A convenient short cut from aromatic iodides to alkynylstannanes and their use for the straightforward preparation of polyacetylene and polymetallaacetylene polymers

Antonelli, Eleonora; Rosi, Patrizia; Sterzo, Claudio Lo; Viola, Egidio

doi:10.1016/s0022-328x(98)01124-3

Cited by 46 publications

(17 citation statements)

References 68 publications

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“…Although spectroscopically pure, these products must be chromatographed (silica, hexanes) to get rid of impurities that will otherwise inactivate the palladium catalyst. 2,5‐Diiodo‐3‐butylthiophene (1d) was prepared by adapting the procedure described for 2,5‐diiodo‐3‐hexadecylthiophene12 (1e) . 1,4‐Bis(tributyltin)ethynyl‐2,5‐bis(butyloxy)benzene (5a) , 1,4‐bis(tributyltin)ethynyl‐2,5‐bis(octyloxy)benzene (5b) , 1,4‐bis(tributyltin)ethynyl‐2,5‐bis(hexadecyloxy)benzene (5c) , and 2,5‐bis(tributyltin)ethynyl‐3‐hexadecylthiophene (5e) were prepared following our previously described procedure 12.…”

Section: Methodsmentioning

confidence: 99%

“…We have recently reported12 an extended one‐pot procedure for the preparation of polyacetylene and polymetallaacetylene copolymers based on an innovative access to difunctionalized organotin derivatives, and their Pd‐catalyzed coupling with organic and organometallic dihalides (Scheme ). In this procedure formation of tributyltin acetylides does not require isolation of the difunctionalized alkyne precursors and polymerization is straightforwardly carried out in the same pot where tributyltin acetylides were formed (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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An efficientone-pot access to poly(arylene ethynylene) homopolymers: Use of the Bu3Sn?moiety as a recyclable carrier to introduce the ethynyl unit into the chain

Giardina

Rosi

Ricci

et al. 2000

J. Polym. Sci. A Polym. Chem.

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The palladium‐catalyzed Stille coupling of an aromatic diiodide with half an equivalent of tributyl(ethynyl)tin results in a complex mixture containing the diethynylaromatic compound, the iodo(ethynyl)aromatic compound, unreacted diiodide and the tributyltin iodide side product. Addition of LDA to this mixture, while leaving the iodoaromatic moieties unaffected, causes deprotonation of the ethynyl functionalities, which immediately recombine with tributyltin iodide to form a mixture of bis(tributylethynyltin)aromatic, iodo(tributylethynyltin)aromatic, and unchanged diiodide. Being the palladium catalyst still active, it is sufficient to warm up this mixture to obtain the coupling of the tributylethynyltin and iodo moieties resulting in the formation of a poly(arylene ethynylene) polymer. Isolation of the polymer is easily and rapidly achieved by precipitation, while distillation of the mother liquor allows recovery of the tributyltin iodide side product. The latter can be utilized for the preparation of new tributyl(ethynyl)tin, thus allowing a convenient turnover of the tributyltin moiety. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2603–2621, 2000

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An efficientone-pot access to poly(arylene ethynylene) homopolymers: Use of the Bu3Sn?moiety as a recyclable carrier to introduce the ethynyl unit into the chain

Giardina

Rosi

Ricci

et al. 2000

J. Polym. Sci. A Polym. Chem.

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“…Ethynylbiphenyl and 4,4-diethynylbiphenyl 27 and 1,4-bis(butyloxy)-2,5-diiodobenzene, 1,4-bis(octyloxy)-2,5-diiodobenzene, 1,4-diethynyl-2,5-bis (butyloxy) benzene and 1,4-diethynyl-2,5-bis(octyloxy) benzene were prepared by literature procedures. 28,29 Solvents were pre-dried from appropriate drying agents and freshly distilled before use. 30 IR spectra were recorded as CH 2 Cl 2 solutions, in a NaCl cell, on Nicolet Nexus FTIR spectrometer.…”

Section: Materials and Measurementsmentioning

confidence: 99%

Synthesis and optical properties of biphenylene ethynylene co-polymers and their model compounds

et al. 2015

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A new series of biphenylene ethynylene co-polymers, poly(2,5-dialkoxy-4-phenyleneethynylene-4,4-biphenyleneethynylene)s of the general formula [-C≡C-4-C 6 H 4-C 6 H 4-4-C≡C-C 6 H 2 (2,5-OR) 2-] n (R = C 4 H 9 P1,C 8 H 17 P2) has been synthesized using a palladium/copper catalyzed coupling reaction between HC≡C-4-C 6 H 4-C 6 H 4-4-C≡C-H and IC 6 H 2 (2,5-OR) 2 I. The new co-polymer [-C≡C-C 6 H 2 (2,5-OC 8 H 17) 2-C≡C-C 6 H 2 (2,5-OC 4 H 9) 2-] n P5 has also been formed where different alkoxy substituents are present on alternate arene rings in the same polymer backbone. All the polymers were characterized by IR, 1 H and 13 C NMR spectroscopy and by GPC. The model compounds C 6 H 5-4-C 6 H 4-C≡C-C 6 H 2 (2,5-OR) 2-4-C 6 H 4-C 6 H 5 (R = C 4 H 9 M1,C 8 H 17 M2) have also been prepared by the reaction between C 6 H 5-4-C 6 H 4-C≡CH and IC 6 H 2 (2,5-OR) 2 I. Single crystal X-ray structures of M1, M2 and Me 3 Si-C≡C-4-C 6 H 4-C 6 H 4-4-C≡C-SiMe 3 were determined with a view to obtain a better understanding of the molecular and intermolecular interactions in the solid state which has been used to explain the optical properties of the polymers derived from them. The absorption and photoluminescence spectra of the polymers, P1, P2 and P5 showed that the lowest energy band is blue shifted due to the introduction of biphenylene fragments into the alkoxy substituted poly(ethynylenephenylene)s.

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“…Thus, he used the Stille coupling to label steroids with the ethynylcyclopentadienyltricarbonylmanganese moiety (via steroidal triflates) [257]. Coupling of diiodobenzene or diiodothiophene with tributylstannylethyne yields bis(stannylethynyl) derivatives, which can be allowed to react further in a one-pot procedure with either aromatic diiodides or iron or platinum iodides to form acetylenic and metallaacetylenic polymers in high yields (DP 3-9) [258]. The same method (''extended one pot'') has been applied in a series of coupling reactions, starting from 2,5-diiodothiophene and tributylethynyltin, to form palladium-ethynylthiophene oligomers [259].…”

Section: Couplings Of Alkynyltinsmentioning

confidence: 99%

Organotin Reagents in Cross‐Coupling Reactions

Martín‐Matute

Szabó

Mitchell

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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A convenient short cut from aromatic iodides to alkynylstannanes and their use for the straightforward preparation of polyacetylene and polymetallaacetylene polymers

Cited by 46 publications

References 68 publications

An efficientone-pot access to poly(arylene ethynylene) homopolymers: Use of the Bu3Sn?moiety as a recyclable carrier to introduce the ethynyl unit into the chain

An efficientone-pot access to poly(arylene ethynylene) homopolymers: Use of the Bu3Sn?moiety as a recyclable carrier to introduce the ethynyl unit into the chain

Synthesis and optical properties of biphenylene ethynylene co-polymers and their model compounds

Organotin Reagents in Cross‐Coupling Reactions

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