An efficient method for synthesis of some heterocyclic compounds

Journal of Sulfur Chemistry

ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20

An efficient method for synthesis of some heterocyclic compounds containing 3-iminoisatin and 1,2,4-triazole using Fe3O4 magnetic nanoparticles Navabeh Nami, Daryoush Zareyee, Maryam Ghasemi, Ameneh Asgharzadeh, Mehdi Forouzani, Somayeh Mirzad & S. Milad Hashemi To cite this article: Navabeh Nami, Daryoush Zareyee, Maryam Ghasemi, Ameneh Asgharzadeh, Mehdi Forouzani, Somayeh Mirzad & S. Milad Hashemi (2017) An efficient method for synthesis of some heterocyclic compounds containing 3-iminoisatin and 1,2,4-triazole using Fe3O4 magnetic nanoparticles, Journal of Sulfur Chemistry, 38:3, 279-290, DOI: 10.1080/17415993.2017.1278761 To link to this article: http://dx.doi.org/10.1080/17415993.2017.1278761

Published online: 25 Jan 2017.

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Date: 18 May 2017, At: 23:22

JOURNAL OF SULFUR CHEMISTRY, 2017 VOL. 38, NO. 3, 279–290 http://dx.doi.org/10.1080/17415993.2017.1278761

An efficient method for synthesis of some heterocyclic compounds containing 3-iminoisatin and 1,2,4-triazole using Fe3 O4 magnetic nanoparticles Navabeh Namia , Daryoush Zareyeea , Maryam Ghasemia , Ameneh Asgharzadeha , Mehdi Forouzanib , Somayeh Mirzadb and S. Milad Hashemic a Department of Chemistry, Qaemshahr Branch, Islamic Azad University, Qaemshahr, Iran; b Department of Chemistry, Payam Noor University, Sari Branch, Sari, Iran; c Department of Chemistry, Guilan University, Guilan, Iran

ABSTRACT

ARTICLE HISTORY

1,2,4-triazole derivatives were prepared by reaction of thiocarbohydrazide and some esters in 60% ethanol. Condensation of 1,2,4triazole derivatives with isatin gave Schiff bases of 3-iminoisatin derivatives. Reaction of malonic or succinic acid dihydrazide with isatin lead to formation of N,N’-bis-(3-imino-1,3-dihydro-indolyl2-one)-malonamide 8a and N,N’-bis-(3-imino-1,3-dihydro-indolyl-2one)succinamide 8b in good yields under mild reaction conditions. These reactions are catalyzed by Fe3 O4 MNPs. The chemical structures were confirmed by Fourier transform-infrared, 1 H-NMR, 13 CNMR, gas chromatography-mass spectrometry spectroscopy, and elemental analysis.

Received 12 June 2015 Accepted 28 December 2016 KEYWORDS

Fe3 O4 magnetic nanoparticles; therphthalic acid ethyl ester; malonic dihydrazide; succinic dihydrazide; thiocarbohydrazide; 3-iminoisatin; 1,2,4-triazole

1. Introduction Magnetic nanoparticles are excellent catalysts for synthesis of organic reactions [1–3]. The magnetic properties make the recovery of the catalyst facile by mean of an external magnetic field [4–7]. In comparison to bulk Fe3 O4 and known magnetic nanoparticles, Fe3 O4 nanoparticles have attracted a great attention as heterogeneous catalysts because of their interesting structure, large surface area, eco-friendly nature, their relatively non-toxic CONTACT Navabeh Nami

[email protected]

© 2017 Informa UK Limited, trading as Taylor & Francis Group

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properties, high coercively, low Curie temperature, ability to be recycled, and high catalytic activities in synthesis of organic compounds [8–10]. A large number of heterocyclic compounds containing 1,2,4-triazoles are well known as drugs [11–16] and have attracted the interest of chemists for a wide variety of chemical properties, synthetic versatility [17–20], and pharmacological antifungal [21, 22], anticonvulsant [23], anticancer [24–26], antibacterial [27], and anti-inflammatory activities [28, 29]. Isatin (1H-indole-2,3-dione) has also been known for several years as a raw material for synthesis of large variety of heterocyclic compounds [30–32]. Isatin derivatives exhibit a wide range of biological and pharmacological activities [33–36]. Because of the above reasons, we have focused on the application of Fe3 O4 magnetic nanoparticles for synthesis of some 1,2,4-triazole and 3-imino isatin derivatives in good yields and under mild reaction conditions.

2. Results and discussion We report that nano Fe3 O4 is a highly efficient and eco-friendly catalyst for synthesis of iminoisatin and 1,2,4-triazole derivatives. A reaction mixture of thiocarbohydrazide and a carboxylic acid ethyl ester was stirred under reflux condition in 60% ethanol in the presence of Fe3 O4 MNPs and monitored by thin layer chromatography (TLC) in n-hexane: ethylacetate/4 : 1. Using these conditions 1,2,4-triazoles were obtained after 1 h. The products were identified by gas chromatography-mass spectrometry (GS-MS), nuclear magnetic resonance (NMR), Fourier transform-infrared (FT-IR) spectra, and physical data and by comparison to authentic samples. Fe3 O4 MNPs were prepared according to previously published procedures [37, 38]. The IR spectra of prepared Fe3 O4 nanoparticles are shown in Figure 1 and are the same as

Figure 1. FT-IR spectra of Fe3 O4 magnetic nanoparticles.

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reported in literature [35, 36]. A strong peak at around 590 cm−1 is corresponds to the Fe–O stretching frequency. The broad band at around 3500–3000 cm–1 is attributed to adsorbed water. The morphology and particle size distribution of Fe3 O4 MNPs were studied using transmission electron microscopy (TEM) and scanning electron microscope (SEM). The SEM image (Figure 2) shows that Fe3 O4 particles composed of small spherical shape particles, and the TEM image(Figure 3) shows the average particle size is about 10–30 nm. X-ray diffraction (XRD) can be used to characterize the crystallinity of nanoparticles, as well as the average nanoparticle diameter. XRD patterns (Figure 4) of Fe3 O4 nanoparticles prepared under standard conditions [39, 40] reveal diffraction peaks, which are the characteristic peaks of the Fe3 O4 crystal [41]. Particle size of Fe3 O4 is quite small from the relatively wide half-peak breadth. With the XRD pattern, the average diameter which can be evaluated from Scherrer equation [42, 43] (D = Kλ/βcosθ, where K is constant, λ is X-ray wavelength and β is the peak width of half-maximum) is obtained as 12.7 nm.

Figure 2. SEM image of Fe3 O4 MNPs.

Figure 3. TEM image of Fe3 O4 MNPs.

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Figure 4. XRD image of Fe3 O4 MNPs.

In the preliminary stage of investigation, the model reaction of thiocarbohydrazide and benzoic acid ethyl ester was carried out using various amounts of Fe3 O4 and Fe3 O4 @SiO2 MNPs with different solvents and under solvent-free conditions. According to Table 1 the best solvent for preparation of triazole is 60% ethanol. In the absence of catalyst, the desired product was obtained in 67% yield after 4 h of reaction (Table 1, Entry 17), but in the presence of Fe3 O4 MNPs the reaction gave the desired product in 60% ethanol after 1 h with good yields. According to Table 1 (Entry 18–21), the yield of the product does not improve with increasing amount of catalyst, whereas it decreased with decreasing the amount of catalyst. The best results were obtained with (5 mol%) Fe3 O4 magnetic nanoparticles. The catalyst was simply recovered by an external magnet, washed with ethanol, and air-dried. Reaction of thiocarbohydrazide with terephthalic acid, benzoic acid, and acetic Table 1. Reaction of thiocarbohydrazide(1 mmol) and benzoic acid ethyl ester (1 mmol) under diﬀerent conditions. Entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27

Solvent

Catalyst

Catalyst (mol%)

Time (h)

Yielda (%)

THF THF THF THF THF CH3 CN CH3 CN n-Hexane n-Hexane EtOEt EtOEt EtOH EtOH EtOH EtOH EtOH EtOH 60% EtOH 60% EtOH 60% EtOH 60% EtOH 60% EtOH 60% (RT) EtOH 60% (50°C) EtOH 60% EtOH 60% Solvent-free Solvent-free

– Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs – Fe3 O4 MNPs – Fe3 O4 MNPs – Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 MNPs Fe3 O4 @SiO2 MNPs Fe3 O4 @SiO2 MNPs Fe3 O4 MNPs Fe3 O4 @SiO2 MNPs

– 3 4 5 7 – 5 – 5 – 5 – 3 4 5 7 – 3 4 5 7 7 7 5 7 7 7

4 4 4 2 2 4 4 4 4 4 4 4 4 4 2 2 4 4 3 1 1 2 2 4 4 4 4

52 60 63 79 78 42 69 trace 48 34 64 62 68 75 83 83 67 80 83 92 91 73 85 73 75 67 56

a Isolated yield.


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acid ethyl esters in the presence of Fe3 O4 MNPs gave 3,3 -(1,4-phenylene)bis(4-amino-1H1,2,4-triazole-5(4H)-thione) 6, 4-amino-3-phenyl-1H-1,2,4-triazole-5(4H)-thione 3a and 4-amino-3-methyl-1H-1,2,4-triazole-5(4H)-thione 3b, respectively, in good yields. The structures of these compounds were determined by IR, NMR, mass spectrometry, and microanalysis. The IR spectra of compound 6 exhibited absorption bands at 1670 cm−1 (C=S), 3270 cm−1 (NH2 ), 3400 cm−1 (NH). The 1 H-NMR spectra of compound 6 showed sharp signal at δ 5.27 ppm arising from NH2, and a broad signal at δ 12.77 ppm from NH. The mass spectra of 6 revealed a molecular ion peak at m/z 306. The fragments at m/z 192 and 116 can be attributed to the loss of C2 H2 N4 S and C8 H6 N4 S from the molecular ion, respectively. Compounds 3a–b, and 6, along with malonic or succinic dihydrazide was added to isatin and Fe3 O4 MNPs, the mixture was refluxed in ethanol to form Schiff bases 3(3-substituted-2,4-dihydro-1,2,4-triazol-5-mercapto-4-yl]iminoisatin 4a–b, (3E,3E’)-3,3 (3,3 -(1,4-phenylene)bis(5-thioxo-1H-1,2,4-triazole-4,3(5H)-diyl))bis(azan-1-yl-ylidene) diindolin-2-one 7, N,N’-Bis-(3-imino-1,3-dihydro-indolyl-2-one)-malonamide 8a and N,N’-Bis-(3-imino-1,3-dihydro-indolyl-2-one)-succinamide 8b, respectively (Scheme 1). The structures were deduced from elemental analyses, IR, NMR and mass spectrometry. The IR spectra of 7 exhibited an absorption band for (NH) vibrations at 3250 cm−1 , and (C=O) vibrations at 1670 cm−1 . The 1 H-NMR spectra of compound 7 showed broad signal at δ 12.44 and 11.17 ppm arising from the indole and triazole NH group. Signals around δ7.08–7.66 ppm are assigned to CHAromatic protons. The mass spectra of 7 revealed a molecular ion peak at m/z 564. The IR spectra of compound 8a showed absorption for (NH) stretching vibrations at 3250 cm−1 , (C=O) vibrations at 1730 cm−1 . The 1 H-NMR spectra of 8a exhibited a broad signals at δ 10.80 and 11.16 ppm for protons of (NH).

Scheme 1. Synthesis of isatin-3-imine, catalyzed by Fe3 O4 magnetic Nanoparticles.

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Scheme 2. Plausible mechanism for synthesis of 1,2,4-triazoles and iminoisatin derivatives using Fe3 O4 MNPs. Table 2. Comparison of the eﬃcacy of Fe3 O4 MNPs with some of those reported in the literature. Compound 4b 4b 8a 8a 8b 8b

Catalyst

Time

Yeild

Ref.

HCl Fe3 O4 MNPs EtOH Fe3 O4 MNPs AcOH Fe3 O4 MNPs

6h 30 min 1h 30 min 1h 30 min

76 94 94 94 80 94

[44] This work [45] This work [46] This work

A plausible mechanism for reaction of thiocarbohydrazide with carboxylic acid ester and 1,2,4-triazole with isatin is envisaged in Scheme 2. The carbonyl group is activated by MNPs (Fe3+ ) to provide a more electrophilic center for intermolecular cyclization and production of 4-amino-3-phenyl-1H-1,2,4-triazole-5(4H)-thione. Reaction of 1,2,4triazole and isatin is catalyzed by MNPs (Fe3+ ). The carbonyl group of isatin is activated by Fe3 O4 MNPs, then the nitrogen of 1,2,4-triazole attacks at the electrophilic center to afford (E)-3-(3-phenyl-5-thioxo-1H-1,2,4-triazole-4(5H)-ylimino)indolin-2-one 4a. A comparison of the efficacy of Fe3 O4 MNPs catalyst with other catalysts reported in the literature is presented in Table 2. In addition to having the general advantages attributed to the inherent magnetic property of nanocatalysts, Fe3 O4 MNPs exhibited exceptionally high catalytic activity compared to other catalysts, to yield the desired products in shorter reaction times and under milder reaction conditions.

3. Conclusions In summary, an efficient and environmentally friendly method for synthesis of 1,2,4triazole derivatives was described. The reactions were performed under reflux condition and the corresponding products were afforded in good to excellent yields. Also, the magnetically recoverable iron oxide nanoparticles are found to be more efficient for the synthesis of triazole and 3-iminoisatin derivatives. The advantages of this method are short reaction time, simple work-up procedure, ease of separation, high conversion, easier and less expensive than the other methods. The magnetic Fe3 O4 nanoparticles are effective in


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green chemistry and increases reaction speed without air pollution, these nanoparticles could be successfully recovered and reused.

4. Experimental The chemical materials and solvents were purchased from Merck and Aldrich Chemical Company. The melting points were obtained using an Electrothermal IA 9100 Digitalmelting point apparatus. The IR spectra were recorded on a Bruker IFS-88 instrument (the samples as KBr disks for the range 4000–400 cm−1 ). The1 H-NMR and13 C-NMR spectra were recorded on a Bruker AC-300 spectrometer (1 H, 400 MHz; 13 C, 75.469 MHz) using trimethylsilyl as an internal standard. Mass spectrometric measurements were made on an Agilent Technologies 6890 N Network GC system. The C, H, and N analyses were performed by the micro analytical service of the NIOC Research Institute of Petroleum Industry. 4.1. Preparation of thiocarbohydrazide Thiocarbohydrazide was synthesized according to previously published procedures [47]. 4.2. Preparation of catalyst MNPs (Fe3 O4 andFe3 O4 @SiO2 ) were synthesized according to previously published procedures [37, 38]. 4.3. General procedure for synthesis of 1,2,4-triazole derivatives (3a–b, 6) Thiocarbohydrazide (1 mmol for 3a-b, 2 mmol for 6) was added to esters (1 mmol) and Fe3 O4 MNs (5mol%). The mixture was stirred in 60% ethanol (10 ml) under reflux conditions. The progress of the reaction was monitored using TLC (n-hexane–ethyl acetate, 1 : 2) and detected by UV lamp (254 and 366 nm). At the end of the reaction (after 30 min1 h), the catalyst was recovered by an external magnet, washed with EtOH, dried at 60°C for 1 h, and reused seven times for the same reaction. The residue of the reaction mixture was filtered. The filtrate was rotary evaporated, the solvent recovered by distillation and the crude product was purified by usual a crystallization procedure in hot water/ethanol (2:1). The pure triazole derivatives were obtained after drying under vacuum. In most cases, the products were white powders. 4.3.1. 4-amino-3-phenyl-1H-1,2,4-triazole-5(4H)-thione [48] (3a) Yield 92%, m.p. 236°C; white powder. IR (KBr) (υ max cm−1 ): 3150 (NH2 ), 1650 (C=S), 1520 (C=C), 1500 (C=N), 1320 (C–N). 1 H-NMR:(400 MHz, d6 -DMSO) δ ppm, 5.78 (S, 2H, NH2 ), 7.53 (s, 3H, Ar-H), 8.01 (s, 2H, Ar-H), 13.91 (S, 1H, NH).

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4.3.2. 4-amino-3-methyl-1H-1,2,4-triazole-5(4H)-thione [49, 50] (3b) Yield 97%, m.p. 202°C; white powder. IR (KBr) (υ max Cm−1 ): 3272 (NH), 3154 (NH2 ), 2800 (C–H), 1660 (C=S), 1600 (C=N), 1340 (C–N). 1 H-NMR:(400 MHz, d6 -DMSO) δ ppm, 2.24 (s, 3H, CH3 ), 5.72 (s, 2H, NH2 ), 13.40 (s, 1H, NH).

4.3.3. 3,3 -(1,4-phenylene)bis(4-amino-1H-1,2,4-triazole-5(4H)-thione) (6) Terphthalic acid ethyl ester and thiocarbohydrazid, yield 92%, m.p. 216°C; white powder. IR (KBr) (υ max Cm−1 ): 3400 (NH), 3270 (NH2 ), 1670 (C=S), 1550 (C=C), 1500 (C=N), 1300 (C–N), 1150 (C–C). 1 H-NMR:(400 MHz, d6 -DMSO) δ ppm, 5.27 (s, 2H, NH2 ), 9.15 (s, 2H, Ar-H), 12.77 (br, 1H, NH).MS: m/z 306 (M+ ). Anal. Calcd For C10 H10 N8 S2 : C, 39.20; H, 3.29; N, 36.57. Found: C, 39.22; H, 3.27; N, 36.60.

4.4. General procedure for synthesis of iminoisatin derivatives (4a–b, 8a–b) 1,2,4-triazole or dihydrazide derivative(1 mmol) and isatin (1 mmol) were added in ethanol (10 mL) to Fe3 O4 MNPs (5 mol%). The mixture was stirred under reflux conditions. The progress of the reaction was monitored using TLC (n-hexane: ethyl acetate 1:2). When the reaction finished (after 30 min), the catalyst was recovered by an external magnetic field, washed with ethanol, air-dried, and could be used for additional reactions. The remaining mixture was cooled and the precipitant was filtered, washed, recrystallized with ethanol, and dried. The products were identified using NMR, IR, mass spectrometry, and microanalysis. 4.4.1. 3-(3-phenyl-2,4-dihydro-1,2,4-triazol-5-mercapto-4-yl]iminoisatin [51] (4a) Yield 88%, m.p. 221°C; orange powder. IR (KBr) (υ max Cm−1 ): 3200 (isatin NH), 3185 (triazole NH), 1727 (C=O), 1616 (C=N), 1511 (C=N), 1474 (C=C), 1200 (C–N), 1125 (C–C).1 H-NMR:(400 MHz, d6 -DMSO) δ ppm, 6.95 (d, J = 7.6 Hz, 3H, Ar-H), 7.10 (t, J = 7.6 Hz, 2H, Ar-H), 7.36 (t, J = 7.6 Hz, 2H, Ar-H), 7.62 (d, J = 7.6 Hz, 2H,Ar-H), 10.98 (s, 1H, NH triazole), 11.97 (br, 1H, NH indole). MS: m/z 321 (M+ ). Anal. Calcd For C16 H11 N5 OS: C, 59.80; H, 3.45; N, 21.79. Found: C, 59.83; H, 3.47; N, 21.83.


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4.4.2. 3-(3-methyl-2,4-dihydro-1,2,4-triazol-5-mercapto-4-yl]iminoisatin [44] (4b) Yield 90%, m.p. 192°C; orange powder. IR (KBr) (υ max Cm−1 ): 3250 (NH), 2800 (CH3 ), 1650 (C=O), 1500(C=N), 1320 (C–N). 1 H-NMR:(400 MHz, d6 -DMSO) δ ppm,2.23 (s, 1H, CH3 ), 6.89 (d, J = 8 Hz, 1H, Ar-H), 7.03 (t, J = 7.2 Hz, 1H, Ar-H), 7.47 (d, J = 7.2 Hz, 1H, Ar-H), 7.56 (t, J = 7.6 HZ, 1H, Ar-H), 11.08 (s, 1H, triazole NH), 13.97 (br, 1H,indole NH).MS: m/z 321 (M+ ). Anal. Calcd For C11 H9 N5 OS: C, 50.95; H, 3.50; N, 27.01. Found: C, 50.92; H, 3.53; N, 26.98.

4.4.3. (3E,3E’)-3,3 -(3,3 -(1,4-phenylene)bis(5-thioxo-1H-1,2,4-triazole-4,3(5H)-diyl)) bis(azan-1-yl-ylidene)diindolin-2-one (7) Yield 87%, m.p. decompose 242°C; orange powder. IR (KBr) (υ max Cm−1 ): 3250 (NH), 1670 (C=O), 1500 (C=C), 1450 (C=N), 1350 (C–N), 1200 (C–C), 1100 (C–O).1 HNMR:(400 MHz, d6 -DMSO) δ ppm, 7.08 (t, J = 7.2 Hz, 2H, Ar-H), 7.17 (d, J = 15.2 Hz, 1H, Ar-H), 7.33 (t, J = 7.6 Hz, 2H, Ar-H), 7.41 (t, J = 7.6 Hz, 2H, Ar-H), 7.53 (d, J = 7.6 Hz, 1H, Ar-H), 7.59 (d, J = 7.2 Hz, 2H, Ar-H), 7.66 (d, J = 7.2 Hz, 2H, Ar-H), 11.17 (br, 2H, NH), 12.44 (br, 2H, indole NH).13 C-NMR:(100 MHz, d6 -DMSO) δ ppm, 111.8, 120.1, 121.7, 123.1, 131.1, 132.6, 134.2, 139.5, 140.6, 143.4, 163.2, 175.7.MS: m/z 564 (M+ ). Anal. Calcd For C26 H16 N10 O2 S2 : C, 55.31; H, 2.86; N, 24.81 Found: C, 55.39; H, 2.90; N, 24.79.

4.4.4. N,N -Bis-(3-imino-1,3-dihydro-indolyl-2-one)-malonamide [45] 8a Malonic dihydrazide and isatin, yield 92%, M.p. 183°C; yellow crystals. IR (KBr) (υ max Cm−1 ): 3250 (NH), 1730 (C=O), 1630 (C=N), 1500 (C=C), 1480 (CH2 ), 1350 (C–N). 1 H-NMR:(400 MHz, d -DMSO) δ ppm, 3.15 (s, 2H, CH ), 6.90 (d, J = 7.6 Hz, 1H, Ar6 2 H), 7.04 (t, J = 7.2 Hz, 2H, Ar-H), 7.09 (d, J = 7.6 Hz, 1H, Ar-H), 7.37 (t, J = 7.6 Hz, 1H,

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Ar-H), 7.55 (d, J = 7.0 Hz, 1H, Ar-H), 8.12 (d, J = 7.6 Hz, 2H, Ar-H), 10.80 (s, 2H, amidic NH), 11.16 (s, 2H, indole NH).

4.4.5. N,N’-Bis-(3-imino-1,3-dihydro-indolyl-2-one)-succinamide [46] 8b Yield 94%, m.p. 242°C; yellow crystals. IR (KBr) (υ max Cm−1 ): 3280 (NH), 1700 (C=O), 1600 (C=N), 1450 (C=C), 1350 (C–N). 1 H-NMR:(400 MHz, d6 -DMSO) δ ppm, 3.15 (s, 2H, CH2 ), 6.95 (d, J = 8.0 Hz, 1H, Ar-H), 7.09 (t, J = 7.6 Hz, 1H, Ar-H), 7.37(t, J = 7.0 Hz, 1H, Ar-H), 7.56 (d, J = 7.2 Hz, 1H, Ar-H), 11.26 (s, 1H, amidic NH), 12.56 (s,1H, indole NH). 13 C-NMR:(100 MHz, d6 -DMSO) δ ppm, 36.25, 111.0, 120.27, 122.12, 131.89, 132.86, 134.51, 144.07, 162.98, 165.11.

Acknowledgement The authors wish to thanks Islamic Azad University in Qaemshahr Branch and Payame Noor University in Sari Branch for the institutional support.

Disclosure statement No potential conflict of interest was reported by the authors.

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