ChemInform Abstract: CYANOACETYLENE AND ITS DERIVATIVES. 1. SYNTHESIS OF SUBSTITUTED CYANOACETYLENES AND THEIR REACTION WITH GLYCOLS

Skvortsov, Yu. M.; Малькина, А. Г.; Volkov, A. N.; Трофимов, Б. А.; Oleinikova, E. B.; Kazin, I. V.; Gedymin, V. V.

doi:10.1002/chin.197837238

Cited by 3 publications

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“…[12] Methyl propiolate (2a) is a commercial reagent ("Merck"), and cyanophenylacetylene (2b) was obtained by a literature procedure. [10] Column and thin-layer chromatography were carried out on neutral …”

Section: Methodsmentioning

confidence: 99%

“…Because cyanophenylacetylene is readily available from bromophenylacetylene and copper cyanide, [10] these reactions are of general character and significantly contribute to the chemistry and application of 2-functionalized imidazoles. To extend these findings, we tried to capture the intermediate zwitterions generated from 1-substituted imidazole and electron-withdrawing acetylenes by an appropriate electrophile as a third component.…”

Section: Introductionmentioning

confidence: 99%

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C2‐Functionalization of 1‐Substituted Imidazoles with Aldehydes and Electron‐Deficient Acetylenes: A Novel Three‐Component Reaction

et al. 2010

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

C2‐Functionalization of 1‐Substituted Imidazoles with Aldehydes and Electron‐Deficient Acetylenes: A Novel Three‐Component Reaction

et al. 2010

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“…Tris[2-(4-pyridyl)ethyl]phosphine oxide (1) was prepared by a literature procedure 7 and 3-(1-hydroxycyclohexyl)-2-propynenitrile (2) was obtained using techniques described elsewhere. 9,10…”

Section: Methodsmentioning

confidence: 99%

Reaction of 3-(1-Hydroxycyclohexyl)-2-propynenitrile with Tris[2-(4-pyridyl)ethyl]phosphine Oxide

Трофимов¹,

Andriyankova²,

Shaikhudinova³

et al. 2002

Synthesis

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3-(1-Hydroxycyclohexyl)-2-propynenitrile reacts with tris[2-(4-pyridyl)ethyl]phosphine oxide to form mono-, bis-and tris{5-spirocyclohexyl-4-cyanomethylene-1,3-oxazolidine[3,2-a]-2-[4-(1,2-dihydropyridyl)]ethyl}phosphine oxides.Activated acetylenic compounds, in particular the methyl ether of acetylenecarboxylic acid and the dimethyl ether of acetylenedicarboxylic acid, form (normally, in low yields) heterocyclic compounds such as quinolizines, indolizines, cyclazines, by reaction with pyridine and pyridine derivatives. 1,2 Recently, 3 we have found that the reaction of pyridine and its derivatives with nitriles of a,bacetylenic g-hydroxy acids (the reactivity of which has been discussed in reviews 4,5 ) proceeds in high yields under mild conditions (r.t., without solvents and catalysts) involving the hydroxy group to give a new heterocyclic system, oxazolidinedihydropyridines. In the present work we have used the reaction for the synthesis of polyfunctional phosphine oxides from nitriles of a,b-acetylenic ghydroxy acids and recently available tris[2-(4-pyridyl)ethyl]phosphine oxide. 6,7 The present work reports some results of the research into the reaction of tris[2-(4-pyridyl)ethyl]phosphine oxide (1) with 3-(1-hydroxycyclohexyl)-2-propynenitrile (2) performed in order to obtain new organophosphorus compounds containing pyridine and oxazolidine rings, which are regarded as rather promising intermediates for organic synthesis and biologically active compounds. The reaction of hydroxycyclohexylpropynenitrile 2 with phosphine oxide 1 occurs at 20-25 °C in acetonitrile and a molar ratio of 1:10 (1:2) for 10 hours to form selectively tris{5-spirocyclohexyl-4-cyanomethylene-1,3-oxazolidine[3,2-a]-2-[4-(1,2-dihydropyridyl)]ethyl}phosphine oxide (3) in 90% yield (Scheme).The initial stages are characterized by the formation of zwitterionic intermediates A, B 3 further stabilized by closure to a 1,3-oxazolidine ring.Under comparable conditions (MeCN, 20-25 °C, 10 h) at a three-fold molar excess of the nitrile 2 the formation of mono{5-spirocyclohexyl-4-cyanomethylene-1,3-oxazolidine[3,2-a]-2-[4-(1,2-dihydropyridyl)]ethyl}phosphine oxide (4), bis{5-spirocyclohexyl-4-cyanomethylene-1,3-oxazolidine[3,2-a]-2-[4-(1,2-dihydropyridyl)]ethyl}-phosphine oxide (5) and tris{5-spirocyclohexyl-4-cyanomethylene-1,3-oxazolidine[3,2-a]-2-[4-(1,2-dihydropyridyl)]ethyl}phosphine oxide (3) occurs (total yield 55%, 3:4:5 ratio = 2:3:4) (Figure 1).An increase in the reaction time of up to 36-40 hours does not affect the ratio of isomers. It was not possible to separate the adducts (column chromatography, fractional crystallization). The reaction of phosphine oxide 1 with acetylene 2 in octane (1:2 molar ratio = 1:3, 20-25 °C) needs more time (up to 60 h) to be completed. In this case the ratio of adducts 3-5 does not change, the total yield being 40%. SchemeDownloaded by: University of Pittsburgh. Copyrighted material.

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“…The purity of the initial [5,6] and obtained compounds was checked by TLC on Silufol UV-254 plates. The preparative separation of the reaction mixtures was carried out by column chromatography on silica gel Chemapol (40100 mm) at gradient elution with 210% ethyl acetate solutions in hexane.…”

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confidence: 99%

Nitration of phenylpropiolic acid derivatives in HSO3F and reactions of vinyl type cations formed therefrom

2004

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Nitration of phenylpropiolic acid derivatives ArCºCX (X=CN, CO 2 Me) in HSO 3 F at -75...50°C afforded mononitro compounds, for instance, m-O 2 NC 6 H 4 CºCX. Vinyl type cations generated in HSO 3 F from methyl 3-arylpropiolates ArC + =CHCO 2 Me react along two pathways. The first among them results in formation of fluorosulfonates ArC(OSO 2 F)=CHCO 2 Me, and the second one after the attack of vinyl cation on the aryl moiety of the substrate affords a dimer that on nitration is converted into a nitro product with conserved triple bond.

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ChemInform Abstract: CYANOACETYLENE AND ITS DERIVATIVES. 1. SYNTHESIS OF SUBSTITUTED CYANOACETYLENES AND THEIR REACTION WITH GLYCOLS

Abstract: Läßt man Kaliumcyanid in Alkohol auf Bromethinyl‐dimethylcarbinol (I) einwirken, so entstehen über das Cyanethinyldimethylcarbinol (II) die Nitrile (III) und (IV).

Cited by 3 publications

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C2‐Functionalization of 1‐Substituted Imidazoles with Aldehydes and Electron‐Deficient Acetylenes: A Novel Three‐Component Reaction

C2‐Functionalization of 1‐Substituted Imidazoles with Aldehydes and Electron‐Deficient Acetylenes: A Novel Three‐Component Reaction

Reaction of 3-(1-Hydroxycyclohexyl)-2-propynenitrile with Tris[2-(4-pyridyl)ethyl]phosphine Oxide

Nitration of phenylpropiolic acid derivatives in HSO3F and reactions of vinyl type cations formed therefrom

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