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BMC Chemistry

, 13:120 | Cite as

Crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H) tethered to nano-Fe3O4 as a superior catalyst for the synthesis of 1,3-thiazoles

  • Hossein Shahbazi-AlaviEmail author
  • Sheida Khojasteh-Khosro
  • Javad Safaei-Ghomi
  • Maryam Tavazo
Open Access
Research article
  • 78 Downloads
Part of the following topical collections:
  1. Organic Chemistry

Abstract

Crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H) attached to nano-Fe3O4 as a superior catalyst has been used for the synthesis of 3-alkyl-4-phenyl-1,3-thiazole-2(3H)-thione derivatives through a three-component reactions of phenacyl bromide or 4-methoxyphenacyl bromide, carbon disulfide and primary amine under reflux condition in ethanol. A proper, atom-economical, straightforward one-pot multicomponent synthetic route for the synthesis of 1,3-thiazoles in good yields has been devised using crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H) tethered to nano-Fe3O4. The catalyst has been characterized by Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), dynamic light scattering (DLS), X-ray powder diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA) and vibrating-sample magnetometer (VSM).

Keywords

Polyacrylamide Thiazole Nanocatalyst Nano-Fe3O4 

Abbreviations

Cross-PAA-SO3H

crosslinked sulfonated polyacrylamide

FT-IR

Fourier-transform infrared spectroscopy

SEM

scanning electron microscope

XRD

X-ray powder diffraction

EDS

energy-dispersive X-ray spectroscopy

TGA

thermogravimetric analysis

VSM

vibrating-sample magnetometer

AAM

acrylamide

AAMPS

2-acrylamido-2-methylpropanesulfonic acid

DLS

dynamic light scattering

Introduction

1,3-thiazoles show anticancer [1], antimicrobial [2], anti-inflammatory [3], and anti-candida properties [4]. The synthesis of 1,3-thiazole derivatives have been developed in the presence of different catalysts including DBU [5], HClO4-SiO2 [6], Bi(SCH2COOH)3 [7], [Et3NH][HSO4] [8], Ytterbium(III) Triflate [9] 2-pyridinecarboxaldehyde oxime [10] and potassium iodide [11]. The synthetic strategies of 1,3-thiazole derivatives were recently reviewed [12]. Despite the use of these ways, there remains a need for further new procedures for the preparation of 1,3-thiazoles. The modifying crosslinked polyacrylamides make them attractive objects in chemistry and polymer science [13, 14, 15]. Sulfonated polyacrylamides have unique characteristics such as high strength, hydrophilicity, and proton conductivity [16, 17]. Recently, magnetic nanoparticles (MNPs) have been successfully utilized to immobilize enzymes, polymers, transition metal catalysts and organocatalysts [18, 19]. Different stabilizers-electrostatic (surfactants), [20] or steric (polymers) [21, 22, 23] have been proposed to overcome the aggregation of magnetite (Fe3O4). In the current study, we investigated an easy and rapid method for the synthesis of thiazole-2(3H)-thione through three-component reactions of phenacyl bromide or 4-methoxyphenacyl bromide, carbon disulfide and primary amine using crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H) attached to nano-Fe3O4, as an efficient catalyst under reflux condition in ethanol (Scheme 1). A schematic representation of the catalyst is provided in Scheme 2.
Scheme 1

Synthesis of 1,3-thiazoles

Scheme 2

A schematic illustration for the formation of Nano Fe3O4@PAA-SO3H

Results and discussion

Characterization of the nanocatalyst

In this study, we synthesized the crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H) with simultaneous radical co-polymerization in presence of initiator and crosslinking agent. The FT-IR absorbance spectra of the dried crosslinked sulfonated polyacrylamide (poly AAM-co-AAMPS), Fe3O4 and Cross-PAA-SO3H@nano-Fe3O4 are shown in Fig. 1 (AAM is abbreviation acrylamide; AAMPS is abbreviation 2-acrylamido-2-methylpropanesulfonic acid).
Fig. 1

The FT-IR spectra of (a) Fe3O4 NPs, (b) Cross-PAA-SO3H and (c) Cross-PAA-SO3H@ nano-Fe3O4

The peaks at 3100–3500 cm−1 are related to O–H (sulfonic acid group) and N–H (amide groups) in AAM and AAMPS. The strong band in the 1654 cm−1 can be ascribed to the stretching vibrations of carbonyl groups in both AAM and AAMPS. The sharp peak at 1040 cm−1 is related to sulfonic acid (–SO3H) group. The bands at 700–800 cm−1 and 1540 cm−1 are related to the bending vibration of the N–H bond (primary and secondary amide respectively). Table 1 gives the main characteristic peak assignment of the FT-IR spectra. Meanwhile, a schematic illustration of the reaction is presented in the Scheme 3. The results in Fig. 1c suggest the integration of Fe3O4 NPs and Cross-PAA-SO3H. The carbon nuclear magnetic resonance (13C NMR) of Cross-PAA-SO3H is displayed in Fig. 2. The peaks at 63.16 (CH2SO3H), 46.83 (CHCONH2), 37.36 (CNHMe2), 34.23 (–CCH2CO), 29.15 (CH2), 22.91, 22.16 ppm (2 CH3), 18.14 (CH2CHCONH2) are shown in Fig. 2. The 13C NMR spectrum of the Cross-PAA-SO3H in DMSO-d6 displayed two peaks at 176.36 and 173.89 ppm due to amide groups.
Table 1

Peak assignment of crosslinked Sulfonated Polyacrylamide (Cross-PAA-SO3H)

Peak position (cm−1)

Assignment

3100–3500

N–H stretching of NH2, OH stretching of (–SO3H)

1658

C=O stretching of CO in AAM and AAMPS

1545

N–H bending (Secondary amid band of AAMPS)

1042

Sulfonic acid (–SO3H) group

1175–1216

Symmetric band of SO2

1453

Stretching of the C–N band (amid)

700–800

N–H bending (primary amide)

Scheme 3

Preparation of crosslinked Sulfonated Polyacrylamide (Cross-PAA-SO3H)

Fig. 2

The 13C NMR spectra of Cross-PAA-SO3H

The morphology of Cross-PAA-SO3H@nano-Fe3O4 was determined by Scanning Electronic Microscopy (SEM). It is observed that the particles are strongly aggregated and glued with very large and continuous aggregates (Fig. 3). In order to investigate the size distribution of nanocatalysts [24, 25], dynamic light scattering (DLS) measurements of the nanoparticles were showed in Fig. 4. The size distribution is centered at a value of 52.4 nm. The dispersion for DLS analysis (2.5 g nanocatalyst at 50 mL ethanol) was prepared using an ultrasonic bath (60 W) for 30 min.
Fig. 3

SEM image of Cross-PAA-SO3H@nano-Fe3O4

Fig. 4

The DLS of Cross-PAA-SO3H@nano-Fe3O4

XRD patterns of Cross-PAA-SO3H, Fe3O4 and Cross-PAA-SO3H@nano-Fe3O4 are shown in Fig. 5. The patterns for Cross-PAA-SO3H indicate a peak at 2θ = 28° which is the most intense peak height (Fig. 5a). All the strong peaks appeared at 2θ = 30.08°, 35.40°, 43.17°, 53.59°, 57.20°, 62.86°, and 74.02° can be easily indexed to nano-Fe3O4 (Fig. 5b). The pattern agrees well with the reported pattern for Fe3O4 (JCPDS No. 75-1609). The particle size diameter (D) of the nanoparticles has been calculated by the Debye–Scherrer equation (D = Kλ/β cosθ), where β FWHM (full-width at half-maximum or half-width) is in radian and θ is the position of the maximum of the diffraction peak. K is the so-called shape factor, which usually takes a value of about 0.9, and λ is the X-ray wavelength (1.5406 Å for CuKα). The crystallite size of Cross-PAA-SO3H@nano-Fe3O4 was calculated by the Debye–Scherer equation is about 48–52 nm. The weaker diffraction lines of Cross-PAA-SO3H@nano-Fe3O4 (Fig. 5c) compared with Fe3O4 nanoparticles indicate that the Fe3O4 nanoparticles were covered by amorphous polymer.
Fig. 5

The XRD pattern of (a) Cross-PAA-SO3H, (b) Fe3O4 and (c) Cross-PAA-SO3H@nano-Fe3O4

An EDS (energy dispersive X-ray) spectrum of Cross-PAA-SO3H@nano-Fe3O4 (Fig. 6) exhibits that the elemental compositions are carbon, oxygen, sulfur, iron and nitrogen.
Fig. 6

EDS spectrum of Cross-PAA-SO3H@nano-Fe3O4

The magnetic attributes of nano-Fe3O4 and Cross-PAA-SO3H@nano-Fe3O4 were given with the help of a vibrating sample magnetometer (VSM) (Fig. 7). The amount of saturation-magnetization for nano-Fe3O4 and Cross-PAA-SO3H@nano-Fe3O4 is 47.2 emu/g and 26.8 emu/g.
Fig. 7

The VSM curve of: a nano-Fe3O4 and b Cross-PAA-SO3H@nano-Fe3O4

Thermogravimetric analysis (TGA) evaluates the thermal stability of the Cross-PAA-SO3H and Cross-PAA-SO3H@nano-Fe3O4. The curve displays a weight loss about 37.5% for Cross-PAA-SO3H@nano-Fe3O4 from 240 to 550 °C, resulting from the destruction of organic spacer attaching to the nanoparticles. Hence; the nanocatalyst was stable up to 240 °C, confirming that it could be stably utilized in organic reactions at temperatures between the ranges of 80–160 °C (Fig. 8).
Fig. 8

TGA curve of Cross-PAA-SO3H and Cross-PAA-SO3H@nano-Fe3O4

Catalytic behaviors of Cross-PAA-SO3H@nano-Fe3O4 for the synthesis of 1,3-thiazoles

Initially, we had optimized conditions for the synthesis of 3-alkyl-4-phenyl-1,3-thiazole-2(3H)-thione derivatives by the reaction of phenacyl bromide, carbon disulfide and benzyl amine as a model reaction. The model reactions were performed by CAN, NaHSO4, InCl3, ZrO2, p-TSA, nano-Fe3O4, Cross-PAA-SO3H and Cross-PAA-SO3H@nano-Fe3O4. The reactions were tested using diverse solvents including ethanol, acetonitrile, water or dimethylformamide. The best results were gained in EtOH and we found that the reaction gave convincing results in the presence of cross-PAA-SO3H@nano-Fe3O4 (7 mg) under reflux conditions (Tables 2). However, the activity of catalysts is determined by the acid–base properties, surface area, the distribution of sites and the polarity of the surface sites [26, 27]. We studied the feasibility of the reaction by selecting some representative substrates (Table 3). To investigate the extent this catalytic process, phenacyl bromide or 4-methoxyphenacyl bromide, carbon disulfide and primary amine were elected as substrates. Seeking of the reaction scope demonstrated that various primary amines can be utilized in this method (Table 3).
Table 2

Optimization of reaction conditions

Entry

Solvent (reflux)

Catalyst

Time (min)

Yield (%)a

1

EtOH

500

39

2

EtOH

CAN (7 mol%)

250

53

3

EtOH

NaHSO4 (5 mol%)

300

45

4

EtOH

InCl3 (4 mol%)

200

56

5

EtOH

ZrO2 (6 mol%)

250

60

6

EtOH

p-TSA (3 mol%)

200

64

7

EtOH

Nano-Fe3O4 (10 mg)

200

52

8

EtOH

Cross-PAA-SO3H (10 mg)

150

56

9

EtOH

nano-Fe3O4 (5 mg) + Cross-PAA-SO3H (5 mg)

150

60

10

H2O

Cross-PAA-SO3H@nano-Fe3O4 (7 mg)

150

77

11

DMF

Cross-PAA-SO3H@nano-Fe3O4 (7 mg)

150

82

12

CH3CN

Cross-PAA-SO3H@nano-Fe3O4 (7 mg)

150

89

13

EtOH

Cross-PAA-SO3H@nano-Fe3O4 (5 mg)

150

92

14

EtOH

Cross-PAA-SO3H@nano-Fe3O4 (7 mg)

150

94

15

EtOH

Cross-PAA-SO3H@nano-Fe3O4 (9 mg)

150

94

Phenacyl bromide (1 mmol), carbon disulfide (1 mmol) and benzyl amine (1 mmol)

aIsolated yield

Table 3

Synthesis of thiazoles using Cross-PAA-SO3H@nano-Fe3O4

aIsolated yield

Scheme 4 displays a proposed mechanism for this reaction in the presence of cross-PAA-SO3H@nano-Fe3O4 as catalyst. Initially the nucleophilic attack by amines on a carbon disulfide generates intermediate (I), The next step involves nucleophilic attack of intermediate (I) on the methylene carbon of phenacyl bromide, leading to intermediate (II), and then ring closure by intramolecular attack of nitrogen at the carbonyl carbon to afford the 3-alkyl-4-phenyl-1,3- thiazole-2(3H)-thione derivatives 4. In this mechanism the surface atoms of cross-PAA-SO3H@nano-Fe3O4 activate the C=S and C=O groups for better reaction with nucleophiles.
Scheme 4

Proposed reaction pathway for the synthesis of 1,3-thiazoles

The reusability of Cross-PAA-SO3H@nano-Fe3O4 was studied for the reaction of phenacyl bromide, carbon disulfide and benzyl amine and it was found that product yields reduced to a small extent on each reuse (run 1, 94%; run 2, 94%; run 3, 93%; run 4, 93%; run 5, 92%; run 6, 92%;). After completion of the reaction, the nanocatalyst was separated by an external magnet. The catalyst was washed four times with ethanol and dried at room temperature for 18 h. The possibility of recycling of the catalyst is an important process from different aspects such as environmental concerns, and commercial applicable processes.

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 4).
Table 4

The large-scale synthesis of some 1,3-thiazoles using cross-PAA-SO3H@nano-Fe3O4

Entry

Product

Time (min)

Yield (%)a

1

4a

200

90

2

4e

200

84

3

4g

250

82

4

4i

250

75

5

4j

250

78

To compare the efficiency of Nano Fe3O4@ PAA-SO3H with the reported catalysts for the synthesis of 1,3-thiazoles, we have tabulated the results in Table 5. As Table 5 indicates, nano Fe3O4@ PAA-SO3H is superior with respect to the reported catalysts in terms of reaction time, yield and conditions. As expected, the increased surface area due to small particle size increased reactivity of catalyst. This factor is responsible for the accessibility of the substrate molecules on the catalyst surface.
Table 5

Comparison of catalytic activity of nano Fe3O4@ PAA-SO3H with other reported catalysts for the synthesis 1,3-thiazoles

Entry

Catalyst (condition)

Time (min)

Yielda, %

[Refs]

1

Bi(SCH2COOH)3 (15 mol%, 70 °C)

180

80

[7]

2

Yb(OTf)3 (15 mol%)

240

60

[9]

2

2-pyridinecarboxaldehyde oxime (20 mol%, DMF)

400

85

[10]

3

potassium iodide (10 mol%, CH3OH)

400

80

[11]

4

Nano Fe3O4@ PAA-SO3H (7 mg, EtOH (under reflux condition)

150

94

This work

aIsolated yield

Conclusions

In conclusion, we have reported an efficient way for the synthesis of 3-alkyl-4-phenyl-1,3-thiazole-2(3H)-thione derivatives using cross-PAA-SO3H@nano-Fe3O4 under reflux condition in ethanol. The method offers several advantages including easy availability, high yields, shorter reaction times, reusability of the catalyst and low catalyst loading. The present catalytic procedure is extensible to a wide diversity of substrates for the synthesis of a variety-oriented library of thiazoles.

Experimental section

Chemicals and apparatus

NMR spectra were obtained on a Bruker spectrometer with CDCl3 as solvent and TMS as an internal standard. Chemical shifts (δ) are given in ppm and coupling constants (J) are given in Hz. FT-IR spectra were recorded with KBr pellets by a Magna-IR, spectrometer 550 Nicolet. CHN compositions were measured by Carlo ERBA Model EA 1108 analyzer. Powder X-ray diffraction (XRD) was carried out on a Philips diffractometer of X’pert Company with monochromatized Cu Kα radiation (λ = 1.5406 Å). Microscopic morphology of products was visualized by SEM (MIRA3). The thermogravimetric analysis (TGA) curves are recorded using a V5.1A DUPONT 2000. The mass spectra were recorded on a Joel D-30 instrument at an ionization potential of 70 eV. The magnetic property of magnetite nanoparticle has been measured with a vibrating sample magnetometer (VSM) (Meghnatis Daghigh Kavir Co.; Kashan Kavir; Iran) at room temperature.

Preparation of crosslinked sulfonated polyacrylamide (Cross-PAA-SO3H)

In a round-bottom flask (200 mL) equipped with magnetic stirrer and condenser, 5 g of acrylamide (AAM) (70 mmol) and 5.17 g of 2-acrylamido-2-methylpropanesulfonic acid (25 mmol) (AAMPS), [approximately AAM/AAMMPS (3/1)] and 0.77 g of N,N-methylene-bis-acrylamide (NNMBA) (5 mmol) as crosslinking agent and benzoyl peroxide as initiator were added to 80 mL EtOH under reflux condition for 5 h. After completion of reaction, the white precipitate was formed, filtered, washed and dried in vacuum oven in 70 °C for 12 h. The weight of polymer was 10.1 gr with the yield of 91.8%. Cross-PAA-SO3H was characterized with infrared spectroscopy and back titration acid–base to confirm sulfonation and determine accurate sulfonation levels. Acidic capacity of this catalyst was estimated 1.1 mmol/g.

Preparation of crosslinked sulfonated polyacrylamide@nano-Fe3O4

1 gr of synthesized polymers were poured in 100 mL round bottom flask under stirring at room-temperature, then 50 mL HCl (0.4 M) was added to it. Our target molecules was synthesized by magnetic nanocatalyst with mass ratio polymer/nano-Fe3O4 = 2/1. So, 0.43 g (2.1 mol) FeCl2·4H2O and 1.17 g (2 × 2.1) FeCl3·6 H2O were added and the mixture was stirred until dissolved completely (flask1). In another 500 ml round-bottom flask no 2, 400 mL aqueous solution of NH3 (0.7 M) was poured under argon gas. Then flask 1 was added to flask 2 immediately. Nanocatalyst was filtered and washed with water (2 × 25 mL) and dried in oven on 50 °C.

General procedure for the synthesis of 1,3-thiazoles

A mixture of primary amine (1.0 mmol) and carbon disulfide (1.0 mmol) in ethanol (8 mL) was stirred for 5 min and then phenacyl bromide or 4-methoxyphenacyl bromide (1.0 mmol) and Cross-PAA-SO3H attached to nano-Fe3O4 (7 mg) were added, and the mixture was stirred for the appropriate times. The reaction was monitored by TLC (n-hexane/ethyl acetate 8:2). After completion of the reaction, the nanocatalyst was easily separated using an external magnet. The solvent was evaporated and the solid obtained washed with EtOH to get pure product. The characterization data of the compounds are given below and in Additional file 1.

3-Benzyl-4-phenyl-1,3-thiazole-2(3H)-thione (4a)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3102, 3005, 1602, 1479, 1202 cm−1; 1H NMR (250 MHz, CDCl3): δ 4.90 (s, 2H, CH2), 6.03 (s, 1H, CH of alkene), 6.95–7.36 (m, 10H, CH, ArH). 13C NMR (62.5 MHz, CDCl3): δ 47.24, 98.85, 127.06, 127.42, 128.52, 128.55, 129.08, 133.32, 137.45, 154.85, 178.37, 197.18. MS (EI, 70 eV): m/z (%) = 283 (5), 267 (68), 181 (7), 91 (100), 77 (4), 65 (12), 45 (4). Anal. Calcd. for C16H13NS2 (283): C, 67.81; H, 4.62; N, 4.94. Found: C, 67.70; H, 4.52; N, 4.73%.

3-(3,4-dichlorobenzyl)-4-phenyl-1,3-thiazole-2(3H)-thione (4b)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3152, 3004, 1628, 1603, 1477, 1302, 1104 cm−1. 1H NMR (250 MHz, CDCl3): δ 4.83 (s, 2H, CH2), 6.05 (CH of alkene), 6.75–7.97 (m, 8H, CH of ArH). 13C NMR (62.5 MHz, CDCl3): δ 46.07, 99.25, 126.72, 128.65, 128.74, 129.35, 129.66, 133.54, 130.50, 135.38, 136.62, 137.21, 172.70, 194.15. Anal. Calcd. for C16H11Cl2NS2 (350): C, 54.55; H, 3.15; N, 3.98. Found: C, 54.36; H, 3.05; N, 3.84%.

3-(2-Naphthyl methyl)-4-phenyl-1,3-thiazole-2(3H)-thione (4c)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3102, 3009, 1652, 1605, 1479, 1204 cm−1. 1H NMR (250 MHz, CDCl3): δ 3.95 (s, 2H, CH2), 6.12 (s, 1H, CH of alkene), 6.92–7.97 (m, 12H, CH of ArH). 13C NMR (62.5 MHz, CDCl3): δ 45.35, 99.05, 123.77, 125.32, 125.84, 126.34, 128.06, 128.68, 128.75, 133.54, 122.52, 129.28, 131.50, 135.08, 172.44, 194.16. Anal. Calcd. for C20H15NS2 (333): C, 72.03; H, 4.53; N, 4.20. Found: C, 72.05; H, 4.40; N, 4.15%.

3-(2-Furyl methyl)-4-phenyl-1,3-thiazole-2(3H)-thione (4d)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3105, 3002, 1653, 1607, 1474, 1202 cm−1. 1H NMR (250 MHz, CDCl3): δ 4.84 (s, 2H, CH2), 6.10 (s, 1H, CH of alkene), 6.22 (1H, CH of furan), 7.25–8.05 (m, 7H, CH of ArH and CH of furan). 13C NMR (62.5 MHz, CDCl3): δ 44.25, 98.32, 109.52, 110.83, 127.08, 128.76, 129.58, 142.12, 144.54, 147.92, 155.44, 192.18. Anal. Calcd. for C14H11NOS2 (273): C, 61.51; H, 4.06; N, 5.12. Found: C, 61.46; H, 4.04; N, 5.09%.

3-(4-Fluorobenzyl)-4-phenyl-1,3-thiazole-2(3H)-thione (4e)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3153, 3005, 1628, 1604, 1473, 1302, 1108 cm−1. 1H NMR (250 MHz, CDCl3): δ 4.85 (s, 2H, CH2), 6.05 (s, 1H, CH of alkene), 6.85 (d, 2H, J = 6.8 Hz, CH arom), 7.02–7.59 (m, 5H, CH of ArH), 7.98 (d, 2H, J = 7.5 Hz, CH of ArH).13C NMR (62.5 MHz, CDCl3): δ 46.45, 99.08, 114.53, 128.67, 128.78, 133.51, 129.05, 135.46, 137.57, 153.28, 159.50, 194.19. Anal. Calcd. for C16H12FNS2 (301): C, 63.76; H, 4.01; N, 4.65. Found: C, 63.60; H, 4.04; N, 4.42%.

3-(2-Methoxybenzyl)-4-phenyl-1,3-thiazole-2(3H)-thione (4f)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3150, 3000, 1650, 1600, 1470, 1200, 1100 cm−1. 1H NMR (250 MHz, CDCl3): δ 3.62 (s, 3H, OCH3), 4.90 (s, 2H, CH2), 6.03 (s, 1H, CH of alkene), 6.71–7.98 (m, 9H, CH, ArH).13C NMR (62.5 MHz, CDCl3): δ 42.56, 55.05, 98.47, 110.05, 120.53, 128.38, 128.46, 128.55, 128.78, 129.05, 133.54, 127.12, 135.45, 156.35, 194.14. Anal. Calcd. for C17H15NOS2 (313): C, 65.14; H, 4.82; N, 4.47. Found: C, 65.03; H, 4.74; N, 4.35%.

3-(4-Methylbenzyl)-4-(4-methoxyphenyl)-1,3-thiazole-2(3H)-thione (4g)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3156, 3008, 1648, 1612, 1475, 1206, 1108 cm−1. 1H NMR (250 MHz, CDCl3): δ 2.23 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 4.95 (s, 2H, CH2), 5.98 (s, 1H, CH of alkene), 6.82–7.35 (m, 8H, CH of ArH).13C NMR (62.5 MHz, CDCl3): δ 21.35, 48.54, 55.95, 98.68, 115.38, 123.42, 125.64, 130.65, 131.25, 132.59, 139.25, 160.20, 174.25, 183.56. Anal. Calcd. for C18H17NOS2 (327): C, 66.02; H, 5.23; N, 4.28;. Found: C, 65.90; H, 5.14; N, 4.12%.

3-benzyl-4-(4-methoxyphenyl)-1,3-thiazole-2(3H)-thione (4h)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3157, 3012, 1645, 1616, 1478, 1209, 1107 cm−1. 1H NMR (250 MHz, CDCl3): δ 3.89 (s, 3H, OCH3), 5.25 (s, 2H, CH2), 6.28 (s, 1H, CH of alkene), 6.85–7.39 (m, 9H, CH of ArH).13C NMR (62.5 MHz, CDCl3): δ 48.50, 55.37, 99.86, 110.55, 114.54, 122.54, 128.38, 129.54, 132.86, 137.54, 145.68, 160.85, 185.36. MS (EI, 70 eV): m/z (%) = 313 (M). Anal. Calcd. for C17H15NOS2 (313): C, 65.14; H, 4.82; N, 4.47; Found: C, 65.02; H, 4.56; N, 4.34; %.

3-(2-Furyl methyl)-4-(4-methoxyphenyl)-1,3-thiazole-2(3H)-thione (4i)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3144, 3012, 1658, 1615, 1478, 1209, 1112 cm−1. 1H NMR (250 MHz, CDCl3): δ 3.88 (s, 3H, OCH3), 4.82 (s, 2H, CH2), 5.98 (2H, CH of furan), 6.20 (s, 1H, CH of alkene), 6.75–7.42 (m, 5H, CH of furan and CH of ArH). 13C NMR (62.5 MHz, CDCl3): δ 41.35, 55.34, 98.36, 108.35, 110.35, 118.35, 122.54, 130.22, 138.54, 142.35, 150.65, 161.25, 178.25. Anal. Calcd. for C15H13NO2S2 (303): C, 59.38; H, 4.32; N, 4.62; Found: C, 59.15; H, 4.14; N, 4.42. %.

3-(2-methoxybenzyl)-4-(4-methoxyphenyl)-1,3-thiazole-2(3H)-thione (4j)

Colorless viscous oil; FT-IR (KBr): \(\bar{\nu }\) = 3142, 3010, 1654, 1611, 1472, 1205, 1116 cm−1. 1H NMR (250 MHz, CDCl3): δ 3.68 (s, 3H, OCH3), 3.84 (s, 3H, OCH3), 4.89 (s, 2H, CH2), 6.05 (s, 1H, CH of alkene), 6.72–7.53 (m, 8H, CH of ArH). 13C NMR (62.5 MHz, CDCl3): δ 43.54, 56.45, 56.48, 98.45, 110.25, 115.28, 120.54, 122.54, 125.85, 125.64, 128.54, 130.42, 138.20, 158.64, 160.24, 172.54. Anal. Calcd. for C18H17NO2S2 (343): C, 62.94; H, 4.99; N, 4.08; Found: C, 62.72; H, 4.70; N, 3.91. %.

Notes

Acknowledgements

The authors acknowledge a reviewer who provided helpful insights.

Associated content

Copies of 1H-NMR and 13C-NMR spectra of all compounds are provided in Additional file 1.

Authors’ contributions

HSHA has designed the study, participated in discussing results and revised the manuscript. MT, JSG and GHM have designed, carried out the literature study, performed the assay, conducted the optimization, purification of compounds and prepared the manuscript. All authors read and approved the final manuscript.

Funding

Not applicable.

Competing interests

The authors declare that they have no competing interests.

Supplementary material

13065_2019_637_MOESM1_ESM.docx (2.3 mb)
Additional file 1. The spectral data of products are described in the additional file 1.

References

  1. 1.
    Dawood KM, Gomha SM (2015) Synthesis and anti-cancer activity of 1, 3, 4-thiadiazole and 1, 3-thiazole derivatives having 1, 3, 4-oxadiazole moiety. J Heterocyclic Chem 52:1400–1405CrossRefGoogle Scholar
  2. 2.
    Abdel-Wahab BF, Abdel-Aziz HA, Ahmed EM (2009) Synthesis and antimicrobial evaluation of some 1,3-thiazole, 1,3,4-thiadiazole, 1,2,4-triazole, and 1,2,4-triazolo[3,4-b][1,3,4]-thiadiazine derivatives including a 5-(benzofuran-2-yl)-1-phenylpyrazole moiety. Monatsh Chem 140:601–605CrossRefGoogle Scholar
  3. 3.
    Sharma RN, Xavier FP, Vasu KK, Chaturvedi SC, Pancholi SS (2009) Synthesis of 4-benzyl-1, 3-thiazole derivatives as potential anti-inflammatory agents: an analogue-based drug design approach. J Enzyme Inhib Med Chem 24:890–897CrossRefGoogle Scholar
  4. 4.
    Maillard LT, Bertout S, Quinonéro O, Akalin G, Turan-Zitouni G, Fulcrand P, Demirci F, Martinez J, Masurier N (2013) Synthesis and anti-Candida activity of novel 2-hydrazino-1, 3-thiazole derivatives. Bioorg Med Chem Lett 23:1803–1807CrossRefGoogle Scholar
  5. 5.
    Masquelin T, Obrecht D (2001) A new general three component solution-phase synthesis of 2-amino-1, 3-thiazole and 2, 4-diamino-1, 3-thiazole combinatorial libraries. Tetrahedron 57:153–156CrossRefGoogle Scholar
  6. 6.
    Kumar D, Sonawane M, Pujala B, Jain VK, Chakraborti AK (2013) Supported protic acid-catalyzed synthesis of 2, 3-disubstituted thiazolidin-4-ones: enhancement of the catalytic potential of protic acid by adsorption on solid supports. Green Chem 15:2872–2884CrossRefGoogle Scholar
  7. 7.
    Foroughifar N, Ebrahimi S (2013) One-pot synthesis of 1, 3-thiazolidin-4-one using Bi (SCH2COOH)3 as catalyst. Chin Chem Lett 24:383–391CrossRefGoogle Scholar
  8. 8.
    Subhedar DD, Shaikh MH, Arkile MA, Yeware A, Sarkar D, Shingate BB (2016) Facile synthesis of 1, 3-thiazolidin-4-ones as antitubercular agents. Bioorg Med Chem Lett 26:1704–1708CrossRefGoogle Scholar
  9. 9.
    Su W, Liu C, Shan W (2008) Ytterbium (III) triflate catalyzed one-pot synthesis of 1, 3-thiazolidin-2-imines from epichlorohydrin and thioureas. Synlett 5:725–727CrossRefGoogle Scholar
  10. 10.
    Khalaj A, Khalaj M (2016) Organo-catalytic synthesis of 1,3-thiazole derivatives. J Chem Res 40:445–448CrossRefGoogle Scholar
  11. 11.
    Safaei-Ghomi J, Salimi F, Ramazani A (2013) The reaction of carbon disulphide with α-haloketones and primary amines in the presence of potassium iodide as catalyst. J Chem Sci 125(1087):1092Google Scholar
  12. 12.
    Nayak S, Gaonkar SL (2019) A review on recent synthetic strategies and pharmacological importance of 1,3-thiazole derivatives. Mini-Rev Med Chem 19:215–238CrossRefGoogle Scholar
  13. 13.
    Shach-Caplan M, Narkis M, Silverstein MS (2002) Modification of porous suspension-PVC particles by stabilizer-free aqueous dispersion polymerization of absorbed acrylate monomers. Polym Adv Technol 13:151–161CrossRefGoogle Scholar
  14. 14.
    Tamami B, Ghasemi S (2010) Palladium nanoparticles supported on modified crosslinked polyacrylamide containing phosphinite ligand: a novel and efficient heterogeneous catalyst for carbon–carbon cross-coupling reactions. J Mol Catal A: Chem 322:98–105CrossRefGoogle Scholar
  15. 15.
    Tamami B, Ghasemi S (2011) Modified crosslinked polyacrylamide anchored Schiff base–cobalt complex: a novel nano-sized heterogeneous catalyst for selective oxidation of olefins and alkyl halides with hydrogen peroxide in aqueous media. Appl Catal A Gen 393:242–250CrossRefGoogle Scholar
  16. 16.
    Rashidi M, Blokhus AM, Skauge A (2011) Viscosity and retention of sulfonated polyacrylamide polymers at high temperature. J Appl Polym 119:3623–3629CrossRefGoogle Scholar
  17. 17.
    Aalaie J, Vasheghani-Farahani E, Rahmatpour A, Semsarzadeh MA (2008) Effect of montmorillonite on gelation and swelling behavior of sulfonated polyacrylamide nanocomposite hydrogels in electrolyte solutions. Eur Polym J 44:2024–2031CrossRefGoogle Scholar
  18. 18.
    Kim K, Ju H, Kim J (2016) Surface modification of BN/Fe3O4 hybrid particle to enhance interfacial affinity for high thermal conductive material. Polymer 91:74–80CrossRefGoogle Scholar
  19. 19.
    Low LE, Tey BT, Ong BH, Tang SY (2018) Unravelling pH-responsive behaviour of Fe3O4@ CNCs-stabilized Pickering emulsions under the influence of magnetic field. Polymer 141:93–101CrossRefGoogle Scholar
  20. 20.
    Hyeon T, Lee SS, Park J, Chung Y, Na HB (2001) Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process. J Am Chem Soc 123:12798–12801CrossRefGoogle Scholar
  21. 21.
    Harris LA, Goff JD, Carmichael AR, Riffle JS, Harburn JJ, Pierre TG, Saunders M (2003) Magnetite nanoparticle dispersions stabilized with triblock copolymers. Chem Mater 15:1367–1377CrossRefGoogle Scholar
  22. 22.
    Lutz JF, Stiller S, Hoth A, Kaufner L, Pison U, Cartier R (2006) One-pot synthesis of pegylated ultrasmall iron-oxide nanoparticles and their in vivo evaluation as magnetic resonance imaging contrast agents. Biomacromol 7:3132–3138CrossRefGoogle Scholar
  23. 23.
    Mincheva R, Stoilova O, Penchev H, Ruskov T, Spirov I, Manolova N, Rashkov I (2008) Synthesis of polymer-stabilized magnetic nanoparticles and fabrication of nanocomposite fibers thereof using electrospinning. Eur Polym J 44:615–627CrossRefGoogle Scholar
  24. 24.
    Bootz A, Vogel V, Schubert D, Kreuter J (2004) Comparison of scanning electron microscopy, dynamic light scattering and analytical ultracentrifugation for the sizing of poly(butylcyanoacrylate) nanoparticles. Eur J Pharm Biopharm 57:369–375CrossRefGoogle Scholar
  25. 25.
    Na K, Zhang Q, Somorjai GA (2014) Colloidal metal nanocatalysts: synthesis, characterization, and catalytic applications. J Clust Sci 25:83–114CrossRefGoogle Scholar
  26. 26.
    Safaei-Ghomi J, Shahbazi-Alavi H, Heidari-Baghbahadorani E (2014) SnO nanoparticles as an efficient catalyst for the one-pot synthesis of chromeno[2,3-b]pyridines and 2-amino-3,5-dicyano-6-sulfanyl pyridines. RSC Adv. 4:50668–50677CrossRefGoogle Scholar
  27. 27.
    Safaei-Ghomi J, Shahbazi-Alavi H (2017) Synthesis of dihydrofurans using nano-CuFe2O4@ Chitosan. J Saudi Chem Soc 21:698–707CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Young Researchers and Elite ClubIslamic Azad University, Kashan BranchKashanIran
  2. 2.Department of Organic Chemistry, Faculty of ChemistryUniversity of KashanKashanIran

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