Reaction Of Diphenylacetylene Research Articles

Simple Modifications for the Facile Preparation of 1,1,2,3,4,4‐Hexaaryl‐1,3‐butadienes

AbstractA facile preparation of 1,1,2,3,4,4‐hexaaryl‐1,3‐butadienes which are important molecules due to their aggregation‐induced emission (AIE) activity was achieved by simple modifications of the reaction conditions reported in the previous work. In this reaction system, the insertion of alkynes into the palladium−carbon bond will be accelerated by changing the palladium intermediate to the cationic one. When silver nitrate was used, the reaction of diarylalkynes with arylboronic acids took place smoothly under mild reaction conditions without any ligand to give the coupling diene products in excellent yields. On the contrary, the reaction hardly proceeded with silver oxide and silver carbonate. Poly(hexaphenyl‐1,3‐butadiene) (PHB) with a similar molecular weight to the previously prepared one was also synthesized from the reaction of diphenylacetylene with phenyldiboronic acid under mild reaction conditions.

Ru(0)-Catalyzed Synthesis of Borylated-Conjugated Triene Building Blocks by Cross-Dimerization and Their Use in Cross-Coupling Reactions

Abstract Borylated-conjugated polyenes are used widely as synthetic building blocks for the preparation of many biologically active molecules. Nevertheless, access to these building blocks has been limited. In this study, borylated-conjugated trienes were synthesized by Ru-catalyzed cross-dimerizations for use in cross-coupling reactions. A reaction of diphenylacetylene with (E)-butadien-1-ylboronic acid pinacol ester catalyzed by [Ru(naphthalene)(1,5-cod)] (10 mol %) at r.t., in benzene produced (1E,3E,5Z)-5,6-diphenylhexa-1,3,5-trien-1-yl boronic acid pinacol ester within 10 min in 93% yield. A similar treatment using pent-1-yn-1-yl boronic acid diisopropyl ester with methyl (E)-pentadienoate afforded methyl (2E,4E,6E)-7-(diisopropyloxyboraneyl)-6-propylhexa-2,4,6-trienoate in 89% yield. A series of mono- and diborylated-conjugated trienes were synthesized by cross-dimerization and assessed for their potential use in cross-coupling reactions. Using this protocol, the total synthesis of navenone B, a sea slug pheromone, was achieved in only three steps in 45% total yield.

Calcium Hydride Insertion Reactions with Unsaturated C–C Bonds

The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), reacts with terminal alkenes to provide the corresponding alkyl derivatives. With 1-octene, 3,3-dimethyl-1-butene, 3-phenyl-1-propene, and 4-phenyl-1-butene, the ultimate products are dimeric alkyl species, which form sequentially via dinuclear calcium hydrido-alkyl intermediates. Reaction of diphenylacetylene with [(BDI)CaH]2 provides a tetra-calcium complex in which a stilbene dianion bridges symmetrically between two hydrido-bridged bis-β-diketiminato calcium units, while treatment with trans-stilbene yields a dicalcium benzyl-hydride derivative, [{(BDI)Ca}2(H)(PhCHCH2Ph)]. Reaction of [(BDI)CaH]2 and 1,5-hexadiene has previously been observed to provide facile 5-exo-trig cyclization to calcium cyclopentylmethyl derivatives. In contrast, analogous reaction with 1,7-octadiene provides exclusive intermolecular insertion to yield a dimeric open chain calcium oct-7-en-1-yl derivative. Reaction with the internal alken...

Formation of (Alkenylphosphonio)phenylruthenium Complexes from Diphenylacetylene and a [CpRu(dppm)] Cation: Experimental Evidence for the Equilibrium between η1-Disubstituted Vinylidene and η2-Internal Alkyne

The reaction of diphenylacetylene at a cationic ruthenium complex with a dppm (Ph2PCH2PPh2) ligand, [CpRu(dppm)]+, has been studied to reveal essentially for the first time the existence of an equilibrium between an η2-internal alkyne and η1-disubstituted vinylidene at a transition metal center. The reaction mixture at 70 °C for 69 h unexpectedly afforded a coupling product of diphenylacetylene and the dppm ligand, an (alkenylphosphonio)phenyl complex [CpRu{Ph2PCH2P(C6H4)Ph(η2-C(Ph)═CHPh)}]+ with the extremely rare coordination mode of κ1P,η1C,η2C,C′. The (alkenylphosphonio)phenyl complex further undergoes inversion of the coordination face of the alkene moiety at p-xylene reflux temperature. Both isomers of (alkenylphosphonio)phenyl complexes as well as the intermediary η2-internal alkyne and η1-disubstituted vinylidene complexes were fully characterized spectroscopically and crystallographically. By considering the structure of the (alkenylphosphonio)phenyl complexes obtained, the coupling reaction has been proposed to involve the attack of a phosphorus atom on the coordinated diphenylacetylene, which is in equilibrium with an η1-diphenylvinylidene ligand, and the C–H bond activation of a phenyl group on the cationic phosphorus atom leading to the products. Theoretical calculations support the proposed mechanism.

Reactive Iron Carbonyl Reagents via Reaction of Metal Alkoxides with Fe(CO)5 or Fe2(CO)9: Synthesis of Cyclobutenediones via Double Carbonylation of Alkynes

Alkoxy bases such as t-BuOK react with Fe(CO)(5) to give reactive iron carbonyl intermediates that in turn react with alkynes at 70 °C in THF to give 1,2-cyclobutenediones in 70-93% yields after CuCl(2)·2H(2)O oxidation. A novel 1,2-diacyloxyferrole derivative was isolated in the reaction of diphenylacetylene with Fe(CO)(5)/t-BuOK in the presence of acetyl chloride in contrast to the formation of a 1,4-diacyloxyferrole complex formed in the reaction using Fe(CO)(5)/Me(3)NO. The Fe(2)(CO)(9)/t-BuOK reagent system also converts the alkynes to corresponding cyclobutenediones in 63-90% yields under similar reaction conditions.

Synthesis of trans-stilbene through the hydrogenation of diphenylacetylene

Trans-stilbene ( trans-ST) was produced through the hydrogenation of diphenylacetylene (DPA). Pd-based intermetallic compounds (IMCs) supported on silica were applied to the selective hydrogenation of DPA into cis- and trans-ST. Pd 3Bi/SiO 2 showed the highest selectivity to stilbenes without accelerating the deep hydrogenation into diphenylethane (DPE), after DPA was completely converted. Proton-type zeolites were examined for the isomerization of cis-ST, the main product in the hydrogenation of DPA, into trans-ST. H-USY zeolite partially exchanged with Na + ions gave the highest activity owing to the appropriate acid strength and enough space inside the pores for cis-ST to enter. The mixture of Pd 3Bi/SiO 2 and H-USY gave trans-ST yield of 74 mol% through the one-pot reaction of DPA. The isomerization rate was significantly retarded by coexisting DPA and DPE molecules.

ChemInform Abstract: Palladium-Assisted Formation of Carbon-Carbon Bonds. Stoichiometric Synthesis of Indenols and Indenones. Catalytic Synthesis of an Indenol.

Abstract Reactions of diphenylacetylene or dimethylacetylenedicarboxylate with Q2[Pd2R2Cl2(μ-Cl)2] (1) [Q = (PhCH2)Ph3P; R = 2,3,4-trimethoxy-6-formylphenyl] give metallic palladium and 2,3-diphenyl-, or 2,3-dimethylcarboxylate-, 5,6,7-trimethoxyindenone (2 or 3), respectively whereas diphenylacetylene reacts with [PdR(bipy)(MeCN)]ClO4 (4), to give 2,3-diphenyl-5,6,7-trimethoxyindenol (5) and [Pd2 (OH)2(bipy)2](ClO4)2 (6). Catalytic synthesis of 5 is achieved by reaction of [HgR2], Ph2C2, and CuCl2 in the presence of (Me4N)2[Pd2Cl6] (molar ratios 1:2:2:0.1).

The high pressure reactivity of substituted acetylenes: a vibrational study on diphenylacetylene

This article is part of an extended study concerning the reactivity of acetylenic systems at high pressure and aims to the investigation of the high pressure synthesis and stabilization of polyacetylenic chains. The data for diphenylacetylene (DPA) are interpreted by establishing a comparison with the results obtained for acetylene, phenylacetylene, DPA and benzene. The room temperature high-pressure reaction of DPA was studied by means of Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopy using a membrane diamond anvil cell (MDAC). The appearance of the sp3 C–H stretching absorption in the Infrared (IR) spectrum at about 9 GPa, indicates the formation of chemical bonds among the aromatic rings belonging to different DPA molecules. For higher pressures, the Raman data indicate the involvement of the internal C≡C moiety in the chemical transformation. Therefore, due to the steric hindrance of the phenyl rings, the pressure threshold for the reactivity of the two molecular fragments appears in this case to be reversed with respect to other molecular systems. The reaction smoothly occurs until the highest investigated pressure (26.6 GPa), and further proceeds on decompression. The recovered sample, deeply red coloured, was characterized by means of FTIR spectroscopy as an amorphous hydrogenated carbon containing locally ordered polymeric or oligomeric structures, where unreacted DPA molecules may be embedded.

Efficient CF and CC Activation by a Novel N‐Heterocyclic Carbene–Nickel(0) Complex

The NHC-stabilized complex [Ni2(iPr2Im)4(cod)] (1) was isolated in good yield from the reaction of [Ni(cod)2] with 1,3-diisopropylimidazole-2-ylidene (iPr2Im). Compound 1 is a source of the [Ni(iPr2Im)2] complex fragment in stoichiometric and catalytic transformations. The reactions of 1 with ethylene and CO under atmospheric pressure or with equimolar amounts of diphenylacetylene lead to the compounds [Ni(iPr2Im)2(eta2-C2H4)] (2), [Ni(iPr2Im)2(eta2-C2Ph2)] (3), and [Ni(iPr2Im)2(CO)2] (4) in good yields. In all cases the [Ni(iPr2Im)2] complex fragment is readily transferred without decomposition or fragmentation. In the infrared spectrum of carbonyl complex 4, the CO stretching frequencies are observed at 1847 and 1921 cm(-1), and are significantly shifted to lower wavenumbers compared with other nickel(0) carbonyl complexes of the type [NiL2(CO)2]. Complex 1 activates the C--F bond of hexafluorobenzene very efficiently to give [Ni(iPr2Im)2(F)(C6F5)] (5). Furthermore, [Ni2(iPr2Im)4(cod)] (1) is also an excellent catalyst for the catalytic insertion of diphenylacetylene into the 2,2' bond of biphenylene. The reaction of 1 with equimolar amounts of biphenylene at low temperature leads to [Ni(iPr2Im)2(2,2'-biphenyl)] (6), which is formed by insertion into the strained 2,2' bond. The reaction of diphenylacetylene and biphenylene at 80 degrees C in the presence of 2 mol % of 1 as catalyst yields diphenylphenanthrene quantitatively and is complete within 30 minutes.

Reactions of Diamidonaphthalene-Bridged Diiridium Tetrahydrides with Alkynes: Hydrogenation, Vinylidene Formation, and Catalytic C−C Coupling

The diamidonaphthalene-bridged diiridium tetrahydride [Ir2{μ-1,8-(NH)2C10H6}(μ-H)H3(NCMe)(PiPr3)2] (1) reacts with an excess of internal alkynes such as diphenylacetylene, 2-butyne, or 1-phenyl-1-propyne to give the diiridium(I) alkene compounds [Ir2{μ-1,8-(NH)2C10H6}{η2-Z-CH(R)CHR‘}2(PiPr3)2] (R, R‘ = Ph, 4; R, R‘ = Me, 5; and R = Ph, R‘ = Me, 6), respectively. The bis-Z-alkenyl reaction intermediate [Ir2{μ-1,8-(NH)2C10H6}(μ-H)H{Z-C(Ph)CHPh}2(NCMe)(PiPr3)2] (3) has been isolated and characterized in the case of diphenylacetylene as substrate. The reactions of diphenylacetylene and 2-butyne with the carbonyl analogue of 1, [Ir2{μ-1,8-(NH)2C10H6}(μ-H)H3(CO)(PiPr3)2] (2), afford the alkene-carbonyl compounds [Ir2{μ-1,8-(NH)2C10H6}{η2-Z-CH(R)CHR}(CO)(PiPr3)2] (R = Ph, 7; R = Me, 8). Similar reactions using silyl-substituted alkyne substrates seem to involve alkyne to vinylidene rearrangements. Thus, reaction of 1 with excess trimethylsilyl-1-propyne affords the product [Ir2{μ-1,8-(NH)2C10H6){η2-CH2C(Me)SiMe3}2(PiPr3)2] (10) through the bis-gem-alkenyl intermediate [Ir2{μ-1,8-(NH)2C10H6}(μ-H)H{CHC(Me)SiMe3}2(NCMe)(PiPr3)2] (9). A similar reaction with bis(trimethylsilyl)acetylene forms the bis-vinylidene complex [Ir2{μ-1,8-(NH)2C10H6){CC(SiMe3)2}2(PiPr3)2] (11) together with 2 equiv of H2CC(SiMe3)2. The corresponding reactions of these silyl-substituted alkynes with complex 2 give the mixed-valence compound [Ir2{μ-1,8-(NH)2C10H6}H{CHC(Me)SiMe3}(CO)(PiPr3)2] (12) and the vinylidene-carbonyl derivative [Ir2{μ-1,8-(NH)2C10H6){CC(SiMe3)2}(CO)(PiPr3)2] (13) as final products, respectively. The complexes 4−6 and 11 are effective catalysts for 1-alkyne couplings to give mixtures of Z-butenyne dimers and hexadienyne trimers.

Reactions of diphenylacetylene and dihydrogen with chalcogenide- or methylidyne-capped trinuclear iron, ruthenium and cobalt clusters Evidence for the formation and recombination of metal fragments

Abstract We have studied the behaviour of transition metal carbonyl clusters in homogeneous and solid–gas hydrogenation catalysis trying to evidence structure–reactivity relationships. Here, we report on the behaviour of trinuclear homo- and hetero-metallic clusters containing “capping” sulphido or selenido ligands, as well as methylidyne ligands. Very modest results have been obtained in homogeneous hydrogenation reactions of diphenylacetylene. The low activity observed indicates that these complexes do not act as cluster catalysts. In effect of the capping ligands—which are supposed to stabilize the clusters and prevent fragmentation—do not act as expected. Formation and recondensation of metal fragments, to give inactive (and somewhat unexpected) reaction byproducts have been evidenced. These processes presumably occur at the expenses of fragment catalysis. Reaction pathways, supported by IR, 1 H NMR and mass spectrometric evidence are proposed.

Reaction of ferrocenylcarbene complexes of Cr, Mo and W with alkynes: synthesis of ferrocenylcyclobutenones, ferrocenylfurans and ferrocenylketoesters

Ferrocenylcarbene complexes of Cr, Mo and W react with alkynes to produce cyclobutenones, furans and/or ketoesters. The reaction is quite sensitive to the substituents of the alkyne, regardless of the identity of the metal. Cyclobutenones are formed only in the reactions of diphenylacetylene, a rare occurrence for metal carbene complexes. Ketoesters are secondary reaction products and result from oxidation of furan derivatives during the course of the reaction and/or silica-gel chromatography.

ChemInform Abstract: Unexpected Formation of E-1-Methylthio-1,2-diphenyl-2-chloroethene in Reaction of Diphenylacetylene with DMSO in the Presence of Sulfur Trioxide and CCl4.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Oxidation of alkynes by cobalt acetate bromide: a new mode of action for an important industrial catalyst

The catalytic oxidation of a variety of alkyne substrates has been studied using the well-known catalyst system, cobalt acetate bromide, under an O 2 atmosphere. Aryl-substituted alkynes generally gave diketones which cleaved to carboxylic acids under prolonged reaction. In some cases the diketone intermediates could be isolated in good yield. For example, reaction of diphenylacetylene with Co(OAc) 2/NaBr and 0.02 eq. Mn(OAc) 2 as a promoter in 95% AcOH/H 2O at 70°C for 7 h gave benzil in 78% selectivity. Whilst [Co(OAc)Br] oxidation catalysis normally involves H-atom abstraction, many of the alkynes used in our study could not proceed by this mechanism. The electron-richness of the alkyne was important in determining reaction rates. Thus, slower reaction was found for PhCC–CC–Ph than diphenylacetylene itself, and no reaction at all was observed for [PhCCC 6H 4–NO 2]. On the other hand, the internal aliphatic acetylene, 4-octyne, did proceed via H-atom abstraction, giving the corresponding acetylenic ketone [CH 3CH 2CH 2CCCOCH 2CH 3] in 80% yield.

The reaction of hydrogallium(III) dichloride (HGaCl 2) with olefines, acetylenes, and α,β-unsaturated ketones

The reaction of HGaCl 2 with 1-octene yields 1-octylgallium(III) dichloride in 77% yield, but with 2-octene a 2:1 mixture of 2- and 3-octylgallium dichloride(III) is obtained in 88% yield, and the reaction of E-stilbene gives an even more complex mixture. Hydrogallation of 1,4-diphenylbutadiene with HGaCl 2 followed by hydrolysis yields 1,4-diphenylbutane in 53% yield. The reactions of diphenylacetylene and 4-octyne under the same conditions give E-stilbene and E-4-octene in 76% and 63% yield, respectively, while 1-octyne undergoes polymerization. 2-Benzoylstyrene (calcone) reacts with HGaCl 2 to give, as the main product, a compound arising from 1,4-addition of the HGa bond across the enone system, together with a double hydrogallation product.

Cluster synthesis. 41. New platinum-ruthenium cluster complexes from the reaction of diphenylacetylene PhC.tplbond.CPh with Pt2Ru4(CO)18. Synthesis and structural characterizations of Pt2Ru3(CO)8(.mu.3-.eta.2-PhC2Ph)2(.mu.4-.eta.2-PhC2Ph), Pt3Ru6(CO)14(.mu.3-.eta.2-PhC2Ph)3, Pt2Ru4(CO)14(.mu.3-.eta.2-PhC2Ph)(.mu.4-.eta.2-PhC2Ph), Pt3Ru6(CO)18(.mu.3-.eta.2-PhC2Ph)3, and PtRu2(CO)6(.mu.3-.eta.2-PhC2Ph)(dppe)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCluster synthesis. 41. New platinum-ruthenium cluster complexes from the reaction of diphenylacetylene PhC.tplbond.CPh with Pt2Ru4(CO)18. Synthesis and structural characterizations of Pt2Ru3(CO)8(.mu.3-.eta.2-PhC2Ph)2(.mu.4-.eta.2-PhC2Ph), Pt3Ru6(CO)14(.mu.3-.eta.2-PhC2Ph)3, Pt2Ru4(CO)14(.mu.3-.eta.2-PhC2Ph)(.mu.4-.eta.2-PhC2Ph), Pt3Ru6(CO)18(.mu.3-.eta.2-PhC2Ph)3, and PtRu2(CO)6(.mu.3-.eta.2-PhC2Ph)(dppe)Richard D. Adams and Wengan WuCite this: Organometallics 1993, 12, 4, 1248–1256Publication Date (Print):April 1, 1993Publication History Published online1 May 2002Published inissue 1 April 1993https://doi.org/10.1021/om00028a047RIGHTS & PERMISSIONSArticle Views104Altmetric-Citations27LEARN 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-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Palladium-assisted formation of carbon-carbon bonds. Stoichiometric synthesis of indenols and indenones. Catalytic synthesis of an indenol

Reactions of diphenylacetylene or dimethylacetylenedicarboxylate with Q 2[Pd 2R 2Cl 2(μ-Cl) 2] ( 1) [Q = (PhCH 2)Ph 3P; R = 2,3,4-trimethoxy-6-formylphenyl] give metallic palladium and 2,3-diphenyl-, or 2,3-dimethylcarboxylate-, 5,6,7-trimethoxyindenone ( 2 or 3), respectively whereas diphenylacetylene reacts with [PdR(bipy)(MeCN)]ClO 4 ( 4), to give 2,3-diphenyl-5,6,7-trimethoxyindenol ( 5) and [Pd 2 (OH) 2(bipy) 2](ClO 4) 2 ( 6). Catalytic synthesis of 5 is achieved by reaction of [HgR 2], Ph 2C 2, and CuCl 2 in the presence of (Me 4N) 2[Pd 2Cl 6] (molar ratios 1:2:2:0.1).

ChemInform Abstract: Acylation of Acetylenes with Acetyl Fluorosulfonate. Unusual Reaction of Diphenylacetylene with Acetyl Fluorosulfonate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reaction of (μ-H)Os 3(CO) 10(μ 3-CPh) with diphenylacetylene. Alkylidynealkyne coupling and the crystal structure of Os 3(CO) 8(μ,η 2-CPhCHPh)(μ,η 3-C 3Ph 3)

The reaction of diphenylacetylene with (μ-H)Os 3(CO) 10(μ 3-CPh) yields two isomers ( A and B) of stoichiometry Os 3(CO) 8(H(CPh) 5) and two isomers ( C and D) of stoichiometry Os 3(CO) 9(H(CPh) 5). The interconversions of these species have been studied and an X-ray structural study of B shows it to be Os 3(CO) 8(μ,η 2-CPhCHPh)(μ-η 3-C 3Ph 3) containing a σ,π-vinyl and a dimetallaallyl fragment. Compound B crystallizes in the centrosymmetric monoclinic space group P2 1/ c (No. 14) with a 10.1908(18), b 16.6521(23), c 23.1817(48) Å, β 91.725(16)°, V 3932.1(12) Å 3 and Z = 4.

Reaction of diphenylacetylene and diphenyldiazomethane on the carbene bond of [Fe2(CO)7{.mu.,.eta.2-C(Me)CN(C2H5)2}] leading to [Fe2(CO)6{C(Me)C(NEt2)C(Ph)C(Ph)}] and to [Fe2(CO)6{C(Me)C(NEt2)NN(CPh2)}

Reaction of diphenylacetylene and diphenyldiazomethane on the carbene bond of [Fe2(CO)7{.mu.,.eta.2-C(Me)CN(C2H5)2}] leading to [Fe2(CO)6{C(Me)C(NEt2)C(Ph)C(Ph)}] and to [Fe2(CO)6{C(Me)C(NEt2)NN(CPh2)}