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Synlett 2016; 27(11): 1720-1724
DOI: 10.1055/s-0035-1561952
DOI: 10.1055/s-0035-1561952
letter
Synthesis of 2-Amino-4-(3-amino-5-hydroxy-4H-pyrazol-4-ylidene)-4H-chromene-3-carbonitriles
Authors
Weitere Informationen
Publikationsverlauf
Received: 09. Januar 2016
Accepted after revision: 03. März 2016
Publikationsdatum:
05. April 2016 (online)
Abstract
A simple and efficient protocol was developed for the synthesis of 2-amino-4-(3-amino-5-hydroxy-4H-pyrazol-4-ylidene)-4H-chromene-3-carbonitriles by the potassium phosphate-catalyzed reaction of salicylaldehydes, malononitrile, and 2-cyanoacetohydrazide in ethanol. The method offers advantages such as a simple workup procedure and good yields. When the method was extended to two equivalents of 2-cyanoacetohydrazide instead of malononitrile, the unexpected formation of a salicylaldehyde azine was observed, leading to a novel route for the synthesis of salicylaldehyde azines.
Supporting Information
- Experimental details and detail spectral data (IR, 1H and 13C NMR, and mass spectra) of unknown synthesized compounds are provided in a supplementary
file. Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561952.
- Supporting Information (PDF)
-
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- 17 2-Amino-4-(3-amino-5-hydroxy-4H-pyrazol-4-ylidene)-4H-chromene-3-carbonitriles 4a–f; General Procedure A mixture of the appropriate salicylaldehyde 1 (1 mmol) and malononitrile (2; 1 mmol) in EtOH (2 mL) in a 25 mL round-bottomed flask was stirred at r.t. in the presence of K3PO4 (20 mol%) for 10–20 min. 2-Cyanoacetohydrazide (3; 1 mmol) was added, and the mixture was stirred under reflux in an oil bath for the appropriate time (Table 2) while the progress of reaction was monitored by TLC. When the reaction was complete, the mixture was poured into ice-cold water, and the precipitate was collected by filtration and washed with EtOH. 2-Amino-4-(3-amino-5-hydroxy-4H-pyrazol-4-ylidene)-4H-chromene-3-carbonitrile (4a) Yellow powder; yield: 200 mg (75%); mp 270 °C. IR (KBr): 3400 (OH), 3359–3282 (NH2), 2206 (CN), 1615 (C=N), 1496, 1353, 760 cm–1. 1H NMR (300 MHz, DMSO-d 6): δ = 5.66 (s, 2 H, NH2, D2O exchangeable), 6.89–6.98 (m, 2 H, Ar), 7.15–7.18 (m, 1 H, Ar), 7.28–7.34 (m, 1 H, Ar), 8.31 (s, 2 H, NH2, D2O exchangeable), 10.02 (s, 1 H, OH, D2O exchangeable). 13C NMR (75 MHz, DMSO-d 6): δ = 75.83, 88.0, 115.86, 116.50, 116.76, 119.40, 122.41, 129.56, 131.63, 154.30, 156.92, 158.56, 159.75. MS (EI): m/z (%) = 267 (100) [M+], 250, 238, 210, 181, 126, 88, 63, 51.