Accepted Manuscript Original article 4-(4'-diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous Fe3O4@SiO2 NPs: as a reusable and efficient catalyst for the synthesis of ethyl 2-amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates Javad Safaei-Ghomi, Nasrin Enayat-Mehri, Fahime Eshteghal PII: DOI: Reference:
S1319-6103(17)30065-0 http://dx.doi.org/10.1016/j.jscs.2017.05.007 JSCS 881
To appear in:
Journal of Saudi Chemical Society
Received Date: Revised Date: Accepted Date:
8 April 2017 2 May 2017 19 May 2017
Please cite this article as: J. Safaei-Ghomi, N. Enayat-Mehri, F. Eshteghal, 4-(4'-diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous Fe3O4@SiO2 NPs: as a reusable and efficient catalyst for the synthesis of ethyl 2-amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates, Journal of Saudi Chemical Society (2017), doi: http://dx.doi.org/10.1016/j.jscs.2017.05.007
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4-(4'-diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous Fe3O4@SiO2 NPs: as a reusable and efficient catalyst for the synthesis of ethyl 2amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates Javad Safaei-Ghomi*, Nasrin Enayat-Mehri, Fahime Eshteghal Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, P.O. Box 87317-51167, I. R.Iran Corresponding author. E-mail addresses:
[email protected], Fax: +98-31-55912397; Tel.: +98-31-55912385 Received: March, 2017;
4-(4'-diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous (HMMS) Fe3O4@SiO2 NPs has been used as a novel and efficient catalyst in the preparation of ethyl 2amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates by a simple onepot three-component reaction of aldehydes, ethyl cyanoacetate and 2-hydroxynaphthalene-1,4-dione under reflux conditions in ethanol.
Wide range of products, excellent yields in short times,
reusability of the catalyst, low catalyst loading and environmental benignity are some of the important features of this protocol.
KEYWORDS: HMMS, nano- Fe3O4@SiO2, benzo[g]chromene, hollow magnetic; mesoporous NPs
1. Introduction
The improvement of MCRs employed to produce elaborate biologically active compounds has become a significant area of research in organic and medicinal chemistry [1]. On the other hand, one-pot multi-component reaction are useful tools due to significant advantages including their lower costs, least waste production, simple approach, shorter times, and environmentally
friendliness [2]. Hence these reactions have attracted great interest among synthetic chemists as powerful tools for the rapid generation of molecular synthesis such as chromene compounds in organic chemistry [3]. In addition compound with chromenes structures are important for their drug properties [4] and also benzo[g]chromenes exhibit an extensive range of biological activities [5] including anticancer [6] anti-inflammatory [7] antimalarial [8] and pesticides activities [9]. Recently, reports have been developed on synthesis of chromenes using the catalysts including lipase [10], Et3N [11], Zn(L-proline)2 [12], Fe3O4-functionalized nanoparticles with chitosan [13], triethylbenzylammonium chloride (TEBA) [14] p-toluenesulfonic acid (p-TSA) [15] and ionic liquids [16]. However, some of the reported methods tolerate disadvantages such as long reaction times, harsh reaction conditions and use of toxic and non-reusable catalyst. Therefore, to avoid these limitations, the exploration of an efficient, easily available catalyst with high catalytic activity and short reaction times for the preparation of benzo[g]chromenes is still favored. Consequently, the provision of a facile and environmentally benign method using of efficient catalysts for the synthesis of chromenes has become a stimulating challenge [17]. In recently year’s hollow magnetic nanoparticles are used as suitable kinds in applications of drug delivery and catalytic [18]. Hollow mesoporous silica spheres (HMS) have attracted substantial attention due to their superior pores, low density, ordered and tunable size [19]. Therefore they were introduced as useful catalyst carriers for synthesis of organic compounds [20]. Also these hollow mesoporous can be used as nano-reactors for applications in adsorption, separation and catalysis [21, 22]. The hollow magnetic nanoparticles as newfound catalyst for synthesis of important organic compounds have received a great attention because of a comprehensive range of special characterizations such as high stability, excellent activity and good recovery [23, 24]. In this study, we wish to report the synthesis of ethyl 2-amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylate derivatives by a simple one-pot three-component reaction of
aldehydes, ethyl cyanoacetate and 2-hydroxynaphthalene-1,4-dione using hollow-Fe3O4@SiO2@4(4'-diamino-di-phenyl)-sulfone under reflux conditions (Scheme 1).
Scheme 1. Synthesis of benzo[g]chromene-3-carboxylates using HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
2. Methods
Nanostructures were characterized using a Holland Philips Xpert X-ray powder diffraction (XRD) diffractometer (Cu K, radiation, λ = 0.154056 nm), at a scanning speed of 2 °/min from 10 º to 100 ° (2θ). Scanning electron microscope (SEM) of nanoparticles was performed on a Model FESEM. The magnetic properties of nanoparticles have been measured by a vibrating sample magnetometer (VSMF, PPMS-9T) at 300 K Danesh Pajoh magnetic co. in Science and Technology Park, University of kashan, Kashan Iran. Preparation of nano-HMMS: Nano-HMMS was prepared according to the procedure reported in the literature [5]. Preparation of nano-HMMS@4-(4'-diamino-di-phenyl)-sulfone In a 250 mL round-bottomed three-necked flask, Nano-HMMS (1.0 g) and deionized water (60 mL) were vigorously stirred under a mechanical stirrer, and then a solution of 25 mL oleate sodium was added under nitrogen protection. The suspension was retaining for 20 min with constant stirring. The 4-(4'-diamino-di-phenyl)-sulfone /ethanol solution whit ratio 1/4 was added to the suspension. Then, the mixture was kept under ultrasonic vibration for 20 min. The products were purified by magnetic field separation and decantation with water after cooling of the suspension at room temperature. The products were dried under vacuum at 60 °C for 10 h (Scheme 2).
Scheme 2. Synthesis of HMMS@ 4(4´-diamino-di-phenyl)-sulfone
General procedure for the preparation of ethyl 2-amino -5, 10-dihydro -5, 10-dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylate derivatives A mixture of benzaldehyde (1 mmol), ethyl cyanoacetate (1 mmol) and 2-hydroxynaphthalene-1,4dione (1 mmol) and 0.06 gr of nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone in ethanol (10 mL) was refluxed. The reaction was monitored by TLC. After completion of the reaction, the mixture was treated with water and cold ethanol. The nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone were recovered from the aqueous phase by magnetic field. The solid separated out was filtered and recrystallized with ethanol to get pure product. The structures of the products were fully established on the basis of their 1H NMR, 13C NMR and FTIR spectra. Spectral data Ethyl 2-amino-5, 10-dihydro-5, 10-dioxo-4-phenyl -4H-benzo [g]chromene -3 –carboxylate (4a): Orange solid; m.p.185-189 ºC, IR (KBr) cm-1: 3412.11, 1681; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.34 (t, 3H, J = 7.2 Hz), 4.12 (q, 2H, J = 7.2 Hz), 5.12 (s, 1H), 6.38 (s, 2H, NH2),7.15 (d, J = 8, 1H), 7.25 (d, J =8 Hz, 2H), 7.35 (d, J = 7 Hz, 2H), 7.7 (d, J = 7 Hz, 2H), 8.01 (d, J = 8 Hz, 1H), 8.12 (d, J = 8 Hz, 1H); 13C NMR (100 MHz,CDCl3): δ (ppm): 14.8, 37.9, 61.5, 75.8, 120.3, 125.9, 126.6, 127.5, 128.7, 130.7, 131.9, 135.8, 144.8, 160.5, 162, 167.1, 178.5, 183.8; Anal. Calcd.for C22H17NO5: C 70.32, H 4.56, N 3.73 Found: C 70.30, H 4.66, N 3.84; MS (EI) (m/z): 375. Ethyl
2-amino-4-(4-chlorophenyl)-5,10-dihydro-5,10-dioxo-4H-benzo[g]chromene-3-carboxylate
(4b): Orange solid; m.p. 198-204 ºC, IR (KBr) cm-1:3461.46, 1681.56; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.32 (t, 3H, J = 7.6 Hz), 4.22 (q, 2H, J = 7.6 Hz), 5.10 (s, 1H), 6.47 (s, 2H, NH2), 7.20 (d, J = 7 Hz, 2H), 7.26 (d, J = 7 Hz, 3H), 7.65 (d, J = 8 Hz, 2H), 8.1-8.14 (d, J = 8 Hz, 1 H);
13
C NMR (100 MHz, CDCl3): δ (ppm): 14.6, 37.4, 61.1, 75.9, 125.2, 126.1, 128.9, 130.7, 130.9,
131.5, 131.9, 135.4, 142.1, 160.5, 162.9, 167.6, 178.9, 183.8; Anal. Calcd.for C22H16ClNO5: C 64.48, H 3.94, N 3.42 Found: C 64.44, H 4.05, N 3.55 MS (EI) (m/z): 409. Ethyl
2-amino-4-(4-methylphenyl)-5,10-dihydro-5,10-dioxo-4H-benzo[g]chromene-3-carboxylate
(4c): Yellow solid;m.p.208-212 ºC, IR (KBr) cm-1: 3463.85, 1679.5; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.22 (t, 3H, J = 8.2 Hz ), 2.25 (s, 3H), 4.14 (q, 2H, J = 8.2 Hz ), 5.15 (s, 1H), 6.43 (s, 2H, NH2), 7.03 (d, J = 7 Hz, 2H), 7.23 (d, J = 7 Hz, 2H), 7.72 (d, J = 8 Hz, 2H), 8 (d, J = 8 Hz, 1H), 8.12 (d, J = 8 Hz, 1H);
13
C NMR (100 MHz,CDCl3): δ (ppm): 14.9, 21.7, 37.1, 61.1, 75.9, 120.4,
126.2, 128.6 ,130.9, 131.6, 135.8, 135.9, 141.5, 160.6, 162.4, 167.7, 178.1, 183.6; Anal. Calcd.for C23H19NO5: C 70.94, H 4.92, N 3.60 Found: C 70.90, H 5.03, N 3.71 MS (EI) (m/z): 389. Ethyl 2-amino-4-(4-nitrophenyl)-5, 10-dioxo-5, 10-dihydro-4H-benzo [g]chromene-3-carboxylate (4d): Orange Solid; m.p.197-200 ºC, IR (KBr) cm-1: 3408.14, 1681.02 ; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.22 (t, 3H, J = 8.0 Hz ), 4.08 (q, 2H, J = 8.0 Hz), 5.12 (s, 1H), 6.51 (s, 2H, NH2), 7.53 (d, J = 7.2 Hz, 2H), 7.72-7.83 (d, J = 7.2 Hz, 2H), 8.13 (d, J = 8.0 Hz, 2H), 8.32 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,CDCl3): δ (ppm): 14.4, 37.3, 61.9, 75.3, 120.8, 123.4, 126.3, 126.6, 130.5, 131.7, 135.9, 144.3, 150.8, 160.4, 162.4, 167.5, 178.6, 183.1; Anal. Calcd.for C22H16N2O7: C 62.86, H 3.84, N 6.66 Found: C 62.98, H 3.95, N 6.56 MS (EI) (m/z): 420. Ethyl2-amino-4-(3-nitrophenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxylate (4e): Orange solid;m.p. 198-202 ºC, IR (KBr) cm-1:3432.80, 1681.72 ; 1H NMR (400 MHz,CDCl3): δ (ppm): 1.27 (t, 3H, J = 8.0 Hz), 4.15 (q, 2H, J = 8.0 Hz ), 5.11 (s, 1H), 6.63 (s, 2H, NH2), 7.48 (m, 1H), 7.76 (m, 3H), 8.02 (m, 2H), 8.15 (m, 1H), 8.21 (s, 1H);
13
C NMR (100
MHz,CDCl3): δ (ppm): 14.3, 36.7, 61.8, 75.4, 120.7, 120.8, 121.3, 121.7, 126.4, 130.3, 131.4, 134.6, 135.1, 145.8, 147.4, 160.7, 162.9, 167.4, 178.1, 183.2; Anal. Calcd.for C22H16N2O7: C 62.86, H 3.84, N 6.66 Found: C 62.98, H 3.95, N 6.56 MS (EI) (m/z): 420.
Ethyl 2-amino- 4-(2-chlorophenyl)-5, 10-dihydro-5, 10-dioxo-4H-benzo [g]chromene-3-carboxylate (4f): Orange solid;m.p. 208-215 ºC, IR (KBr) cm-1: 3413, 1680.92; 1H NMR (400 MHz, DMSOd6): δ (ppm): 1.12 (t, 3H, J = 7.6 Hz), 3.9 (q, 2H, J = 7.6 Hz), 5.32 (s, 1H), 7.10 (s, 2H, NH2), 7.14 (m, 1H),7.23 (m, 1H), 7.80-7.88 (m, 5H), 8.02 (m, 1H); 13C NMR (100 MHz, DMSO-d6): δ (ppm): 14.7, 32.1, 61.6, 75.2, 120.8, 126.5, 126.6, 126.7, 127.9, 128.4, 130.5, 131.5, 131.9, 135.4, 143.1, 160.2, 162.8, 167.3, 178.9, 183.9; Anal. Calcd.for C22H16ClNO5: C 64.48, H 3.94, N 3.42 Found: C 64.44, H 4.05, N 3.50 MS (EI) (m/z): 409. Ethyl
2-amino-5,
10-dihydro
-4-(4-methoxyphenyl)-5,
10-dioxo-4H-benzo
[g]chromene-3-
carboxylate (4g): Orange solid; m.p. 220-225 ºC, IR (KBr) cm-1: 3466.85 1680.19; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.24 (t, 3H, J = 7.2 Hz ), 3.52 (s, 3H), 4.16 (q, 2H, J = 7.2 Hz), 5.14 (s, 1H), 6.45 (s, 2H, NH2), 6.80 (d, J = 7.4 Hz, 2H), 7.27 (d, J = 7.4 Hz, 2H), 7.7 (d, J = 8.2 Hz, 2H), 8 (d, J = 8.2 Hz, 1H), 8.1 ( d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ (ppm): 14.6, 37.1, 55.4, 61.4, 114.8, 120.4, 126.4, 130.4, 130.7, 131.5, 135.3, 136.1, 157.4, 160.6, 162.4, 167.3, 178.4, 183.7 ; Anal. Calcd.for C23H19NO6: C 68.14, H 4.72, N 3.46 Found: C 68.22, H 4.76, N 3.47; MS (EI) (m/z): 405. Ethyl2-amino-4-(2,3-dimethoxyphenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3carboxylate (4h): Orange solid;m.p. 224-227 ºC, IR (KBr) cm-1: 3412.48, 1680.25 ; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.23 (t, 3H, J = 7.6 Hz), 3.83 (s, 6H), 4.12 (q, 2H, J = 7.6 Hz ), 5.12 (s, 1H), 6.55 (s, 2H, NH2), 6.80 (d, J = 7.6 Hz, 1H), 7.04 (t, J = 7.2 Hz, 1H) 7.12 (d, J = 8 Hz, 1H), 7.52 (d, J= 7 Hz, 2H), 7.92 (d, J = 7 Hz, 1H), 8.12 (d, J = 8 Hz, 1H); 13C NMR (100 MHz,CDCl3): δ (ppm): 14.8, 32.1, 56,8, 60.9, 61.4, 75.2, 112.2, 120.9, 121.4, 122.5, 122.7, 126.1, 130.7, 131.9, 135.4, 145.2, 150.8, 160.3, 162.8, 167.6, 178.7, 183.2; Anal. Calcd.for C24H21NO7: C 66.20, H 4.86, N 3.22 Found: C 66.18, H 4.92, N 3.30 MS (EI) (m/z): 435.
Ethyl2-amino-4-(4-bromophenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxylate (4i): Orange solid; m.p.190-196 ºC, IR (KBr) cm-1 :3425.10, 1681.16 ; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.22 (t, 3H, J = 7.6 Hz ), 4.15 (q, 2H, J = 7.6 Hz ), 5.10 (s,1H), 6.62 (s, 2H, NH2), 7.23 (d, J = 7.6 Hz , 2H), 7.38 (d, J = 7.4 Hz, 2H), 7.72 (d, J = 8.2 Hz, 2H), 8.02 (d, J = 8.2 Hz, 1H), 8.15 (d, J = 7.4 Hz, 1H);
13
C NMR (100 MHz, CDCl3): δ (ppm): 14.3, 37.9, 61.3, 75.7, 120.7, 120.8,
126.2, 130.5, 131.3, 131.7,131.9, 135.7, 143.2, 160.5, 162.2, 167.2, 178.3, 183.9; Anal. Calcd.for C22H16BrNO5: C 58.17, H 3.55, N 3.08 Found: C 58.25, H 3.64, N 3.16 MS (EI) (m/z): 453. Ethyl2-amino-4-(3-hydroxyphenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxylate (4j): Orange solid; m.p. 205-210 ºC, IR (KBr) cm-1: 3419.78,3316.40, 1672.31; 1H NMR (400 MHz, DMSO): δ (ppm): 1.12 (t, 3H, J = 7.6 Hz ), 4.08 (q, 2H, J = 7.6 Hz ), 4.82 (s, 1H), 6.48 (s, 2H, NH2), 6.52 (d, J = 8 Hz, 1H), 7.02 (d, J = 7.2 Hz, 3H), 7.82 (d, J = 7.4 Hz, 2H), 7.95 (d, J = 6.9 Hz, 1H), 8.05 (d, J = 7.4 Hz, 1H); 9.24 (s, 1H, OH); 13C NMR (100 MHz, DMSO): δ (ppm): 14.3, 38.7, 61.1, 75.6, 112.4, 114.6, 120.6, 120.9, 126.2, 130.6, 130.9, 131.4, 135.3,143.1, 156.2, 160.9, 162.8, 167.1, 178.4, 183.2; Anal. Calcd.for C22H17NO6: C 67.51, H 4.38, N 3.58 Found: C 67.58, H 4.45, N 3.66 MS (EI) (m/z): 391. Ethyl2-amino-4-(2-methoxyphenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3-carboxylate (4k): Orange Solid; m.p.223-228 ºC, IR (KBr) cm-1: 3423.89, 1683.93; 1H NMR (400 MHz,CDCl3): δ (ppm): 1.22 (t, 3H, J = 7.2 Hz), 3.75 (s, 3H), 4.02 (q, 2H, J = 7.2 Hz), 5.26 (s, 1H), 6.34 (s, 2H, NH2), 6.82 (d, J = 8.2 Hz, 1H), 6.92 (t, J = 8.0 Hz, 1H), 7.15 (t, 1H), 7.43 (d, J = 7.2 Hz, 1H),7.72 (m, 2H), 7.92 (m, 1H), 8.12 (m, 1H); 13C NMR (100 MHz, CDCl3): δ (ppm): 14.9, 31.4, 56.7, 61.3, 75.6, 112.7, 120.9, 121.6, 126.8, 126.9, 129.4, 130.2, 130.9, 131.7, 135.8, 158.4, 160.9, 162.7, 167.4, 178.6, 183.2; Anal. Calcd.for C23H19NO6: C 64.14, H 4.72, N 3.46 Found: C 64.22, H 4.76, N 3.47 MS (EI) (m/z): 405.
Ethyl2-amino-4-(2,4-dichlorophenyl)-5,10-dioxo-5,10-dihydro-4H-benzo[g]chromene-3carboxylate (4l): Orange solid;m.p. 233-235 ºC, IR (KBr) cm-1: 3422.98, 3307.46, 1681.16; 1H NMR (400 MHz, DMSO): δ (ppm): 1.14 (t, 3H, J = 7.2 Hz ), 4.09 (q, 2H, J = 7.2 Hz), 5.22 (s, 1H), 7.12 (s, 2H, NH2), 7.22-7.37 (m, 2H), 7.43 (s, 1H), 7.87 (d, J = 8 Hz, 2H), 7.88(s, 1H), 8.02(d, J = 8 Hz, 1H); 13C NMR (100 MHz, DMSO): δ (ppm): 14, 32.64, 59.04, 75.58, 120.69, 125.74, 125.76, 126.31, 128.9, 129.89, 130.84, 131.1, 132.30, 132.56, 133.94, 139.1, 139.84, 148.20, 159.4, 168.1, 183.45; Anal. Calcd.for C22H15Cl2NO5: C 59.48, H 3.40, N 3.15 Found: C 59.46, H 3.46, N 3.21 MS (EI) (m/z): 443. Ethyl 2-amino- 4-(2-nitrophenyl)-5, 10-dioxo-5, 10-dihydro-4H-benzo [g]chromene-3-carboxylate (4m): Brown solid; m.p. 214-216 ºC, IR (KBr) cm-1: 3397.70, 3295.09, 1681.70; 1H NMR (400 MHz, CDCl3): δ (ppm): 1.13 (t, 3H, J = 7.2 Hz ), 4.12 (4, 2H, J = 7.2 Hz), 6.14 (s, 1H), 6.72 (s, 2H, NH2), 7.25 (d, J = 8 Hz, 1H), 7.4 (m, 1H), 7.48 (m, 1H), 7.7 (d, J = 8 Hz, 2H), 7.9 (m, 1H), 8.0 (m, 1H, J = 7.2 Hz), 8.12 (m, 1H, J = 7.2 Hz); 13C NMR (100 MHz, CDCl3): δ (ppm): 14.6, 33.4, 61.2, 75.9, 120.4, 124.1, 126.7, 126.9, 130.0, 130.5, 131.7, 131.9, 134.9, 135.2,147.8, 160.4, 162.6, 167.3, 178.6, 183.78; Anal. Calcd.for C22H16N2O7: C 62.86, H 3.84, N 6.66 Found: C 62.98, H 3.95, N 6.56 MS (EI) (m/z): 420.
3. Results and discussion
Phase investigation of the crystalline Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-diphenyl)-sulfone was studied using XRD and the diffraction pattern is presented in Fig 1. The average MNP diameter of Fe3O4, nano-HMMS and nano- HMMS@ 4-amino-di-phenyl-sulfone were calculated to be about 28, 48 and 52 nm, respectively, from the XRD results by the Scherer formula on the highest intensity peak for each sample.
Fig. 1 . XRD pattern of (a) Fe3O4, (b) HMMS, (c) nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
In order to obtain the morphology and particle size of nanoparticles, SEM images of the nanoparticles were obtained and are presented in Figure 2. The SEM images of shows particles with diameters in the range of nanometers. The results show that the nanoparticles have a uniform size and spherical shape respectively as shown in Figure 2. Figure 3 shows the EDS (energy dispersive spectroscopy) spectrum of nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone. EDS confirmed the presence of Fe, O, Si, S and N in the compound.
Fig 2. nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone Fig 3. EDS spectrum of nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
The magnetization curve for Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone are shown in Figure 4. Room temperature specific magnetization (M) versus for both samples is obtained, which indicates that the saturation magnetization value (Ms) for bare Fe3O4, nano-HMMS and nano- HMMS@ 4-amino-di-phenyl-sulfone is 67.55 emu g-1 and 42.01 emu g-1 and 10.20 emu g-1 respectively. These results indicate that the magnetization feature decreases by coating and functionalization.
Fig 4. Magnetization curves for the (a) nano-Fe3O4, (b) nano-HMMS and (c)
nano- HMMS@4-(4'-diamino-di-
phenyl)-sulfone
The thermal behaviors of the magnetic nanocatalyst were investigated by TGA. The thermogravimetric analysis curve of the nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone shows
the mass loss of the organic materials as it decomposes upon heating (Fig. 5). The initial weight loss from the catalyst up to 25-150 °C which could be assigned to the loss of bound water or physically adsorbed solvent. The next TGA peak is a weight loss of 30% about 200–700 °C attributed to the decomposition of the organic species. Thus, the catalyst was stable up to 150 ºC.
Fig. 5. TGA curve of nano- HMMS@4-(4'-diamino-di-phenyl)-sulfone
Fig. 6 shows the FT-IR spectrum of Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-diphenyl)-sulfone. The results in Fig 6 suggest the integration of 4-(4'-diamino-di-phenyl)-sulfone and nano- HMMS in the nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone.
Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
We attempted a three-component condensation of 4-chlorobenzaldehyde (1 mmol), ethyl cyanoacetate (1 mmol) and 2-hydroxynaphthalene-1, 4-dione (1 mmol) as a model reaction in different conditions. Yields were determined in the presence of NEt3, MgO NPs, nano- Fe3O4, nanoFe3O4@SiO2, nano-HMMS, 4-(4'-diamino-di-phenyl)-sulfone (dapsone) and nano-HMMS@ 4-(4'diamino-di-phenyl)-sulfone (Table 1). Nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone gave the best yields in the shortest time and a very good yield of 95 % was obtained with 0.06 g, which was not improved by increasing to 0.08 g. A reaction run in the absence of any catalyst gave a yield of only 5 %. It was demonstrated that EtOH was the best solvent compared with water, CH3CN, CHCl3 (Table 1).
Table 1: Optimization of reaction conditions using different catalysts
The reusability of nano-HMMS@4-(4'-diamino-di-phenyl)-sulfone was also considered. After completion of the reaction, ethanol/water was added to dilute the reaction mixture after terminating the reaction. Then the activity of the recycled nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone was investigated in the same reaction (Fig 7).
Fig 7. Reusability of HMMS@ 4(4´-diamino-di-phenyl)-sulfone as catalyst for the synthesis of 4a
We observed aromatic aldehydes with electron-withdrawing groups reacted faster than those with electron-donating groups. The excellent yields were obtained with substrates having electronwithdrawing groups as para-chloro group (Table 2, entries 2). With the optimal conditions in hand, we turned to explore the efficacy of the catalyst using different aromatic aldehydes and the results are summarized in Table 2.
Table 2. Synthesis of benzo[g]chromenes
To study the applicability of this method in larger scale synthesis, we performed selected reactions at 10 mmol scale. As can be seen, the reactions at large scale gave the product with a gradual decreasing of reaction yield (Table 3). Table 3
A possible mechanism for the reaction using nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone was shown in Scheme 3. The formation of product can be rationalized by initial Knoevenagel condensation reaction between an aldehyde 1 and ethyl cyanoacetate 2; then, Michael addition
reaction between intermediate (I) with the 2-hydroxynaphthalene- 1,4-dione 3 leads to the intermediate (II) on the active sites of nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone followed by intramolecular cyclization with the elimination of H2O giving rise to the cyclized product benzo[g]chromene-3-carboxylates (Scheme 3).
Scheme 3. Proposed reaction pathway for the synthesis of ethyl 2-amino-5,10-dihydro-5, 10-dioxo-4-phenyl4H benzo[g]chromene-3-carboxylates.
4. Conclusions In this research we have developed an effective procedure for the synthesis of ethyl 2-amino-5,10dihydro-5,10-dioxo-4-phenyl-4H-benzo[g]chromene-3-carboxylate derivatives by one-pot threecomponent reaction of benzaldehydes, ethyl cyanoacetate and 2-hydroxynaphthalene-1,4-dione using nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone as a hollow magnetic catalyst. High yields, simple reaction process, easy work-up, atom economy, shorter reaction times, explored substrate scope using ethyl cyanoacetate, reusability of the catalyst and low catalyst loading are some of the considerable advantages of the current protocol. Acknowledgments The authors are grateful to University of Kashan for supporting this work by Grant NO: 159196/XXI.
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Figure captions
Fig. 1. XRD pattern of (a) Fe3O4, (b) HMMS, (c) nano- HMMS@ 4(4´-diamino-di-phenyl)-sulfone Fig 2. Nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone Fig 3. EDS spectrum of nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone Fig 4. Magnetization curves for the (a) nano-Fe3O4, (b) nano-HMMS and (c)
nano- HMMS@4-(4'-diamino-di-
phenyl)-sulfone Fig. 5. TGA curve of nano- HMMS@4-(4'-diamino-di-phenyl)-sulfone Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone Fig 7. Reusability of HMMS@ 4(4´-diamino-di-phenyl)-sulfone as catalyst for the synthesis of 4a
Fig. 1 . XRD pattern of (a) Fe3O4, (b) HMMS, (c) nano- HMMS@ 4(4´-diamino-di-phenyl)sulfone
Fig 2. Nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
Fig 3. EDS spectrum of nano-HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
Fig 4. Magnetization curves for the (a) nano-Fe3O4, (b) nano-HMMS and (c) phenyl)-sulfone
nano- HMMS@4-(4'-diamino-di-
Fig. 5. TGA curve of nano- HMMS@4-(4'-diamino-di-phenyl)-sulfone
Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- HMMS@ 4-(4'-diamino-di-phenyl)-sulfone
Fig 7. Reusability of HMMS@ 4(4´-diamino-di-phenyl)-sulfone as catalyst for the synthesis of 4a
H2N
NH2
H2N
R NH2 O
H2N O
CHO O + Et
1
R
CN +
O
H2N OH
O
NH2
Et
NH2
O
nanocatalyst O
Ethanol/reflux
NH2
O
2 3
O
4a-m
Scheme 1. Synthesis of benzo[g]chromene-3-carboxylates using HMMS@ 4-(4'-diamino-diphenyl)-sulfone
PEG
Calcination
TEOS
Fe3O4
PEG@Fe3O4
HMMS
PEG@Fe3O4@SiO2
t so diu
m
H2N NH2
O2S
H2N
S O2
HN
O2S HN
HN
H N
N H
NH NH SO2
H2N
ole a
O2S
H2N
S O2
NH2
SO2
NH SO2
NH2
NH2
HMMS@4-(4'-diamino-di-phenyl)-sulfone
Scheme 2. Synthesis of HMMS@ 4(4´-diamino-di-phenyl)-sulfone
H2N
H2N
SO2
CN H H CH CN
O
O Et
-H2O
O
H OH
O
NC
O
Et
O
H O Et
R
H2N
O
-H2O
O
O
(I)
O
O
Et
O
O O
4a-m
O
O
H O C Et HN O (III) O
O Et
N
H
H
O
C
O (II)
O
catalyst
Scheme 3. Proposed reaction pathway for the synthesis of ethyl 2-amino -5, 10-dihydro -5, 10dioxo-4-phenyl-4H benzo[g]chromene-3-carboxylates.
Table 1: Optimization of reaction conditions using different catalysts Entry
Catalyst
Solvent (reflux)
Time (min)
Yield,b%
1
Catalyst-free
EtOH
120
5
2
Catalyst-free
H2O
120
10
3
Et3N (10 mol %)
EtOH
60
45
4
MgO (5 mo1%)
EtOH
60
40
5
Nano- Fe3O4 (0.05g)
EtOH
60
15
6
Nano- Fe3O4/SiO2(0.05g)
EtOH
25
35
8
nano- HMMS (0.06g)
EtOH
25
44
9
4-(4'-diamino-di-phenyl)-sulfone (dapsone) ( 8 mo1%)
EtOH
25
52
9
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.06 g)
CHCl3
20
50
10
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.06 g)
CH3CN
20
57
11
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.06 g)
H2O
20
75
12
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.06 g)b
EtOH
20
95
13
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.08 g)
EtOH
25
95
14
nano- HMMS@ 4-(4'-diamino-di-phenyl)sulfone (0.04 g)
EtOH
25
88
15
mixture of 4-(4'-diamino-di-phenyl)-sulfone (Dapsone) and the nano-HMMS (0.12 g)
EtOH
25
58
a
Reaction conditions: a mixture of 4-chlorobenzaldehyde (1 mmol), ethyl cyanoacetate (1 mmol) and 2hydroxynaphthalene-1, 4-dione (1 mmol) and catalyst for various times b Isolated yield
Table 2. Synthesis of benzo[g]chromenes M. p. (ºC) Entry
aldehyde
Product
Time (min)
Yield (%)
[Ref]
M.p. (ºC) Found
O O
CHO
NH2
1
30
82
188-189 [25]
185-189
20
95
189-191 [26]
198-204
30
76
211-214 [25]
208-212
20
93
194-196 [25]
197-200
COOEt O
4a O O
CHO
NH2
2 COOEt O
Cl
Cl
4b O O
CHO
NH2
COOEt
3 O
CH3 CH3
4c O O
CHO
NH2
4 COOEt O
NO2 NO2
4d
O O
CHO
NH2
5
25
93
--------
198-202
30
88
--------
208-215
35
75
220-222 [18]
220-225
35
70
--------
224-227
25
90
--------
190-196
COOEt O
NO2 NO2
4e O O
CHO
6
NH2
Cl COOEt Cl
O
4f O O
NH2
7 COOEt O
OCH3
4g O O
NH2
8 COOEt OCH3
O
OCH3
4h O O
9
NH2
COOEt O
Br
4i
O O
NH2
10
30
74
--------
205-210
35
72
--------
223-228
25
85
235-237 [9]
233-235
25
89
223-224 [1]
214-216
COOEt O
OH
4j O O
NH2
11 COOEt OCH3
O
4k O O
NH2
12 COOEt Cl
O
Cl
4l O O
NH2
13 COOEt NO2
O
4m a
Isolated yield
Table 3. The large-scale synthesis of some of benzo[g]chromenes using nanocatalyst
a
Entry
product
Aldehyde (R)
Time (min)
Yielda(%)
1
4a
H
55
73
2
4b
4- Cl
45
82
3
4c
4- Me
80
65
4
4i
4- Br
45
80
5
4j
3- OH
80
60
Isolated yield.