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One-pot synthesis of dihydropyrano[c]chromene derivatives by using BF3•SiO2 as catalyst

  • Ali Akbari EMAIL logo
Published/Copyright: November 22, 2013
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Heterocyclic Communications
From the journal Heterocyclic Communications Volume 19 Issue 6

Abstract

Silica-supported boron trifluoride (BF3•SiO2) is an efficient, readily available, and reusable catalyst for the synthesis of 2-amino-5-oxo-4-aryl-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile or carboxylic acid ethyl ester derivatives by condensation of 4-hydroxycoumarin, an aldehyde, and an alkylnitrile.

Keywords: aldehyde; alkyl nitriles; BF3•SiO2; 4-hydroxycoumarin; pyrano[3,2-c]chromene

Introduction

Silica-supported boron trifluoride, BF3•SiO2, is easy to prepare, shows unusually high Brønsted acidity that can be controlled by activation temperature, and exhibits considerable catalytic activity [1]. BF3•SiO2 is a solid super acid [2]. It is used as a catalyst in several organic transformations, such as Claisen-Schmidt condensations [3], synthesis of 14-substituted 14H-dibenzo[a,j]xanthenes [4] and 1,2,4,5-tetrasubstituted imidazoles [5], polymerization of styrene [6], and the preparation of polyfunctionalized piperidin-4-ones [7], α-amino phosphonates [8], quinoxalines [9], and 3,4-dihydropyrimidin-2(1H)-ones [10].

Pyrans constitute one of the major classes of naturally occurring compounds [11–15]. Pyran derivatives exhibit biological activities, can be photochromic [16–20], and can be used as intermediates for the synthesis of various compounds, including pyranopyridines [21], polyazanaphthalenes [22], pyrano[2]pyrimidines [23], and pyridin-2-ones [24]. Recently, several methods have been reported for the synthesis of 2-amino-5-oxo-dihydropyrano[3,2-c]chromene derivatives through a three-component condensation of 4-hydroxycoumarin with aldehydes and alkyl nitriles. This reaction can be catalyzed by a variety of catalysts [25–37].

Results and discussion

We report that BF3•SiO2 is an efficient and reusable catalyst for the synthesis of 2-amino-5-oxo-4-aryl-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile or carboxylic acid ethyl ester derivatives (Table 1). The reaction of 4-hydroxycoumarin (2 mmol) with 4-nitrobenzaldehyde (2.1 mmol) and malononitrile (2.1 mmol) was investigated for optimization of the reaction conditions (Table 1, entry 3). The optimized conditions are given in Experimental section. It should be noted that the best results were obtained in the absence of any solvent. The reusability of the BF3•SiO2 catalyst was also examined. After each run, the reaction mixture was cooled to room temperature, and the catalyst was separated from the organic product by treatment with chloroform. It was shown that the catalyst could be reused many times, although a gradual decline in activity was observed.

Table 1

Synthesis of 2-amino-5-oxo-4-aryl-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile or carboxylic acid ethyl ester derivatives in the presence of BF3•SiO2.

EntryArRYield (%)/mp (°C); this workYield (%)/mp (°C); reported [ref.]
14-F-C6H4CN93/260–26196/260–262 [26]
22,3-Cl2-C6H3CN92/281–28290/280–282 [25]
34-O2N-C6H4CN95/177–17885/177–178 [35]
43-O2N-C6H4CN95/257–25884/257–258 [34]
53-Cl-C6H4CN94/247–24886/246–248 [26]
64-MeO-C6H4CN93/220–22278/220–222 [34]
74-Cl-C6H4CN92/257–25988/256–258 [30]
84-Br-C6H4CN93/247–24880/247–249 [26]
92-Cl-C6H4CN90/263–26480/262–264 [35]
102-Me-C6H4CN88/264–26587/264–266 [26]
112,4-Cl2-C6H3CN90/257–25886/255–257 [25]
124-Me-C6H4CN89/219–22080/219–220 [35]
132-Me-C6H4CN88/264–26587/264–266 [26]
14C6H5CN90/253–25410/253–255 [34]
154-Cl-C6H4COOEt90/192–19489/192–194 [27]
163-O2N-C6H4COOEt91/248–25090/247–250 [25]
174-O2N-C6H4COOEt91/240–24291/241–243 [27]

See Experimental for conditions.

Conclusions

The preparation of 2-amino-5-oxo-4-aryl-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile or carboxylic acid ethyl ester derivatives by the reaction of 4-hydroxycoumarin, an aldehyde, and an alkyl nitrile is efficiently catalyzed by BF3•SiO2. In contrast to many other acidic catalysts, this reagent does not need special precautions for handling or storage.

Experimental

General

The catalyst BF3•SiO2 was prepared as previously reported [1, 2]. Products were characterized by IR and 1H NMR spectroscopy and by comparison of their melting points with the literature values. Melting points were determined on a Buchi melting point B-540 B.V.CHI apparatus.

General procedure for the synthesis of compounds shown in Table 1

A mixture of 4-hydroxycoumarin (2 mmol), an aldehyde (2.1 mmol), an alkyl nitrile (2.1 mmol), and BF3•SiO2 (0.6 g, 25 mol%) was heated at 50°C. The progress of the reaction was monitored by TLC. After completion of the reaction, 15–25 min, the mixture was extracted with chloroform and filtered to recover the catalyst. The chloroform extract was concentrated and the residue was crystallized from isopropanol to afford the 2-amino-5-oxo-4-aryl-4H,5H-pyrano[3,2-c]chromene-3-carbonitrile or carboxylic acid ethyl ester derivative.

Corresponding author: Ali Akbari, Department of Chemistry, Faculty of Science, University of Jiroft, P.O. Box 7867161167, Jiroft, Iran, e-mail:

Financial support for this work by the Research Council of University of Jiroft is gratefully acknowledged.

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Received: 2013-2-11
Accepted: 2013-5-21
Published Online: 2013-11-22
Published in Print: 2013-12-01

©2013 by Walter de Gruyter Berlin Boston

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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https://doi.org/10.1515/hc-2013-0058
Keywords for this article
aldehyde; alkyl nitriles; BF3•SiO2; 4-hydroxycoumarin; pyrano[3,2-c]chromene
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Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Reviews
  4. Polyoxin and nikkomycin analogs: recent design and synthesis of novel peptidyl nucleosides
  5. Synthesis of fused heterocycles derived from 2H-1,4-benzoxazin-3(4H)-ones
  6. Research Articles
  7. Green synthesis of 1-monosubstituted 1,2,3-triazoles via ‘click chemistry’ in water
  8. Synthesis of a novel fused tricyclic heterocycle, pyrimido[5,4-e][1,4]thiazepine, and its derivatives
  9. Synthesis of 2-[(quinolin-8-yloxy)methyl]quinoline-3-carboxylic acid derivatives
  10. Pyrimidine-5-carbonitriles – part III: synthesis and antimicrobial activity of novel 6-(2-substituted propyl)-2,4-disubstituted pyrimidine-5-carbonitriles
  11. Tungstic acid-catalyzed synthesis of 3,3-bis (1H-indol-3-yl)indolin-2-one derivatives
  12. One-pot synthesis of dihydropyrano[c]chromene derivatives by using BF3•SiO2 as catalyst
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