SPIONs as a nanomagnetic catalyst for the synthesis and anti-microbial activity of 2-aminothiazoles derivatives

Samar A. Abubshait; Haya A. Abubshait; Sara Nabil; Asma M. Elsharif; Hamad M. Alkahtani; Fadilah Sfouq Aleanizy; M. Nasiruzzaman Shaikh

doi:10.1016/j.arabjc.2022.103878

View/Download PDF

Buy Reprints

PDF

Translate this page into:

Original article

07 2022

:15;

103878

doi:

10.1016/j.arabjc.2022.103878

SPIONs as a nanomagnetic catalyst for the synthesis and anti-microbial activity of 2-aminothiazoles derivatives

Samar A. Abubshait^{^a,^b,⁎}, Haya A. Abubshait^{^c}, Sara Nabil^{^a,^b}, Asma M. Elsharif^{^a}, Hamad M. Alkahtani^{^d}, Fadilah Sfouq Aleanizy^{^e}, M. Nasiruzzaman Shaikh^{^f}

a Department of Chemistry, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia

b Basic and Applied Scientific Research Center, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia

c Basic Sciences Department, Deanship of Preparatory Year and Supporting Studies, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia

d Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, P.O. Box 2457, Riyadh 11451, Saudi Arabia

e Department of Pharmaceutics, College of Pharmacy, King Saud University, Riyadh, Saudi Arabia

f Interdisciplinary Research Center for Hydrogen and Energy Storage (IRC-HES), King Fahd University of Petroleum and Minerals (KFUPM), Dhahran 31261, Saudi Arabia

⁎Corresponding author.

Received: 2022-1-12, Accepted: 2022-3-28,

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

A series of aminothiazole derivatives have been synthesized by using ultrasmall superparamagnetic iron oxide nanoparticles (SPIONs) nanomagnetic catalysis, which were prepared by reducing the Fe(II) and Fe(III) precursors using aqueous ammonia then characterized by the XRD, FTIR, SEM, and TEM. The 2-aminothiazole derivatives were obtained by coupling 2-aminothiazole diazonium salt with active methylene compounds then cyclization with hydrazine hydrate to afford pyrazolyl derivatives. The one-pot reaction of 2-aminothiazole with an aromatic aldehydes in the presence of Fe₃O₄ NPs to give Schiff bases derivatives. An efficient protocol is developed proudest yields and reduction reaction time and easy separation. Therefore, all synthesized compounds were evaluated for anti-microbial activity.

Keywords

Nanomagnetic catalysis

2-aminothiazole derivatives

Pyrazolyl derivatives

Schiff bases

Aromatic aldehyde

Anti-microbial activity

1 Introduction

Thiazole is a core structural element plays an important role in nature and has a wide range of applications in medicinal chemistry (Xue et al., 2014). Thiazole heterocycle is a main structural motif of many natural compounds such as vitamin B1 (thiamine), penicillin, and carboxylase (Zhu et al. 2012; Das et al., 2016). 2-Aminothiazoles are one of the most important classes of heterocyclic compounds, that contain nitrogen and sulfur are present in compounds possessing scaffolds due to the medical and pharmaceutical applications (Das et al., 2016; Smith et al., 2012; Giridhar et al, 2001; Ali and Sayed, 2021; Hussein et al., 2020 ), such as antihypertension (Patt et al., 1992), antibacterial (Joseph et al., 2017), anti-inflammation, antiviral (Venkatachalam et al., 2001), antimycobacterial (Makam et al., 2013; Elsadek et al., 2021; Dayan et al., 2021 ), anticonvulsant (Siddiqui and Ahsan, 2010), antileishmanial (Bhuniya et al., 2015), HIV infections (Bell et al., 1995), anticancer (Elsadek et al., 2021; Chugunova et al., 2021; Kuzhandaivel et al., 2021; Özbek and Gürdere, 2021 ), antitumor (Hersi et al., 2020), antidiabetic (Iino et al., 2009) and antioxidative (Uchikawa et al., 1996). Therefore, in recent times, increasing attention has been paid to the synthesis of heterocycles compounds the development of an environmentally benign and efficient procedure for the synthesis of 2-aminothiazoles derivatives (Ali et al., 2010) has become particularly fascinating and remains a great challenge. Recently, nanomagnetic catalysts have been used as heterogeneous green catalysts. However, this study focuses on the development synthesis of 2-aminothiazoles derivatives by using the nanomagnetic catalyst for the effective synthesis via the one-pot reaction.

Table 1 Anti-microbial activity of 2-aminothiazoles derivatives (6–18).

Compd. No	Inhibition Zone (mm ± SD)
Compd. No	*E. coli*	*P. aeruginosa*	*Bacillus*	*S. aureus*	*Candida*
(1)	9.8 ± 0.2	Nil	Nil	Nil	Nil
(2)	10.15 ± 0.4	Nil	Nil	Nil	Nil
(6)	22 ± 0.8	16	Nil	Nil	Nil
(7)	16 ± 1.4	Nil	8.6 ± 0.4	12.3 ± 0.9	12 ± 0
(8)	20.6 ± 0.9	Nil	10.6 ± 0.4	Nil	Nil
(9)	8.8 ± 0.4	8 ± 0	Nil	Nil	Nil
(10)	14.3 ± 0.4	Nil	Nil	Nil	Nil
(11)	12.3 ± 0.9	11.8 ± 0.6	8.6 ± 0.9	10.6 ± 0.4	Nil
(12)	13.3 ± 1.2	Nil	Nil	10.3 ± 0.7	Nil
(13)	14.95 ± 0.5	9 ± 0.8	11.3 ± 0.4	9.6 ± 0.3	Nil
(14)	12.3 ± 0.4	Nil	10.3 ± 0.4	Nil	Nil
(15)	12.6 ± 0.5	Nil	Nil	Nil	Nil
(16)	13 ± 0.4	Nil	12.3 ± 0.4	13 ± 0.1	Nil
(17)	10.95 ± 0.3	Nil	Nil	9.3 ± 0.4	Nil
(18)	16.2 ± 0.9	14.6 ± 0.7	10 ± 0.2	11.3 ± 0.4	Nil

Concentration of Piperacillin = 4 µg/ml; Ceftazidime = 1 µg/ml; Oxacillin = 2 µg/ml; Fluconazole = 0.5 mg/ml.

As ideal supports and nanocatalysts have attracted much attention in catalytic processes, due to their intriguing nanoscale dimensions, high activity, low cost, high surface area, nontoxicity, magnetically separation from the reaction media, and easy modification with other organic or inorganic species (Sadeghi et al., 2016; Azgomi and Mokhtary, 2015; Zarnegar and Safari, 2016 ). In recent years, magnetic nanostructures such as Fe₃O₄ nanoparticle (Fe₃O₄ NPs) was applied in the presence of atmospheric air as a green efficient, heterogeneous, and reusable catalytic system for synthesis of the heterocyclic compounds (Zolfigol et al., 2012; Bhaskaruni et al., 2020; Esfahani et al., 2011; Polshettiwar and Varma, 2010 ). Although, this efficient greener protocol and cleaner conditions, milder, shorter reaction time, an excellent yield of products higher purity and easier work-up procedure, easy separation using a simple external magnetic field, low cost and operational simplicity promoted us to developed novel 2-aminothiazoles derivatives by using Fe₃O₄ NPs.

2 Experimental

2.1

2.1 Materials and methods

Melting points utilized via Stuart SMP30 Digital Advanced MP apparatus were taken in open capillary and uncorrected. FTIR spectra were carried out on IR Affinity (FTIR spectrometer) from Shimadzu, the sample prepared on a glass plate contain solid KBr. Liquid chromatography–mass spectrometry (LC/MS) were recorded on spectroscopy A LCMS-8040 Shimadzu corporation, model CAT-30A, Serial no. L20574900241 AE, 220-240v ∼ 50/60 HZ 300VA. ¹H NMR and ¹³CNMR were recorded on BRUKER spectrometer, 400 MHZ. The samples were prepared by dissolution at DMSO‑d₆. Chemical shifts (δ) are presented in part per million (ppm) using tetramethylsilane (TMS) an internal standard. Elemental microanalysis were done on Carlo Erba analyzer model 110. X-ray diffraction (XRD) patterns were recorded on a Rigaku model Ultima-IV diffractometer employing Cu-Kα radiation (λ = 1.5406 Å) at 40 kV and 25 mA over a 2θ range between 20 and 80°. All XRD measurement is handled in the air atmosphere. Samples for Scanning electron microscope (SEM) were prepared from ethanolic suspensions on single-sided alumina tape placed on alumina stubs. For the elemental analysis and mapping, the energy-dispersive X-ray spectra (EDS) were collected on a Lyra 3 (Tescan from the Chezch Republic) attachment to the SEM. TEM micrographs were obtained from a high-resolution transmission electron microscopy (HRTEM) (JEOL JEM-2100F) equipped with an energy dispersive X-ray spectrometer (EDX) operated at 200 kV. 300 mesh copper grids coated with carbon films were used for the imaging. The transmission electron microscopy (TEM) samples were prepared by dropping it on a copper grid from an ethanolic suspension and drying at room temperature.

2.2

2.2 Synthesis of nanomagentic catalyst

Magnetic nanoparticles with the range of 6–8 nm were prepared as the literature procedure (Nezhad and Mohammadi, 2015). Scheme 1 shows the synthetic route for the magnetic nanoparticles. In a 250 ml, round bottom flask, hydrated ferrous chloride (FeCl₂·H₂O) (5 mmol, 1 g) and ferric chloride (FeCl₃·H₂O) (10 mmol, 4.04 g) were dissolved in de-ionized water (DI-H₂O) (100 ml) under nitrogen atmosphere with a continuous stirring speed of 600 rpm. Then NH₄OH (25%) solution (25 ml) was added slowly at 90 °C to raise the pH at 9. The orange color solution was turned black in 15 min and continued stirring for another 3 h to complete the reduction. The mixture was allowed to precipitate and collected using a simple magnet. The black solid was washed several times (5 × 25 ml) to remove the unreacted metal precursors and ammonia. The powdered material was dried and used for characterization and catalytic reaction.

2.3

2.3 Synthesis of 2-(chlorodiazenyl)thiazole (2)

Dissolve (1 mmol) of 2-aminothiazole in 3 ml of HCl keep this solution in ice at 0˚C diazotize this solution by using NaNO₂ (5 mmol) solution (prepared by dissolving 5 mmol of NaNO₂ in 1 ml H₂O). The reaction mixture was kept onto ice bath for 3 h to give compound (2) as pink powder; yield (89.78%), mp.: 126.7 °C. FT‐IR (KBr, ν, cm^‐1): absence of (NH₂), 3010, appearance of 2980 (CH), and 1530 (N⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm), 6.90 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.27 (d, 1H, J = 8.0 Hz, H-3-thiazole); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 170.1 (S-C-N), 150.4 (C⚌N thiazolyl), 127.0, 108.3 (C-thiazolyl); MS (m/z): 146.98 (M⁺, 80.5%); Anal. calcd. for C₃H₂ClN₃S (146.96): C, 24.41; H, 1.37; Cl, 24.02; N, 28.47; S, 21.73%; found: C, 24.93; H, 1.39; Cl, 24.00; N, 28.45; S, 21.77%.

2.4

2.4 Coupling with active methylene compounds (3–5)

Reflux an equivalent mixture of (2) (1 mmol) and/or (1 mmol) ethyl acetoacetate, ethyl cyanoacetate, and acetylacetone respectively in presence of 25 ml ethanol for 1 h. The solid formed was recrystallized from ethanol to give (3–5) respectively.

2.4.1

2.4.1 Ethyl 3-oxo-2-(thiazol-2yldiazenyl)butanoate (3)

Light orange powder; yield (60.78%), mp.: 135.4 °C; FT‐IR (KBr, ν, cm⁻¹): 3010, 2980 (CH), 1750 (C⚌O ester and ketone) and 1590 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 1.35, 2.08 (m, 3H, 2CH₃), 4.11 (m, 2H, —CH₂—), 4.70 (s, 1H, CH—N); 7.16 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.55 (d, 1H, J = 8.0 Hz, H-3-thiazole), ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 171.0 (C⚌O ester), 166.9 (C⚌O), 150.4 (C⚌N thiazolyl), 125.0, 119.8 (C-thiazolyl), 62.9 (C—N), 13.6, 20.0 (CH₃); 59.2 (CH₂); MS (m/z): 240.05 (M⁺−1, 11.33%); Anal. calcd. for C₉H₁₁N₃O₃S (241.05): C, 44.80; H, 4.60; N, 17.42; S, 13.29%; found: C, 43.93; H, 4.44; N, 17.45; S, 13.39%.

2.4.2

2.4.2 Ethyl 2-cyano-2-(thiazol-2-yldiazenyl)acetate (4)

Orange powder; yield (65.45%), mp.: 144.3 °C; FT‐IR (KBr, ν, cm^‐1): 3010, 2980 (CH), 1749 (C⚌O), 1590 (C⚌N), 2260–2222 (CN); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 1.65 (s, 3H, CH₃), 2.12 (m, 3H, —CH₂—), 7.15 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.5 (d, 1H, J = 8.0 Hz, H-3-thiazole); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 171.1 (C⚌O), 152.4 (C⚌N thiazolyl), 125.0, 119.7 (CH-thiazolyl), 114.9 (CN), 50.9 (C—N), 58.7 (—CH₂), 22.9 (CH₃); MS (m/z): 224.04 (M⁺, 11.69%); Anal. calcd. for C₈H₈N₄O₂S (224.04): C, 42.85; H, 3.60; N, 24.99; S, 14.30%; found: C, 42.55; H, 3.68; N, 25.10; S, 14.40%.

2.4.3

2.4.3 3-(Thiazol-2-yl-hydrazono)-pentane-2,4-dione (5)

Yellow powder; yield (60.02%), mp.: 165.2 °C; FT‐IR (KBr, ν, cm^‐1): 3010, 2980 (CH), 1750 (C⚌O) and 1590 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 2.09 (s, 6H, 2CH₃), 7.15 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.51 (d, 1H, J = 8.0 Hz, H-3-thiazole); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 206.0 (C⚌O), 85.7 (C⚌N), 151.4 (C⚌N thiazolyl), 125.0, 119.7 (C-thiazolyl), 19.3 (CH₃); MS (m/z): 211.24 (M⁺, 22.01%); Anal. calcd. for C₈H₉N₃O₂S (211.24): C, 45.49; H, 4.29; N, 19.89; O, 15.15; S, 15.18%; found: C, 46.10; H, 4.32; N, 19.69; O, 15.05; S, 15.08%.

2.5

2.5 Synthesis of pyrazol-5-one derivatives (6–8)

An equivalent mixture of (1 mmol) of (3–5) and (2 mmol) hydrazine hydrate in presence of (0.01 mmol) of Fe₃O₄ the reaction mixture was stirred for 2 h at room temperature. The solid formed was recrystallized from ethanol to give (6–8) respectively.

2.5.1

2.5.1 3-methyl-4-(thiazol-2-yldiazenyl)-1H-pyrazol-5(4H)-one (6)

Beige powder; yield (87.02%), mp.: 155.5 °C; FT‐IR (KBr, ν, cm^‐1): 3250 (NH), 3010, 2980 (CH), 1750 (C⚌O) and 1590 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 1.75 (s, 3H, CH₃), 7.16 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.55 (d, 1H, J = 8.0 Hz, H-3-thiazole), 8.70 (s, 1H, NH-pyrazolyl); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 166.9 (C⚌O), 156.7 (C⚌N pyrazolyl), 150.4 (C⚌N thiazolyl), 125.0, 119.7 (C-thiazolyl), 62.9 (C—N), 22.9 (CH₃); MS (m/z): 209.06 (M⁺, 55.05%); Anal. calcd. for C₇H₇N₅OS (209.04): C, 40.18; H, 3.37; N, 33.47; S, 15.33%; found: C, 41.00; H, 3.26; N, 33.27; S, 15.13%.

2.5.2

2.5.2 3-amino-4-(thiazol-2-yldiazenyl)-1H-pyrazol-5(4H)-one (7)

Orange powder; yield (80.66%), mp. 172.0 °C; FT‐IR (KBr, ν, cm^‐1): 3330, 3250 (NH₂, NH), 3010, 2850 (CH), 1715 (C⚌O) and 1600 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 1.81 (s, 3H, CH₃), 7.69 (d, 1H, J = 8.0 Hz, H-2-thiazole), 7.88 (d, 1H, J = 8.0 Hz, H-3-thiazole), 8.26 (s, 1H, NH-pyrazolyl), 8.54 (s, 1H, NH₂); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 163.3 (C⚌O), 159.2 (C⚌N pyrazolyl), 140.9 (C⚌N pyrazolyl), 140.0 (C-thiazolyl), 62.9 (C—N), 15.4 (CH₃); MS (m/z): 210.01 (M⁺, 33.2%); Anal. calcd. for C₆H₆N₆OS (210.03): C, 34.28; H, 2.88; N, 39.98; S, 15.25%; found: C, 33.20; H, 2.90; N, 40.00; S, 15.35%.

2.5.3

2.5.3 (3,5-Dimethyl-4H-pyrazol-4-yl)-thiazol-2-yl-diazene (8)

Yellow powder; yield (82.03%), mp.: 186.0 °C; FT‐IR (KBr, ν, cm^‐1): 3380 (NH), 3010, 2850 (CH, CH₃), and 1600 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 2.01 (s, 6H, 2CH₃), 7.46 (d, 1H, J = 8.0 Hz, H-2-thiazole), 8.00 (d, 1H, J = 8.0 Hz, H-3-thiazole), 8.00 (s, 1H, NH-pyrazolyl). ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 164.5 (C⚌N pyrazolyl), 33.4 (C⚌N pyrazolyl), 153.0, 143.0 (C-thiazolyl), 62.9 (C—N), 15.4 (CH₃); MS(m/z): 207.10 (M⁺, 22.11%); Anal. calcd. for C₈H₉N₅S (207.06): C, 46.36; H, 4.38; N, 33.79; S, 15.47%; found: C, 45.49; H, 4.40; N, 33.81; S, 15.45%.

2.6

2.6 General procedure for Schiff bases synthesis of compounds (9–18)

An equivalent mixture of (1 mmol) of 1 and various aromatic aldehydes (1 mmol) namely: benzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, p-hydroxybenz- aldehyde, salicylladehyde, p-/o-anisaldehyde, 2,4-/2,3-dimethoxybenzaldehyde, and 2-methyl indolyl-3-carboxaldehyde in presence of (0.01 mmol) of Fe₃O₄ the reaction medium at room temperature (RT) for 1 h. The solid formed was recrystallized from ethanol to give the corresponding Schiff bases derivatives (9–18).

2.6.1

2.6.1 N-(benzylidene)thiazol-2-amine (9)

Yellow powder; yield (81.00%), mp.: 113–115 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2990 (CH), 1590 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 7.37–7.74 (m, 5H, CH-aromatic), 7.54 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.20 (d, 1H, J = 8.0 Hz, H-5-thiazole), 9.01 (s, ¹H, CH⚌N); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 171.9 (N⚌C—S), 167.1 (HC⚌N), 141.6, 119.8 (C-thiazolyl), 127.8, 124.4, 123.9 (C-aromatic); MS(m/z): 188.10 (M⁺, 44.05%); Anal. calcd. for C₁₀H₈N₂S (188.04): C, 63.80; H, 4.28; N, 14.88; S, 17.03%; found: C, 63.76; H, 4.20; N, 14.91; S, 17.13%.

2.6.2

2.6.2 N-(4-chlorobenzylidene)thiazol-2-amine (10)

Brown crystal; yield (88.05%), mp.: 134.8 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3010, 2990 (CH), 1580 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 7.66–8.02 (m, 4H, CH-aromatic), 7.60 (d, 1H, J = 8.0 Hz, H-4-thiazole), 6.65 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.03 (s, 1H, CH⚌N); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 171.9 (N⚌C—S), 166.6 (HC⚌N), 141.7, 119.9 (C-thiazolyl), 131.2, 129.7, 128.8 (C-aromatic); MS (m/z): 222.00 (M⁺, 18.52%); Anal. calcd. for C₁₀H₇ClN₂S (222.00): C, 53.93; H, 3.17; Cl, 15.92; N, 12.58; S, 14.40%; found: C, 53.83; H, 3.20; Cl, 15.99; N, 12.50; S, 14.51%.

2.6.3

2.6.3 N-(2-nitrobenzylidene)thiazol-2-amine (11)

Orange powder; yield (80.97%), mp.: 163.5 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2990 (CH), 1610 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 6.54–7.76 (m, 4H, CH-aromatic), 7.02 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.01 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.51 (s, 1H, CH⚌N); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 166.8 (N⚌C—S), 148.6 (HC⚌N), 134.4, 110.7 (C-thiazolyl), 134.2, 130.5, 129.0, 124.4 (C-aromatic); MS(m/z): 233.02 (M⁺, 80%); Anal calcd. for C₁₀H₇N₃O₂S (233.03): C, 51.49; H, 3.02; N, 18.02; S, 13.75%; found: C, 51.55; H, 3.32; N, 18.12; S, 13.75%.

2.6.4

2.6.4 4-((thiazol-2-ylimino)methyl)phenol (12)

Yellow powder; yield (85.43%), mp.: 175.2 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2890 (CH), 1605 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 6.38–7.33 (m, 4H, CH-aromatic), 7.07 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.72 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.27 (s, 1H, CH⚌N), 9.84 (s, 1H, OH); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 173.0 (N⚌C—S), 162.2 (HC⚌N), 141.3, 115.9 (C-thiazolyl), 138.6, 132.1, 116.1 (C-aromatic); MS (m/z): 206.05 (M⁺+2, 23.07%); Anal. calcd. for C₁₀H₈N₂OS (204.04): C, 58.80; H, 3.95; N, 13.72; S, 15.70%; found: C, 58.92; H, 3.98; N, 13.75; S, 15.75%.

2.6.5

2.6.5 2-((thiazol-2-ylimino)methyl)phenol (13)

Brown powder; yield (90.00%), mp.: 165.8 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3320 (OH), 3010, 2880 (CH), 1610 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 10.25 (s, 1H, OH), 6.92–8.54 (m, 4H, CH-aromatic), 7.64 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.01 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.21 (s, 1H, CH⚌N); ¹³C NMR: (400 MHz, DMSO‑d6, δ, ppm): 160.8 (N⚌C—S), 154.3 (HC⚌N), 122.3, 119.5, 119.5 (C-aromatic); MS (m/z): 204.04 (M⁺, 55.01%); Anal. calcd. for C₁₀H₈N₂OS (204.04): C, 58.80; H, 3.95; N, 13.72; S, 15.70%; found: C, 58.78; H, 3.75; N, 13.62; S, 15.68%.

2.6.6

2.6.6 N-(4-methoxybenzylidene)thiazol-2-amine (14)

Yellow powder; yield (87.07%), mp.: 102–103 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2990 (CH), 1610 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 6.35–7.31 (m, 4H, CH-aromatic), 7.60 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.21 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.12 (s, 1H, CH⚌N), 3.38 (s, 6H, OCH₃); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 161.5 (N⚌C—S), 156.0 (HC⚌N), 135.5, 120.6 (C-thiazolyl), 129.5, 128.4, 126.1 (C-aromatic), 62.9, 55.8 (OCH₃); MS (m/z): 218.10 (M⁺, 60.0%); Anal. calcd. for C₁₁H₁₀N₂OS (218.05): C, 60.53; H, 4.62; N, 12.83; S, 14.69%; found: C, 60.71; H, 4.66; N, 12.88; S, 14.72%.

2.6.7

2.6.7 N-(2-methoxybenzylidene)thiazol-2-amine (15)

Orange powder; yield (90.05%), mp.:150.9 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3009, 2890 (CH), 1605 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 6.37–7.21 (m, 4H, CH-aromatic), 7.60 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.21 (d, 1H, J = 8.0 Hz, H-5-thiazole), 8.12 (s, 1H, CH⚌N), 3.33 (s, 6H, OCH₃); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 161.5 (N⚌C—S), 156.0 (HC⚌N), 135.5, 120.6 (C-thiazolyl), 129.5, 128.5, 126.1 (C-aromatic), 62.9, 55.8 (OCH₃); MS (m/z): 218.10 (M⁺, 66.03%); Anal. calcd. for C₁₁H₁₀N₂OS (218.05): C, 60.53; H, 4.62; N, 12.83; S, 14.69%; found: C, 60.73; H, 4.74; N, 11.93; S, 13.99%.

2.6.8

2.6.8 N-(2,4-dimethoxy-benzylidene)-thiazol-2-yl-amine (16)

Orange powder; yield (87.50%), mp.:135.2 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2990 (CH), 1590 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 7.37–7.67 (m, 3H, CH-aromatic), 7.60 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.20 (d, 1H, J = 8.0 Hz, H-5-thiazole), 9.01 (s, 1H, CH⚌N), 3.49 (s, 6H, 2CH₃); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 173.6 (N⚌C—S), 167.1 (HC⚌N), 141.7, 119.7 (C-thiazolyl), 126.9, 124.5, 123.7 (C-aromatic), 62.8, 55.8 (OCH₃); MS (m/z): 188.10 (M⁺, 88.01%); Anal. calcd. for C₁₂H₁₂N₂O₂S (248.06): C, 58.05; H, 4.87; N, 11.28; S, 12.91%; found: C, 59.04; H, 4.86; N, 11.29; S, 12.90%.

2.6.9

2.6.9 N-(2,3-dimethoxybenzylidene)thiazol-2-amine (17)

Yellow powder; yield (89.09%), mp.: 152.0 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3020, 2990 (CH), 1609 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 7.37–7.64 (m, 3H, CH-aromatic), 7.64 (d, 1H, J = 8.0 Hz, H-4-thiazole), 7.20 (d, 1H, J = 8.0 Hz, H-5-thiazole), 9.29 (s, 1H, CH⚌N), 3.44 (s, 6H, 2CH₃); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 172.6 (N⚌C—S), 167.1 (HC⚌N), 141.6, 119.8 (C-thiazolyl), 127.9, 124.5, 123.9 (C-aromatic), 62.8, 55.8 (OCH₃); MS (m/z): 248.10 (M⁺, 100%); Anal. calcd. for C₁₂H₁₂N₂O₂S (248.06): C, 58.05; H, 4.87; N, 11.28; S, 12.91%; found: C, 59.05; H, 4.89; N, 11.30; S, 12.71%.

2.6.10

2.6.10 N-((2-methyl-1H-indol-3-yl)methylene)thiazol-2-amine (18)

Yellow powder; yield (86.34%), mp.:180.2 °C; FT‐IR (KBr, ν, cm^‐1): absence of (C⚌O, NH₂), 3010, 2980 (CH), 1600 (C⚌N); ¹H NMR: (400 MHz, DMSO‑d₆, δ, ppm): 11.99 (s, 1H, NH-indolyl), 7.13–8.02 (m, 4H, CH-aromatic), 7.16 (d,1H, J = 8.0 Hz, H-4-thiazole), 7.14 (d,1H, J = 8.0 Hz, H-5-thiazole), 8.04 (s, 1H, CH⚌N), 2.67 (s, 3H, CH₃); ¹³C NMR: (400 MHz, DMSO‑d₆, δ, ppm): 184.1 (N⚌C—S), 148.5, 111.4 (C-thiazolyl), 150.0 (HC⚌N), 135.3, 125.6, 122.6, 121.8, 119.9, 113.6 (C-aromatic); MS (m/z): 241.10 (M⁺, 66.09%); Anal. calcd. for C₁₃H₁₁N₃S (241.07): C, 64.70; H, 4.59; N, 17.41; S, 13.29%; found: C, 64.55; H, 4.48; N, 17.38; S, 13.31%.

3 Results and discussion

Ultrasmall nanomagnetic catalysts are prepared by the co-precipitation technique using Fe(II) and Fe(III) precursors using NH₄OH as a reductant. The black powdered materials are collected by a magnet and non-magnetic materials are removed by washing with water repeatedly Scheme 1. The crystallinity of the prepared nanocatalyst is confirmed by the XRD signature. The XRD patterns of Fe₃O₄ display characteristic peaks at 2θ 30.2, 35.7, 43.1. 53.4, 57.1, and 63.2 indicate the formation of crystalline cubic (Fd3m) spinnel structure (JCPDS card no. 01-075-0449) (Shaikh et al., 2018; Pinna et al., 2005). Scanning electron microscopic (SEM) images demonstrated highly agglomerated particles with extremely smaller-sized particles with smooth surfaces. The higher surface interaction among the bared-surface ultrasmall nanoparticle leads to aggregation of the particles. Transmission electron microscopic (TEM) images show spherically shaped, uniformly distributed, nano-sized particles with 6–8 nm diameter, Fig. 1. The magnetic nature of the Fe₃O₄ NPs have been investigated and the results are shown below. The magnetization field (M−H) curve is recorded at room temperature using PMC Micromag 3900 model vibrating sample magnetometer (VSM) equipped with a 1 Tesla magnet. The magnetic measurement of the Fe₃O₄ NPs shows 62.69 emu g⁻¹, which is magnetic enough to separate the nanoparticles using a simple magnet at the bottom of the vessel after the reaction, Fig. 2.

X-ray diffraction(a) pattern of the Fe3O4 NPs, the SEM (b) and TEM (c) images show spherically shaped, uniformly distributed, nano-sized particles with 6–8 nm.

Magnetic hysteresis loops of Fe3O4 at room temperature with 1 Tesla magnet.

Using nanomagnetic catalysis is a modern technique for preparing organic compounds with high yield in a short time. Previously, we reported the diazotization of amino heterocyclic compounds followed by coupling with various active methylene compounds afford the corresponding coupling products by traditional method in ethanol under reflux for 2 h (Abrams, 2021). Herein, by using nanomagnetic catalysis (Fe₃O₄ NPs) in coupling the diazonium salt of 2-aminothiazole with various active methylene compounds, it seems the reaction is completed in 1 h. In addition to the short time reaction, it affords high yields compared to the conventional method Fig. 3 and Fig. 4 represents the pathway of preparing the target compounds. Coupling diazonium salt of 2-aminothiazole with ethyl acetoacetate, ethyl cyanoacetate, and acetylacetone in presence of a catalytic amount of Fe₃O₄ NPs at room temperature afforded the corresponding coupling products (3–5) respectively in 1 h. The reaction was monitored using the TLC technique. The prepared compounds were proved via their cyclization upon nucleophilic attack within by nucleophile hydrazine hydrate afforded the corresponding pyrazolyl derivatives (6–8) Scheme 2, these novel products were elucidated based on spectral data. The IR spectrum of (6) displayed absorption bands in the region 1750 cm⁻¹ due to C⚌O, and at 3330, 3250 attributable for NH₂ in (7). 1H NMR spectrum of (7) as an example, recorded new signals at δ 8.54, 8.26 ppm assigned for NH₂ and NH, respectively. More details are required such as the absence of CN in 4 and more discussion for other products.

Reaction time (min) of products by used conventional method and with Fe3O4 NPs catalysis.

The effect of the yield (%) of products by used conventional methods and with Fe3O4 NPs catalysis.

Synthesistic pathway for pyrazole derivatives.

Moreover, the formation of Schiff bases from 2-aminothiazole was carried out upon one-pot method by treatment with a various aromatic aldehyde in presence of Fe₃O₄ NPs catalysis at room temperature Scheme 3., The reaction vanished in less time, and furnished high yield than the conventional method (Fig. 3 and Fig. 4).

Synthesistic pathway for Schiff bases derivatives.

The structures of these products were assigned using spectral analysis. IR for all compounds showed the absence of C⚌O and NH₂.

The plausible mechanism is consistent with the literature (Sadeghi et al., 2016; Zolfigol et al., 2012; Safari and Sadeghi, 2017 ). Preparation of intermediate given on proposed mechanism for the production of pyrazole derivatives in Scheme 4. Fe₃O₄ NPs as the catalyst can activate the active methylene compounds (A) through coordination to the oxygen atom of carbonyl group the catalyst can participate in the conversion of (B), Afterwards, Fe₃O₄ NPs promoted cyclization with hydrazine hydrate and dehydration gives pyrazole derivatives (6) (Polshettiwar and Varma, 2010). The nanocatalyst could be magnetically recovered from the reaction mixture during the workup procedure. Furthermore, the proposed mechanism for preparation of the Schiff base derivatives were carried out by activated aromatic aldehyde by Fe(III) of Fe₃O₄ NPs. Then nucleophilic attack of the amino group to carbonyl group of the activated aldehyde via the elimination of H₂O to give Schiff base derivatives.

Plausible mechanism for synthesis pyrazole derivative by using Fe3O4 NPs.

4 Biological activity

All of the synthesized compounds were tested for their antimicrobial activities against five types of microorganisms including gram-negative and positive bacteria as well as fungus. The gram-negative bacteria include E. coli and P. aeruginosa while B. subtilis and S. aureus represented the gram-positive bacteria. C. albicans was the fungus used in the screening. Generally, the tested compounds exhibited better antibacterial activities with E.coli being the most sensitive bacteria. However, all of the tested compounds, except compound (7), showed no antifungal activity against C. albicans. Azo derivatives (1, 2) and (6–8) were slightly more potent than the Schiff bases with average zones of inhibition of 15.71 and 12.87 mm, respectively. Compound (6) showed the most potent antibacterial activity against E. coli whereas compound (9) was the least potent among the tested series of compounds. Unsubstituted benzene in Schiff base (9) was less potent than the substituted analogues. This may suggest that benzene substitution is beneficial for the activity. In addition, the antibacterial activity of the Schiff bases seems to be insensitive to the position and the nature of the substituents. The majority of the synthesized compounds did not exhibit antipseudomonal activity. Only compounds (6, 9, 11, 13) and (18) showed growth inhibition against P. aeruginosa with the most potent activity observed with compound (6). However, none of the compounds was superior to piperacillin. For the gram-positive bacteria, the antibacterial activity was more significant in Schiff base derivatives when compared to azo derivatives. None of the tested compounds showed superior activity to the positive control. Compound (7) was the only pyrazole derivative that showed activity against both B. subtilis and S. aureus whereas, compounds (11, 13) and (16) were the only Schiff bases that exhibited activities against both bacteria Table 1.

5 Conclusion

In summary, we have demonstrated an efficient, simple, efficient, and sable catalyst-Fe for the synthesis pyrazolyl derivatives and 2-aminothiazole Schiff bases derivatives of 2-aminothiazole by comparing showed best results of Fe₃O₄ NPs nanomagnetic catalysis and convention method. This method is quick, and avoids the use of toxic or heavy metals, high temperature, improved product yields, and easy workup procedure.

Acknowledgements

We would like to thanks Deanship of Scientific Research at Imam Abdulrhaman Bin Faisal University for financial support under projects no: (2019-132-sci), thanks for the co-workers and trenching at Basic and Applied Scientific Research Center, Imam Abdulrhaman Bin Faisal University, for making the spectral analyses, and for department of pharmaceutical chemistry and chemistry department at King Saud University to make the biological activity and nmr analysis for this research.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

Abrams J.N., . Alternative method for the synthesis of triazenes from aryl diazonium salts. Tetrahedron. 2021;89:132185.
[Google Scholar]
Ali P., Meshram J., Tiwari V., . Microwave mediated cyclocondensation of 2-Aminothiazole into β-lactam derivatives: virtual screening and In vitro antimicrobial activity with various microorganisms. Int. J. ChemTech. Res.. 2010;2:956-964.
[Google Scholar]
Ali S.H., Sayed A.R., . Review of the synthesis and biological activity of thiazoles. Synthetic Comm.. 2021;51:670-700.
[Google Scholar]
Azgomi N., Mokhtary M., . Nano-Fe₃O₄@SiO₂ supported ionic liquid as an efficient catalyst for the synthesis of 1,3-thiazolidin-4-ones under solvent-free conditions. J. Mol. Catal. A: Chem.. 2015;398:58-64.
[Google Scholar]
Bell F.W., Cantrell A.S., Hogberg M., Jaskunas S.R., Johansson N.G., Jordan C.L., Kinnick M.D., Lind P., Morin J.M., NorBen R., Oberg B., Palkowitz J.A., Parrish C.A., Pranc P., Sahlberg C., Ternansky R.J., Vasileff R.T., Vrang L., West S.J., Zhang H., Zhou X.X., . Phenethylthiazolethiouea (PETT) compounds, a new class of HIV-1 reverse transciptase inhibitors. 1. Synthesis and basic structure activity relationship studies of PETT analogs. J. Med. Chem.. 1995;38:4929-4936.
[Google Scholar]
Bhaskaruni S.V., Maddila S., Gangu K.K., Jonnalagadda S.B., . A review on multi-component green synthesis of N-containing heterocycles using mixed oxides as heterogeneous catalysts. Arabian J. Chem.. 2020;13:1142-1178.
[Google Scholar]
Bhuniya D., Mukhhavilli R., Shivhare R., Launay D., Dere R.T., Deshpandey A., Verma A., Vishwakarma P., Moger M., Pradhan A., Pati H., Gopinath V.S., Gupta S., Puri S., Martin D., . Aminothiazoles: Hit to lead development to identify antileishmanial agents. Eur. J. Med. Chem.. 2015;102:582-593.
[Google Scholar]
Chugunova E., Micheletti G., Telese D., Boga C., Islamov D., Usachev K., Burilov A., Tulesinova A., Voloshina A., Lyubina A., Amerhanova S., Gerasimova T., Gilfanova A., Syakaev V., . Novel hybrid compounds containing benzofuroxan and aminothiazole scaffolds: synthesis and evaluation of their anticancer activity. Int. J. Mol. Sci.. 2021;22:7497.
[Google Scholar]
Das D., Sikdar P., Bairagi M., . Recent developments of 2-aminothiazoles in medicinal chemistry. Eur. J. Med. Chem.. 2016;109:89-98.
[Google Scholar]
Dayan S., Tercan M., Ozdemir F.A., Aykutoglu G., Ozdemir N., Serbetci Z., Dincer M., Dayan O., . Catalytic and biological activities of homoleptic palladium (II) complexes bearing the 2-aminobenzothiazole moiety. Polyhedron. 2021;199:115106.
[Google Scholar]
Elsadek M.F., Ahmed B.M., Farahat M.F., . An overview on synthetic 2-aminothiazole-based compounds associated with four biological activities. Molecules. 2021;26:1449.
[Google Scholar]
Esfahani M.N., Hoseini S.J., Mohammadi F., . Fe₃O₄ nanoparticles as an efficient and magnetically recoverable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones under solvent free conditions. Chin. J. Catal.. 2011;32:1484-1489.
[Google Scholar]
Giridhar T., Reddy R.B., Prasnna B., Chandra Mouli G.V.P., . Amiothiazoles part1-Syntheses and pharmacological evaluation of 4-[isobutylphenyl]-2-substituted aminothiazoles. Indan J. Chem. 2001:1279-1281.
[Google Scholar]
Hersi F., Omar H.A., Al-Qawasmeh R.A., Ahmad Z., Jaber A.M., Zaher D.M., Al-Tel T.H., . Design and synthesis of new energy restriction mimetic agents: Potent anti-tumor activities of hybrid motifs of aminothiazoles and coumarins. Sci. Rep.. 2020;10:2893.
[Google Scholar]
Hussein A.M., Khames A.A., El-Adasy A.A., Atalla A.A., Abdel-Rady M., Hassan M.I.A., Nemr M.T.M., Elshaier Y.A.M., . Design, synthesis, and biological evaluation of new 2-aminothiazole scaffolds as phosphodiesterase type 5 regulators and COX-1/COX-2 inhibitors. RSC Adv.. 2020;10:29723-29736.
[Google Scholar]
Iino T., Tsukahara D., Kamata K., Sasaki K., Ohyama S., Hosaka H., Hasegawa T., Chiba M., Nagata Y., Eiki J., Nishimura T., . Discovery of potent and orally active 3-alkoxy-5-phenoxy-N-thiazolyl benzamides as novel allosteric glucokinase activators. Bioorg. Med. Chem.. 2009;17:2733-2743.
[Google Scholar]
Joseph J., Janaki G.B., Nagashri K., Joseyphus R.S., . Antimicrobial, Antioxidant, and SOD activities of copper (II) complexes derived from 2-Aminobenzo thiazole derivatives. J. Coordination Chem.. 2017;70:242-260.
[Google Scholar]
Kuzhandaivel H., Basha S.B., Charles I.D., Raju N., Singaravelu U., Nallathambi K.S., . Performance of 2-hydroxy-1-naphthaldehyde-2-amino thiazole as a highly selective turn-on fluorescent chemosensor for Al(III) ions detection and biological applications. J. Fluorescence. 2021;31:1041-1053.
[Google Scholar]
Makam P., Kankanala R., Prakash A., Kannan T., . 2-(2-Hydrazinyl) thiazole derivatives: design, synthesis, and in vitro antimycobacterial studies. Eur. J. Med. Chem.. 2013;69:564-576.
[Google Scholar]
Nezhad A.K., Mohammadi S., . Magnetic, acidic, ionic liquid-catalyzed one-pot synthesis of spirooxindoles. New J. Chem.. 2015;39:7293. ACS Comb. Sci. 15 (2013) 512
[Google Scholar]
Ozbek O., Gurdere M.B., . Synthesis and anticancer properties of 2-aminothiazole derivatives. Phosph. Sulfur Silicon Related Eleme.. 2021;196:444-454.
[Google Scholar]
Patt W.C., Hamilton H.W., Taylor M.D., Ryan M.J., Taylor D.G., Connolly C.J.C., Doherty A.M., Klutchko S.R., Sircar I., Steinbaugh B.A., Batley B.L., Painchaud C.A., Rapundalo S.T., Michniewicz B.M., Olson S.C., . Structure activity relationship of a series of 2-amino-4-thiazole-containing renin inhibitors. J. Med. Chem.. 1992;35:2562-2572.
[Google Scholar]
Pinna N., Grancharov S., Beato P., Bonville P., Antonietti M., Niederberger M., . Magnetite nanocrystals: nonaqueous synthesis, characterization, and solubility. Chem. Mater.. 2005;17:3044-3049.
[Google Scholar]
Polshettiwar V., Varma R.S., . Nano-organocatalyst: magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal-Knorr reaction, aza-Michael addition, and pyrazole synthesis. Tetrahedron. 2010;66:1091-1097.
[Google Scholar]
Sadeghi M., Safari J., Zarnegar Z., . Synthesis of 2-aminothiazoles from methylcarbonyl compounds using a Fe₃O₄ nanoparticle-N-halo reagent catalytic system. RSC Adv.. 2016;6:64749-64755.
[Google Scholar]
Safari J., Sadeghi M., . Nanostarch: a novel and green catalyst for synthesis of 2-aminothiazoles. Monatsh Chem.. 2017;148:745-749.
[Google Scholar]
Shaikh M.N., Abdul Aziz M., Kalanthoden A.N., Helal A., Hakeem A.S., Bououdina M., . Facile hydrogenation of N-heteroarenes by magnetic nanoparticle-supported sub-nanometric Rh catalysts in aqueous medium. Catal. Sci. Technol.. 2018;8:4709-4717.
[Google Scholar]
Siddiqui N., Ahsan W., . Triazole incorporated thiazoles as a new class of anticonvulsants: design, synthesis, and in vivo screening. Eur. J. Med. Chem.. 2010;45:1536-1543.
[Google Scholar]
Smith B., Chang H.H., Medda F., Gokhale V., Dietrich J., . Synthesis and biological activity of 2-aminothiazoles as novel inhibitors of PGE₂ production in cells. Bioorg. Med. Chem. Lett.. 2012;22:3567-3570.
[Google Scholar]
Uchikawa O., Fukatsu K., Suno M., Aono T., Doi T., . In vivo biological activity of antioxidative aminothiazole derivatives. Chem. Pharm. Bull.. 1996;44:2070-2077.
[Google Scholar]
Venkatachalam T.K., Sudbeck E.A., Mao C., Uckun F.M., . Anti-HIV activity of aromatic and heterocyclic thiazolyl thiourea compounds. Bioorg. Med. Chem.. 2001;11:523-528.
[Google Scholar]
Xue W.J., Li H.Z., Zheng K.L., Wu A.X., . Iodine-promoted efficient Synthesis of diheteroaryl thioethers via the integration of iodination/ condensation/cyclization/dehydration sequences. Tetrahedron Lett.. 2014;55:5544-5547.
[Google Scholar]
Zarnegar Z., Safari J., . Magnetic carbon nanotube-supportedimidazolium cation based ionic liquid as a highly stable nanocatalyst for the synthesis of 2-aminothiazoles. Appl. Organometal. Chem.. 2016;30:1043-1049.
[Google Scholar]
Zhu Y.P., Yuan J.J., Zhao Q., Lian M., Gao Q.H., Liu M.C., Yang Y., Wu A.X., . I₂/CuO-catalyzed tandem cyclization strategy for one-pot synthesis of substituted 2-aminothiozole from easily available aromatic ketones/α, β-unsaturated ketones and thiourea. Tetrahedron. 2012;68:173-178.
[Google Scholar]
Zolfigol M.A., Khakyzadeh V., Moosavi-Zare A.R., Zare A., Arghavani-Hadi P., Mohammadi Z., Beyzavi M.H., . Nano-Fe₃O₄/O₂: green, magnetic and reusable catalytic system for the synthesis of benzimidazoles. J. Chem.. 2012;65:280-285.
[Google Scholar]

Appendix A

Supplementary material

Supplementary data to this article can be found online at https://doi.org/10.1016/j.arabjc.2022.103878.

Appendix A

Supplementary material

The following are the Supplementary data to this article:

Supplementary data 1

Download

Introduction

Experimental

Materials and methods
Synthesis of nanomagentic catalyst
Synthesis of 2-(chlorodiazenyl)thiazole (2)
Coupling with active methylene compounds (3–5)
Synthesis of pyrazol-5-one derivatives (6–8)
General procedure for Schiff bases synthesis of compounds (9–18)

Results and discussion

Biological activity

Conclusion

Fulltext Views
8

PDF downloads
3

View/Download PDF
Download Citations

BibTeX
RIS

Show Sections

[1] Abrams J.N., . Alternative method for the synthesis of triazenes from aryl diazonium salts. Tetrahedron. 2021;89:132185.
[Google Scholar]

[2] Ali P., Meshram J., Tiwari V., . Microwave mediated cyclocondensation of 2-Aminothiazole into β-lactam derivatives: virtual screening and In vitro antimicrobial activity with various microorganisms. Int. J. ChemTech. Res.. 2010;2:956-964.
[Google Scholar]

[3] Ali S.H., Sayed A.R., . Review of the synthesis and biological activity of thiazoles. Synthetic Comm.. 2021;51:670-700.
[Google Scholar]

[4] Azgomi N., Mokhtary M., . Nano-Fe₃O₄@SiO₂ supported ionic liquid as an efficient catalyst for the synthesis of 1,3-thiazolidin-4-ones under solvent-free conditions. J. Mol. Catal. A: Chem.. 2015;398:58-64.
[Google Scholar]

[5] Bell F.W., Cantrell A.S., Hogberg M., Jaskunas S.R., Johansson N.G., Jordan C.L., Kinnick M.D., Lind P., Morin J.M., NorBen R., Oberg B., Palkowitz J.A., Parrish C.A., Pranc P., Sahlberg C., Ternansky R.J., Vasileff R.T., Vrang L., West S.J., Zhang H., Zhou X.X., . Phenethylthiazolethiouea (PETT) compounds, a new class of HIV-1 reverse transciptase inhibitors. 1. Synthesis and basic structure activity relationship studies of PETT analogs. J. Med. Chem.. 1995;38:4929-4936.
[Google Scholar]

[6] Bhaskaruni S.V., Maddila S., Gangu K.K., Jonnalagadda S.B., . A review on multi-component green synthesis of N-containing heterocycles using mixed oxides as heterogeneous catalysts. Arabian J. Chem.. 2020;13:1142-1178.
[Google Scholar]

[7] Bhuniya D., Mukhhavilli R., Shivhare R., Launay D., Dere R.T., Deshpandey A., Verma A., Vishwakarma P., Moger M., Pradhan A., Pati H., Gopinath V.S., Gupta S., Puri S., Martin D., . Aminothiazoles: Hit to lead development to identify antileishmanial agents. Eur. J. Med. Chem.. 2015;102:582-593.
[Google Scholar]

[8] Chugunova E., Micheletti G., Telese D., Boga C., Islamov D., Usachev K., Burilov A., Tulesinova A., Voloshina A., Lyubina A., Amerhanova S., Gerasimova T., Gilfanova A., Syakaev V., . Novel hybrid compounds containing benzofuroxan and aminothiazole scaffolds: synthesis and evaluation of their anticancer activity. Int. J. Mol. Sci.. 2021;22:7497.
[Google Scholar]

[9] Das D., Sikdar P., Bairagi M., . Recent developments of 2-aminothiazoles in medicinal chemistry. Eur. J. Med. Chem.. 2016;109:89-98.
[Google Scholar]

[10] Dayan S., Tercan M., Ozdemir F.A., Aykutoglu G., Ozdemir N., Serbetci Z., Dincer M., Dayan O., . Catalytic and biological activities of homoleptic palladium (II) complexes bearing the 2-aminobenzothiazole moiety. Polyhedron. 2021;199:115106.
[Google Scholar]

[11] Elsadek M.F., Ahmed B.M., Farahat M.F., . An overview on synthetic 2-aminothiazole-based compounds associated with four biological activities. Molecules. 2021;26:1449.
[Google Scholar]

[12] Esfahani M.N., Hoseini S.J., Mohammadi F., . Fe₃O₄ nanoparticles as an efficient and magnetically recoverable catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones under solvent free conditions. Chin. J. Catal.. 2011;32:1484-1489.
[Google Scholar]

[13] Giridhar T., Reddy R.B., Prasnna B., Chandra Mouli G.V.P., . Amiothiazoles part1-Syntheses and pharmacological evaluation of 4-[isobutylphenyl]-2-substituted aminothiazoles. Indan J. Chem. 2001:1279-1281.
[Google Scholar]

[14] Hersi F., Omar H.A., Al-Qawasmeh R.A., Ahmad Z., Jaber A.M., Zaher D.M., Al-Tel T.H., . Design and synthesis of new energy restriction mimetic agents: Potent anti-tumor activities of hybrid motifs of aminothiazoles and coumarins. Sci. Rep.. 2020;10:2893.
[Google Scholar]

[15] Hussein A.M., Khames A.A., El-Adasy A.A., Atalla A.A., Abdel-Rady M., Hassan M.I.A., Nemr M.T.M., Elshaier Y.A.M., . Design, synthesis, and biological evaluation of new 2-aminothiazole scaffolds as phosphodiesterase type 5 regulators and COX-1/COX-2 inhibitors. RSC Adv.. 2020;10:29723-29736.
[Google Scholar]

[16] Iino T., Tsukahara D., Kamata K., Sasaki K., Ohyama S., Hosaka H., Hasegawa T., Chiba M., Nagata Y., Eiki J., Nishimura T., . Discovery of potent and orally active 3-alkoxy-5-phenoxy-N-thiazolyl benzamides as novel allosteric glucokinase activators. Bioorg. Med. Chem.. 2009;17:2733-2743.
[Google Scholar]

[17] Joseph J., Janaki G.B., Nagashri K., Joseyphus R.S., . Antimicrobial, Antioxidant, and SOD activities of copper (II) complexes derived from 2-Aminobenzo thiazole derivatives. J. Coordination Chem.. 2017;70:242-260.
[Google Scholar]

[18] Kuzhandaivel H., Basha S.B., Charles I.D., Raju N., Singaravelu U., Nallathambi K.S., . Performance of 2-hydroxy-1-naphthaldehyde-2-amino thiazole as a highly selective turn-on fluorescent chemosensor for Al(III) ions detection and biological applications. J. Fluorescence. 2021;31:1041-1053.
[Google Scholar]

[19] Makam P., Kankanala R., Prakash A., Kannan T., . 2-(2-Hydrazinyl) thiazole derivatives: design, synthesis, and in vitro antimycobacterial studies. Eur. J. Med. Chem.. 2013;69:564-576.
[Google Scholar]

[20] Nezhad A.K., Mohammadi S., . Magnetic, acidic, ionic liquid-catalyzed one-pot synthesis of spirooxindoles. New J. Chem.. 2015;39:7293. ACS Comb. Sci. 15 (2013) 512
[Google Scholar]

[21] Ozbek O., Gurdere M.B., . Synthesis and anticancer properties of 2-aminothiazole derivatives. Phosph. Sulfur Silicon Related Eleme.. 2021;196:444-454.
[Google Scholar]

[22] Patt W.C., Hamilton H.W., Taylor M.D., Ryan M.J., Taylor D.G., Connolly C.J.C., Doherty A.M., Klutchko S.R., Sircar I., Steinbaugh B.A., Batley B.L., Painchaud C.A., Rapundalo S.T., Michniewicz B.M., Olson S.C., . Structure activity relationship of a series of 2-amino-4-thiazole-containing renin inhibitors. J. Med. Chem.. 1992;35:2562-2572.
[Google Scholar]

[23] Pinna N., Grancharov S., Beato P., Bonville P., Antonietti M., Niederberger M., . Magnetite nanocrystals: nonaqueous synthesis, characterization, and solubility. Chem. Mater.. 2005;17:3044-3049.
[Google Scholar]

[24] Polshettiwar V., Varma R.S., . Nano-organocatalyst: magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal-Knorr reaction, aza-Michael addition, and pyrazole synthesis. Tetrahedron. 2010;66:1091-1097.
[Google Scholar]

[25] Sadeghi M., Safari J., Zarnegar Z., . Synthesis of 2-aminothiazoles from methylcarbonyl compounds using a Fe₃O₄ nanoparticle-N-halo reagent catalytic system. RSC Adv.. 2016;6:64749-64755.
[Google Scholar]

[26] Safari J., Sadeghi M., . Nanostarch: a novel and green catalyst for synthesis of 2-aminothiazoles. Monatsh Chem.. 2017;148:745-749.
[Google Scholar]

[27] Shaikh M.N., Abdul Aziz M., Kalanthoden A.N., Helal A., Hakeem A.S., Bououdina M., . Facile hydrogenation of N-heteroarenes by magnetic nanoparticle-supported sub-nanometric Rh catalysts in aqueous medium. Catal. Sci. Technol.. 2018;8:4709-4717.
[Google Scholar]

[28] Siddiqui N., Ahsan W., . Triazole incorporated thiazoles as a new class of anticonvulsants: design, synthesis, and in vivo screening. Eur. J. Med. Chem.. 2010;45:1536-1543.
[Google Scholar]

[29] Smith B., Chang H.H., Medda F., Gokhale V., Dietrich J., . Synthesis and biological activity of 2-aminothiazoles as novel inhibitors of PGE₂ production in cells. Bioorg. Med. Chem. Lett.. 2012;22:3567-3570.
[Google Scholar]

[30] Uchikawa O., Fukatsu K., Suno M., Aono T., Doi T., . In vivo biological activity of antioxidative aminothiazole derivatives. Chem. Pharm. Bull.. 1996;44:2070-2077.
[Google Scholar]

[31] Venkatachalam T.K., Sudbeck E.A., Mao C., Uckun F.M., . Anti-HIV activity of aromatic and heterocyclic thiazolyl thiourea compounds. Bioorg. Med. Chem.. 2001;11:523-528.
[Google Scholar]

[32] Xue W.J., Li H.Z., Zheng K.L., Wu A.X., . Iodine-promoted efficient Synthesis of diheteroaryl thioethers via the integration of iodination/ condensation/cyclization/dehydration sequences. Tetrahedron Lett.. 2014;55:5544-5547.
[Google Scholar]

[33] Zarnegar Z., Safari J., . Magnetic carbon nanotube-supportedimidazolium cation based ionic liquid as a highly stable nanocatalyst for the synthesis of 2-aminothiazoles. Appl. Organometal. Chem.. 2016;30:1043-1049.
[Google Scholar]

[34] Zhu Y.P., Yuan J.J., Zhao Q., Lian M., Gao Q.H., Liu M.C., Yang Y., Wu A.X., . I₂/CuO-catalyzed tandem cyclization strategy for one-pot synthesis of substituted 2-aminothiozole from easily available aromatic ketones/α, β-unsaturated ketones and thiourea. Tetrahedron. 2012;68:173-178.
[Google Scholar]

[35] Zolfigol M.A., Khakyzadeh V., Moosavi-Zare A.R., Zare A., Arghavani-Hadi P., Mohammadi Z., Beyzavi M.H., . Nano-Fe₃O₄/O₂: green, magnetic and reusable catalytic system for the synthesis of benzimidazoles. J. Chem.. 2012;65:280-285.
[Google Scholar]

SPIONs as a nanomagnetic catalyst for the synthesis and anti-microbial activity of 2-aminothiazoles derivatives

Abstract

Keywords

Nanomagnetic catalysis

2-aminothiazole derivatives

Pyrazolyl derivatives

Schiff bases

Aromatic aldehyde

Anti-microbial activity

1 Introduction

2 Experimental

2.1 Materials and methods

2.2 Synthesis of nanomagentic catalyst

2.3 Synthesis of 2-(chlorodiazenyl)thiazole (2)

2.4 Coupling with active methylene compounds (3–5)

2.4.1 Ethyl 3-oxo-2-(thiazol-2yldiazenyl)butanoate (3)

2.4.2 Ethyl 2-cyano-2-(thiazol-2-yldiazenyl)acetate (4)

2.4.3 3-(Thiazol-2-yl-hydrazono)-pentane-2,4-dione (5)

2.5 Synthesis of pyrazol-5-one derivatives (6–8)

2.5.1 3-methyl-4-(thiazol-2-yldiazenyl)-1H-pyrazol-5(4H)-one (6)

2.5.2 3-amino-4-(thiazol-2-yldiazenyl)-1H-pyrazol-5(4H)-one (7)

2.5.3 (3,5-Dimethyl-4H-pyrazol-4-yl)-thiazol-2-yl-diazene (8)

2.6 General procedure for Schiff bases synthesis of compounds (9–18)

2.6.1 N-(benzylidene)thiazol-2-amine (9)

2.6.2 N-(4-chlorobenzylidene)thiazol-2-amine (10)

2.6.3 N-(2-nitrobenzylidene)thiazol-2-amine (11)

2.6.4 4-((thiazol-2-ylimino)methyl)phenol (12)

2.6.5 2-((thiazol-2-ylimino)methyl)phenol (13)

2.6.6 N-(4-methoxybenzylidene)thiazol-2-amine (14)

2.6.7 N-(2-methoxybenzylidene)thiazol-2-amine (15)

2.6.8 N-(2,4-dimethoxy-benzylidene)-thiazol-2-yl-amine (16)

2.6.9 N-(2,3-dimethoxybenzylidene)thiazol-2-amine (17)

2.6.10 N-((2-methyl-1H-indol-3-yl)methylene)thiazol-2-amine (18)

3 Results and discussion

4 Biological activity

5 Conclusion

Acknowledgements

Declaration of Competing Interest

References

Appendix A

Supplementary material

Appendix A

Supplementary material

Supplementary data 1

Suggested read for related articles: