Startseite Naturwissenschaften Para toluenesulfonic acid-catalyzed one-pot, three-component synthesis of benzo[5,6]chromeno[3,2-c]quinoline compounds in aqueous medium
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Para toluenesulfonic acid-catalyzed one-pot, three-component synthesis of benzo[5,6]chromeno[3,2-c]quinoline compounds in aqueous medium

  • Naser Sadeghpour Orang , Hadi Soltani EMAIL logo , Mehdi Ghiamirad und Mehdi Ahmadi Sabegh
Veröffentlicht/Copyright: 6. Oktober 2021
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Heterocyclic Communications
Aus der Zeitschrift Heterocyclic Communications Band 27 Heft 1

Abstract

A new series of benzo[5,6]chromeno[3,2-c]quinoline derivatives were successfully synthesized using various arylglyoxal monohydrates, quinoline-2,4-dione, and β-naphthol in H2O:EtOH (2:1) as a green solvent in the presence of catalytic amounts p-toluenesulfonic acid as a mild catalyst under reflux conditions with high yields (83–92%). The reaction conditions were optimized in different solvents at variable thermal conditions, and the optimized reaction condition for this synthesis has been reported. The structures of all new products were defined by 1H-NMR, 13C-NMR, FT-IR, mass spectral data, and HRMS.

Graphical abstract

Keywords: arylglyoxal; chromenes; one-pot; three-component reaction; pyran; p-toluenesulfonic acid; quinoline

1 Introduction

In this research, ten new analogs of 4H-pyran compounds were successfully synthesized using a one-pot, multicomponent reaction approach, which may have medicinal and pharmacological properties. Polyfunctionalized 4H-pyran nucleus is a fertile source of important biological molecules with a wide range of interestingly biological and pharmaceutical activities [1]. 4H-pyran and chromene structures have had an effective role in the pharmaceutical research in recent years and have been used as precursors in synthesizing pharmaceutically active compounds [2].

Some reported crucial features of these therapeutic compounds are as follows: anti-tumor activities [3,4], antibacterial [3,5], anti-viral [3,6], anti-oxidant [7], anti-diabetic [8], anti-allergenic [9], anti-rheumatic [10], antispasmodics [11], anti-cancer [12,13,14], anti-HIV protease inhibitors [15], anticonvulsants [16], antimicrobials [17], anti-Schizophrenia [18], psychotropic, anti-inflammatory [19], cardiotonic activities [20], anti-malaria [21], and treatment of neurodegenerative disorders including Alzheimer and Parkinson [22]. Due to the widespread and useful applications of heterocyclic derivatives incorporating the 4H-pyrans and chromenes scaffold [23], the development of this method to synthesize other new derivatives has been considered by chemists and pharmacists in recent years; hence, it can be emphasized that heterocyclic compounds play a significant and fundamental role in the development of modern organic chemistry [24,25]. As mentioned, many pyrans and chromenes have some effects in the field of pharmacy, and some of them are currently used as potent drugs in some clinical treatments [26,27,28,29,30,31,32].

For example: 4-(allyloxy)-2H-chromen-2-one (Figure 1a) [33] and N-(3-cyano-5-oxo-4,7-diphenyl-5,6,7,8-tetrahydro-4H-chromen-2-yl)acetamide (Figure 1b) [34] nowadays are being developed as anti-cancer agents. Moreover, 2-amino-3-cyano-4,7-dihydro-4-(3,4,5-trimethoxyphenyl)-pyrano[2,3-e]indole (Figure 1c) [35] is also used as an antibacterial agent. Additionally, 2-(3,4-dihydroxyphenyl)3,5-dihydroxy-7-methoxy chromen-4-one (Figure 1d) [36] exhibits an effect of anti-rheumatism usage.

Figure 1 Chromene-based active molecules.
Figure 1

Chromene-based active molecules.

In addition, the selected method has been one of the best available techniques for the synthesis of biologically active heterocycles in recent years because of some remarkable targeted advantages such as simplicity of isolation and purification steps, use of green solvent, more productivity with chemo- and regioselectivity, having environmentally sustainable conditions, green strategy, avoiding unwanted and undesirable by-products and economic cost-effectiveness and easy handling [37,38,39,40,41,42,43,44]. As mentioned earlier, a one-pot three-component reaction protocol is used in this research to synthesize the new series of benzo[5,6]chromeno[3,2-c]quinoline derivatives.

2 Results and discussion

In continuation of our work on arylglyoxal-based synthesis of heterocyclic compounds, using one-pot, multicomponent strategies, herein, it is reported as a convenient one-pot, three-component process for the synthesis of chromeno derivatives, using arylglyoxals, quinoline-2,4(1H,3H)-dione, and naphthalen-2-ol in the presence of p-TSA in EtOH:H2O (1:2). This synthetic strategy is promising for the synthesis of novel chromene structures that may have pharmaceutical and biological activities (Figure 2).

Figure 2 Synthesis of chromeno derivatives using arylglyoxals, quinoline-2,4(1H,3H)-dione, and naphthalen-2-ol in the presence of p-TSA in EtOH:H2O (1:2).
Figure 2

Synthesis of chromeno derivatives using arylglyoxals, quinoline-2,4(1H,3H)-dione, and naphthalen-2-ol in the presence of p-TSA in EtOH:H2O (1:2).

To find the optimal reaction conditions, this investigation started with the synthesis of benzo[5,6]chromeno[3,2-c]quinoline derivatives by a systematic study on the model reaction of arylglyoxals, quinoline-2,4(1H,3H)-dione, and naphthalen-2-ol (molar ratio 1:1:1) using various solvents, catalysts, times, and temperatures to evaluate the rate and the yield of reactions.

To find the best catalyst for these reactions, the reactions were performed using p-TSA, l-cysteine, DABCO, l-proline, β-alanine, and Et3N as selected catalysts, and the best result was obtained in terms of yield (92%) and reaction time (1 h) when the reaction was performed using 20 mol% of p-TSA (Table 1, entry 5).

Table 1

Optimization of the reaction conditions for the synthesis of compound 4c

Entry Catalyst Temperature (°C) Solvent Time (h) Yield (%)
1 No catalyst 50 EtOH/H2O 5 No reaction
2 No catalyst Reflux EtOH/H2O 3 47
3 p-TSA (20 mol%) Reflux H2O 5 No reaction
4 p-TSA (20 mol%) Reflux EtOH 5 50
5 p-TSA (20 mol%) Reflux EtOH/H2O 1 92
6 P-TSA (20 mol%) Reflux THF 1 66
7 P-TSA (20 mol%) Reflux CH2Cl2 1 63
8 l-Cysteine (20 mol%) Reflux EtOH/H2O 1 61
9 DABCO (20 mol%) Reflux EtOH/H2O 1 62
10 l-Proline (20 mol%) Reflux EtOH/H2O 1 63
11 β-Alanine (20 mol%) Reflux EtOH/H2O 1 63
12 Et3N (20 mol%) Reflux EtOH/H2O 1 47
13 K2CO3 (20 mol%) Reflux EtOH/H2O 1 48

DABCO: 1,4-diazabicyclo[2,2,2]octane; p-TSA: p-toluene sulfonic acid.

To determine the best solvent, the reactions were repeated in various solvents such as water (H2O), ethanol (EtOH), EtOH:H2O (1:2), tetrahydrofuran (THF), and dichloromethane (CH2Cl2). The use of EtOH:H2O (1:2) proved to be the best in terms of yield and reaction time (Table 1, entry 5). The products were fully characterized by their FT-IR, 1H-NMR, and 13C-NMR spectral data and mass analysis.

We explored the optimized condition to different arylglyoxal derivatives 1a–j (monohydrate form), naphthalen-2-ol (2), and quinoline-2,4(1H,3H)-dione (3) to form the desired products 4a–j in high yields. The results with various arylglyoxals, product, melting points, and yields are summarized in Table 2.

Table 2

Synthesis of chromeno derivatives 4a–j via the one-pot, three-component reaction

Entry Arylglyoxal monohydrates Products Time (h) M.P. (oC) Yield (%) Color
1(a) 2 299–300 87 White
2(b) 1 297–298 90 White
3(c) 1 281–282 92 White
4(d) 2 294 (Dec.) 86 White
5(e) 1 274–275 84 White
6(f) 1 288–289 85 White
7(g) 1 294 (Dec.) 83 White
8(h) 1 211–212 91 Light yellow
9(i) 1 293 (Dec.) 86 White
10(j) 2 224–225 89 Light yellow

In the first stage, arylglyoxal monohydrates 1a–j are converted to free arylglyoxal in the presence of para-toluenesulfonic acid catalyst by removing a water molecule. This catalyst also converts quinoline-2,4-dione (3) to its enol form (enolate ion). Then Knoevenagel condensation between free glyoxal and quinoline enol form leads to the production of intermediate A, which is converted to intermediate B by the loss of a water molecule with the help of a catalyst.

Adding Michael β-naphthol (2) to intermediate B in the presence of para-toluene catalyst produces intermediate sulfonic acid C, which has a keto-enol totomerization. In the next step, the intermediate C in the presence of para-toluene sulfonic acid catalyst produces D through intramolecular density. By removing a water molecule from compound D in the presence of an acid catalyst, new heterocyclic derivatives 4a–j are synthesized. The possible mechanism is shown in Figure 3.

Figure 3 A plausible mechanism for the synthesis of benzo[5,6]chromeno[2,3-d]pyrimidine derivatives catalyzed by p-TSA.
Figure 3

A plausible mechanism for the synthesis of benzo[5,6]chromeno[2,3-d]pyrimidine derivatives catalyzed by p-TSA.

All of the synthesized products, except 4h and 4j, are white powder and have a stable keto form. In 4j and 4h products, a stable enol form of eno l-keto tautomerization can be seen. It can be considered that the presence of the nitro group in 4j product and chloro group in h product on para position caused to form a stable enol form. The synthesized enol and keto form products have light yellow and white colors, respectively.

3 Conclusion

We have synthesized the 4H-pyran derivatives 4a–j by one-pot, three-component reaction of various arylglyoxals, quinoline-2,4-dione, and β-naphthol in H2O:EtOH (2:1) as a green solvent in the presence of catalytic amounts para toluenesulfonic acid as a mild and efficient catalyst under reflux conditions with high yields (83–92%). The simplicity of operation, high yields, environmentally benign, regioselectivity, and green solvents are the key advantages of this method.

4 Experimental

The chemicals and reagents used for the synthesis were obtained from Merck and Sigma Aldrich. Melting points were measured on an Electrothermal 9,200 apparatus and are uncorrected. Infrared spectra were measured on a Spectrum Tensor 27, Bruker, Equinox 55 FT-IR instrument using KBr disks. 1H (500 MHz) and 13C (125 MHz) NMR spectra were recorded on a Varian-Inova spectrometer in DMSO-d 6 with TMS as an internal reference. Analytical thin-layer chromatography (TLC) was carried out on pre-coated aluminum sheet with silica gel 60 F 254 obtained from Merck, and the detection was made with the help of a UV lamp (λ 254 nm). Mass analysis was performed on an Agilent Technology (HP) 5,973 Network Mass Selective Detector, and high-resolution mass spectra were recorded on a Kratos mass spectrometry (MS) 25RF spectrometer.

4.1 General procedure for the synthesis of benzo[5,6]chromeno[3,2-c]quinoline derivatives (4a–j)

To a suspension of aryl glyoxal monohydrates 1a–j (1 mmol) in H2O:EtOH (2:1) (5 mL), p-TSA (20 mol%) was added. The reaction mixture was heated and stirred under reflux conditions for 15 min to dissolve the reactant. Then, 4-hydroxyquinolin-2(1H)-one (2, 1 mmol, 161 mg) and β-naphthalene (3, 1 mmol, 144 mg) were added to the reaction mixture, which were stirred at the above-mentioned temperature for appropriate times as listed in Table 2. The development of the reaction was controlled by TLC (MeOH:CHCl3/1:10 as eluent). After completion of the reaction, the precipitate was filtered and washed with water to give the desired products 4a-j in high yield (83–92%).

4.2 7-Benzoyl-5,7-dihydro-6H-benzo[5,6]chromeno[3,2-c]quinolin-6-one (4a)

White powder; mp: 299–300°C; FT-IR ν max: 2,947, 1,696, 1,633, 1,602, 1,444, 1,400, 818, 755, 673 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.56 (s, 1H, OH, D2O exch.), 12.17 (s, 1H, OH, D2O exch.), 7.98 (d, J = 7.7 Hz, 2H, Ar), 7.70 (d, J = 7.4 Hz, 2H, Ar), 7.59 (t, J = 7.3 Hz, 2H, Ar), 7.44 (t, J = 7.3 Hz, 2H, Ar), 7.39–7.34 (m, 3H, Ar), 7.33–7.28 (m, 3H, Ar), 6.35 (s, 1H, Ar); 13C NMR (125 MHz, DMSO-d 6) δ 183.8, 183.4, 179.4, 175.0, 174.5, 165.7, 161.9, 159.3, 149.5, 147.9, 144.7, 137.5, 132.5, 131.8, 128.48, 127.9, 123.7, 123.1, 116.4, 112.0, 109.8, 106.3, 102.4, 99.2, 88.1; LRMS (EI, 70 eV) m/z (%): 403 (M+, 33), 333 (100), 315 (26), 277 (40), 248 (47), 220 (10), 174 (19), 161 (31), 146 (13), 120 (33), 105 (74), 92 (28), 77 (68), 51 (12); HRMS (ESI): m/z (M)+ calcd for C27H17 NO 3 + : 403.1208; found: 403.1205.

4.3 (E)-7-(Hydroxy(p-tolyl)methylene)-7H-benzo[5,6]chromeno[3,2-c]quinolin-6-ol (4b)

White powder; mp: 297–298°C; FT-IR ν max: 2,952, 1,730, 1,694, 1,634, 1,604, 1,547, 1,401, 1,305, 807, 761, 669 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.53 (s, 1H, OH, D2O exch.), 12.16 (s, 1H, OH, D2O exch.), 7.98 (d, J = 8.1 Hz, 2H, Ar), 7.59 (t, J = 8.3 Hz, 4H, Ar), 7.37 (d, J = 8.2 Hz, 2H, Ar), 7.30 (t, J = 7.5 Hz, 3H, Ar), 7.14 (d, J = 7.9 Hz, 2H, Ar), 6.31 (s, 1H, Ar), 2.25 (s, 3H, Me); 13C NMR (125 MHz, DMSO-d 6) δ 194.9, 192.1, 186.3, 185.5, 184.4, 180.0, 177.1, 174.2, 169.8, 165.8, 164.5, 162.1, 142.8, 137.5, 135.2, 134.6, 131.8, 129.9, 129.1, 128.1, 123.7, 123.1, 116.4, 115.8, 109.9, 21.5; LRMS (EI, 70 eV) m/z (%): 417 (M+, 11), 333 (100), 315 (21), 240 (34), 119 (51), 91 (34), 65 (11); HRMS (ESI): m/z (M)+ calcd for C28H19 NO 3 + : 417.1365; found: 417.1368.

4.4 7-(4-Methoxybenzoyl)-5,7-dihydro-6H-benzo[5,6]chromeno[3,2-c]quinolin-6-one (4c)

White powder; mp: 281–282°C; FT-IR ν max: 2,947, 1,696, 1,638, 1,603, 1,394, 1,313, 827, 758 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.51 (s, 1H, OH, D2O exch.), 12.15 (s, 1H, OH, D2O exch.), 7.98 (d, J = 8.0 Hz, 2H, Ar), 7.68 (d, J = 8.6 Hz, 2H, Ar), 7.59 (t, J = 7.4 Hz, 2H, Ar), 7.38 (d, J = 8.0 Hz, 2H, Ar), 7.30 (t, J = 7.4 Hz, 3H, Ar), 6.89 (d, J = 8.7 Hz, 2H, Ar), 6.28 (s, 1H, Ar), 3.74 (s, 3H, OMe); 13C NMR (125 MHz, DMSO-d 6) δ 182.7, 181.9, 177.8, 175.2, 172.1, 168.2, 165.8, 162.0, 159.2, 151.6, 149.2, 145.3, 142.8, 137.5, 134.3, 131.8, 130.1, 123.9, 123.1, 120.7, 116.4, 113.9, 103.8, 99.2, 52.4; LRMS (EI, 70 eV) m/z (%): 433 (M+, 49), 412 (18), 396 (15), 368 (12), 340 (42), 313 (85), 285 (41), 264 (85), 239 (100), 211 (47), 171 (19), 135 (51), 98 (40), 83 (35), 57 (41); HRMS (ESI): m/z (M)+ calcd for C28H19 NO 4 + : 433.1314; found: 433.1326.

4.5 (E)-7-(Hydroxy(3-methoxyphenyl)methylene)-7H-benzo[5,6]chromeno[3,2-c]quinolin-6-ol (4d)

White powder; mp: 294°C (Dec.); FT-IR ν max: 2,874, 1,736, 1,683, 1,618, 1,435, 828, 756 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.52 (s, 1H, OH, D2O exch.), 12.16 (s, 1H, OH, D2O exch.), 7.96 (d, J = 8.2 Hz, 2H, Ar), 7.57 (t, J = 7.5 Hz, 2H, Ar), 7.35 (d, J = 8.1 Hz, 2H, Ar), 7.28 (t, J = 9.5 Hz, 2H, Ar), 7.23 (m, 4H, Ar), 7.00 (bs, 1H, Ar), 6.32 (s, 1H, Ar), 3.64 (s, 3H, OMe); 13C NMR (125 MHz, DMSO-d 6) δ 187.0, 182.9, 176.6, 172.8, 169.7, 166.6, 160.6, 158.9, 153.8, 150.6, 149.0, 145.8, 144.4, 141.2, 132.8, 128.8, 126.7, 123.2, 118.3, 114.5, 110.0, 103.2, 100.8, 96.0, 94.0, 84.4, 81.6, 50.2; LRMS (EI, 70 eV) m/z (%): 433 (M+, 8), 333 (39), 309 (72), 278 (30), 264 (14), 248 (33), 174 (26), 161 (38), 146 (10), 135 (100), 119 (22), 107 (24), 92 (50), 77 (31), 64 (14); HRMS (ESI): m/z (M)+ calcd for C28H19 NO 4 + : 433.1314; found: 433.1319.

4.6 (E)-7-((3,4-Dimethoxyphenyl)(hydroxy)methylene)-7H-benzo[5,6]chromeno[3,2-c]quinolin-6-ol (4e)

White powder; mp: 274–275; FT-IR ν max: 3,366, 3,002, 2,837, 1,640, 1,603, 1,458, 1,399, 1,260, 1,231, 1,147, 1,027, 798, 762; 1H NMR (500 MHz, DMSO-d 6) δ 11.72 (s, 1H, OH, D2O exch.), 10.59 (s, 1H, OH, D2O exch.), 8.04 (d, J = 7.6 Hz, 1H, Ar), 7.96 (d, J = 7.8 Hz, 1H, Ar), 7.93–7.85 (m, 3H, Ar), 7.64 (s, 1H, Ar), 7.42 (d, J = 33.3 Hz, 3H, Ar), 7.33–7.24 (m, 3H, Ar), 7.03 (d, J = 8.4 Hz, 1H, Ar), 3.76 (s, 3H, OMe), 3.58 (s, 3H, OMe); 13C NMR spectrum could not be recorded due to the low solubility of the sample; LRMS (EI, 70 eV) m/z (%): 463 (M+, 100), 448 (8), 388 (3), 360 (3), 298 (3), 232 (6), 216 (4), 200 (6), 186 (4), 146 (5), 120 (5), 92 (4); HRMS (ESI): m/z (M)+ calcd for C29H21 NO 5 + : 463.1420; found: 463.1413.

4.7 (E)-7-(Hydroxy(4-hydroxy-3-methoxyphenyl)methylene)-7H-benzo[5,6]chromeno[3,2 c]quinolin-6-ol (4f)

White powder; mp: 288–289°C; FT-IR ν max: 3,078, 2,617, 1,685, 1,637, 1,602, 1,389, 1,316, 1,270, 1,184, 817, 769 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.54 (s, 1H, OH, D2O exch.), 12.16 (s, 1H, OH, D2O exch.), 9.80 (s, 1H, OH, D2O exch.), 7.98 (d, J = 7.8 Hz, 2H, Ar), 7.59 (t, J = 7.7 Hz, 2H, Ar), 7.38 (d, J = 8.1 Hz, 2H, Ar), 7.33–7.27 (m, 4H, Ar), 7.20 (d, J = 8.0 Hz, 1H, Ar), 6.68 (d, J = 8.3 Hz, 1H, Ar), 6.26 (s, 1H, Ar), 3.60 (s, 3H, OMe); 13C NMR (125 MHz, DMSO-d 6) δ 195.1, 179.8, 174.1, 173.1, 171.7, 168.3, 165.8, 161.9, 159.0, 151.1, 147.2, 142.6, 137.4, 131.8, 128.3, 123.7, 123.1, 122.3, 116.4, 115.1, 112.0, 109.1, 108.5, 107.3, 102.3, 99.6, 55.6, 42.0; LRMS (EI, 70 eV) m/z (%): 449 (M+, 1), 325 (26), 174 (11), 161 (41), 151 (100), 119 (28), 108 (7), 92 (21), 77 (10), 65 (9), 52 (7); HRMS (ESI): m/z (M)+ calcd for C28H19 NO 5 + : 449.1263; found: 449.1271.

4.8 (E)-7-((4-Fluorophenyl)(hydroxy)methylene)-7H-benzo[5,6]chromeno[3,2-c]quinolin-6-ol (4g)

White powder; mp: 294°C (Dec.) °C; FT-IR ν max: 2,948, 1,696, 1,634, 1,602, 1,439, 1,401, 1,304, 1,230, 1,154, 834, 751 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.53 (s, 1H, OH, D2O exch.), 12.18 (s, 1H, OH, D2O exch.), 7.98 (d, J = 8.1 Hz, 2H, Ar), 7.78–7.75 (m, 2H, Ar), 7.59 (t, J = 7.7 Hz, 2H, Ar), 7.37 (d, J = 8.2 Hz, 2H, Ar), 7.30 (t, J = 7.7 Hz, 3H, Ar), 7.19 (t, J = 8.6 Hz, 2H, Ar), 6.36 (s, 1H, Ar); 13C NMR (125 MHz, DMSO-d 6) δ 198.2, 173.4, 171.9, 171.3, 165.6, 163.6, 162.1, 155.0, 143.9, 142.0, 137.5, 133.9, 131.9, 130.7, 123.8, 123.1, 119.6, 116.35, 115.4, 109.5, 107.9, 102.6, 101.6, 96.7, 42.3; LRMS (EI, 70 eV) m/z (%): 421 (M+, 100), 404 (28), 298 (7), 273 (6), 244 (23), 120 (6), 92 (7). HRMS (ESI): m/z (M)+ calcd for C27H16F NO 3 + : 421.1114; found: 421.1110.

4.9 7-(4-Chlorobenzoyl)-5,7-dihydro-6H-benzo[5,6]chromeno[3,2-c]quinolin-6-one (4h)

Light yellow powder; mp: 211v212°C; FT-IR ν max: 2,947, 2,860, 1,659, 1,607, 1,578, 1,493, 1,443, 1,293, 1,259, 994, 882, 828, 749, 652 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 11.71 (s, 1H, OH, D2O exch.), 8.94 (d, J = 8.3 Hz, 1H, Ar), 7.97 (d, J = 8.7 Hz, 1H, Ar), 7.93 (d, J = 8.2 Hz, 1H, Ar), 7.80 (d, J = 8.0 Hz, 1H, Ar), 7.61 (t, J = 8.4 Hz, 3H, Ar), 7.56 (t, J = 8.7 Hz, 3H, Ar), 7.46 (d, J = 8.8 Hz, 1H, Ar), 7.41 (t, J = 8.5 Hz, 2H, Ar), 7.25 (t, J = 7.6 Hz, 1H, Ar), 5.54 (s, 1H, CH); 13C NMR (125 MHz, DMSO-d 6) δ 192.6, 171.3, 162.6, 160.5, 155.3, 140.4, 137.1, 135.1, 132.4, 131.4, 130.5, 129.5, 128.7, 127.4, 126.1, 125.5, 124.5, 122.9, 122.5, 119.6, 116.1, 112.3, 110.1, 110.0, 55.5; LRMS (EI, 70 eV) m/z (%): 439 ([M + 2]+, 37), 437 (M+, 100), 420 (28), 298 (11), 226 (25), 201 (10), 187 (23), 120 (12), 92 (10); HRMS (ESI): m/z (M)+ calcd for C27H16Cl NO 3 + : 437.0819; found: 437.0827.

4.10 (E)-7-((4-Bromophenyl)(hydroxy)methylene)-7H-benzo[5,6]chromeno[3,2-c]quinolin-6-ol (4i)

White powder; mp: 293°C (Dec.); FT-IR ν max: 2,957, 1,695, 1,634, 1,602, 1,441, 1,303, 1,008, 949, 806, 752, 701, 648 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 12.52 (s, 1H, OH, D2O exch.), 12.18 (s, 1H, OH, D2O exch.), 7.97 (d, J = 7.9 Hz, 2H, Ar), 7.64–7.55 (m, 7H, Ar), 7.37 (d, J = 8.2 Hz, 2H, Ar), 7.30 (t, J = 7.6 Hz, 2H, Ar), 6.36 (s, 1H, Ar); 13C NMR (125 MHz, DMSO) δ 165.7, 162.2, 137.5, 136.5, 132.4, 131.9, 131.5, 129.8, 127.6, 126.3, 123.7, 123.2, 116.4, 42.3; LRMS (EI, 70 eV) m/z (%): 483 ([M + 2]+, 96), 481 (M+, 100), 464 (22), 385 (15), 357 (46), 333 (84), 315 (21), 298 (18), 240 (37), 226 (38), 201 (19), 183 (75), 161 (59), 146 (23), 120 (71), 92 (69), 76 (35), 65 (23); HRMS (ESI): m/z (M)+ calcd for C27H16Br NO 3 + : 481.0314; found: 481.0321.

4.11 (6-Hydroxy-7H-benzo[5,6]chromeno[3,2-c]quinolin-7-yl)(4-nitrophenyl)methanone (4j)

Light yellow powder; mp: 224–225°C; FT-IR ν max: 2,865, 1,662, 1,631, 1,608, 1,524, 1,349, 1,254, 1,010, 853, 807, 702 cm−1; 1H NMR (500 MHz, DMSO-d 6) δ 11.72 (s, 1H, OH, D2O exch.), 8.93 (d, J = 8.4 Hz, 1H, Ar), 8.30 (d, J = 8.7 Hz, 2H, Ar), 7.97 (d, J = 8.9 Hz, 1H, Ar), 7.92 (d, J = 8.3 Hz, 1H, Ar), 7.86 (d, J = 8.7 Hz, 2H, Ar), 7.79 (d, J = 7.8 Hz, 1H, Ar), 7.61–7.52 (m, 2H, Ar), 7.46 (d, J = 8.9 Hz, 1H, Ar), 7.40 (t, J = 7.7 Hz, 2H, Ar), 7.24 (t, J = 7.4 Hz, 1H, Ar), 5.62 (s, 1H, CH); 13C NMR (125 MHz, DMSO-d 6) δ 189.5, 179.6, 174.0, 169.1, 162.6, 160.4, 155.2, 144.4, 140.4, 138.6, 132.5, 131.5, 130.6, 128.8, 127.1, 126.2, 124.7, 122.6, 119.5, 116.1, 112.3, 109.9, 107.7, 99.9, 55.7; LRMS (EI, 70 eV) m/z (%): 448 (M+, 100), 431 (21), 385 (10), 372 (6), 298 (5), 226 (13), 187 (7), 120 (7), 92 (8); HRMS (ESI): m/z (M)+ calcd for C27H16N2O5 +: 448.1059; found: 448.1056.

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Acknowledgment

The authors gratefully acknowledge the financial assistance from Islamic Azad University, Ahar branch.

  1. Funding information: The authors state no funding involved.

  2. Conflict of interest: The authors state no conflict of interest.

  3. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2020-10-19
Revised: 2021-08-16
Accepted: 2021-09-07
Published Online: 2021-10-06

© 2021 Naser Sadeghpour Orang et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/hc-2020-0128
Schlagwörter für diesen Artikel
arylglyoxal; chromenes; one-pot; three-component reaction; pyran; p-toluenesulfonic acid; quinoline
Creative Commons
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Artikel in diesem Heft

  1. Research Articles
  2. Molecular, Electronic, Nonlinear Optical and Spectroscopic Analysis of Heterocyclic 3-Substituted-4-(3-methyl-2-thienylmethyleneamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones: Experiment and DFT Calculations
  3. Lewis acid / Base-free Strategy for the Synthesis of 2-Arylthio and Selenyl Benzothiazole / Thiazole and Imidazole
  4. Synergistic promoting effect of ball milling and Fe(ii) catalysis for cross-dehydrogenative-coupling of 1,4-benzoxazinones with indoles
  5. Magnetic nanoparticle-supported sulfonic acid as a green catalyst for the one-pot synthesis of 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions
  6. Synthesis, characteristic fragmentation patterns, and antibacterial activity of new azo compounds from the coupling reaction of diazobenzothiazole ions and acetaminophen
  7. Para toluenesulfonic acid-catalyzed one-pot, three-component synthesis of benzo[5,6]chromeno[3,2-c]quinoline compounds in aqueous medium
  8. Design and microwave-assisted synthesis of a novel Mannich base and conazole derivatives and their biological assessment
  9. Quantum chemical studies on structural, spectroscopic, nonlinear optical, and thermodynamic properties of the 1,2,4-triazole compound
  10. Design, synthesis, and biological evaluation of phenyl-isoxazole-carboxamide derivatives as anticancer agents
  11. Quantum chemistry study on the promoted reactivity of substituted cyclooctynes in bioorthogonal cycloaddition reactions
  12. Quantum chemical calculations of phenazine-based organic dyes in dye-sensitized solar cells
  13. Rapid Communications
  14. One-pot synthesis of benzofurans via heteroannulation of benzoquinones
  15. Design and development of novel thiazole-sulfonamide derivatives as a protective agent against diabetic cataract in Wistar rats via inhibition of aldose reductase
  16. Review Articles
  17. Organic electrochemistry: Synthesis and functionalization of β-lactams in the twenty-first century
  18. Some applications of deep eutectic solvents in alkylation of heterocyclic compounds: A review of the past 10 years
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