Chemical fixation of CO2 to 2-aminobenzonitriles: A straightforward route to quinazoline-2,4(1H,3H)-diones with green and sustainable chemistry perspectives

doi:10.1016/j.jcou.2017.08.006

Journal of CO2 Utilization

Volume 21, October 2017, Pages 342-352

https://doi.org/10.1016/j.jcou.2017.08.006 Get rights and content

Highlights

•
Important developments in the synthesis of quinazoline diones through chemical fixation of CO2 to 2-Aminobenzonitriles.
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Green and Sustainable Chemistry Perspectives in synthesis of quinazoline diones.
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Synthesis of quinazoline diones using organocatalyzed, metal catalyzed, and ionic liquid catalyzed, inorganic base catalyzed and catalyst-free reactions.

Abstract

Quinazoline-2,4(1H,3H)-dione derivatives are important intermediates in the pharmaceutical industry as a key building blocks in the synthesis of many commercially available drugs, including Zenarestat, Prazosin, Bunazosin, and Doxazosin. However, despite their wide importance in the pharmaceutical and biotechnology industries, safe and environmentally friendly synthesis of titled compounds still remains to be a difficult problem. Therefore, the development of practical and convenient synthetic methods that benefit from nontoxic, inexpensive, readily available, and simple starting materials for their preparation is of prime importance in organic synthesis. Chemical fixation of CO₂ to 2-aminobenzonitriles has emerged over the past few years as a powerful and novel strategy to the synthesis of functionalized quinazoline-2,4(1H,3H)-diones. In this mini review, we have highlighted the advances in this chemistry which will be helpful in the development of improved methods for the green synthesis of these important heterocyclic compounds.

Introduction

Carbon dioxide chemistry (carbon capture, storage, and utilization) has been drawing more and more attention over the last decades from the scientific community due to growing concerns about the global warming associated with emission of this greenhouse gas to the earth’s atmosphere (72% of the totally emitted greenhouse gases is CO₂) [1], [2]. As well known, as an abundant, inexpensive, nonflammable, and nontoxic biorenewable carbon resource, CO₂ can be converted into a variety of value-added chemicals. The transformation of CO₂ into the industrially important chemicals is one of the hottest research topics in modern organic synthetic chemistry and is very important in view of the sustainable chemistry and Green Chemistry concept [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14].

Nitrogen-containing heterocycles are one of the most privileged family of organic compounds that constitute an extensive number of natural products [15] and display a broad range of pharmaceutical and biological activities [16]. Therefore, synthetic chemists continue to be interested in the preparation of these compounds [17]. Quinazoline-2,4(1H,3H)-dione is one of the most important N-heterocyclic compound having the chemical formula C₈H₆N₂O₂. Quinazoline-2,4(1H,3H)-diones are extremely important key intermediates in the pharmaceutical industry in the synthesis of many commercially available drugs (Fig. 1) [18], including zenarestat 1, prazosin 2, bunazosin 3, and doxazosin 4. Although several methods have been developed for the synthesis of titled compounds [19], [20], [21], [22], they invariably limited by require specialized reagents, by require very toxic reagents, or both. Therefore, the development of novel and convenient procedures that benefit from nontoxic, inexpensive, readily available, and simple starting materials for the construction of these cores is highly desirable. In last three years great efforts have been directed toward synthesis of functionalized quinazoline-2,4(1H,3H)-diones via chemical fixation of CO₂ to cheap and commercially available 2-aminobenzonitriles (Fig. 1). This new page of quinazoline-2,4(1H,3H)-diones synthesis play an important role in green and sustainable chemistry, as in this procedure CO₂ act as a green C1 resource in place of toxic phosgene. Since a large number of developments in this chemistry have occurred from 2000 to present, a comprehensive review on this interesting field seems to be timely. In continuation of our works [23], in this review, we have classified the reactions based on the type of catalysts to synthesis of quinazoline-2,4(1H,3H)-dione (Fig. 2).

Section snippets

Oranocatalyzed reactions

In 2000, the groups of Mizuno reported the first organocatalyzed fixation of CO₂ with 2-aminobenzonitriles 5 using DBU (3 equiv.) under very mild conditions (1.0 atm pressure of CO₂ and 20 °C) (Scheme 1). In their optimization study, they found that DBN (1,5-diazabicyclo[4.3.0]non-5-ene) also promoted the reaction; however, in lower yields. No reaction occurred in the absence of the catalyst. Using the optimized conditions, both electron-poor and electron-rich 2-aminobenzonitriles gave

Metal-catalyzed reactions

The possibility of metal-catalyzed cyclization of 2-aminobenzonitriles with CO₂ to quinazoline-2,4(1H,3H)-diones was first realized by Bhanage and co-workers, who synthesized a series of functionalized quinazoline-2,4(1H,3H)-dione derivatives 14 from corresponding 2-aminobenzonitriles 13 in the presence of MgO/ZrO₂ as catalyst in DMF. As shown in Scheme 8, the reaction showed remarkable flexibility and desired products were formed in good to high yields with both electron-rich and

Ionic liquids catalyzed reactions

In 2009, Bhanage and co-workers published the first example of ionic liquid catalyzed synthesis of quinazoline-2,4(1H,3H)-diones 20 from the reaction of 2-aminobenzonitriles 19 and carbon dioxide under solvent-free conditions (Scheme 11). Among all the tested ionic liquid catalysts such as [Bimim][BF₄], [Bimim][HSO₄], [Bimim][OH], only [Bimim][OH] gives the best results. This protocol is suitable for various electron-rich and electron-deficient 2-aminobenzonitriles to afford the corresponding

Inorganic base catalyzed reactions

In 2008, the group of Bhanage reported that inexpensive and commercially available cesium carbonate are efficient catalyst for the fixation of CO₂ onto 2-aminobenzonitriles. Thus, by using 25 mol% of Cs₂CO₃ as catalyst in DMF, at 100 °C and under CO₂ atmosphere, the 2-aminobenzonitriles 23 afforded corresponding quinazoline-2,4(1H,3H)-diones 24 in moderate to excellent yields (Scheme 13). The major advantage of this method is the user friendly product separation and catalyst recovery.

Catalyst-free reactions

In 2013, the Han laboratory reported a green and efficient process for the synthesis of functionalized quinazoline-2,4(1H,3H)-diones 26 through the fixation of CO₂ with 2-aminobenzonitriles 25 under catalyst-free conditions by employing water as solvent. The reaction was performed in compressed CO₂ at 160 °C and the quinazoline-2,4-diones derivatives 2 were obtained in yields ranging from 80 to 93% (Scheme 15) [49]. The mechanism proposed for this CO₂-fixation reaction is shown in Scheme 16. It

Conclusion

Despite wide importance of quinazoline-2,4(1H,3H)-diones in pharmaceutical and biotechnology industries, safe, non-toxic, and highly efficient synthesis of these compounds still remains to be a difficult problem. As illustrated, the fixation of carbon dioxide onto 2-aminobenzonitrile derivatives opens a new entry into a large variety of quinazoline-2,4(1H,3H)-diones. This new page of quinazoline-2,4(1H,3H)-diones synthesis play an important role in green and sustainable chemistry, as in this

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Review ArticleChemical fixation of CO2 to 2-aminobenzonitriles: A straightforward route to quinazoline-2,4(1H,3H)-diones with green and sustainable chemistry perspectives

Highlights

Abstract

Introduction

Section snippets

Oranocatalyzed reactions

Metal-catalyzed reactions

Ionic liquids catalyzed reactions

Inorganic base catalyzed reactions

Catalyst-free reactions

Conclusion

Coord. Chem. Rev.

Curr. Opin. Green. Sus.

Curr. Opin. Green. Sus.

J. CO2 Util.

J. CO2 Util.

Catal. Lett.

Inorg. Chem.

Catal. Sci. Tech.

Phys. Chem. Chem. Phys.

Chemical fixation of carbon dioxide using a green and efficient catalytic system based on sugarcane bagasse-An agricultural waste

ACS Sustain. Chem. Eng.

Post-combustion CO2 capture using solid sorbents: a review

Ind. Eng. Chem. Res.

Catalytic C-H carboxylation of terminal alkynes with carbon dioxide

ACS Catal.

Carbon dioxide as a carbon source in organic transformation: carboncarbon bond forming reactions by transition-metal catalysts

Chem. Commun.

Using carbon dioxide as a building block in organic synthesis

Nat. Commun.

Substrate-assisted carbon dioxide activation as a versatile approach for heterocyclic synthesis

Synthesis

Upgrading carbon dioxide by incorporation into heterocycles

ChemSusChem

Efficient, selective and sustainable catalysis of carbon dioxide

Green Chem.

Recent advances in synthesis of functionalized β-Lactams through cyclization of N-Propargyl Amine/Amide derivatives

Curr. Org. Chem.

Pyrrole, pyrrolidine, pyridine, piperidine and tropane alkaloids

Nat. Prod. Rep.

Pyrrole: a resourceful small molecule in key medicinal hetero-aromatics

RSC Adv.

A new avenue to the synthesis of highly substituted pyrroles: synthesis from N-propargylamines

RSC Adv.

Cesium carbonate catalyzed efficient synthesis of quinazoline-2,4(1H,3H)-diones using carbon dioxide and 2-aminobenzonitriles

Green. Chem. Lett. Rev.

Benzoylene urea

Org. Synth.

Synthesis of new 1H, 3H-quinazoline-2, 4-diones

Bull. Chem. Soc. Chim. Fr.

The synthesis of 2 4 [1H, 3H] quinazolinedione and some of its 3-aryl substituted derivatives

Org. Prep. Proc. Int.

Review Article
Chemical fixation of CO₂ to 2-aminobenzonitriles: A straightforward route to quinazoline-2,4(1H,3H)-diones with green and sustainable chemistry perspectives

J. CO₂ Util.