products. Ethyl β-methylaminocrotonate gives a pyrroline derivative, in which case the initial alkylation product undergoes an intramolecular condensation with subsequent hydrogen chloride elimination. The dienamine, 1-N-morpholino-1,3-butadiene, adds to α-chloroacrylonitrile by a Diels—Alder reaction.

Cyclization towards carbon-carbon double bond. 3. A new synthesis of 1-pyrroline derivatives and a synthesis of 1,2-dialkyl-3-diphenylmethylenepyrrolidine alkyl halide, an anti-acetylcholine substance.

2-Subsituted 3-diphenylmethylene-1-pyrrolines (III) were synthesized in one step by the reaction of 1, 1-diphenyl-1, 4-butanediol (VII), 2, 2-diphenyltetrahydrofuran (VI), or 4-bromo-1, 1-diphenyl-1-butene (V) with nitrile-stannic chloride complex. 2, 5-Dimethyl (XI) and 2, 5, 5-trimethyl-3-diphenylmethylene-1-pyrroline (XII) were obtained respectively from 1, 1-diphenyl-1, 4-pentanediol (IX) and 1, 1-diphenyl-4-methyl-1, 4-pentanediol (X). The fact that 2-methyl-3-isopropylidene-1-pyrroline (XIV) was obtained from 2-methyl-2, 5-pentanediol (XIII) and 2, 2-dimethyltetrahydrofuran (XV) by the same reaction was of interest in contrast with preparation of 1-pyrrolines (II) by the Ritter reaction. Reduction of the methiodide of III with sodium borohydride gave 1-methyl-2-alkyl-3-diphenylmethylenepyrrolidine. The methiodide of the 2-methyl compound (XVIc) was found to have a comparatively strong anti-acetylcholine activity.

The Synthesis and Transformations of a Steroid Pyrroline Derivative

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe Synthesis and Transformations of a Steroid Pyrroline DerivativeFrederick C. Uhle and F. SallmannCite this: J. Am. Chem. Soc. 1960, 82, 5, 1190–1199Publication Date (Print):March 1, 1960Publication History Published online1 May 2002Published inissue 1 March 1960https://doi.org/10.1021/ja01490a041RIGHTS & PERMISSIONSArticle Views94Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Extension of the Bischler-Napieralski reaction—II: Synthesis of pyrroline derivatives

Acyl derivatives of 4-phenyl-but-3-enylamine on treatment with phosphoryl chloride gave good yields of pyrrolines. Pyridine derivatives were not obtained.