Phenylpropargyl Aldehyde Research Articles

Extraction of Acetals of Phenyl-Propargyl Aldehyde Using the Metod of Liquid Column Chromotography

The interreaction of substrates containing cyclopropane fragment with initial allyl and butyl alcohol, the influence of bromide atom in a gem-dichlorocyclopropane ring on the direction of the reaction with alcohol. The reaction of O-alkyllation 2-bromide-2-phenyl-gem-dichlorocyclopropane with alcohol in dimethylformamide with solid sodium hydroxide and without a phase transfer catalyst occurs selectively and produces the corresponding acetals of phenyl-propargyl aldehyde. The optimal conditions were selected for the reaction. It was researched and established that gem-dichlorocyclopropanes with a bromide atom in the cycle can also participate in such transformations. Acetals of phenyl-propargyl aldehyde were extracted from the reaction mix using the method of liquid column chromotography

Repetition of chemistry from a recently retracted paper. A cautionary note

The base-catalyzed condensation reaction between (E)-4-phenylbut-2-enal and phenylpropargyl aldehyde recently reported in the literature to provide formylcyclobutadiene was repeated under the published conditions. The product obtained was identified as (E)-5-phenyl-2-((E)-styryl)pent-2-en-4-ynal rather than the reported 2-phenyl-3-styrylcyclobutadiene-1-carboxaldehyde. The structure assignment is supported by NMR and IR data and a x-ray structure of the crystalline alcohol obtained by Luche reduction.

NMR and experimental reinvestigation of the condensation reaction between γ-methylene-α,β-unsaturated aldehydes and propargyl aldehydes.

The condensation reaction between a γ-methylene-α,β-unsaturated aldehyde and phenylpropargyl aldehyde was revisited and, guided by extensive DFT calculations of NMR shifts, was found to afford a deconjugative aldol condensation product. In this manner, a simple protocol for the preparation of valuable cross-conjugated oxatrienes was uncovered.

Asymmetric syntheses of diarylheptanoid natural products (−)-centrolobine and (−)-de- O-methylcentrolobine via hetero-Diels–Alder reaction catalyzed by dirhodium(II) tetrakis[( R)-3-(benzene-fused-phthalimido)-2-piperidinonate

Catalytic asymmetric syntheses of (−)-centrolobine and (−)-de- O-methylcentrolobine have been achieved, incorporating a hetero-Diels–Alder (HDA) reaction between 4-aryl-2-silyloxy-1,3-butadienes and phenylpropargyl aldehyde derivatives as a key step. The HDA reaction using dirhodium(II) tetrakis[( R)-3-(benzene-fused-phthalimido)-2-piperidinonate], Rh 2( R-BPTPI) 4, as a chiral Lewis acid catalyst provides exclusively cis-2,6-disubstituted tetrahydropyran-4-ones in up to 93% ee.

Process Development and Scale-Up of the PPAR Agonist NNC 61-4655

A scalable synthetic route of the nonselective but PPARα-preferring potent PPAR agonist NNC 61-4655 aimed for treatment of type 2 diabetes was developed. The synthetic pathway comprises the convergent synthesis and coupling of the two key intermediates E-5-(chloropent-3-en-1-ynyl)benzene 8 (prepared in a five-step synthesis in 18% overall yield) and (S)-2-ethoxy-3-(4-hydroxyphenyl)propanoic acid isopropyl ester 9. The 2-aminoethanol salt of NNC 61-4655 was selected in a preclinical salt selection program as the appropriate salt form for further development. More than 900 g of NNC 61-4655, 2-aminoethanol was finally synthesized under GMP in 98.7% purity. In comparison to the original medicinal chemistry route, starting from phenylpropargyl aldehyde 1, the overall yield towards NNC 61-4655 could be enhanced from 24 to 37%. An improved scalable two-step synthesis for 8 was developed on a laboratory scale (≥33−35% overall yield) shortly after the GMP batch.

Enantiopure 1-phosphanorbornadiene-2-carboxaldehydes

The reaction of phenylpropargyl aldehyde diethyl acetal with 1-phenyl-3,4-dimethylphosphole at 140°C or 1,2,5-triphenylphosphole at 170°C leads, after deprotection, to the corresponding 1-phosphanorbornadiene-2-carboxaldehydes 3 and 4 in 88 and 45% yields, respectively. The resolution of 3 and 4 was carried out by chromatography or fractional crystallization of the acetals derived from ( S,S)-1,2-diphenylethane-1,2-diol. The absolute configurations were established by X-ray analysis of one of these acetals or of a 2-bromomethyl derivative.

A Practical Synthesis of Phenylpropargyl Aldehyde from Phenylacetylene and N-Formylmorpholine

ADVERTISEMENT RETURN TO ISSUEPREVTechnical NoteNEXTA Practical Synthesis of Phenylpropargyl Aldehyde from Phenylacetylene and N-FormylmorpholineAtsuhiko ZankaView Author Information Technological Development Laboratories, Fujisawa Pharmaceutical Co. Ltd., 2-1-6 Kashima, Yodogawa-ku, Osaka, 532-8514, Japan Cite this: Org. Proc. Res. Dev. 2000, 4, 1, 46–48Publication Date (Web):December 1, 1999Publication History Received24 June 1999Published online1 December 1999Published inissue 1 January 2000https://doi.org/10.1021/op9900582Copyright © 2000 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views1112Altmetric-Citations8LEARN 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 Read OnlinePDF (53 KB) Get e-AlertsSUBJECTS:Aldehydes,Chemical reactions,High-performance liquid chromatography,Hydrolysis,Reagents Get e-Alerts

Selective Reactions of Functionalized Ruthenium(II) σ-Alkynyl Complexes with Dicobalt Octacarbonyl and Tetracobalt Dodecacarbonyl: Synthesis of Cyclopentenone Derivatives via Intermolecular Pauson−Khand Reactions

Treatment of [Ru{C⋮CCPh2(C⋮CH)}(η5-C9H7)(PPh3)2] (1) with [Co2(CO)8] leads to the formation of the adduct [Ru{C⋮CCPh2(μ2-η2-C⋮CH)Co2(CO)6}(η5-C9H7)(PPh3)2] (3) through the selective coordination of the Co2(CO)6 fragment at the terminal alkyne group on 1. Similarly, the enynyl complex [Ru{C⋮CCHCH(C⋮CPh)}(η5-C9H7)(PPh3)2] ((E,Z)-2), prepared via a Wittig reaction from [Ru{C⋮CCH2(PPh3)}(η5-C9H7)(PPh3)2][PF6] (5) and phenylpropargyl aldehyde, also reacts with [Co2(CO)8] to yield selectively the adduct [Ru{C⋮CCHCH(μ2-η2-C⋮CPh)Co2(CO)6}(η5-C9H7)(PPh3)2] ((E,Z)-6). Protonation of complexes 3 and (E,Z)-6 with HBF4·Et2O affords the cationic vinylidene derivatives [Ru{CC(H)CPh2(μ2-η2-C⋮CH)Co2(CO)6}(η5-C9H7)(PPh3)2][BF4] (4) and [Ru{CC(H)CHCH(μ2-η2-C⋮CPh)Co2(CO)6}(η5-C9H7)(PPh3)2][BF4] ((E,Z)-7), respectively. Dicobalt adduct complexes 3 and (E,Z)-6 undergo Pauson−Khand cyclization processes with strained cyclic alkenes (norbornadiene and norbornene) to afford regioselectively the tricyclic cyclopentenone derivatives 8a,b, 9a,b, (E,Z)-10, and 11. (E,Z)-6 reacts with [Co4(CO)12] to give an unprecedented ruthenium(II) vinylidene complex containing a tetranuclear “butterfly” type cobalt cluster (12), which has been characterized by X-ray diffraction.

Unusual reaction of phenylpropargyl aldehyde with diethylamine and acetone cyanohydrin

An unusual product was obtained by the reaction of phenylpropargyl aldehyde with acetone cyanohydrin and diethylamine, which has the structure of 1,6-dicyano-1,6-bis(diethylamino)-3,4-diphenyl-1,5-hexadiene.

Syntheses with α‐heterosubstituted phosphonate carbanions. VIII. An unexpected entry into quinolines

AbstractThe carbanions derived of certain diphenyl‐1‐(4‐nitroanilino)‐1‐(substituted‐aryl)methanephosphonates reacted with phenylpropargyl aldehyde, giving not the expected yne‐enamines, but rather 2‐phenyl‐4‐benzyIquinolines.

A New Synthesis of 3-Aryl-5-Arylmethylene-2(5H)-Furanones

Abstract A recent report about the synthesis of di and tri-substituted 2 (5H)-furanones starting from bromoaldehydes and potassium phenyl-acetate1 prompts us to report our own studies on the preparation of 3-aryl-5-arylmethylene-2 (5H)-furanones (or butenolides) 1. We have earlier reported2 a general method for the synthesis of 1 from phenylpropargyl aldehyde, 2 and arylacetic acids. Although several methods have been reported for the synthesis of the parent compound 1 (R = R1 = Ph)3–6, these methods have not been extended to other substituted furanones. Saikachi and Taniguchi7 prepared 1 (R = 5-nitro-2-thenyl, R1 = 2-thenyl and 2-furyl) in 16–17% yields.

Dimerisation of polyacetylenic aldehydes with elimination of carbon monoxide

Hexa-2,4-diynal, octa-2,4-diynal, and octa-2,4,6-triynal (R[CC]n·CHO) dimerise in concentrated solution with evolution of carbon monoxide, to give products of the type R[CC]n– 1·CHC(CHO)·[CC]nR; above 100° even phenylpropargyl aldehyde reacts analogously. Both geometrical isomers of the ‘dimers’ were detected and characterised.

A new rearrangement of phenylpropargyl aldehyde

The authors have discovered a new rearrangement of phenylpropargyl aldehyde during the reaction with acetone cyanohydrin in the presence of triethylamine, leading to a mixture of cis- and trans-cinnamates.

PHENYLPROPARGYL ALDEHYDE

PHENYLPROPARGYL ALDEHYDE