Zirconocene-mediated selective synthesis of 1,4-bis(alkynyl)benzenes

A series of novel 1,4-bis(alkynyl)benzene derivatives were synthesized from trimethylsilyl-substituted alkynes by the mediation of zirconocene with excellent regioselectivity in high yields. The 3,6-bis(trimethylsilyl)-4,5-dialkylphthalic acid dimethyl esters were prepared by cycloaddition of 2,5-bi...

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Bibliographic Details
Published inJournal of chemical research Vol. 44; no. 9-10; pp. 571 - 575
Main Authors Zhang, Bo, Qu, Hongmei, Li, Zhongxuan, Zhai, Yuanyuan, Zhou, Xiaolu, Liu, Liqiang
Format Journal Article
LanguageEnglish
Published London, England SAGE Publications 01.09.2020
Sage
Sage Publications Ltd
Subjects
Acids
Alkynes
Benzene
Chemical reactions
Chemistry
Chemistry, Multidisciplinary
Cycloaddition
Derivatives
Ethyl esters
Fluorescence
Hydrocarbons
Iodination
Iodine
Iodobenzoic acids
NMR spectroscopy
Oligomers
Optical properties
Physical Sciences
Regioselectivity
Science & Technology
Spectrum analysis
Sonogashira coupling
1,4-bis(alkynyl)benzene
oligomer
zirconocene
2,5-bis(trimethylsilyl)zirconacyclopentadienes
1
2
OLIGO(PHENYLENE ETHYNYLENE)S
BENZENE
5-bis(trimethylsilyl)zirconacyclopentadienes
ZIRCONIUM
ALKYNES
4-bis(alkynyl)benzene
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Summary:A series of novel 1,4-bis(alkynyl)benzene derivatives were synthesized from trimethylsilyl-substituted alkynes by the mediation of zirconocene with excellent regioselectivity in high yields. The 3,6-bis(trimethylsilyl)-4,5-dialkylphthalic acid dimethyl esters were prepared by cycloaddition of 2,5-bis(trimethylsilyl)zirconacyclopentadienes to dimethyl acetylenedicarboxylate. After iodination with iodine monochloride, 3,6-diiodo-4,5-dialkylphthalic acid dimethyl esters reacted with terminal alkynes to prepare the corresponding 1,4-bis(alkynyl)benzene derivatives by Sonogashira coupling reactions. After removal of trimethylsilyl, 4,5-dibutyl-3,6-bis(ethynyl)phthalic acid dimethyl ester (compound 3) reacted with 4-iodobenzoic acid ethyl ester and 2-iodothiophene, respectively, to obtain the corresponding products 4a and 4c. Compound 3 can be extended to higher oligomers, which reacted with 1-bromo-4-iodobenzene and phenylacetylene in a stepwise manner under Sonogashira conditions to give the phenylene-ethynylene oligomer 5 in an isolated yield of 85%. The structures of the products were confirmed by 1H NMR spectroscopy, 13C NMR spectroscopy, and MS. The optical properties of the 1,4-bis(alkynyl)benzene derivatives were studied by UV-Vis spectroscopy and fluorescence spectra. The results indicated that some can be developed into potential photovoltaic materials.
ISSN:1747-5198
2047-6507
DOI:10.1177/1747519820912675