Acetylenic Compounds Research Articles

Bioactive acetylenic metabolites

This article focuses on anticancer, and other biological activities of acetylenic metabolites obtained from plants and fungi. Acetylenic compounds belong to a class of molecules containing triple bond(s). Naturally occurring acetylenics are of particular interest since many of them display important biological activities and possess antitumor, antibacterial, antimicrobial, antifungal, and immunosuppressive properties. There are of great interest for medicine, pharmacology, medicinal chemistry, and pharmaceutical industries. This review presents structures and describes cytotoxic activities of more than 100 acetylenic metabolites, including fatty alcohols, ketones, and acids, acetylenic cyclohexanoids, spiroketal enol ethers, and carotenoids isolated from fungi and plants.

New Tricks for Old Molecules: Development and Application of Porous N‐doped, Carbonaceous Membranes for CO2 Separation

A new strategy is successfully applied to "old" acetyl compounds. A free-standing, porous, N-doped carbonaceous membrane is facilely prepared from the thermal treatment of a pyrrole-ring-containing polymeric membrane based on the superacid-catalyzed copolymerization of acetyl monomers. An exceptional ideal CO2 /N2 permselectivity of 43.2 is achieved with a good CO2 permeability of 1149.3 Barrer, exceeding the recent upper bound for CO2 /N2 .

New Antibacterial Germacrene from Verbesina negrensis

Several health benefits have been attributed to members of the Verbesina genus, including promotion of urinary and gastrointestinal health. Verbesina species are also reported to exhibit antibacterial, antiparasitic, and antioxidant activities. Although members of the Verbesina genus produce various pharmacologically relevant chemicals as secondary metabolites, including eudesmanes, flavonoids, guanidine alkaloids, acetylenic compounds, and germacrenes, the active compounds required for these benefits remain unknown. To investigate potential antimicrobial activities of Verbesina negrensis, crude extracts from plant aerial structures were evaluated. Following chemical fractionation, the chloroformic extract from Verbesina negrensis was subjected to bioassay-guided isolation using disk diffusion assays to determine antimicrobial activity. The active compound was characterized as 6β-cinnamoyloxy-1β-hydroxy-10α-metoxy-3-oxo-germacra-4,5Z-ene (1). Fractions containing 1 inhibited both Enterococcus faecalis (ATCC 29 212) and Staphylococcus aureus (ATCC 29213). The MIC for 1 was determined by microbroth dilution assay to be 64 µg/mL for both E. faecalis and S. aureus.

Chemical and Biological Aspects of the Genus Verbesina

The current paper reviews the published literature up to March 2012 regarding the phytochemical components and biological activities of Verbesina species (Asteraceae). A compilation of compounds isolated from several members of this genus is presented. Eudesmanes are the most common secondary metabolites found within this genus. Flavonoids, guanidine alkaloids, acetylenic compounds, and several other terpenes with a great variety of hydrocarbon skeletons have also been isolated. The botanical classification, ethnopharmacology and pharmacological applications of Verbesina species are discussed. Keywords: Antihypertensive, asteraceae (compositae), eudesmanes, guanidine alkaloids, verbesina, terpenoids.

Recent Advances in the Synthesis of 1-Monosubstituted 1,2,3-Triazoles

1-Monosubstituted 1,2,3-triazoles have widespread applications in diverse fields, and their preparation has attracted increasing attention. This review mainly covers the modern advances in the synthesis of these heterocycles based on different methods including the substitution of 1H-1,2,3-triazole and cycloaddition reactions involving moieties, such as acetylene, substituted acetylene,and vinyl compounds, among others.

Synthesis of some Acetylenic Morpholine Derivatives via Grignard Reactions

New derivatives for acetylenic morpholine were prepared. Acetylenic amine (Npropargyl morpholine 1) was synthesized by the reaction of propargyl bromide with morpholine in aqueous medium. This compound was used as a synthone for hydroxy acetylenic compounds. Compound (1) was converted to the Grignard reagent (2) by the reaction with methyl magnesium iodide. The reaction of the intermediate (2) with different carbonyl compounds afforded hydroxy acetylenic compound (3). Finally, prepared Npropargyl ether morpholino (4a-i) was prepared by the reaction of the hydroxy acetylenic compound with chloro acetanilide, benzyl chloride via willamson reaction. The structure of the synthesized compounds has been elucidated by the available physical and spectral methods.

ChemInform Abstract: A Facile One‐Pot Synthesis of Substituted Quinolines via New Multicomponent Reaction.

AbstractQuinoline derivatives (IV), (VI) are efficiently obtained in a one‐pot three‐component reaction of alkyl 4‐chloroacetate or ethyl chloropyruvate and activated acetylenic compounds in the presence of the nucleophilic form of isatin in water.

Condensation of phenols and alcohols with 1,2-dichloroethyl-gem-dichlorocyclopropanes

Dichlorocarbenation of 3,4-dichlorobut-1-ene by Makosza method results in the stereoisomeric 1,2-dichloroethyl-gem-dichlorocyclopropanes in a 1:1 ratio. The reaction of the mixture of stereoisomeric gem-dichlorocyclopropanes with phenols and alcohols in dimethylsulfoxide in the presence of solid sodium hydroxide gives rise to the corresponding ketals containing the exocyclic double and triple bonds. In this case, the acetylene compounds dominate in the reaction products. The ratio of the reaction products containing the double and triple bonds depends on the nucleophile nature.

One‐Pot Three‐Component Synthesis of Oxazine Derivatives in Water

A one‐pot synthesis of oxazine derivatives via reaction between activated acetylenic compounds, benzoyl cyanide, and N‐nucleophiles in water as the solvent is described‎.

ChemInform Abstract: Facile Synthesis of Phosphonates via Catalyzed‐Free Multicomponent Reactions in Water.

AbstractReaction of activated acetylenic compounds with trivalent phosphorus nucleophiles in the presence of a benzofuranyl derivative or hydroxycoumarin leads to a facile synthesis of the stable and functionalized phosphonates (IV) and (VI) in good yields.

Selective hydrosilylation of alkynes with a nanoporous gold catalyst

The hydrosilylation of acetylenic compounds proceeded smoothly in the presence of a reusable nanoporous gold catalyst under mild conditions and the β-(E)-cis-addition products were obtained in good to high yields regio- and stereoselectively.

Regioselective Syntheses of 3-Benzyl-Substituted 7H-Thiazolo[3,2-a]pyrimidine-7-ones through Palladium-Catalyzed Heteroannulation of Acetylenic Compounds

An efficient synthesis of 3-benzyl-substituted 7H-thiazolo[3,2-a]pyrimine-7-ones in acetonitrile is accomplished via Pd- and Cu-catalyzed reaction of 2-mercaptopropargylpyrimidone with various aryl iodides in the presence of triethylamine as the base.

ChemInform Abstract: Analogous Porous Metal—Organic Frameworks: Synthesis, Stability and Application in Adsorption

AbstractReview: 114 refs.

Expeditious Solvent-Free Synthesis of Chromene Derivatives via Three- Component Reactions of N-Nucleophiles

Multicomponent reactions involving 4-hydroxycumarine, activated acetylenic compounds and N-nucleophiles under solvent-free conditions were investigated. The reactions could also be extended to quinoline or CH-acides. Substituted chromen could be obtained from this routine, which may have potential applications in drugs fields.

An Experimental and Theoretical Study on Influence of H‐bonding on the Synthesized Azo Derivatives Structures

AbstractWe have reported a simple and efficient reaction for the synthesis of some new functionalized azo structures which were prepared by electron deficient acetylenic compounds in the presence of triphenylphosphine. The characterization of the synthesized azo compounds has been determined by FTIR, UV‐Vis, 1H NMR, 13C NMR and Mass spectroscopic techniques. The influence of H‐bonding on the products has been shown by different experimental analysis. Also, the regioselectivity of the reaction, tautomerization equilibrium and the stability of products was investigated using DFT calculations at the B3LYP/6‐31G level of theory.

ChemInform Abstract: One‐Pot Synthesis of 1‐Ethynylcyclohexyl Vinyl Ether from Cyclohexanone and Acetylene.

Vinyl ether derived from tertiary acetylenic alcohols have not been reported so far. The reason is that such alcohols are unstable on heating in the presence of bases (classical retro-Favorskii reaction) [1–3]. Nevertheless, insofar as the Favorskii reaction is reversible, we can presume that O-vinylation of a tertiary acetylenic alcohol present in the reaction mixture even at a small concentration should eventually lead to expected vinyl ether due to continuous displacement of the equilibrium (Scheme 1). Therefore, vinyl ethers of tertiary acetylenic alcohols could be obtained in one step by heating ketones with acetylene in the presence of a base. Screening of the reaction conditions and superbasic catalytic systems, as well as of ketones and acetylenic compounds used as reactants, has shown that 1-ethynylcyclohexyl vinyl ether (III) is indeed formed upon treatment of cyclohexanone (I) with acetylene in the presence of a base. In the reaction performed in a suspension of KOH in DMSO (molar ratio I–KOH 1 : 1) at 90°C under acetylene pressure the yield of vinyl ether III reached 40% (Scheme 2). An important condition is acetylene pressure which ensures its high concentration in the liquid phase and favors displacement of equilibrium toward formation of 1-ethynylcyclohexan-1-ol (II) which then undergoes vinylation (Scheme 2). ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 6, pp. 858–859. © Pleiades Publishing, Ltd., 2012. Original Russian Text © B.A. Trofimov, E.Yu. Shmidt, I.A. Bidusenko, E.V. Ivanova, N.V. Zorina, A.I. Mikhaleva, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 6, pp. 860–861.

Variation in the Volatile Constituents of Different Plant Parts of Ligusticopsis wallichiana from Western Himalaya, India

The essential oil composition of the leaves, stem, flowers and roots of Ligusticopsis wallichiana (DC.) Pimenov & Kljuykov were analyzed by GC-FID and GC-MS methods. Forty-five constituents, forming 93.2%-97.8% of the oil compositions, were dominated by acetylenic (31.5%-92.8%) compounds and sesquiterpenoids (0.3%-44.4%). The leaf essential oil was mainly composed 3,5-nonadiyne (35.8%), beta-selinene (20.9%), alpha-funebrene (10.1%) and (Z)-falcarinol (6.1%). The stem oil was dominated by acetylenic compounds (73.8%) represented by 3,5-nonadiyne (67.8%) and (Z)-falcarinol (5.7%). On the contrary, the major components of the flower essential oil were sesquiterpenoids (37.5%), such as germacrene D (16.6%), alpha-funebrene (7.4%), and acetylenic compounds (31.5%), such as (Z)-falcarinol (21.0%) and 3,5-nonadiyne (10.0%). Monoterpenoids constituted 23.9% of the flower oil with limonene (19.9%) as the single major constituent. The essential oil of the roots was dominated by 3,5-nonadiyne (90.5%). The results showed considerable qualitative and quantitative variations in the essential oil compositions of the different plant parts of L. wallichiana. (Z)-Falcarinol (1.9%-21.0%) and alpha-funebrene (0.1%-10.1%) were reported for the first time from the essential oils of L. wallichiana.

Synthesis of a New Class of Highly Functionalized Phosphorus Ylides Containing Heterocyclic Compounds

AbstractThe zwitterionic intermediate generated from the reaction of triphenylphosphine with electron deficient acetylenic compounds was trapped by various NH acids. The synthesis resulted in a new class of highly functionalized heterocyclic compounds. Some of the reactions produced E and Z isomers. And the stability and transformation of them were studied by dynamic 1H NMR and density functional theory (DFT) calculations.

Antifungal activity of enynediesters and acetylenic compounds obtained by synthesis and in silico prediction pattern

In this paper, we describe the preparation and synthesis of several enynediesters, conjugated diynes and acetylenic compounds from starting materials comprising one hydroxyl and one acetylenyl group and their antifungal activity. For synthesis of the compounds, a combined solution of N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridin in CH2Cl2 was added to a solution of compound containing one hydroxyl group and propiolic acid at 0°C over a period of 1 hour. As the reaction occurs under very mild conditions this procedure offers easy access to 1,3-diynes in a very short reaction time. Some of the compounds are commercially available. The antifungal activity of these compounds against Candida albicans, Aspergillus niger and Saccharomyces cerevisiae was investigated. Among the compounds tested, some showed potent activity. The results of synthesis showed that the direct coupling of two acetylenes is suitable for the preparation of diynes. The in silico study used here was able to predict if the compound with triple bond can posses the antifungal activity with a reasonable prediction. The result of investigations at both in silico and in vitro levels confirmed that the position of the triple bond is important for antifungal activity.

A Facile One‐Pot Synthesis of Substituted Quinolines via New Multicomponent Reaction

An efficient synthesis of quinoline derivatives is described via the reaction between ethyl chloropyruvate or alkyl 4‐chloroacetoacetate and activated acetylenic compounds in the presence of nucleophilic form of isatin in water as the solvent. Nucleophilic form of isatin is produced from the reaction of isatin and triethylamin.