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Facile Synthesis of Flexible Bis(pyrazol-1-yl)alkane and Related Ligands in a Superbasic Medium

✍ Scribed by Andrei S. Potapov; Galina A. Domina; Andrei I. Khlebnikov; Vladimir D. Ogorodnikov


Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
115 KB
Volume
2007
Category
Article
ISSN
1434-193X

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✦ Synopsis


Abstract

Flexible ligands 1,3‐bis(pyrazol‐1‐yl)propanes, bis[2‐(pyrazol‐1‐yl)ethyl] ethers, and bis[2‐(3,5‐dimethylpyrazol‐1‐yl)ethyl]amine were prepared by a facile procedure involving the reaction of pyrazoles with 1,3‐dibromopropane, bis(2‐chloroethyl) ether or bis(2‐chloroethyl)amine hydrochloride in a superbasic medium (dimethyl sulfoxide/potassium hydroxide). Reaction of bis(2‐chloroethyl)amine and pyrazole unexpectedly led to 1,4‐bis[2‐(pyrazol‐1‐yl)ethyl]piperazine. The corresponding 4,4′‐diiodo‐substituted bis(pyrazole) derivatives were prepared by oxidative iodination with I~2~/HIO~3~/H~2~SO~4~ in acetic acid. Vilsmeier–Haak formylation of some of the prepared compounds yielded the corresponding dialdehydes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)


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a b s t r a c t Reaction of 2-bromopyridine with 2 equiv of sodium indazolide in diglyme at 140 °C affords 2,6-bis-(indazol-1-yl)pyridine and 2-(indazol-1-yl)-6-(indazol-2-yl)pyridine in purified yields of 24% and 68% respectively. A similar reaction, using 1 equiv of sodium indazolide at 70 °C, giv