sulfone supported on hollow magnetic mesoporous

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Accepted Manuscript Original article 4-(4'-diamino-di-phenyl)-sulfone supported on hollow magnetic mesoporous [email protected] 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 [email protected] 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 [email protected] 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) [email protected] 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- [email protected], 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 [email protected]@4(4'-diamino-di-phenyl)-sulfone under reflux conditions (Scheme 1).

Scheme 1. Synthesis of benzo[g]chromene-3-carboxylates using [email protected] 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 [email protected](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 [email protected] 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 [email protected] 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 [email protected] 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);

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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- [email protected] 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- [email protected] 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- [email protected] 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- [email protected] 4-(4'-diamino-di-phenyl)-sulfone. EDS confirmed the presence of Fe, O, Si, S and N in the compound.

Fig 2. nano- [email protected] 4-(4'-diamino-di-phenyl)-sulfone Fig 3. EDS spectrum of [email protected] 4-(4'-diamino-di-phenyl)-sulfone

The magnetization curve for Fe3O4, nano-HMMS and nano- [email protected] 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- [email protected] 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- [email protected](4'-diamino-di-

phenyl)-sulfone

The thermal behaviors of the magnetic nanocatalyst were investigated by TGA. The thermogravimetric analysis curve of the nano- [email protected] 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- [email protected](4'-diamino-di-phenyl)-sulfone

Fig. 6 shows the FT-IR spectrum of Fe3O4, nano-HMMS and nano- [email protected] 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- [email protected] 4-(4'-diamino-di-phenyl)-sulfone.

Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- [email protected] 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, [email protected], nano-HMMS, 4-(4'-diamino-di-phenyl)-sulfone (dapsone) and [email protected] 4-(4'diamino-di-phenyl)-sulfone (Table 1). [email protected] 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 [email protected](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 [email protected] 4-(4'-diamino-di-phenyl)-sulfone was investigated in the same reaction (Fig 7).

Fig 7. Reusability of [email protected] 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 [email protected] 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 [email protected] 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 [email protected] 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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substituted

3,4-dihydropyrano[3,2-c]chromenes,

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2-amino-4H-

benzo[h]chromenes and 2-amino-4H benzo[g]chromenes in aqueous medium, Tetrahedron. 66 (2010) 5637-5641. [2] M. Mokhtary, M. Torabi, Nano magnetite (Fe3O4), an efficient and robust catalyst for the one-pot

synthesis of 1 (aryl(piperidin-1-yl)methyl)naphthalene-2-ol and 1-(α-amido alkyl)-2-naphthol under ultrasound irradiation, J. Saudi Chem. Soc. 21 (2017) 299-304. [3] L. Zhao, G. Cheng, Y. Hu. A novel multicomponent reaction to synthesize substituted furo[3,2-

c]chromenes via a Pd-catalyzed cascade process, Tetrahedron Lett. 49 (2008) 7364-7367. [4] S. Jain, P.K. Paliwal, G.N. Babu, A. Bhatewara, DABCO promoted one-pot synthesis of

dihydropyrano(c)chromene and pyrano[2,3-d]pyrimidine derivatives and their biological activities, J. Saudi Chem. Soc. 18 (2014) 535-540. [5] J. Safaei-Ghomi, F. Eshteghal, H. Shahbazi-Alavi, A facile one-pot ultrasound assisted for an

efficient synthesis of benzo[g]chromenes using Fe3O4/polyethylene glycol (PEG) core/shell nanoparticles, Ultrasonics Sonochem. 33 (2016) 99-105. [6] M. Ough, A. Lewis, E.A. Bey, J. Gao, J.M. Ritchie, W. Bornmann, D.A. Boothman, L.W. Oberley,

J.J. Cullen, Efficacy of beta-lapachone in pancreatic cancer treatment: therapeutic target NQO1,Cancer Biology and Therapy, 4 (2005) 95-102.

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Pinto, M.G. Zalis, L.H. Carvalho, A.U. Krettli, Antimalarial activity of phenazines from lapachol, βlapachone and its derivatives against Plasmodium falciparum in vitro and Plasmodium berghei in vivo, Bioorg. Med. Chem. Lett. 14 (2004) 1145-1149. [9] J.M. Khurana, D. Magoo, A. Chaudhary, Efficient and green approaches for the synthesis of 4H-

Benzo[g]chromenes in water, under neat conditions, and using task-specific ionic liquid, Synth. Commun. 42 (2012) 3211-3219. [10] F. Yang, H. Wang, L. Jiang, H. Yue, H. Zhang, Z. Wang, L. Wang, A green and one-pot synthesis

of benzo[g]chromene derivatives through a multi-component reaction catalyzed by lipase, RSC Adv. 5 (2015) 5213–5216. [11] A. Shaabani, R. Ghadari, S. Ghasemi, M. Pedarpour, A.H. Rezayan, A. Sarvary, S.W. Ng, Novel

onep three- and pseudo-five-component reactions: synthesis of functionalized benzo[g]- and dihydropyrano[2,3-g]chromene derivatives, J. Comb. Chem. 11 (2009) 956–959. [12] B. Maleki, S. Babaee, R. Tayebee, Zn(L-proline)2 as a powerful and reusable organometallic catalyst

for the very fast synthesis of 2-amino-4H-benzo[g]chromene derivatives under solvent-free conditions, Appl. Organometal. Chem. 29 (2015) 408–411. [13] J. safari, L. Javadian, Ultrasound assisted the green synthesis of 2-amino-4H-chromene derivatives

catalyzed by Fe3O4-functionalized nanoparticles with chitosan as a novel and reusable magnetic catalyst, Ultrasonics. Sonochem. 22 (2015) 341-348.

[14] C. Yao, C. Yu, T. Li, S. Tu, An efficient synthesis of 4H-benzo[g]chromene-5,10-dione Derivatives

through triethylbenzylammonium chloride catalyzed multicomponent reaction under solvent-free conditions. Chin. J. Chem. 27 (2009) 1989-1994. [15] R. Ghahremanzadeh, T. Amanpour, A. Bazgir, An efficient, three-component synthesis of

spiro[benzo[g]chromene-4,3´-indoline]-3-carbonitrile and spiro[indoline-3,5´-pyrano[2,3d]pyrimidine]-6´-carbonitrile derivatives, J. Heterocyclic Chem. 46 (2009) 1266-1270. [16] H.R. Shaterian, M. Mohammadnia, Effective preparation of 2-amino-3-cyano-4-aryl-5,10-dioxo-

5,10-dihydro-4H-benzo [g]chromene and hydroxyl naphthalene-1,4-dione derivatives under ambient and solvent-free conditions, J. Mol. Liq. 177 (2013) 353–360 [17] Z. Lasemi, R. Azimi, M.A. Amiri, Efficient synthesis of 9,10-dihydropyrano[2,3-h]chromene-2,8-

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the Catalytic Interface inside a Hollow Nanoreactor: Exploitation of the Bidirectional Behavior of Mixed-Valent Mn3O4 Phase in the Galvanic Replacement Reaction, Chem. Mater. 28 (2016) 90499055. [23] L. Huang, L. Ao, X. Xie , G. Gao, M.F. Foda, W. Su, Iron oxide nanoparticle layer templated by

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organocatalyst for the one-pot three-component synthesis of various 2-amino-4H-chromene derivatives in water, Tetrahedron, 69 (2013) 1074-1085. [26] Y. Yu, H. Guo, X. Li, An improved procedure for the three-component synthesis of

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Figure captions

Fig. 1. XRD pattern of (a) Fe3O4, (b) HMMS, (c) nano- [email protected] 4(4´-diamino-di-phenyl)-sulfone Fig 2. Nano- [email protected] 4-(4'-diamino-di-phenyl)-sulfone Fig 3. EDS spectrum of [email protected] 4-(4'-diamino-di-phenyl)-sulfone Fig 4. Magnetization curves for the (a) nano-Fe3O4, (b) nano-HMMS and (c)

nano- [email protected](4'-diamino-di-

phenyl)-sulfone Fig. 5. TGA curve of nano- [email protected](4'-diamino-di-phenyl)-sulfone Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- [email protected] 4-(4'-diamino-di-phenyl)-sulfone Fig 7. Reusability of [email protected] 4(4´-diamino-di-phenyl)-sulfone as catalyst for the synthesis of 4a

Fig. 1 . XRD pattern of (a) Fe3O4, (b) HMMS, (c) nano- [email protected] 4(4´-diamino-di-phenyl)sulfone

Fig 2. Nano- [email protected] 4-(4'-diamino-di-phenyl)-sulfone

Fig 3. EDS spectrum of [email protected] 4-(4'-diamino-di-phenyl)-sulfone

Fig 4. Magnetization curves for the (a) nano-Fe3O4, (b) nano-HMMS and (c) phenyl)-sulfone

nano- [email protected](4'-diamino-di-

Fig. 5. TGA curve of nano- [email protected](4'-diamino-di-phenyl)-sulfone

Fig. 6. FT-IR spectrum of Fe3O4, nano-HMMS and nano- [email protected] 4-(4'-diamino-di-phenyl)-sulfone

Fig 7. Reusability of [email protected] 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 [email protected] 4-(4'-diamino-diphenyl)-sulfone

PEG

Calcination

TEOS

Fe3O4

[email protected]

HMMS

[email protected]@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

[email protected](4'-diamino-di-phenyl)-sulfone

Scheme 2. Synthesis of [email protected] 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- [email protected] 4-(4'-diamino-di-phenyl)sulfone (0.06 g)

CHCl3

20

50

10

nano- [email protected] 4-(4'-diamino-di-phenyl)sulfone (0.06 g)

CH3CN

20

57

11

nano- [email protected] 4-(4'-diamino-di-phenyl)sulfone (0.06 g)

H2O

20

75

12

nano- [email protected] 4-(4'-diamino-di-phenyl)sulfone (0.06 g)b

EtOH

20

95

13

nano- [email protected] 4-(4'-diamino-di-phenyl)sulfone (0.08 g)

EtOH

25

95

14

nano- [email protected] 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.

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