Issue 11, 2003

Synthesis of the silver(i) complex of CH2[CH(pz4Et)2]2 containing the unprecedented [Ag(NO3)4]3− anion: A general method for the preparation of 4-(alkyl)pyrazoles

Abstract

A general two-step method for the syntheses of 4-(alkyl)pyrazoles has been developed. The first step involves the reaction between organyl diethylacetals and the Vilsmeier reagent to give a mixture of ethoxy- and dimethylamino- acroleins. This mixture reacts directly with hydrazine monohydrogenchloride to yield the desired (4-substituted)pyrazoles. The 4-(phenyl)pyrazole derivative exhibited a markedly lower solubility in common organic solvents. In the solid state structure the phenyl and pyrazolyl groups are nearly coplanar and extensive intermolecular CH–π interactions organize the molecules in two-dimensional sheets that are held in a three dimensional arrangement by NH⋯N hydrogen bonds. Tetrakis[(4-ethyl)pyrazolyl]propane, CH2[CH(pz4Et)2]2, was prepared by a transamination reaction and reacts with Ag(NO3) to yield a compound with a 4 ∶ 3 metal ∶ ligand mole ratio that when crystallized by diffusion of Et2O into an acetone solution produced [Ag2{μ-CH2[CH(pz4Et)2]2}2]3[Ag(NO3)4]2 (1). This complex contains dimeric units in which two silver cations are sandwiched between two CH2[CH(pz4Et)]2 ligands and the counterion is the unprecedented tetra(nitrato)argentate anion. ESI mass spectral data support the existence of both the cationic dimeric units and the [Ag(NO3)4] anion in solution.

Graphical abstract: Synthesis of the silver(i) complex of CH2[CH(pz4Et)2]2 containing the unprecedented [Ag(NO3)4]3− anion: A general method for the preparation of 4-(alkyl)pyrazoles

Supplementary files

Article information

Article type
Paper
Submitted
27 Jun 2003
Accepted
26 Jul 2003
First published
01 Sep 2003

New J. Chem., 2003,27, 1670-1677

Synthesis of the silver(I) complex of CH2[CH(pz4Et)2]2 containing the unprecedented [Ag(NO3)4]3− anion: A general method for the preparation of 4-(alkyl)pyrazoles

D. L. Reger, J. R. Gardinier, T. Christian Grattan, M. R. Smith and M. D. Smith, New J. Chem., 2003, 27, 1670 DOI: 10.1039/B307306H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements