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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lsrt20

Nano Silica Sulfuric Acid an Efficient and Recoverable Heterogeneous Catalyst for the Preparation of Amidoalkyl Naphthols under Solvent-Free Conditions a

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Keivan Ghodrati , Azita Farrokhi , Changiz Karami & Zohre Hamidi

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Department of Chemistry, Faculty of Science , Islamic Azad University , Kermanshah Branch, Kermanshah , Iran b

Young Researchers Club, Kermanshah Branch , Islamic Azad University , Kermanshah , Iran Accepted author version posted online: 08 Jul 2014.

To cite this article: Keivan Ghodrati , Azita Farrokhi , Changiz Karami & Zohre Hamidi (2014): Nano Silica Sulfuric Acid an Efficient and Recoverable Heterogeneous Catalyst for the Preparation of Amidoalkyl Naphthols under Solvent-Free Conditions, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry To link to this article: http://dx.doi.org/10.1080/15533174.2013.809746

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ACCEPTED MANUSCRIPT Nano Silica Sulfuric Acid an Efficient and Recoverable Heterogeneous Catalyst for the Preparation of Amidoalkyl Naphthols under Solvent-Free Conditions Keivan Ghodrati, 1 Azita Farrokhi,2 Changiz Karami1 and Zohre Hamidi2 1

Department of Chemistry, Faculty of Science, Islamic Azad University, Kermanshah Branch,

Kermanshah. Iran.

Downloaded by [185.24.254.77] at 11:45 09 July 2014

2

Young Researchers Club, Kermanshah Branch, Islamic Azad University, Kermanshah, Iran

Fax: +98(831)7265130 E-mail: [email protected]

ABSTRACT An efficient and green method has been developed for the synthesis of amidoalkyl naphthol derivatives through a one-pot three-component condensation of 2-naphthol, aldehydes and amide in the presence of nano silica sulfuric acid as heterogeneous catalyst under solvent-free conditions. Keywords: nanocatalyst, nannano silica sulfuric acid, multicomponent reaction, amidoalkyl naphthol, solvent-free.

 Corresponding author. Tel.: +98 831 7265130; fax: +98 831 7265130; e-mail: [email protected], [email protected]

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ACCEPTED MANUSCRIPT INTRODUCTION Multicomponent reactions (MCRs) are very important and attractive subjects in organic synthesis because of formation of carbon–carbon and carbon–hetero atom bonds in one pot.[1] The advantages of these reactions are simple procedures, high bond forming efficiency, time and energy saving, and low expenditures.[2] however, researchers have made great efforts to find and


develop new methods for MCRs. In recent years, there has been an increasing interest in developing greener processes. [3] In this context, heterogeneous catalysis[4] is developing as an alternative to homogeneous processes since catalysts can be recovered after the reaction and re-used several times to achieve very high turn-over numbers. However, One strategy to transform a homogeneous into heterogeneous process is to anchor the active site onto a large surface solid carrier provided that the anchoring methodology maintains the intrinsic activity and selectivity of the catalytic center.[5] Among various solid supports, silica is usually preferred since, and it displays many advantageous such as properties-excellent stability (chemical and thermal), high surface area, good accessibility, environmentally friendly material, and robustly anchored of organic groups on surface, to provide catalytic centers[5, 6]. Therefore, in recent years, organic reactions on silica-supported reagents have received considerable attention in organic synthesis.[7, 8] On the other hand, newly, the application of nanoparticles (NPs) in catalysis have attracted considerable attention because of their improved efficiency and facile reaction condition.[9] Nanoparticle materials have enormously large and highly reactive surface area, because these materials exhibit some unique properties in comparison to bulk materials. Because of individual

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ACCEPTED MANUSCRIPT property of silica-based NPs comparison other one, it have been well studied.[10] Recently, silica functionalized sulfonic acid as heterogeneous solid acid catalyst has been used to carry out variety of reactions.[11] However, no studies are known in literature exploiting nano silica sulfuric acid as an efficient heterogeneous catalyst for this purpose. Compounds bearing 1, 3-amino-oxygenated functional groups are ubiquitous to a variety of biologically important natural products and potent drugs including a number of nucleoside


antibiotics and HIV protease inhibitors, such as ritonavir and lipinavir. [12] Amidoalkyl naphthol derivatives are of significant importance because of their promising biological and pharmaceutical activities.[13] The preparation of amidoalkyl naphthols can be carried out by multi-component condensation of aryl aldehydes, 2-naphthol and benzamide or acetamide or acrylamide in the presence of Lewis or Brønsted acid catalysts such as immobilized acidic ILs,[14] Ce(SO4)2,[15] iodine,[16] K5CoW12O40.3H2O,[17] p-TSA,[18] sulfamic acid,[19] cation-exchange resins,[20] silica-sodium hydrogen sulphate,[21] silica-perchloric acid,[22] acidic ionic liquid[23] and phosphorus pentaoxide.[24] Although these methods are quite useful, many of these methods suffer from limitations such as the requirement for a large excess of reagents, long reaction times, harsh reaction conditions, and also involvement of toxic solvents. In connection with our work on application of nano silica as a catalyst in organic reaction, we now show that amidoalkyl naphthols can be produced by using nano silica sulfuric acid as an efficient heterogeneous catalyst (Scheme 1) under thermal solvent-free conditions. EXPERIMENTAL

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ACCEPTED MANUSCRIPT Chemicals and Instruments All reagents and solvents were commercially available and were used as such. Silicon Oxide (SiO2, 99.5%, 15 nm) was purchased from Nanostructured & Amorphous Materials, Inc (http://www.nanoamor.com). The IR spectra of the samples (as KBr pellets) were recorded using a Rayleigh WQF-510 spectrophotometer in the range of 400–4000 cm−1. Melting points were determined using Barnstead–Electro thermal 9300 Melting Point. 1H NMR spectra were recorded


on Bruker 200 MHz NMR spectrometer. Transmission electron microscopy was carried out on a Philips CM200 FEG scanning transmission electron microscope at 200 keV equipped with a CCD camera.

Catalyst Preparation Following the literature procedure,[25] Sulfonated nano silica was prepared by reacting silica with neat chlorosulfonic acid at room temperature, as shown in (Figure 1).

General Procedure General procedure for synthesis of sulfonated nano silica : A 50 ml suction flask equipped with a constant-pressure dropping funnel and a gas inlet tube for conducting of HCl gas over an

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ACCEPTED MANUSCRIPT adsorbing solution (i.e. water) were used. It was charged with silicon oxide (SiOx, 99.5%, 15 nm) (1 g). Chlorosulfonic acid (0.4 g, 0.0034 mol) was added dropwise over a period of 30 min at room temperature. HCl gas immediately evolved from the reaction vessel. After the addition was completed, the mixture was shaken for 30 min. A white solid of nano silica sulfuric acid (1.2 g) was obtained. The liberated H3O+ was titrated by standard NaOH and the amount of H+ in silica sulfuric acid was calculated (0.015 g of silica sulfuric acid equal to 0.16 mmol).


General procedure for synthesis of amidoalkyl naphthols 4 : A mixture of 2-naphthol (1 mmol), aromatic aldehyde (1 mmol), amide (1.2 mmol) and nano silica sulfuric acid (0.015 g) was stirred at 80 °C for the time indicated in figure 1. After completion of the reaction as monitored by the TLC, ethyl acetate (10 mL) was added and the reaction mixture was filtered. The catalyst was removed by filtration and recrystallized from ethanol to afford pure product. RESULTS AND DISCUSSION To optimize the reaction temperature, the reaction of 4-chlorobenzaldehyde, 2-naphthol and benzamide under thermal solvent-free conditions was selected as a model. The best result was obtained by carrying out the reaction using 0.015 g of catalyst at 80 °C under solvent-free conditions (Table 1).

Catalyst Characterization Thermal Gravimetric Analysis (TGA)

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ACCEPTED MANUSCRIPT The weight change of catalyst precursors was measured using a TGA simultaneous thermal analyzer apparatus of Polymer laboratory Company (PL 1500 Model) under a flow of dry air. Using a linear programmer at a heating rate of 10 °C/min, the temperature was raised from room temperature to 600 °C. The sample weight was 20 mg. The TGA curves for the catalyst are illustrated in (Figure 2). The weight losses found from TGA measurements agree fairly well with


those expected for the decomposition of silica sulfuric acid to silica and SOx.

For this catalyst, the thermo gravimetric curve seems to indicate two-stage decomposition which considered to be due to removal of physical absorbed water (80–100 °C) and complete loss of all the covalently attached organic structure is seen in the 120–600 °C temperature range leaving SiO2, and the organic fraction corresponds to the acidic chlorosulfonic acid. FT-IR Spectrum of nano silica sulfuric acid The FT-IR spectrum of the catalyst was shown in (Figure 3). The catalyst is solid and solid state IR spectrum was recorded using the KBr disk technique. For nano silicon oxide (SiO2), the major peaks are broad anti symmetric Si-O-Si stretching from 1000 to 1200 cm-1 and symmetric Si-OSi stretching near 800 cm-1 and broad OH stretching absorption around 3700 and 2800 cm-1 (Figure 3a). For nano silica sulfonic acid catalyst, the FT-IR absorption range of the S-O stretching mode lying in 550–650 cm-1 would be going on and the O-S-O asymmetric and symmetric stretching modes lies in 1120–1230 and 1010–1080 cm-1 respectively. FT-IR spectrum shows the overlap asymmetric and symmetric stretching bands of SO2 with Si–O–Si

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ACCEPTED MANUSCRIPT stretching bands in the nano silica sulfuric acid. The spectrum also shows a broad OH stretching absorption around 3700 and 2800 cm-1 (Figure 3b). TEM Characterization The size and morphology of nano silica sulfuric acid particles analyzed by TEM is represented in (Figure 4). This image reveals the product consists of spherical particles with the average size of


10-15 nm. In order to evaluate the generality of the process, several diversified examples illustrating the present method for the synthesis of amidoalkyl naphthols were studied (Table 2). The reaction of 2-naphthol with various aromatic aldehydes bearing electron withdrawing groups (such as nitro, halide) or electron releasing groups (such as methyl, methoxy) and amides was carried out in the presence of nano silica sulfuric acid as catalyst. The yields obtained were high to excellent without formation of any side products.

To show the merit of the present work in comparison with reported results in the literature, we compared the reactions of nano silica sulfuric acid with thiamine hydrochloride, [26] montmorillonite K10,[27] sulphamic acid,[28] Ph3CCl3,[29] K5CoW12O40.3H2O,[17] iodine[30], and zwitterionic salt[31] in the synthesis of amidomethyl naphthol derivatives. As shown in Table 2, nano silica sulfuric acid is a better catalyst with respect to reaction times and yields of the products (Table 3).

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ACCEPTED MANUSCRIPT The anticipated mechanism for the nano silica sulfuric acid catalyzed preparation of amidoalkyl naphthols from the reaction of 2-naphthol, aromatic aldehydes and benzamide under solvent-free conditions is shown in Scheme 2. The recovery and reuse of catalysts is highly preferable for a greener process. Thus, the reusability of the catalyst was investigated by using 3-nitrobenzaldehyde, 2-naphthol and


benzamide as model substrates. The catalyst was easily recovered by filtration after the reaction and washed with ethyl acetate and drying at 100 °C. After being dried, it was subjected to another reaction with identical substrates. The catalyst was recovered in excellent yields and catalyst was used in the mentioned reaction for five times, it showed the same activity such as fresh catalyst without any loss of its activity. CONCLUSIONS In conclusion, we have demonstrated that nano silica supported sulfonic acid is a new efficient and green catalyst for synthesis of amidoalkyl naphthols. Amidoalkyl naphthol derivatives were prepared via a three-component reaction of aryl aldehydes, 2-naphthol, and benzamide or acetamide in the presence of catalytic silica supported sulfonic acid in three conditions. The thermal solvent-free green procedure offer advantages such as shorter reaction times, simple work-up, environmentally benign, excellent yield, cost effective recovery, and reusability of catalyst for a number of times without appreciable loss of activity.

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SELECTED DATA N-[(phenyl)-(2-hydroxy naphthalen-1-yl)-methyl] acetamide (4a). 1H NMR (200 MHz, DMSO): δ 1.97 (s, 3H), 7.16-7.37 (m, 9H), 7.72-7.85 (m, 3H), 8.45 (d, J = 8.2 Hz, 1H), 9.89 (s, 1H). FTIR (KBr): 3400, 3244, 3062, 1639, 1581, 1522, 1373, 1279, 1061, 808, 771, 696, 623, cm-1.


N-[(3-nitro-phenyl)-(2-hydroxy naphthalen-1-yl) methyl] acetamide (4e). 1H NMR (200 MHz, DMSO): δ 2.03 (s, 3H), 7.16-7.56 (m, 6H), 7.77-8.05 (m, 5H), 8.63 (d, J = 7.9 Hz, 1H), 10.00 (s, 1H). 13C NMR (50 MHz, DMSO): 27.34, 52.43, 122.58, 123.25, 125.22, 126.04, 127.41, 127.57, 131.58, 133.19, 133.49, 134.37, 134.70, 136.95, 137.65, 150.19, 152.52, 158.18, 174.54. FT-IR (KBr): 3373, 3194, 3066, 1647, 1577, 1523, 1350, 1298, 1111, 1063, 806, 705, cm-1. N-[(4-methyl-phenyl)-(2-hydroxy naphthalen-1-yl)-methyl] acrylamide (4i).

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H NMR (200

MHz, DMSO): δ 2.17 (s, 3H), 5.58 (d, J = 12.1 Hz, 1H), 6.10 (d, J = 17.0 Hz, 1H), 6.58 (dd, J1 = 6.9 Hz, J2 = 27.0 Hz, 1H), 7.03-7.38 (m, 8H), 7.72-7.86 (m, 3H), 8.67 (d, J = 8.3 Hz, 1H), 9.83 (br, 1H).

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C NMR (50 MHz, DMSO): 20.59, 47.88, 118.50, 118.67, 122.41, 123.34, 123.64,

126.09, 126.32, 128.48, 128.58, 128.65, 129.29, 131.84, 132.35, 135.23, 139.19, 153.23, 164.46. FT-IR (KBr): 3392, 3066, 3028, 1655, 1614, 1581, 1518, 1336, 1271, 1158, 1066, 816, cm-1. N-[(3-nitro-phenyl)-(2-hydroxy naphthalen-1-yl)-methyl] acrylamide (4k). 1H NMR (200 MHz, DMSO): δ 5.64 (d, J=10.1 Hz, 1H), 6.17 (d, J = 17.0 Hz, 1H), 6.61 (dd, J1 = 6.9 Hz, J2 = 27.0 Hz, 1H), 7.21-8.03 (m, 15H), 8.89 (d, J = 7.7 Hz, 1H), 10.00 (br, 1H). FT-IR (KBr): 3381, 3140, 1655, 1620, 1579, 1518, 1348, 1275, 1221, 1066, 982, 800, cm-1.

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ACCEPTED MANUSCRIPT N-[(3-nitro-phenyl)-(2-hydroxy naphthalen-1-yl) methyl] benzamide (4p).1H NMR (200 MHz, DMSO): δ 3.38 (s, 3H), 7.23-7.51 (m, 9H), 7.58 (d, J = 7.8 Hz, 1H), 7.81-7.90 (m, 4H), 8.088.12 (m, 3H), 9.13 (d, J = 7.8 Hz, 1H), 10 (s, 1H).

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C NMR (50 MHz, DMSO): 49.01, 117.34,

118.67, 121.01, 121.69, 122.56, 122.88, 127.10, 127.41, 128.45, 128.50, 128.79, 129.80, 130.05, 131.62, 132.25, 133.33, 134.06, 144.60, 147.86, 153.50, 166.30. FTIR (KBr): 3375, 3265, 1633,


1577, 1529, 1485, 1439, 1346, 1309, 1281, 812, 733, cm-1.

ACKNOWLEDGMENTS We gratefully acknowledge financial support from the Research Council of Islamic Azad University, Kermanshah Branch.

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TABLE 1. Effect of temperature.

Entry

Temperature (oC)

Time(min)

Yield (%)

1

40

100

10

2

50

68

35

3

60

60

75

4

70

50

85

5

80

17

95

6

90

15

97

7

100

15

98

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ACCEPTED MANUSCRIPT TABLE 2. Nano silica sulfuric acid catalyzed one-pot synthesis of amidoalkyl naphthols. Entry

R1

R2

Time

Yield (%)


(min)

MP Found

Report

1a

C6H5–

CH3

10

91

218-220

218-220 23

1b

4-CH3–C6H4

CH3

8

88

214-216

214-216 23

1c

3-CH3O–C6H4

CH3

4

87

218-220

218-220 23

1d

4-NO2–C6H4

CH3

10

94

222-223

222-223 23

1e

3-NO2–C6H4

CH3

18

93

238-240

238-240 23

1f

4-Cl–C6H4

CH3

6

90

229-230

224-227 15

1g

2-Cl–C6H4

CH3

10

87

192-194

192-194 23

1h

C6H5–

C2H3

5

93

249-250

-

1i

4-CH3–C6H4

C2H3

5

89

218-220

-

1j

4-CH3O–C6H4

C2H3

4

88

219-221

-

1k

3-NO2–C6H4

C2H3

6

94

248

-

1l

C6H5–

C6H5

5

93

234-236

234-236 23

1m

4-CH3–C6H4

C6H5

10

90

209-211

209-211 23

1n

3-CH3O–C6H4

C6H5

8

89

214-216

214-216 23

1o

4-Cl–C6H4

C6H5

17

92

180-182

180-182 23

1p

3-NO2–C6H4

C6H5

15

95

233-235

233-235 23

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ACCEPTED MANUSCRIPT TABLE 3. Comparison result of nano silica sulfuric acid with those obtained by the recently reported catalysts. in the synthesis of amidoalkyl naphthol.

Entry Product

Yield (catalyst) / conditions

Catalyst amount

Time (%)

1

4e

Nano SiO2-SO3H/80 °C, Solvent-Free

0.015 g

10 min

93

0.1 g

30 min

96

Montmorillonite K10/125 °C, Solvent2

4e


Free

27

3

4e

Sulphamic acid/r.t., ClCH2CH2Cl 28

0.1 mmol

420 min

82

4

4e

Ph3CCl3/r.t. 29

0.028 g

90 min

94

1 mol%

180 min

78

0.015 g

15 min

95

0.1 g

30 min

96

K5CoW12O40.3H2O/125 °C, solvent-free 5

4e 17

6

4p

Nano SiO2-SO3H/80 °C, Solvent-Free Montmorillonite K10/125 °C, Solvent-

7

4p Free 27

8

4p

I2, r.t., ClCH2CH2Cl 30

0.1 mmol

600 min

84

9

4p

Zwitterionic salt/80 °C, Solvent-Free 31

0.0025 g

120 min

90

10

4p

Thiamine hydrochloride, 80 °C, EtOH 26

0.5 mmol

240 min

90

11

4p

Sulphamic acid/r.t., ClCH2CH2Cl 28

0.1 mmol

540 min

72

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ACCEPTED MANUSCRIPT OH

NHCOR 2

R1

OH

SiO 2 -SO 3 H 1 +

1

R CHO

2

R CONH 2

2

Solvent-free 80 oC 4

3


Scheme 1.

O

R1

NHCOR2

SiO2

S

O

H

O

O

HO

R1

H

H O

O R2

NH2 R1

HO

H

R1 H

O

-HOH

O

Scheme 2.

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SO 2O

H

ACCEPTED MANUSCRIPT

O H

OH

O

Cl-SO2OH O

r.t OH SO 2

HO

2

HO

OH SiO2

SO 2OH

O

SO

HO HO

SiO2

O O

O

SO

2 OH

2 OH

SO


FIG. 1. Synthesis of nano silica sulfuric acid.

FIG. 2. TGA, and weight loss curves for the nano silica sulfuric acid.

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Tra nsm itta nce (%)

(a)

(b)

3392 850 885

582

1200


1097

3900

3400

2900

2400 1900 Wavenumbers / (cm -1 )

1400

900

400

FIG. 3. a) FT-IR spectra of nano SiO2. b) FT-IR spectra of. nano silica sulfuric acid.

FIG. 4. TEM image and histogram acquired for a sample of the nano silica sulfuric acid

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