Novel synthesis of silica-coated magnetic nano-particles based on acidic ionic liquid, as a highly efficient catalyst for three component system leads to furans derivatives

Journal Pre-proofs Original article Novel synthesis of silica-coated magnetic nano-particles based on acidic ionic liquid, as a highly efficient catalyst for three component system leads to furans derivatives Moheb Shirzaei, Ebrahim Mollashahi, Malek Taher Maghsoodlou, Mojtaba Lashkari PII: DOI: Reference:

S1319-6103(20)30001-6 https://doi.org/10.1016/j.jscs.2020.01.001 JSCS 1097

To appear in:

Journal of Saudi Chemical Society

Received Date: Revised Date: Accepted Date:

23 September 2019 28 November 2019 4 January 2020

Please cite this article as: M. Shirzaei, E. Mollashahi, M. Taher Maghsoodlou, M. Lashkari, Novel synthesis of silica-coated magnetic nano-particles based on acidic ionic liquid, as a highly efficient catalyst for three component system leads to furans derivatives, Journal of Saudi Chemical Society (2020), doi: https://doi.org/10.1016/j.jscs. 2020.01.001

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Novel synthesis of silica-coated magnetic nano-particles based on acidic ionic liquid, as a highly efficient catalyst for three component system leads to furans derivatives Moheb Shirzaei1, Ebrahim Mollashahi*,1, Malek Taher Maghsoodlou1, Mojtaba Lashkari2 1

Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, P. O. Box

98135-674 Zahedan, Iran 2

Faculty of Science, Velayat University, Iranshahr, Iran

Corresponding author. E-mail: [email protected]

In this work, thiocarbohydrazide doped iron nanoparticles as a novel, green, heterogeneous, and inexpensive catalyst is reported. This catalyzed the three components reaction of dialkylacetylenedicarboxylate with aromatic aldehydes and aromatic amines to yield the corresponding furan derivatives EtOH. An indispensable part of green chemistry is to be able to recover and reuse catalysts without any notable drop in catalytic activity. The analysis of catalyst and application of that for the synthesis of title compounds in high yields reveal this property. The formation, size of the metal ions present in the material is confirmed by powdered X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA).

Novel synthesis of silica-coated magnetic nano-particles based on acidic ionic liquid, as a highly efficient catalyst for three component system leads to furans derivatives

Moheb Shirzaei1, Ebrahim Mollashahi*,1, Malek Taher Maghsoodlou1, Mojtaba Lashkari2 1

Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, P. O. Box

98135-674 Zahedan, Iran 1

2

Faculty of Science, Velayat University, Iranshahr, Iran

Corresponding author. E-mail: [email protected]

Abstract In this work, thiocarbohydrazide doped iron nanoparticles as a novel, green, heterogeneous, and inexpensive catalyst is reported. This catalyzed the three components reaction of dialkylacetylenedicarboxylate with aromatic aldehydes and aromatic amines to yield the corresponding furan derivatives EtOH. An indispensable part of green chemistry is to be able to recover and reuse catalysts without any notable drop in catalytic activity. The analysis of catalyst and application of that for the synthesis of title compounds in high yields reveal this property. The formation, size of the metal ions present in the material is confirmed by powdered X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). KEYWORDS: Nano particles, Heterogeneous Catalyst, Thiocarbohydrazide, Green Chemistry

Introduction In this contemporary era, to prevent contamination, there is generated more and more demand for the development of eco-friendly approaches to synthesis and applications of different kinds of catalysts. Because of the fact that catalysis plays a crucial role to reduce pollution. There are two kinds of them: homogenous and heterogeneous. Since extracting heterogeneous catalysts is far easier than a homogenous one. As a result, it is recommendable for all chemists to apply them in reactions1-3. Recently, magnetic nanoparticles (MNPs) in particular iron oxide nanoparticles 2

because of their magnetic properties and simple way to elicit from the reaction mixture with a series of some small organic compounds have received huge attention, and their extensive application has been investigated4-11. Ionic liquids (ILs), on the other hand, can be considered as valuable key precursor compounds for catalysts as well as new environmentally technique leading to modern synthetic chemistry12-15. Recently, they have been utilized as a catalyst, however, they were applied as a solvent for years because of their special properties like low vapor pressure, non-flammability, suitable thermal stability, and its ability to dissolve many chemical substrates16-17. The combination of them and catalytically active nanoparticles (NPs) can make a proper heterogeneous system. Unfortunately, some researches demonstrate that their extensive application suffers from several disadvantages like high poison towards cells and living limbs18-21, high viscosity, and cost of usage22-23. As a consequence, we were willing to introduce a route to replace them with more efficient alternatives to improve the marked disadvantages associated with custom ILs. Moreover, it is showed by a large number of researchers that magnetic nanoparticles supported with ionic liquids (ILs) could overcome to these disadvantages mentioned earlier, and operate as excellent supports because of a considerable number of their capabilities like high stability, easy synthesis and applicability, large surface area and facile separation, and likewise low toxicity and price24. It is worth mentioning that, some traditional mineral liquid acid like HCl and H2SO4 are being taken over with SO3H and SO4H functional groups to synthesis magnetic nanoparticles BrÖnsted acid ionic liquid25. For example, MNP@Picolinealdehyde@SO3H26, MNP@ Urea@ SO3H27, and MNP@ Sulfamic acid28 have been applied for the synthesis different heterocyclic system. All of the facts outlined above, when taken together are in favor of a view that we have intensified our endeavor to the synthesis of a new nanocatalyst by immobilization of an ionic liquid on the silica-coated magnetic nanoparticle (MNPs) as support. One of the affordable ways to synthesis sophisticated compounds and drugs from accessible starting materials has been introduced by multicomponent reactions (MCRs). Because of a wide range of their benefits such as their ability to synthesis the desired products with high atom economy by the reaction of three or more starting materials in a one-step, they have been refined in recent years into powerful and useful tools in synthetic organic chemistry29-32. One of the main structures of many bioactive natural products and synthetic drugs like rubrolide, sarcophine, and benfurodilhemisuccinate is furanones. These fivemember heterocyclic compounds containing lactones demonstrate a large number of 3

pharmacological and biological activities such as antifungal, antibacterial, anti-oxidant, and anticancer agent33-37. Furans with highly substituted is essentially important in organic chemistry, not because they are a significant part in many natural products, common subunits in pharmaceuticals and flavors38-41 but because they are an effective unit in synthetic chemistry42. As synthons for a considerable number of functional groups, inter alia, carboxylic acid, aromatics, and alpha-keto esters, their useful applications have found43. For all the reasons mentioned above, the interest of chemists has been attracted by developing new methodologies for the effective synthesis substituted furans. However, some of them have several number of disadvantages like high temperature, low-yield, and long reaction times44-47. As a consequent, in order to proceed our previous researches on multi-component synthesis48-54, we reported a novel catalyst for the synthesis of 3, 4, 5-trisubstituted furan-2(5H)-one at the mild condition. Ar1

H N

NH2

O O

Fe3O4

CO2Me

Ar

1

MeO2C

2

SiO2

4 H

O

Ar2

Fe3O4 SiO2

CO2Me 1

Ar2

3

Scheme 1: The reaction between benzaldehyde (1.0 mmol), aniline (1.0 mmol) and, DMAD (1.0 mmol) to synthesis furans derivatives using novel nanocatalyst

Experimental General procedure for the synthesis of Thiocarbohydrazide A dried three-neck flask equipped with a magnetic stir bar and a condenser were charged with 580 ml hydrazine hydrate 85% at 10 °C. Subsequently, CS2 (121 mL) was added dropwise with a 4

funnel over 30 min period followed by adding water (1500 mL). The reaction mixture was heated to 85 °C for 90 min. Then it was cooled to 10 °C and the residue thus obtained was washed with water 55. General procedure for the preparation of Nano catalyst as a heterogeneous acidic catalyst All the involved chemical agents were analytical grade and used without further purification. At the beginning, FeCl3.6H2O (5.8 g, 5 mmol) and FeCl2.4H2O (2.7 g, 10 mmol) were solved in 100 ml deionized water at 85 °C. Then 10 ml of concentrated ammonia (25%) drop by drop was added to the solution, and the black precipitate appeared immediately. The reaction solution was kept at this temperature for 120 min. Following this, this precipitate was collected with an external magnet, washed with EtOH and water several times until PH reached approximately 7 and dried at 70 °C in the oven. In the following stage, Fe3O4@SiO2 nanoparticles were created according to the Stober-el method. Fe3O4 (1g) was scattered by an ultrasonic bath in a solution of 100 ml EtOH/H2O (80:20) for around 1 hour. After this, 2.5 ml ammonia solution was added which is followed by the addition of 3 ml TEOS. The reaction mixture was held at room temperature for 24 hours. Then it was collected by a magnet, washed by EtOH and dries at 40 °C overnight. Throughout the next stage, Fe3O4@SiO2 (1g) nanoparticles were dispersed in 80 ml EtOH for 30 min after which 2ml of 3-chloropropyltrimethoxysilane was added and refluxed for 24 hours in the oil bath. After completing the reaction, the flask was cooled and the solid phase was filtered and washed with EtOH and water to remove un-reacted CPTES. Once this stage is completed, to a solution of thiocarbohydrazide (2 mmol) in 20 ml CH3CN, Fe3O4@SiO2@ (CH2)3 (1g) was added and reflux for 24 hours. According to the above, the product was washed with CH3CN and EtOH several times. The process ends with the immobilization of ClSO3H on nanoparticles. Chlorosulfonic acid (10 mmol) was added dropwise to the mentioned nanocatalyst during 15 min in dry dichloromethane (30 mL) and stirred for 5 hours at room temperature. After performing similar steps of filtering, Fe3O4@SiO2 (CH2)3-Thiocarbohydrazide-SO3H] Cl was obtained. It is worth noting that, all of the steps described above were operated under N2 atmosphere (Scheme 2).

5

Fe3+ salt + Fe

2+

salt

NH4OH

Fe3O4

o

N2, 80 C, 40 min

TEOS

SiO2 Fe3O4

HO

EtOH, H2O

Cl

OH

HO

MeO OH OH

HO

MeO

Si

SiO2

OMe

O

Fe3O4 O

O

EtOH, Reflux , 24 h

Cl

f, Re e, en lu To

OH

Si

H2N

S

HN

h 24

HN

HO3S

HN

H N

H N S

=

=

=

O O O O O O

Si

Si

Si

Cl

Si

O O O

Fe3O4 SiO2

CH2Cl2

H2N

ClSO3H

H N

H N S

N H

Si

O O O

Fe3O4 SiO2

Cl H N

S N H

N H

Cl- H2+ S N

N H

N H

NH2

HN

O O O

N + H2 -

NH2

SO3H

Scheme 2: General route for the synthesis of Fe3O4@SiO2@IL

General procedure for the synthesis of substituted Furans To a magnetical mixture of aromatic aldehyde (1.0 mmol), amine (1.0 mmol) and dialkylacetylenedicarboxilic acid (1.0 mmol) in EtOH (5 mL), 0.004 g of nanocatalyst was added and held for an appropriate time. Thin-layer chromatography (TLC) is a good tool for monitoring the reactions process. After figuring out that the reactions are completed, to produce a solid precipitate, water was added. Nanomagnetic catalyst was removed by an external magnet and to remove unreacted starting materials and afford the pure products, the products were filtered and washed with H2O and EtOH (99.7 %) and recrystallized by ethanol. Spectral Data for 3,4,5-trisubstituded furan-2-(5H)-ones derivatives

Methyl 5-oxo-2-phenyl-4-(phenylamino)-2,5-dihydrofuran-3-carboxylate (4a) White Solid, m.p. 161-163 °C; IR (KBr, cm-1): 3261, 3210, 1702, 1663, 1569; 1HNMR (400 MHz, CDCl3) 8.90 (br, 1H, NH), 7.52 (d, 2H), 7.23-7.30 (m, 7H), 7.14 (t, 1H), 5.76 (s, 1H), 3.77 6

(s, 3H); 13CNMR (100MHz, CDCl3) 52.1, 61.6, 112.8, 122.3, 125.9, 127.4, 128.6, 128.7, 129.0, 134.9, 136.1, 156.3, 162.7, 165.3. Methyl 2-(4-cyanophenyl)-2,5-dihydro-5-oxo-4-(phenylamino)furan-3-carboxylate (4b) Pale-yellow solid, m.p: 153-155. IR (KBr) δ 3228, 2221, 1697. 1HNMR (300 MHz, CDCl3): δ 8.96 (br, NH), 7.15-7.61 (m, 9H, Ar), 5.83 (s, 1H, CH), 3.79 (s, 3H, CH3). Methyl 2-(4-chlorophenyl)-5-oxo-4-(phenylamino)-2,5-dihydrofuran-3-carboxylate (4c) White solid: 289-292. 1HNMR (300 MHz, CDCl3): δ (300 MHz, CDCl3): δ 9.01 (br, NH), 7.27.83 (m, 9H, Ar), 5.85 (s, 1H, CH), 3.94 (s, 3H, CH3). Methyl 2-(4-bromophenyl)-5-oxo-4-(phenylamino)-2,5-dihydrofuran-3-carboxylate (4d) White solid; m.p. 192-193 °C; IR (KBr, cm-1): 3215, 2932, 1697, 1580; 1HNMR (400 MHz, CDCl3) 9.01 (br, 1H, NH), 7.10-7.47 (m, 9H), 5.73 (s, 1H), 3.78 (s, 3H);

13CNMR

(100MHz,

CDCl3) 52.21, 60.97, 112.46, 122.34, 122.60, 126.19, 129.15, 131.96, 134.18, 135.85, 156.23, 162.68, 165.04. Methyl 4-(p-tolylamino)-2,5-dihydro-5-oxo-2-phenylfuran-3-carboxylate (4f) White Solid, M.P: 281-283 °C; IR (KBr, cm-1): 3228, 2950, 1706, 1677, 1513; 1HNMR (400 MHz, CDCl3) 8.86 (br, 1H, NH), 7.34 (d, 2H, J=8Hz), 7.22-7.27 (m, 5H), 7.09 (d, 2H, J=8Hz), 5.72 (s, 1H), 3.76 (s, 3H), 2.27(s, 3H); 13CNMR (100MHz, CDCl3) 20.9,52, 61.3, 112.6, 122.4, 127.5, 128.5, 128.6, 129.6, 133.5, 135.0, 135.8, 156.4, 162.8, 165.3 Methyl 4-((4-chlorophenyl)amino)-5-oxo-2-phenyl-2,5-dihydrofuran-3-carboxylate (4g) White solid; M.P: 149-151 °C; IR (KBr, cm-1): 3228, 2950, 1706, 1677, 1513; 1HNMR (400 MHz, CDCl3) 8.86 (br, 1H, NH), 7.34 (d, 2H, J=8.4Hz), 7.22-7.27 (m, 5H), 7.09 (d, 2H, J=8Hz), 5.72 (s, 1H), 3.76 (s, 3H), 2.27 (s, 3H);

13CNMR

(100MHz, CDCl3) 20.95, 52.0, 61.3, 112.6,

122.4, 127.5, 128.5, 128.6, 129.6, 133.5 135.0, 156.4, 162.8, 165.3. Methyl 4-((3-nitrophenyl) amino)-5-oxo-2-phenyl-2,5-dihydrofuran-3-carboxylate(4k) White solid; mp: 157-158 °C; IR (KBr, cm-1): 3325, 2967, 1678, 1582; 1HNMR (400 MHz, CDCl3) 8.90 (br, 1H, NH), 7.13-8.18 (m, 9H), 5.90 (s, 1H), 3.76 (s, 3H). 7

Results and discussion Preliminary, in order to optimize the reaction condition, the reaction between aniline, aromatic aldehyde and dialkylacetylenedicarboxylate and different amount of catalyst at room temperature were investigated. According to table 1, the best amount of that is 0.004 g at room temperature (Table1, Entry 4). Surprisingly, the yield was not increased when the amount of catalyst soared from this figure to 0.005 and 0.006 (Table 1, Entry 9, 10). There was trace product in the shortage of catalyst (Table1, Entry 1). So, this amount was selected as the most favorable of that. A mixture of benzaldehyde, Aniline, and DMAD as a typical reaction, using 4 mg of catalyst in various solvents such as water, EtOH, MeOH, MeCN was conducted at room temperature (Figure 1). As can be seen, EtOH is the best media for this reaction, in which products were obtained in 93 yields. After identifying the reaction condition, in order to broaden our horizon about the versatility of the synthesized nanocatalyst, the scope and limitation of this methodology were assessed. As a result, different kinds of aldehydes and amines like aldehydes contained electron-donating and withdrawing substituents on the aromatic rings were investigated (Table 2). As evident from Table 2, the results were good to excellent in terms of time, yield as well as purity. Based on Table 2, aromatic aldehyde possessing an electrondonating group revealed higher yield and shorter time than that of electron-withdrawing ones. A simple and satisfactory mechanism for the formation of 4 is shown in Scheme 3. First of all, according to reaction procedure, MNP catalyst actives carbonyl group to condensation between a and b to give intermediate c. In the next step, MNP catalyst actives carbonyl group of intermediate c and nucleophilic attack through Michael addition produces intermediate d. At the end, this reaction is terminated with removing H+ and thus the product 4 was prepared. Additionally, the reusability of the catalyst was assessed upon the reaction between benzaldehyde, aniline, and DMAD. According to the general procedure, after removing the MNP catalyst with an external magnet, the catalyst was washed, dried and reused for 7 runs (Figure 2). The obtained data showed any considerable loss of activity in comparison to the first use of new catalyst. Eventually, to compare this protocol with other presented ones for the synthesis of furans, we presented in table 3 that illustrates the MNP has a better efficiency in the synthesis of products.

8

Table 1 Optimization the amount of catalyst on the reaction between benzaldehyde (1.0 mmol), aniline (1.0 mmol) and, DMAD (1.0 mmol). CO2Me

CHO

NH2

H N

MeO2C

Reaction Conditions +

+

O

O

CO2Me

Entry 1 2 3 4 5 6 7 8 9 10 11

Catalyst (mol %) 0.001 0.002 0.003 0.004 0.004 0.004 0.004 0.004 0.005 0.006

Isolated Yield (%) Trace 65 73 84 93 93 93 93 93 93 93

T (°C) r.t r.t r.t r.t r.t 50 70 90 100 r.t r.t

Figure 1 Effect of catalyst for the synthesis of furans

9

Time (min) 18 h 420 240 120 55 49 42 30 23 48 39

Table 2 synthesis of 3, 4, 5-trisubstituted furan-2(5H)-ones Entry

Ar1

Ar2

Product

Time

Isolated Yield

M.P ( 0C)

Reported

1

Ph

Ph

4a

49

94

161-163

159-16252

2

Ph

4-CN

4b

42

91

153-155

150-15252

3

Ph

4-Cl

4c

30

90

289-292

290-29352

4

Ph

4-Br

4d

35

92

192-193

193-19449

5

Ph

4-Me

4e

19

89

281-283

284-28742

6

4-Me

Ph

4f

40

95

281-283

284-28749

7

4-Cl

Ph

4g

20

92

149-151

149-15242

8

4-NO2

Ph

4h

51

97

128-130

130-13142

9

4-OMe

Ph

4i

37

89

236-239

239-24249

10

3-NO2

Ph

4k

39

93

157-158

158-15952

Figure 2 Reusability of MNP catalyst for the synthesis of furans. 10

o

Catalyst

Conditions

Time (h)

Yield (%)

Ref

TrCl (15mol %)

EtOH, r.t

2.5

94

44

Vitamin B12 (0.001g)

EtOH, r.t

2

80

52

Lemon Juice (0.25 ml)

EtOH, 110 oC

25 min

80

45

SA-AMBA-Fe3O4

EtOH, 70 oC

2

92

46

SnCl2.2H2O (3 mol%)

EtOH: Ref

6.5

98

47

MNP ( 0.004 g)

EtOH, r.t

55 min

93

This Work

Table 3 Comparison result of novel catalysts with the other reported catalyst for the synthesis

of furan derivatives

..

NH2

MeO2C

+

Ar1

O C OMe

H N ..

Ar1

CO2Me

a

CO2Me 2

1

O

O H C

H

O

O

+

O H C

S

H

O

S

O

O

+

Ar2

Ar2

b

3

O

S

O

O H Ar1

O

H N

Ar1

O N O

O

Ar1

MeO2C H

MeO2C

Ar2

Ar2 4

d

N

O C OMe

.. O

MeO2C H

Ar2

c

Scheme 3: Proposed mechanism for the synthesis of furans derivatives catalyzed with {Fe3O4@SiO2@ (CH2)3- thiocarbohydrazide-SO3H/HCl}. 11

Conclusions In summary, we have reported an original way for the one-pot three-component synthesis of furan derivatives with a novel reusable and heterogeneous catalyst. The most noteworthy merits of this protocol include smooth magnetic recovery, usage of non-toxic ethanol as solvent, mild reaction conditions. As well as, shorter reaction time, a high degree of activity. However, the most obvious feature of the catalyst is its reusability up to 5 times cycles without any desirable loss in efficacy. As a consequence, this catalyst has some superior to other non-magnetic catalysts.

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