Aromatic Diynes Research Articles

Regioselective Synthesis of Pyrrole-Based Poly(arylenevinylene)s via Mn-Catalyzed Hydroarylation Polyaddition.

Mn-catalyzed hydroarylation polyaddition of 1-(2-pyrimidinyl)pyrrole (1a) with aromatic diynes is investigated. The use of commercially available MnBr(CO)5 as a precatalyst under the optimized reaction conditions resulted in a site- and regioselective hydroarylation polyaddition, affording the corresponding poly(arylenevinylene)s (PAVs) with excellent vinylene selectivity. The reaction protocol eliminates the production of stoichiometric amounts of byproducts from the monomers. The nonstoichiometric polyaddition of an excess amount of 1a with aromatic diynes is also demonstrated. The 2-pyrimidinyl substituent promoted the intramolecular transfer of the Mn catalyst walking through the 1a moiety.

Effect of the linking positions on the benzene ring on properties of poly(silane arylether arylacetylene)s

AbstractThree aromatic diynes with para‐, meta‐, and ortho‐oxyphenyloxy structures and dichlorodimethylsilane were used to prepare the corresponding poly(silane arylether arylacetylene) (PSEA) resins, that is, ppp‐PSEA, pmp‐PSEA, and pop‐PSEA, and effect of the linking positions on the benzene ring on properties of PSEA resins was explored. The results show that pmp‐PSEA and pop‐PSEA resins exhibit lower crystallinity but better processability as compared with ppp‐PSEA resin. For the cured PSEA resins, the density increases but the maximum water uptake decreases with the change in the linking position of the benzene ring from para‐position to meta‐position followed by ortho‐position. Cured pmp‐PSEA and pop‐PSEA resins possess higher mechanical property in comparison with cured ppp‐PSEA resin. The cured pop‐PSEA resin shows the highest flexural strength (68.4 MPa) and flexural modulus (2.75 GPa). Furthermore, three cured resins possess excellent heat resistance with the decomposition temperature (Td5) of over 505 °C.

Alkali-Promoted Tandem Polymerization of Nucleophilic Acetylide Monomers and Aldehydes toward Luminescent Polymeric Materials

Alkyne-based polymerizations have been an invaluable tool for the preparation of functional polymers. In the reported polymerizations, alkynes generally function as electrophilic monomers. Theoretically, ethynyl groups of monomers could also be used as nucleophiles, and the polymerization using an ethynyl group as the nucleophile should be developed further. In this work, a potassium tert-butoxide (t-BuOK)-promoted tandem polymerization of aromatic diynes and commercially available benzaldehyde, in which ethynyl groups were used as nucleophiles, was successfully developed. Under optimized conditions, this polymerization could produce polymers with good solubility, well-defined structures, high-weight-averaged molecular weights (Mw, up to 76,000), and yields up to 93% in as short as 15 min at room temperature. Moreover, thanks to their ethynyl vinyl carbinol moieties, the resultant polymers show the interesting luminescent property, and some are aggregation-induced emission (AIE)-active. Thus, the nucleophilic alkyne-based cascade polymerization not only provides a powerful tool for the preparation of functional polymers but also might inspire innovation in the area of polymer chemistry.

Synthesis of Pyrrole-Based Poly(arylenevinylene)s via Co-Catalyzed Hydroarylation of Alkynes.

Polyaddition via the Co-catalyzed hydroarylation of 1-(2-pyrimidinyl)pyrrole with aromatic diynes affords poly(arylenevinylene)s under mild conditions. This reaction avoids production of stoichiometric amounts of by-products. Although structural analysis of the obtained polymers reveals the presence of 1,1-vinylidene unit, switching the counter anion of the Co catalyst and steric hindrance of the diyne monomers improves the regioselectivity of the polymers. When a catalyst with bulky counter anions is used for the reaction of less hindered diyne monomers, 1,2-vinylene linkages are formed dominantly over 1,1-vinylidene linkages (93:7). The effect of the regioselectivity of the polymer on the optical and semiconducting properties is also evaluated.

Dual-mode coupling copolymerization of aryl dialdehyde and alkynylaldehyde monomers via Concurrent McMurry olefination and alkyne [2+2+2] cycloaddition trimerization reactions mediated by a low-valent titanium reagent

The application of a low-valent titanium reagent recently developed in our group, Ti(O-i-Pr)4/Me3SiCl/Mg, to the McMurry coupling polymerization of aryl dialdehyde monomers and [2 + 2 + 2] cycloaddition polymerization of aromatic diyne monomers is described. Furthermore, on the basis of these reactions, a low-valent titanium-mediated dual-mode coupling copolymerization of aryl dialdehyde and alkynylaldehyde monomers via concurrent McMurry olefination and alkyne cyclotrimerization reactions is proposed.

Cobalt-catalyzed [2 + 2 + 2] cycloaddition copolymerization of diyne and internal alkyne monomers to highly branched polymers

A novel synthetic method for hyperbranched polymers is reported. A cobalt catalyst previously developed in our group promotes the catalytic alkyne [2 + 2 + 2] cycloaddition polymerization of aromatic diynes with internal alkynes, which proceeds without gelation or production of insoluble materials to give the corresponding soluble polymer in good yields. The method is reproducible, and the polymerization behavior can readily be predicted by the results of model reactions. Thus, the molecular weight and a degree of branching (DB) of the resulting polymer can be controlled by selecting the internal alkyne monomer and its loading amount. The occurrence of effective endcapping reaction was confirmed by degradation of the polymer derived from a diyne bearing a silyl ether linker, and a high DB of more than 0.5 was obtained.

Heterodinuclear Diphosphane-Bridged Iron–Platinum Diyne Complexes as Metalloligands for the Assembly of Polymetallic Systems (Fe, Pt, Co)

Treatment of [(OC)3Fe(μ-C=O)(µ-dppm)Pt(PPh3)] (1a) (dppm=Ph2PCH2PPh2) with 1,7-octadiyne affords the isomeric dimetallacyclopentenones [(OC)2Fe(µ-dppm)(µ-C(=O)C{(CH2)4C≡CH}=CH)Pt(PPh3)] (2a) and [(OC)2Fe(µ-dppm)(µ-C(=O)C(H)=C{(CH2)4C≡CH})Pt(PPh3)] (2a′). In a similar manner, the reaction with 1,3-diethynylbenzene and 1,4-diethynylbenzene yields [(OC)2Fe(μ-C(=O)C{C6H4–C≡CH}=CH)(μ-dppm)Pt(PPh3)] (2b,c); using [(OC)3Fe(μ-C=O)(µ-dppa)Pt(PPh3)] (1b) (dppa=Ph2PNHPPh2) as starting material provides [(OC)2Fe(μ-C(=O)C{p-C6H4–C≡CH}=CH)(μ-dppa)Pt(PPh3)] (2d). The isomeric μ-vinylidene complexes [(OC)3Fe(µ-dppm){(µ-C=CH(C6H4C≡CH)})Pt(PPh3)] (3b,c) result from treatment of [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(H)(PPh3)] with the two aromatic diynes. Reaction of 2a with a further equivalent of 1a yields the structurally characterized tetranuclear species [(OC)2Fe(µ-dppm)(µ-C(=O)C{(CH2)2}=CH)Pt(PPh3)]2 (4a). A dissymmetric heterotetranuclear dimetallacyclopentenone 4b is produced by reacting 2b with [(OC)3Fe(μ-C=O)(µ-dppa)Pt(PPh3)] (1b). An unusual heterotetranuclear dimetallacyclopentenone-μ-vinylidene compound 4c results from reaction of 3c with 1 equivalent of 1a. The dimetallacyclopentenone-dicobaltatetrahedrane cluster [(OC)2Fe(µ-dppm)(µ-C(=O)C{(CH2)4(η2-HC2Co2(CO)6}=CH)Pt(PPh3)] (5a) is formed by addition of [Co2(CO)8] to 2a. Likewise, [(OC)2Fe(µ-dppm)(µ-C(=O)C{C6H4(η2-HC2Co2(CO)4(µ-dppm)}=CH)Pt(PPh3)] (5b) is produced by mixing [Co2(CO)6(µ2-dppm)] with 2b. When attempting to prepare a heterotetranuclear complex by reacting 2a with [Co2(CO)6{P(OPh)3}2], the targeted compound was not formed. Instead, the substitution product [(OC)2Fe(µ-dppm)(µ-C(=O)C{(CH2)4C≡CH}=CH)Pt{P(OPh)3}] (6a) was isolated. 2b reacts in an analogous manner yielding [(OC)2Fe(μ-C(=O)C{C6H4–C≡CH}=CH)(μ-dppm)Pt{P(OPh)3}] (6b).

Homo- and Copolycyclotrimerization of Aromatic Internal Diynes Catalyzed with Co2 (CO)8 : A Facile Route to Microporous Photoluminescent Polyphenylenes with Hyperbranched or Crosslinked Architecture.

This study reports the first Co2 (CO)8 -catalyzed [2+2+2] polycyclotrimerization by the transformation of internal ethynyl groups of aromatic diyne monomers. The reaction yields polycyclotrimers of polyphenylene-type with either hyperbranched or partly crosslinked architecture. The homopolycyclotrimerization of the monomers with two ethynyl groups per one molecule, namely 1,4-bis(phenylethynyl)benzene, 4,4'-bis(phenylethynyl)biphenyl, and 4-(phenylethynyl)phenylacetylene, gives partly crosslinked, insoluble polyphenylenes. The soluble, hyperbranched polyphenylenes are generated via copolycyclotrimerization of 1,4-bis(phenylethynyl)benzene with 1,2-diphenylacetylene (average number of ethynyl groups per monomer molecule < 2). This one-step polycyclotrimerization path to hyperbranched or partly crosslinked polyphenylenes is an alternative to the synthesis of these polymers by Diels-Alder transformation of substituted cyclopentadienones. All polyphenylenes prepared exhibit photoluminescence with emission maxima ranging from 381 to 495 nm. Polyphenylenes with a less compact packing of segments are microporous (specific surface area up to 159 m2 g-1 ), which is particularly important in the case of soluble polyphenylenes because they can be potentially used to prepare microporous layers.

Superbase catalyzed regio-selective polyhydroalkoxylation of alkynes: a facile route towards functional poly(vinyl ether)s

A superbase of t-BuP4 catalysed polyhydroxylation of aromatic diynes was established, and regio-regular poly(vinyl ether)s with versatile properties were produced.

Multicomponent Tandem Polymerizations of Aromatic Diynes, Terephthaloyl Chloride, and Hydrazines toward Functional Conjugated Polypyrazoles

Multicomponent tandem polymerizations (MCTPs) of alkynes enjoying concise procedure, operational simplicity, synthetic efficiency, large structural diversity, high atom economy, and environmental benefit are recently developed as efficient strategies to synthesize functional conjugated polymers, which have attracted much attention from polymer scientists. In this work, through combination of Sonogashira coupling–Michael addition–cyclocondensation reactions in a one-pot procedure, an efficient three-component tandem polymerization of alkyne, carbonyl chloride, and hydrazine hydrate was reported to proceed smoothly under mild conditions at room temperature, affording polypyrazoles with high molecular weights (Mw up to 19 400 g/mol) in excellent yields (up to 95%). This MCTP also applies to various aromatic diynes and aromatic hydrazines, producing polypyrazoles with improved solubility and processability, higher Mws of up to 30 700 g/mol, and high yields. Structural characterization of the polymers such as ...

Catalyst-Free, Atom-Economic, Multicomponent Polymerizations of Aromatic Diynes, Elemental Sulfur, and Aliphatic Diamines toward Luminescent Polythioamides

Sulfur-containing polymers have been widely studied because of their high refractivity and low dispersion, but the efficient synthetic approach of them is quite limited. In this work, we use the abundantly existed elemental sulfur as monomer to prepare polythioamide directly and efficiently through a facile multicomponent polymerization (MCP) of aromatic diynes, sulfur, and aliphatic diamines. This MCP can proceed smoothly in a catalyst-free manner with high atom utilization to afford polythioamide with well-defined structure, high molecular weight, and high yield. It demonstrates a convenient approach to convert elemental sulfur into functional polythioamide. Fluorescence is observed from the polythioamide, despite the absence of typical fluorophores, owing to the “heterodox clusters” composed of a large number of lone-pair-containing electron-rich heteroatoms. The emission maxima and efficiencies of the polymers depend on the formation of molecular aggregates through intrachain and intermolecular intera...

ChemInform Abstract: Gold‐Catalyzed Carbenoid Transfer Reactions of Diynes — Pinacol Rearrangement versus Retro‐Buchner Reaction.

ChemInformVolume 46, Issue 30 Isocyclic Compounds ChemInform Abstract: Gold-Catalyzed Carbenoid Transfer Reactions of Diynes — Pinacol Rearrangement versus Retro-Buchner Reaction. Tobias Lauterbach, Tobias Lauterbach Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorTakafumi Higuchi, Takafumi Higuchi Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorMatthias W. Hussong, Matthias W. Hussong Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorMatthias Rudolph, Matthias Rudolph Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorFrank Rominger, Frank Rominger Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorKazushi Mashima, Kazushi Mashima Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorA. Stephen K. Hashmi, A. Stephen K. Hashmi Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this author Tobias Lauterbach, Tobias Lauterbach Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorTakafumi Higuchi, Takafumi Higuchi Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorMatthias W. Hussong, Matthias W. Hussong Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorMatthias Rudolph, Matthias Rudolph Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorFrank Rominger, Frank Rominger Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorKazushi Mashima, Kazushi Mashima Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this authorA. Stephen K. Hashmi, A. Stephen K. Hashmi Org.-Chem. Inst., Ruprecht-Karls-Univ., D-69120 Heidelberg, GermanySearch for more papers by this author First published: 14 July 2015 https://doi.org/10.1002/chin.201530127Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume46, Issue30July, 2015 RelatedInformation

Multifunctional Poly(N-sulfonylamidine)s Constructed by Cu-Catalyzed Three-Component Polycouplings of Diynes, Disulfonyl Azide, and Amino Esters

The development of efficient multicomponent polymerization (MCP) to prepare heteroatom-rich macromolecules, especially those with complicated structures and multifunctionality, is gathering increasing research interest from chemists. In this work, we report a facile one-pot three-component polymerization method to prepare multifunctional polymers. The Cu-catalyzed polycoupling reactions of aromatic diynes, disulfonyl azide, and optically active amino esters proceeded in a mild manner under room temperature, furnishing regular poly(N-sulfonylamidine)s with high molecular weights (Mw up to 35 900) and in satisfactory yields (up to 87%). The model compound was synthesized to verify the complete transformation from monomers to the desired polymeric products. All the polymers possess excellent solubility in common organic solvents, good film-forming ability, and high thermal stability. The backbones of the polymers are induced to helically rotate by the optically active chiral amino esters, resulting in the circular dichroism (CD) absorption in the solutions and cast films. The polymers are almost nonemissive in solutions, whereas their nanoaggregates or thin films fluoresce intensely upon photoexcitation, showing a unique phenomenon of aggregation-induced emission (AIE). The thin films of these polymers possess high refractive indices (RI = 1.7327–1.6419) in a wide wavelength region of 400–893 nm and low optical dispersions (D down to 0.0247). Well-resolved two-dimensional fluorescent photopatterns can be generated by UV irradiation of these thin films via a copper photomask in air. This work provides an efficient approach toward synthesizing multifunctional heteroatom-rich polymeric materials, overcoming the drawbacks of conventional polymerizations.

One-Pot Three-Component Tandem Polymerization Toward Functional Poly(arylene thiophenylene) with Aggregation-Enhanced Emission Characteristics

The development of efficient multicomponent tandem polymerization is attractive but challenging, owing to the limitations such as the required strict stoichiometric balance, the poor solubility and low molecular weight of the polymer products, etc. In this work, an efficient one-pot three-component polymerization of alkyne, carbonyl chloride and ethyl 2-mercaptoacetate was reported. The polymerization of aromatic diyne (1), diaroyl chloride (2), and ethyl 2-mercaptoacetate (3) catalyzed by Pd(PPh3)2Cl2/CuI proceeded smoothly under mild conditions at room temperature without strict stoichiometric balance of the monomers, affording poly(arylene thiophenylene) (P1) with high molecular weights (Mw up to 156 000) in excellent yields (up to 97%). Single crystal structure of model compound 4 was obtained, aiding in verification of the complete transformation to the desired polymer product. The thiophene-containing conjugated polymer possesses good solubility in common organic solvents, good film-forming ability ...

ChemInform Abstract: Hydration of Aromatic Terminal Alkynes Catalyzed by Iron(III) Sulfate Hydrate under Chlorine‐Free Conditions.

Abstract The hydration of aromatic terminal alkynes performed in acetic acid in the presence of catalytic hydrate iron III sulfate, Fe 2 (SO 4 ) 3 · n H 2 O (4–9 mol %), yields the derived aryl methyl ketones with good to excellent yields. Under comparable conditions (18 mol %, 95 °C, 24 h), bifunctional substrates were transformed into the monoacetyl or the diacetyl derivatives, depending on the structure of the aromatic diyne. The reaction is compatible with aryl substituents of different nature and ring positions, including hydroxyl, carbonyl groups, and cumulated hydrocarbons. The soft character of the non nucleophilic sulfate anion allows for activation of the triple bond toward carbon oxygen bond formation in the Bronsted acidic medium. The proposed protocol is based on readily available and non toxic materials, in the absence of chlorine atoms in either the solvent or the metal catalyst.

Catalyst-Free Thiol–Yne Click Polymerization: A Powerful and Facile Tool for Preparation of Functional Poly(vinylene sulfide)s

The “thio-click” polymerization is a well-expanded concept of click polymerization. Among the click polymerizations, the thiol–yne click polymerization is less developed and still in its infancy stage. In general, UV light, elevated temperature, amine, or transition metal complexes is needed to catalyze the thiol–yne click polymerization, which greatly complicates the experimental operation and limits its application. In this work, a facile and powerful thiol–yne click polymerization was developed, which could be carried out under very mild conditions without using external catalyst. Simply mixing the aromatic diynes (1a–1e) and dithiols (2–4) with equivalent molar ratio in THF at 30 °C will readily produce soluble and regioregular functional poly(vinylene sulfide)s (PIa–PIe, PII, and PIII) with high molecular weights (Mw up to 85 200) in excellent yields (up to 97%) after as short as 2 h. Furthermore, no double addition product of an ethynyl group was found. This catalyst-free thiol–yne click polymerization has remarkably simplified the reaction conditions and will facilitate the preparation of functional materials applied in diverse areas.

Hydration of aromatic terminal alkynes catalyzed by iron(III) sulfate hydrate under chlorine-free conditions

The hydration of aromatic terminal alkynes performed in acetic acid in the presence of catalytic hydrate ironIII sulfate, Fe2(SO4)3·nH2O (4–9mol%), yields the derived aryl methyl ketones with good to excellent yields. Under comparable conditions (18mol%, 95°C, 24h), bifunctional substrates were transformed into the monoacetyl or the diacetyl derivatives, depending on the structure of the aromatic diyne. The reaction is compatible with aryl substituents of different nature and ring positions, including hydroxyl, carbonyl groups, and cumulated hydrocarbons. The soft character of the non nucleophilic sulfate anion allows for activation of the triple bond toward carbonoxygen bond formation in the Brønsted acidic medium. The proposed protocol is based on readily available and non toxic materials, in the absence of chlorine atoms in either the solvent or the metal catalyst.

ジインおよびエンイン系のドミノ環化反応による縮合ヘテロ多環式化合物合成の新手法

ジインおよびエンイン系のドミノ環化反応による縮合ヘテロ多環式化合物合成の新手法

ChemInform Abstract: Adventures of an Occasional Click Chemist

AbstractReview: 31 refs.

Adventures of an Occasional Click Chemist

In this account, I describe my and my group’s adventures in the field of 1,3-dipolar cycloaddition reactions of alkynes to organic azides. Three different topics are treated: post-functionalization and crosslinking of polymers of the poly(phenylene ethynylene) type, the synthesis of conjugated heterocyclic polymers by clicking aromatic diazides to aromatic diynes, and the synthesis of fluorophore dyes that bind to metal cations. In the last case, as a result of the presence of a binding pocket created by a triazole nitrogen and the nitrogen of a neighboring heterocycle (pyridine, chalcodiazole, or phenazine), the binding event leads to specific changes in the absorption and emission spectra of the complex. This account is limited exclusively to experiments performed by our group, as the topic of 1,3-dipolar cycloadditions of azides to alkynes has already been the subject of many comprehensive reviews and accounts. 1 Introduction 2 Polymeric Clicks 3 Metallosensors by Click Chemistry 4 Outlook and Conclusion