One-pot multi-component process for the synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives catalyzed by the deep eutectic solvent choline chloride-oxalic acid

Mohammad Hosein Sayahi
  • Department of Chemistry, Payame Noor University, P.O. Box 19395-3697, Tehran, I.R. Iran
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, Maryam Gorjizadeh
  • Department of Chemistry, Shoushtar Branch, Islamic Azad University, Shoushtar, I.R. Iran
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, Melan Meheiseni
  • Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr, I.R. Iran
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and Soheil Sayyahi
  • Corresponding author
  • Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr, I.R. Iran
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Abstract

An effective method based on choline chloride (ChCl)-oxalic acid (Ox) deep eutectic solvent was proposed for the synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives. The eutectic mixture worked as both the solvent and acidic catalyst for conversion. The impacts of different variables, including the composition and volume of ChCl-Ox, and temperature, on reaction yield were studied for optimization. The crucial advantages of this process are simplicity of the experimental procedure, high yields, short reaction times, high recyclability, and the use of safe and inexpensive components.

1 Introduction

A multi-component reaction (MCR) is a convergent reaction with at least three components to form a single product, which incorporates most or even all of the starting materials. MCRs have an important role in the synthesis of different types of organic compounds [1], [2], [3]. In recent years, 4H-pyran and 2-pyridone derivatives have been considered as remarkable compounds because of their pharmaceutical activities [4], [5], [6], [7], [8], [9]. They exhibit a wide range of biological properties, including antifungal, antiviral, antibiotic, anti-HIV and antitumor [10], [11], [12], [13], [14].

A number of methods are available in literature for the synthesis of these heterocycles. The acid-catalyzed condensation of dimedone with aromatic aldehydes to get 1,8-dioxo-octahydroxanthenes seems to be a highly efficient reaction [4], [15]. It is worthy to mention that, with the addition of malononitrile to the reaction mixture, the preparation of tetrahydrobenzo[b]pyran scaffolds would be possible [16], [17]. The conventional synthetic method for the preparation of 4-azaphenanthrene-3,10-diones involves a four-component condensation of Meldrum’s acid, an aldehyde, primary amine or ammonium acetate and different 1,3-dicarbonyl compounds under different conditions [8], [9].

A deep eutectic solvent (DES) is a fluid generally composed of two or three cheap and safe components that are capable of associating with each other through hydrogen bond interactions. DESs typically have freezing points lower than those of starting individual components. One of the most widespread components used for the formation of DES is choline chloride (ChCl), an inexpensive, chemically and thermally stable, biodegradable, non-toxic and recyclable quaternary ammonium salt [18], [19], [20]. ChCl is capable of rapidly forming a DES in combination with hydrogen donors such as acids [21], alcohols [22], amines [23] or amides [24]. DES based on ChCl and organic Brønsted acid is a well-known system for synthesizing different heterocycles acting both as a solvent and a Brønsted-acidic catalyst [25].

In continuation of our research work on the applications of green catalysts for organic reactions [26], [27], [28], [29], we have carried out the synthesis of tetrahydrobenzo[b]pyrans (Scheme 1), dioxo-octahydroxanthenes (Scheme 2) and 4-azaphenanthrene-3,10-diones (Scheme 3) using the DESs ChCl and oxalic acid (ChCl-Ox), an ionic liquid, at room temperature.

Scheme 1:
Scheme 1:

Synthesis of tetrahydrobenzopyran derivatives 4a–h from aromatic aldehydes 1a–h, dimedone (2) and malononitrile (3) using ChCl-Ox.

Citation: Zeitschrift für Naturforschung B 75, 3; 10.1515/znb-2019-0155

Scheme 2:
Scheme 2:

Synthesis of 1,8-dioxo-octahydroxanthene derivatives 5a–h from aromatic aldehydes 1a–h and dimedone (2) using ChCl-Ox.

Citation: Zeitschrift für Naturforschung B 75, 3; 10.1515/znb-2019-0155

Scheme 3:
Scheme 3:

Synthesis of 4-azaphenanthrene-3,10-dione derivatives 8a–g from aromatic aldehydes 1a–g with 4-hydroxycoumarin (6), ammonia solution and dimedone (2) using ChCl-Ox.

Citation: Zeitschrift für Naturforschung B 75, 3; 10.1515/znb-2019-0155

2 Results and discussion

As stated before, DESs are cheap ionic liquid-like green solvents. In this work the DES ChCl-Ox was selected where Ox works not only as the hydrogen bond donor but also as the catalyst for the MCR. In order to study the catalytic efficiency of ChCl-Ox, we used 1 mmol of 4-chlorobenzaldehyde (1, Ar=4-Cl–C6H4), 1 mmol of dimedone (2) and 1 mmol of malononitrile (3) as a model reaction for the synthesis of 2-amino-3-cyano-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran (4c; Scheme 1, see Table 2 for formula). The reaction was carried out in different sets of conditions, and the effects of the ratio of ChCl to Ox, amount of catalyst, time and temperature on the yield were studied. To investigate the effect of molar ratio, the ammonium salt ChCl was mixed with Ox at different molar ratios (Table 1, entries 1–4). As is shown in Table 1, by increasing the molar ratio of ChCl to Ox to 1:2, the yield of the desired product increased to 92%. Therefore, this molar ratio of ChCl to Ox was selected as the best DES composition and was used for the following optimization experiments. To optimize the required catalyst amount, the model reaction was carried out in the presence of various amounts of the catalyst, and according to the obtained results, 0.5 mL was chosen as the best catalyst amount (Table 1, entries 5–7). A further increase of the amount of catalyst had no pronounced effect on the yield, indicating that the acidity requirement is well fulfilled by this amount of catalyst (Table 1, entry 8). The effect of the reaction temperature was also studied by performing the model reaction at different temperatures varying from room temperature to 80°C, again using 0.5 mL of the DES. It was found that the condensation reaction proceeded efficiently when the temperature was increased to 60°C (Table 1, entries 9–13). Other ChCl-based DESs such as ChCl-malonic acid, ChCl-glycine, ChCl-citric acid and ChCl-urea were also examined. The results clearly show that ChCl-Ox is the optimal solvent and catalyst for the reaction (Table 1, entries 13–17). It is worth to note that in a blank reaction without a catalyst (entry 18) only trace amounts of the corresponding product were obtained even after prolonged reaction times (2 h).

Table 1:

Investigation of the DES in the synthesis of 2-amino-3-cyano-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran 4c under different conditions.

No.Catalyst (molar ratio)Catalyst amount (mL)Temp. (°C)Time (min)Yielda (%)
1ChCl:oxalic acid (2:1)0.5601560
2ChCl:oxalic acid (1:1)0.5601555
3ChCl:oxalic acid (1:1.5)0.5601580
4ChCl:oxalic acid (1:2)0.5601592
5ChCl:oxalic acid (1:2)0.1601535
6ChCl:oxalic acid (1:2)0.3601568
7ChCl:oxalic acid (1:2)0.4601581
8ChCl:oxalic acid (1:2)0.6601593
9ChCl:oxalic acid (1:2)0.5Rt120Trace
10ChCl:oxalic acid (1:2)0.5401565
11ChCl:oxalic acid (1:2)0.5501581
12ChCl:oxalic acid (1:2)0.5601592
13ChCl:oxalic acid (1:2)0.5701592
14ChCl:citric acid (1:2)0.5601565
15ChCl:glycine (1:2)0.5601550
16ChCl:malonic acid (1:2)0.5601582
17ChCl:urea (1:2)0.5601545
18None60120Trace

aIsolated yields.

With these results in hand, we extended our studies to the reaction of dimedone and malononitrile with a variety of electron-donating and electron-withdrawing aldehydes to evaluate the scope of this methodology (Scheme 1). The results are presented in Table 2. It is found that substituents in the aromatic ring of the aldehydes have a minor effect on the reaction times. Aromatic aldehydes with electron-withdrawing groups reacted faster than those with electron-donating groups.

Table 2:

Three-component reaction of aromatic aldehydes 1a–h, dimedone (2) and malononitrile (3) to give tetrahydrobenzopyran derivatives 4a–h.

No.SubstrateProductTime (min)Yielda (%)M.p. (°C) [ref.]
1article imagearticle image2087229–231 [30]
2article imagearticle image1592201–203 [31]
3article imagearticle image1592211–213 [30]
4article imagearticle image1588118–120 [30]
5article imagearticle image2590218–220 [30]
6article imagearticle image2085210–212 [30]
7article imagearticle image1587178–180 [30]
8article imagearticle image3085205–207 [31]

aIsolated yields.

The scope and generality of this catalytic system was shown in the reaction of various types of aromatic aldehydes with dimedone (Scheme 2). When the reaction was carried out using one equivalent of aromatic aldehyde and two equivalents of dimedone in the presence of 0.5 mL of ChCl-Ox under the same reaction conditions used in the synthesis of the tetrahydrobenzopyran derivatives 4a–h, 1,8-dioxo-octahydroxanthene derivatives 5a–h were obtained in good to excellent yields (Table 3). The progress of the reaction was monitored by thin-layer chromatography (TLC) (EtOAc–hexane, 4:1, v/v). Work-up of the reaction was very easy. After completion of the reaction, simple filtration of the reaction mixture provided the crude product. Evaporation of the solvent under reduced pressure and recrystallization gave the final pure product.

Table 3:

Three-component reaction of aromatic aldehydes and dimedone to give 1,8-dioxo-octahydroxanthene derivatives 5a–h.

No.SubstrateProductTime (min)Yielda (%)M.p. (°C) [ref.]
1article imagearticle image1590200–202 [32]
2article imagearticle image2092232–234 [31]
3article imagearticle image1593225–227 [31]
4article imagearticle image1088240–243 [31]
5article imagearticle image2090210–212 [31]
6article imagearticle image2085219–222 [31]
7article imagearticle image1090220–222 [31]
8article imagearticle image2585242–244 [31]

aIsolated yields.

To show the further applicability of this catalytic system, the synthesis of 4-azaphenanthrene-3,10-dione derivatives 8a–g was investigated (Scheme 3, Table 4). The reaction of aromatic aldehydes with 4-hydroxycoumarin, ammonia solution and dimedone in the presence of catalytic amounts of ChCl-Ox (0.5 mL) produced the corresponding 1-phenyl-1,4-dihydro-2H-9-oxa-4-aza-phenanthrene-3,10-diones in good to excellent yields in short reaction times.

Table 4:

Four-component reaction of 4-hydroxycoumarin (6), ammonia solution, dimedone (2) and aromatic aldehydes 1a–g to give 1,8-dioxo-octahydroxanthene derivatives 8a–g.

No.SubstrateProductTime (min)Yielda (%)M.p. (°C) [ref.]
1article imagearticle image2090184–186 [33]
2article imagearticle image1592201–203 [33]
3article imagearticle image1590218–220
4article imagearticle image1588185–187
5article imagearticle image3090184–186 [33]
6article imagearticle image2585192–194 [33]
7article imagearticle image1590201–203

aIsolated yields.

In general, the mechanism of such synthetic procedures involves the Knoevenagel reaction, Michael addition and intra-molecular cyclization. A proposed mechanism to demonstrate the role of catalyst for the synthesis of tetrahydrobenzo[b]pyran is shown in Scheme 4. The arylidenemalononitrile intermediate (I) was formed initially by the Knoevenagel condensation between activated aldehyde and malononitrile in the presence of ChCl-Ox. Subsequently, the Michael addition of the enolizable dimedone to the arylidenemalononitrile intermediate (I), followed by intramolecular cyclization and final tautomerization of intermediates, afforded the desired product (Scheme 4). A similar mechanism may occur for the formation of 4-azaphenanthrene-3,10-dione and 1,8-dioxo-octahydroxanthene derivatives.

Scheme 4:
Scheme 4:

Possible reaction pathway for the ChCl-Ox-catalyzed synthesis of tetrahydrobenzo[b]pyran derivatives 4a–h.

Citation: Zeitschrift für Naturforschung B 75, 3; 10.1515/znb-2019-0155

In environmentally friendly methodologies, the recovery of the prepared catalyst is highly preferable. For this purpose, the model reaction was selected again to investigate the reusability of the DES catalyst under the optimal conditions. After completion of the reaction, the crude product was separated by simple filtration. The DES catalyst was recovered by removing the aqueous layer under vacuum from the filtrate. As is shown in Fig. 1, the DES could be recycled and reused up to four times with only a slight decrease in catalytic activity.

Fig. 1:
Fig. 1:

The reusability of the solvent/catalyst ChCl-Ox.

Citation: Zeitschrift für Naturforschung B 75, 3; 10.1515/znb-2019-0155

3 Conclusion

In summary, we have developed a novel multi-component approach for the one-pot synthesis of 4-azaphenanthrene-3,10-dione, 1,8-dioxo-octahydroxanthene and tetrahydrobenzo[b]pyran derivatives using a deep eutectic mixture of ChCl and Ox in a molar ratio of 1:2 as a catalyst. High yields, an environmentally benign solvent, the good reusability of the catalyst and simple reaction conditions are the noteworthy aspects of the protocol.

4 Experimental section

4.1 Materials and methods

All chemicals were commercial and were used as received. The reactions were monitored by TLC on silica gel polygram SILG/UV 254 plates. The yields of products refer to isolated compounds. Melting points were determined using Stuart scientific apparatus. FT-IR spectra were obtained as potassium bromide pellets in the range of 400–4000 cm−1 using a BOMEM MB-Series 1998 FT-IR spectrophotometer. The 1H and 13C NMR spectra of samples were recorded with a Bruker Advanced DPX 400-MHz.

4.2 Preparation of a deep eutectic solvent

In this study, the eutectic mixtures of ChCl and Ox were synthesized at molar ratios of 2:1, 1:1 and 1:2 and utilized as solvents and catalyst for the one-pot synthesis of tetrahydrobenzo[b]pyran (4a–h), 1,8-dioxo-octahydroxanthene (5a–h) and 4-azaphenanthrene-3,10-dione derivatives (8a–h). To prepare these mixtures, ChCl and Ox were mixed at T=60°C for approximately 15 min until a homogeneous, colorless liquid formed. The obtained DES was used without any further purification.

4.3 General procedure for the synthesis of tetrahydrobenzo[b]pyrans 4a–h

Aldehyde (1 mol), dimedone (1 mol), malononitrile (1 mol) and DES (0.5 mL) as catalysts were mixed and heated at 60°C for 15–30 min. After completion of the reaction monitored by TLC, water (5 mL) was added and the solid product was filtered and washed with H2O. Then hot EtOH was poured on the precipitate until the product was solved. Finally, products were recrystallized for more purification (Table 2).

4.4 General procedure for the synthesis of 1,8-dioxo-octahydroxanthene 5a–h

Aromatic aldehydes (1 mmol), dimedone (2 mol) and ChCl-Ox (0.5 mL) were added into a 5 mL round-bottom flask and were stirred at 60°C for appropriate time according to Table 3. The progress of the reaction was monitored by TLC. After completion of the reaction, water (5 mL) was added and the solid was separated by filtration. The crude products were obtained in high purity after purification by recrystallization from ethanol. All the products were known compounds and were characterized by comparing spectroscopic data and their melting points to the literature values.

4.5 General procedure for the preparation of 4-azaphenanthrene-3,10-diones 8a–g

To a mixture of 4-hydroxycoumarin (1 mmol), 28–30% ammonia solution (5 mmol), dimedone (1 mmol) and aromatic aldehyde (1 mmol), ChCl-Ox (0.5 mL) was added. The mixture was stirred at 60°C for appropriate time according to Table 4. After completion of the reaction, as indicated by TLC, H2O (5 mL) was added to the reaction mixture and then the precipitate was filtered off and washed with EtOH and water. Finally, the crude product was purified by recrystallization with EtOH to afford the corresponding products in high yields.

4.6 Characterization data for compounds 8c, 8d, 8g and 4e

4.6.1 1-(4-Chloro-phenyl)-1,4-dihydro-2H-9-oxa-4-aza-phenanthrene-3,10-dione (8c)

White powder; m.p. 218–220°C. – FT-IR (KBr, cm−1): ν=3185, 3139, 2923, 1690, 1637, 1605, 1571, 1515, 1464, 1407, 1368, 1318, 1240, 1195, 1012, 999, 829, 769, 739, 627, 547. – 1H NMR (DMSO-d6, 500 MHz, ppm): δ=2.58 (dd, 1H), 3.32 (d, 1H), 4.37 (d, 1H), 7.20–8.24 (m, ArH, 8H), 11.01 (s, NH, 1H). – 13C NMR (DMSO-d6, 125 MHz, ppm): δ=171.6, 160.1, 152.7, 147.2, 141.7, 134.0, 133.1, 130.2, 130.0, 125.7, 124.6, 118.4, 114.5, 104.4, 37.05, 36.4.

4.6.2 1-(2,4-Dichloro-phenyl)-1,4-dihydro-2H-9-oxa-4-aza-phenanthrene-3,10-dione (8d)

White powder; m.p. 185–187°C. – FT-IR (KBr, cm−1): ν=3239, 3038, 2923, 1722, 1692, 1671, 1633, 1609, 1574, 1519, 1463, 1363, 1324, 1200, 1165, 1049, 821, 766, 748, 630, 598, 480. – 1H NMR (DMSO-d6, 500 MHz, ppm): δ=2.53 (dd, 1H), 3.33 (d, 1H), 4.65 (d, 1H), 7.20–8.24 (m, ArH, 7H), 11.13 (s, NH, 1H). – 13C NMR (DMSO-d6, 125 MHz, ppm): δ=170.9, 161.4, 154.3, 148.4, 138.3, 134.9, 134.2, 131.0, 130.2, 129.3, 125.8, 124.8, 118.4, 114.5, 103, 37.6, 34.4.

4.6.3 1-(4-Nitro-phenyl)-1,4-dihydro-2H-9-oxa-4-aza-phenanthrene-3,10-dione (8g)

White powder; m.p. 201–203°C. – FT-IR (KBr, cm−1): ν=3265, 3078, 1723, 1690, 1684, 1625, 1511, 1459, 1411, 1348, 1277, 1231, 1196, 1155, 1112, 1070, 1004, 946, 906, 858, 758, 730, 632, 518. – 1H NMR (DMSO-d6, 500 MHz, ppm): δ=2.89 (dd, 1H), 3.33 (d, 1H), 4.52 (d, 1H), 7.20–8.27 (m, ArH, 8H), 11.10 (s, NH, 1H). – 13C NMR (DMSO-d6, 125 MHz, ppm): δ=171.3, 161.6, 154.3, 150.6, 148.1, 147.6, 134.1, 129.6, 125.7, 125.4, 124.7, 118.4, 114.5, 103.6, 38.9, 36.9.

4.6.4 2-Amino-3-cyano-4-(4-methylphenyl)-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran (4e)

White powder; m.p. 218–220°C. – FT-IR (KBr, cm−1): ν=3425, 3321, 2995, 2187, 1672, 1638, 1598, 1484, 1365. – 1H NMR (DMSO-d6, 500 MHz, ppm): δ=0.89 (s, 3H), 0.96 (s, 3H), 1.89 (d, 1H), 2.03 (d, 1H), 2.12 (s, 3H), 2.33 (s, 2H), 4.13 (s, 1H), 5.8 (s, NH, 2H), 6.90–9.96 (m, ArH, 4H). – 13C NMR (DMSO-d6, 125 MHz, ppm): δ=196.0, 162.7, 158.8, 142.2, 136.0, 129.3, 127.5, 120.1, 113.2, 58.8, 50.4, 39.8, 35.5, 32.2, 28.8, 27.1, 21.0.

5 Supplementary information

Characterization of the products 8c, 8d, 8g and 4e is given as Supplementary information available online (http://dx.doi.org/10.1515/znb-2019-0155).

Acknowledgments

We gratefully acknowledge the financial support of the Mahshahr Branch, Islamic Azad University.

References

  • [1]

    J. Zhu, Q. Wang, M. X. Wang (Eds.), Multicomponent Reactions in Organic Synthesis, Wiley, Hoboken, 2014.

  • [2]

    M. Muntzeck, R. Wilhelm, Z. Naturforsch.201873b, 515–519.

  • [3]

    M. Kidwai, K. Singhal, S. Kukreja, Z. Naturforsch. 200762b, 732–736.

  • [4]

    S. Makone, S. Mahurkar, Green Sustain. Chem.20133, 27–32.

  • [5]

    A. Javid, M. M. Heravi, F. F. Bamoharram, E-J. Chem.20118, 910 –916.

  • [6]

    D. Azarifar, Y. Abbasi, Synth. Commun.201646, 745–758.

  • [7]

    H. Hu, F. Qiu, A. Ying, J. Yang, H. Meng, Int. J. Mol. Sci.2014 15, 6897–6909.

  • [8]

    M. O. Noguez, V. Marcelino, H. Rodríguez, O. Martín, J. O. Martínez, G. A. Arroyo, F. J. Pérez, M. Suárez, R. Miranda, Int. J. Mol. Sci.201112, 2641–2649.

  • [9]

    S. Tu, X. Zhu, J. Zhang, J. Xu, Y. Zhang, Q. Wang, R. Jia, B. Jiang, J. Zhang, C. Yao, Bioorg. Med. Chem. Lett.200616, 2925–2928.

  • [10]

    J. J. Li, X. Y. Tao, Z. H. Zhang, Phosphorus Sulfur Silicon2008183, 1672–1678.

  • [11]

    R. R. Kumar, S. Perumal, J. C. Menéndez, P. Yogeeswari, D. Sriram, Bioorg. Med. Chem.201119, 3444–3450.

  • [12]

    N. M. Sabry, H. M. Mohamed, E. S. A. E. H. Khattab, S. S. Motlaq, A. M. El-Agrody, Eur. J. Med. Chem.201146, 765–772.

  • [13]

    R. J. Cox, D. O’Hagan, J. Chem. Soc. Perkin Trans 1199110, 2537–2540.

  • [14]

    A. M. El-Agrody, A. M. Fouda, E. S. A. E. H. Khattab, Med. Chem. Res.201322, 6105–6120.

  • [15]

    A. Maleki, M. Aghaei, N. Ghamari, Appl. Organomet. Chem. 201630, 939–942.

  • [16]

    I. López, J. L. Bravo, M. Caraballo, J. L. Barneto, G. Silvero, Tetrahedron Lett.201152, 3339–3341.

  • [17]

    F. Shirini, M. Makhsous, M. Seddighi, Iran. J. Catal.20177, 21–26.

  • [18]

    H. R. Lobo, B. S. Singh, G. S. Shankarling, Catal. Commun.201227, 179–183.

  • [19]

    E. Habibi, K. Ghanemi, M. Fallah-Mehrjardi, A. Dadolahi-Sohrab, Anal. Chim. Acta2013762, 61–67.

  • [20]

    A. Shaabani, S. E. Hooshmand, A. Tavousi Tabatabaei, Tetrahedron Lett.201657, 351–353.

  • [21]

    A. K. Sanap, G. S. Shankarling, RSC Adv.20144, 34938–34943.

  • [22]

    A. P. Abbott, R. C. Harris, K. S. Ryder, C. D’Agostino, L. F. Gladden, M. D. Mantle, Green Chem.201113, 82–90.

  • [23]

    S. Khandelwal, Y. K. Tailor, M. Kumar, J. Mol. Liq.2016215, 345–386.

  • [24]

    E. L. Smith, A. P. Abbott, K. S. Ryder, Chem. Rev.2014114, 11060–11082.

  • [25]

    M. Bakavoli, H. Eshghi, M. Rahimizadeh, M. R. Housaindokht, A. Mohammadi, H. Monhemi, Res. Chem. Intermed.201541, 3497–3505.

  • [26]

    A. Shouli, S. Menati, S. Sayyahi, C. R. Chim.201720, 765–772.

  • [27]

    S. Sayyahi, A. Azin, S. J. Saghanezhad, J. Mol. Liq. 2014198, 30–36.

  • [28]

    A. Amini, S. Sayyahi, S. J. Saghanezhad, Catal. Commun. 201678, 11–16.

  • [29]

    N. Kakesh, S. Sayyahi, R. Badri, C. R. Chim.201821, 1023–1028.

  • [30]

    F. Heidarizadeh, N. Taheri, Res. Chem. Intermed.201642, 3829 –3846.

  • [31]

    M. Hajjami, F. Gholamian, R. H. E. Hudson, A. M. Sanati, Catal. Lett.2019149, 228–247.

  • [32]

    J. Albadia, M. Keshavarz, M. Abedini, M. Khoshakhlagh, J. Chem. Sci.2013125, 295–298.

  • [33]

    M. H. Sayahi, S. J. Saghanezhad, M. Mahdavi, Res. Chem. Intermed.201844, 739–747.

Footnotes

Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/znb-2019-0155).

If the inline PDF is not rendering correctly, you can download the PDF file here.

  • [1]

    J. Zhu, Q. Wang, M. X. Wang (Eds.), Multicomponent Reactions in Organic Synthesis, Wiley, Hoboken, 2014.

  • [2]

    M. Muntzeck, R. Wilhelm, Z. Naturforsch.201873b, 515–519.

  • [3]

    M. Kidwai, K. Singhal, S. Kukreja, Z. Naturforsch. 200762b, 732–736.

  • [4]

    S. Makone, S. Mahurkar, Green Sustain. Chem.20133, 27–32.

  • [5]

    A. Javid, M. M. Heravi, F. F. Bamoharram, E-J. Chem.20118, 910 –916.

  • [6]

    D. Azarifar, Y. Abbasi, Synth. Commun.201646, 745–758.

  • [7]

    H. Hu, F. Qiu, A. Ying, J. Yang, H. Meng, Int. J. Mol. Sci.2014 15, 6897–6909.

  • [8]

    M. O. Noguez, V. Marcelino, H. Rodríguez, O. Martín, J. O. Martínez, G. A. Arroyo, F. J. Pérez, M. Suárez, R. Miranda, Int. J. Mol. Sci.201112, 2641–2649.

  • [9]

    S. Tu, X. Zhu, J. Zhang, J. Xu, Y. Zhang, Q. Wang, R. Jia, B. Jiang, J. Zhang, C. Yao, Bioorg. Med. Chem. Lett.200616, 2925–2928.

  • [10]

    J. J. Li, X. Y. Tao, Z. H. Zhang, Phosphorus Sulfur Silicon2008183, 1672–1678.

  • [11]

    R. R. Kumar, S. Perumal, J. C. Menéndez, P. Yogeeswari, D. Sriram, Bioorg. Med. Chem.201119, 3444–3450.

  • [12]

    N. M. Sabry, H. M. Mohamed, E. S. A. E. H. Khattab, S. S. Motlaq, A. M. El-Agrody, Eur. J. Med. Chem.201146, 765–772.

  • [13]

    R. J. Cox, D. O’Hagan, J. Chem. Soc. Perkin Trans 1199110, 2537–2540.

  • [14]

    A. M. El-Agrody, A. M. Fouda, E. S. A. E. H. Khattab, Med. Chem. Res.201322, 6105–6120.

  • [15]

    A. Maleki, M. Aghaei, N. Ghamari, Appl. Organomet. Chem. 201630, 939–942.

  • [16]

    I. López, J. L. Bravo, M. Caraballo, J. L. Barneto, G. Silvero, Tetrahedron Lett.201152, 3339–3341.

  • [17]

    F. Shirini, M. Makhsous, M. Seddighi, Iran. J. Catal.20177, 21–26.

  • [18]

    H. R. Lobo, B. S. Singh, G. S. Shankarling, Catal. Commun.201227, 179–183.

  • [19]

    E. Habibi, K. Ghanemi, M. Fallah-Mehrjardi, A. Dadolahi-Sohrab, Anal. Chim. Acta2013762, 61–67.

  • [20]

    A. Shaabani, S. E. Hooshmand, A. Tavousi Tabatabaei, Tetrahedron Lett.201657, 351–353.

  • [21]

    A. K. Sanap, G. S. Shankarling, RSC Adv.20144, 34938–34943.

  • [22]

    A. P. Abbott, R. C. Harris, K. S. Ryder, C. D’Agostino, L. F. Gladden, M. D. Mantle, Green Chem.201113, 82–90.

  • [23]

    S. Khandelwal, Y. K. Tailor, M. Kumar, J. Mol. Liq.2016215, 345–386.

  • [24]

    E. L. Smith, A. P. Abbott, K. S. Ryder, Chem. Rev.2014114, 11060–11082.

  • [25]

    M. Bakavoli, H. Eshghi, M. Rahimizadeh, M. R. Housaindokht, A. Mohammadi, H. Monhemi, Res. Chem. Intermed.201541, 3497–3505.

  • [26]

    A. Shouli, S. Menati, S. Sayyahi, C. R. Chim.201720, 765–772.

  • [27]

    S. Sayyahi, A. Azin, S. J. Saghanezhad, J. Mol. Liq. 2014198, 30–36.

  • [28]

    A. Amini, S. Sayyahi, S. J. Saghanezhad, Catal. Commun. 201678, 11–16.

  • [29]

    N. Kakesh, S. Sayyahi, R. Badri, C. R. Chim.201821, 1023–1028.

  • [30]

    F. Heidarizadeh, N. Taheri, Res. Chem. Intermed.201642, 3829 –3846.

  • [31]

    M. Hajjami, F. Gholamian, R. H. E. Hudson, A. M. Sanati, Catal. Lett.2019149, 228–247.

  • [32]

    J. Albadia, M. Keshavarz, M. Abedini, M. Khoshakhlagh, J. Chem. Sci.2013125, 295–298.

  • [33]

    M. H. Sayahi, S. J. Saghanezhad, M. Mahdavi, Res. Chem. Intermed.201844, 739–747.

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Zeitschrift für Naturforschung B is an international scientific journal which publishes original papers, microreviews, and letters from all areas of inorganic chemistry, solid state chemistry, coordination chemistry, molecular chemistry, and organic chemistry.

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    Synthesis of tetrahydrobenzopyran derivatives 4a–h from aromatic aldehydes 1a–h, dimedone (2) and malononitrile (3) using ChCl-Ox.

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    Synthesis of 1,8-dioxo-octahydroxanthene derivatives 5a–h from aromatic aldehydes 1a–h and dimedone (2) using ChCl-Ox.

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    Synthesis of 4-azaphenanthrene-3,10-dione derivatives 8a–g from aromatic aldehydes 1a–g with 4-hydroxycoumarin (6), ammonia solution and dimedone (2) using ChCl-Ox.

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    Possible reaction pathway for the ChCl-Ox-catalyzed synthesis of tetrahydrobenzo[b]pyran derivatives 4a–h.

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    The reusability of the solvent/catalyst ChCl-Ox.