Abstract
Green reaction under solvent-free conditions is considered as the golden achievement in the synthesis of different products. The twelve principles of “green chemistry” were formulated in the 1990s by Paul Anastas and John Warner. Accordingly, the synthesized products and related processes should comply with the twelve principles of green chemistry which offers better human health, cleaner earth, and the environment. This goal is achieved to a large extent through green chemistry under solvent-free conditions. This chapter describes the important reactions carried out in organic synthesis under solvent-free conditions.
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Keywords
- Green reactions
- Solvent-free conditions
- Environmentally friendly reaction
- Heterocyclic compounds
- Neat conditions
1 Introduction
The green chemistry movement has promoted the industry to be much cleaner. As it was mentioned, the twelve principles of “green chemistry” were introduced in the 1990s by Paul Anastas and John Warner [1]. These points were implemented by chemists, academia, and even industries based on the synthetic strategy to minimize the production of toxic materials in different reaction conditions [1].
Green chemistry is an increasing agreement to accomplish organic reactions without damaging our environment and the most important way to achieve this goal is by conducting reactions under solvent-free conditions [2,3,4,5,6]. These trends are pretty more widespread due to its many advantages like cost, energy, and time-saving which create cleaner, safer, and more facile reactions. In this scenario, it is worthwhile to design reactions under favorable conditions in water or without any solvent [7].
In this area, there are several reactions to be highlighted through solvent-free approaches, which were accomplished in the presence of different catalysts and functionalized supports such as magnetic types [8, 9] mesoporous [10] graphene oxide [11,12,13,14,15], and other metal oxides [16,17,18,19].
Synthesis of various biologically active compounds [20] was reported under solvent-free conditions via different reagents such as pyrimidines [18, 21] which are significant heterocycles present in the core of various biologically active materials [22]. These compounds provided numerous medicinal properties such as antibacterial [23] antidiabetic [24] anticancer [21] antileishmanial [25] antiallergic [26] antifungal [27] antipyretic [28] analgesic [29], and antidepressant [30]. Some of the important biologically active compounds such as afloqualone, epirizole, lamivudine, and minoxidil which are applied as anti-inflammatory [31] analgesic [31] anti-HIV [32] and antihypertensive [33] drugs are shown in Fig. 1. Several methods of green synthesis of pyrimidine derivatives under solvent-free conditions are reported.
Another important biologically active heterocyclic core is pyran, which is also synthesized under solvent-free conditions through various methods [34,35,36,37]. In this arena, pyrroles [38] quinazolinones [39, 40] benzodiazepines [41], and imidazoles [42, 43] also show biological activities and are synthesized under neat conditions.
A large number of reports dealing with the synthesis of compounds under solvent-free conditions are available. This chapter highlights and summarizes the recent (2016–2020) achievements in the green synthesis of important scaffolds under neat conditions and is classified as shown below [44].
2 Synthesis of Different Scaffolds Under Solvent-Free Conditions
Here, the green chemistry conditions applied in the synthesis of different scaffolds are highlighted.
2.1 The Synthesis of α-Aminophosphonate Derivatives
The α-aminophosphonate derivatives 4, which are essential from medicinal perspectives [45] are the structural analogues of amino acids wherein a carboxylic moiety is replaced by phosphonic group. Cirandur et al., in 2019, synthesized the anti-oxidant and anti-inflammatory α-aminophosphonate derivatives 4 through a one-pot, three-component coupling reaction from 2-aminothiazole 1 with numerous aldehydes 2 and dialkyl phosphites 3 using caffeine hydrogen sulfate (CHS) as a recyclable catalyst under microwave (MW) irradiation and solvent-free conditions at room temperature in excellent yields as shown in Scheme 1 [46].
Cirandur and co-workers [47] also reported various synthetic α-aminophosphonates 6 from 2-methoxy-5-trifluoromethyl aniline 5, numerous aldehyde derivatives 2, and diethyl phosphite 3 in the presence of meglumine sulfate (MS) as an eco-friendly catalyst at room temperature under solvent-free conditions in high yields and short reaction time (Scheme 2).
In another report, Cirandur, and co-workers [48] accomplished the above reaction through Kabachnik–Fields method [49] in the presence of the nano-CuO-Au catalyst to yield α-amino phosphonates 7, which act as α-glucosidase inhibitor and antioxidant, via three-component reaction of diverse aromatic aldehydes 2, 2-aminophenol 5, and dimethyl phosphite 3 in solvent-free conditions at 60 °C (Scheme 3).
In another report, Aribi-Zouioueche and co-workers reacted different aromatic aldehydes 2, diverse compounds of aniline 5, and dimethyl phosphite 3 under solvent-free conditions at room temperature using Candida Antarctica lipase as a biocatalyst to produce α-aminophosphonate compounds 8 (Scheme 4) [50]. Also, Esmaeilpour and co-workers [51] disclosed the mentioned process in the presence of Fe3O4@SiO2imid-PMAn without any solvent, at room temperature or by ultrasonic irradiation.
In 2019, Cirandur et al. [52] developed a process for the creation of cytotoxic α-aminophosphonates 10 by a simple and proficient one-pot three-component reaction of 3-(4-amino-3-fluorobenzyl)-N-methylbenzamide 9 with diverse aromatic aldehydes 2 and dialkyl phosphite 3 using nano-Sb2O3 catalyst under solvent-free conditions in high yields at 40–50 °C as shown in Scheme 5.
2.2 The Synthesis of Pyrimidine Derivatives
In 2019, Esnaashari et al. [53] outlined the preparation of pyrimidines through multi-component reactions using triethylenediamine or imidazole Brönsted acidic, ionic liquid-supported Zr metal–organic structure (TEDA/IMIZ-BAIL@UiO-66). The dihydropyrido[2,3-d]pyrimidine compounds 13 were yielded from the reaction of 6-amino-1,3-dimethyl uracil 11, several aromatic aldehydes 2, and acetylacetone 12 in solvent-free conditions (Scheme 6).
The metal–organic structure called MIL-53(Fe) was used as a catalyst to provide the pyrimido[4,5-d]pyrimidine compounds 15 in one-step three-component reaction from isothiocyanate 14, aromatic aldehydes 2, and 6-aminouracil or N,N-dimethyl-6-aminouracil 11 in solvent-free condition at 110 °C in high yield. The other valuable advantage of this study is the recoverable nature of the catalyst supporting green chemistry (Scheme 7) [54].
Foroughifar and co-workers [55] reported the synthesis of dihydropyrimidine derivatives 17 as potent antibacterial agents from thiourea or urea 16, acetylacetone 12, and different aryl aldehydes 2 under solvent-free conditions in the presence of the Mn0.5Fe0.25Ca0.25Fe2O4@starch@aspartic acid magnetic nanoparticles (MnFeCaFe2O4@starch@aspartic acid MNPs) as a catalyst. The merits of this reaction are easy workup, high-yield, and easy separation of catalyst (Scheme 8).
In another study, Bordoloi and co-workers [56] in 2019 demonstrated the synthesis of dihydropyrimidine derivatives 20 from various aldehydes 2, the benzil 18, and ammonium acetate 19 under the solvent-free condition at room temperature during 6–8 h in the presence of the water-extractable pomelo (WEP) as citrus fruit (Scheme 9).
Moradi and co-workers [57], in 2019, demonstrated the synthesis of benzochromenopyrimidines 23 from aldehydes 2, β‐naphthol 21, and barbituric acids 22 by a green approach without any solvent through aminated multi-walled carbon nanotubes, which were functionalized by phosphotungstic acid and tungsten called (MWCNTs@NHBut/PTA) (Scheme 10).
Saleh and co-workers reported the synthesis of fused pyrimidine compounds 26 from enaminone 24 and various heterocyclic amines 25 under solvent-free conditions in the presence of the nano-like magnesium oxide (MgO) using ball-mill process. The merits of the reaction are easy workup, high-yield, and reusable catalyst. It is important to mention that the aromatic aldehyde with electron-withdrawing groups reacted faster in comparison with electron-releasing groups (Scheme 11) [58].
A series of biologically active pyrimidine derivatives were successfully synthesized by Pal et al. [22] using graphite oxide as a green metal-free carbon catalyst (Scheme 12). In this method, cyanobenzaldehyde 2, dimedone 27, and 2-aminobenzothiazole 1 were reacted in the presence of graphite oxide tunder solvent-free reaction conditions (SFRC) at 60 °C for 20 min to provide the product 28 in 88% yield.
The synthesis of the pyrimidine derivatives 30 and 31 was developed through one-step multi-component reactions from 6-amino-1,3-dimethyl uracil 11, 3,4-methylenedioxyphenol 29 or naphthalen-2-ol 21 and the suitable aryl aldehyde 2 in solvent-free conditions in the presence of SMA/Py/ZnO, which was prepared by the reaction of poly(styrene-co-maleic anhydride) with 3-aminopyridine and zinc oxide (Scheme 13) [59].
Pyrimidine scaffold was fused with triazole and pyrazole via a three-component reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one 33, various aromatic aldehydes 2, and 3-amino-1,2,4-triazole 32 or pyrazole to yield the 4-aryl-substituted dihydropyrimidine derivatives 34 under solvent-free condition using tungstate sulfuric acid (TSA) as the green catalyst (Scheme 14) [60].
This attempt reported the synthesis of the pyrimidine-triones 36 from various benzaldehydes 2, barbituric acid 22, and 4-amino-2H-chromene-2-one 35 using p-toluenesulfonic acid as catalyst under microwave irradiation and solvent-free conditions in high yields (Scheme 15) [61].
The heterogeneous copper ferrite (CuFe2O4) was used as a nanocatalyst to synthesize benzylpyrazolyl pyrido[1,2-a]pyrimidine derivatives 38 and pyrazole 39 through a three-component reactions from various aryl aldehydes 2, 2-hydroxy-4H-pyrido[1,2-a]pyrimidine-4-ones 37, and 3-methyl-1-phenyl-1H-pyrazol-5-one 32 in solvent-free conditions, and here, the catalyst could be easily removed magnetically from the mixture of reaction (Scheme 16) [62].
Through one-pot multi-component reactions, chromeno[2,3-d]pyrimidinetrione derivatives 40 were yielded from numerous aromatic aldehydes 2, dimedone 27, or cyclohexane-1,3-dione and barbituric acid 22 in the presence of Sc(OTf)3 as catalyst under solvent-free condition at 100° C for 2 h (Scheme 17) [63].
Pyrimidine-3-carbonitriles 43 were produced through multi-component condensation reaction of various aromatic aldehydes 2, 3H-pyrido[1,2-a]pyrimidine-2,4-dione 41, and malononitrile 42 using ZnO nanoparticles as suitable catalyst under solvent-free conditions (Scheme 18) [64].
In 2018, Rawat and co-workers [18] synthesized the biologically active fused imidazo[1,2-a]pyrimidines 46 through coupling reaction involving 2-aminobenzimidazole 44, aldehyde 2, and terminal alkyne 45 in the presence of copper oxide nanoparticles as catalyst under solvent-free condition (Scheme 19).
In a similar study, Kim and co-workers [65] outlined a process to synthesize pyrimidine amine scaffolds 48 from 1H-benzo[d]imidazol-2-amine 44 and (E)-N-methyl-1-(methylthio)-2-nitroethenamine 47 with various aldehydes 2 under solvent-free condition at 80 °C using catalytic amounts of PEGMA-g-TEGBDIM (Scheme 20).
A series of pyrazolopyranopyrimidines 51 were obtained from four-component reaction of different aromatic aldehydes 2, substituted barbituric acids 22, hydrazine monohydrate 49, and ethyl acetoacetate 50 in three methods (Method A: using SB-DABCO+Cl−; Method B: using SB-DBU+Cl−; and Method C: using NSB-DBU+Cl−) under solvent-free conditions (Scheme 21) [66].
2.3 The Synthesis of the Pyran Derivatives
Ghasemzadeh and co-workers [36] synthesized tetrahydrobenzopyran derivatives 52 from different aromatic aldehydes 2, dimedone 27, ammonium acetate 19, and ethyl acetoacetate 50 through a four-component coupling reaction in the presence of Co3O4 as nanocatalyst under solvent-free condition at 100 °C (Scheme 22).
Maghsoodlou and co-workers [37] reported the synthesis of the spiro–2–amino–4H–pyran derivatives 55 through a one-step three-component condensation reaction from malononitrile 45, CH-acids 53, and isatin 54 using Na2EDTA as catalyst under solvent-free conditions at 70 °C (Scheme 23).
Siddiqui and co-workers [67] performed the synthesis of pyranopyrazole moieties 58 in the presence of the functionalized mesoporous silica and NdCl3 called Nd-SM at 70 °C under solvent-free condition by Knoevenagel condensation [68] between various aromatic aldehydes 2 and ethyl cyanoacetate 56 [69]. The resulting product reacts with substituted pyrazoline 57 through cyclization reaction to provide pyranopyrazole scaffolds (Scheme 24).
2.4 The Synthesis of the Pyrrole Derivatives
Pyrroles are one of the most significant moieties found in many natural compounds and biologically activate compounds [70]. Atar and co-workers disclosed the synthesis of tetrasubstituted pyrroles 61 which by the reaction of various types of amines 5, substituted dialkyl acetylenedicarboxylates 60, and β-nitrostyrene 59 in presence of the imidazolium Brønsted acidic ionic liquid as a metal-free catalyst under solvent-free condition. In this attempt, functionalized tetrasubstituted pyrroles were produced in acceptable yields (Scheme 25) [71].
After finding optimized conditions, nitromethane 62, various aryl aldehydes 2, 1,3‐dicarbonyl derivatives 51, and amine 5 were treated at room temperature through a one‐step four‐component reaction to afford polysubstituted pyrrole scaffolds 63 using functionalized Fe3O4 as the magnetic nanoparticle (Scheme 26) [72]. In the same study, the biologically active substituted pyrrole derivatives were formed from various ethyl acetoacetate, nitromethane, different benzaldehydes, and a variety of anilines in the presence of Cu@imine/Fe3O4 MNPs at 100 °C under solvent-free conditions in 15-25 min in 89–97% yield [38].
2.5 The Synthesis of the Imidazole Derivatives
Imidazole is a beneficial heterocyclic moiety found in many synthetic or natural compounds that attracted much attention through diverse and multi-purpose biological activity [73]. These properties marked them as valuable scaffolds for further study. Thus, Khandan-Barani and co-workers [74] designed the synthesis of 1,2,4,5-tetrasubstituted imidazoles 64 through multi-component reaction between various aryl aldehydes 2, 1,2-dicarbonyl derivatives 11, different amines 2, and ammonium acetate 18 using glutamic acid as catalyst under solvent-free condition at 60 °C during 2–4 h in acceptable yields (Scheme 27).
In a study, the functionalized catalyst called γ‐Fe2O3@TiO2 (g-Fe2O3@TiO2-EG-Cu(II)) yielded the tetrasubstituted imidazole scaffolds 65 from different types of aldehydes 2, benzil 11, and ammonium acetate 18 and substituted amines 5 under solvent‐free conditions at 100 °C [75]. The mentioned catalyst was made up of γ‐Fe2O3 core and TiO2 as a shell which was functionalized with guanidinated epibromohydrin and Cu (II) (Scheme 28).
In 2018, Sakram’s group [42] developed a process by the condensation reaction of the benzil 11, different aldehydes 2, and ammonium acetate 18 under solvent-free condition to yield 2,4,5-trisubstituted imidazoles 66. The best result was obtained at 300 W within 2–4 min in the presence of the poly(4-vinylpyridinium) bromide APVPB as an ionic liquid catalyst (Scheme 29).
2.6 The Synthesis of the Propargylamine Derivatives
Negrón-Silva and co-workers [76] demonstrated the synthesis of diastereoselective propargylamine 69 using Cu functionalized mesoporous catalyst called Cu-MCM-41 [77]. The pyrrolidine 67, phenylacetylene 68, and different aldehydes 2 reacted through C–H activation to obtain various propargylamines using Cu-MCM-41 (Scheme 30).
Layek and co-workers [78] disclosed the synthesis of propargylamines 71 through one-pot multi-component reaction of different types of aldehydes 2 with various alkynes 70 and amines 5 using [Zn(L-proline)2] as the catalyst (Scheme 31).
Zhang and co-workers [79] reported the synthesis of various propargylamines 73 using Cu(0)NPs@CMC as copper nanoparticle catalyst assembled on carboxymethylcellulose in solvent-free condition at 120 °C. To simplify the reaction process, several amines 5 were reacted with phenylpropiolic acid 72 and various aldehydes 2 in presence of the catalyst under neat conditions (Scheme 32).
3 Conclusion
The synthesis of different compounds through green reactions under solvent-free conditions is highly demanding in chemistry due to the great concern on our environment. There has been a great interest in developing environmentally benign reactions using green solvents and protocols, which lead to a series of reports using solvent-free green chemistry. A significant merit of this reaction is that many of these methods are simple and well organized. It is seen that α-amino phosphonates, pyrimidines, pyrans, pyrroles, imidazoles, and propargylamines are easily accessible by green chemistry process. The many successful models reported are applied in medicinal chemistry, drug discovery, organic synthesis, and material science. There is a future study to synthesis vast amounts of reactions in green chemistry under solvent-free conditions which reduce the cost of designing reactions.
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We highly appreciate the support of the Research Council of Alzahra University.
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Mohammadi Ziarani, G., Mohajer, F., Moradi, R. (2021). Green Reactions Under Solvent-Free Conditions. In: Anilkumar, G., Saranya, S. (eds) Green Organic Reactions. Materials Horizons: From Nature to Nanomaterials. Springer, Singapore. https://doi.org/10.1007/978-981-33-6897-2_5
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