Organic Chemistry InternationalVolume 2013 (2013), Article ID 502343, 5 pageshttp://dx.doi.org/10.1155/2013/502343

Research Article

Rapid and Efficient Synthesis of Hydroxytriarylmethanes under Ultra Sonic Irradiation Using Keggin Heteropolyacids and Preyssler Catalysts in Green Conditions

Hooshang Hamidian

Department of Chemistry, Payame Noor University (PNU), 19395-4697 Tehran, Iran

Received 25 September 2012; Revised 26 November 2012; Accepted 18 December 2012

Academic Editor: Dipakranjan Mal

Copyright © 2013 Hooshang Hamidian. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

A new synthesis of hydroxytriarylmethane derived from the reaction of 2-sulfobenzoic anhydride and phenols in the presence of heteropolyacids as green, reusable, and efficient catalyst (using catalytic amount) under ultrasonic irradiation is reported in this paper.

1. Introduction

Triarylmethanes (TAMs) are highly colored materials and have been used as dyes and pigments for a very long time [1]. They have received much attention and have been widely used for many purposes such as for photochromic agents [2], protective groups [3], building blocks for dendrimers and NLOs [4, 5]. Some triarylmethanes have shown a wide range of pharmaceutical properties such as antioxidant, antivirus, and antitumor activities [6, 7].

Two basic methods to synthesize triarylmethanes (TAMs) are the Grignard reaction of various carbonyl compounds like benzophenone and methyl benzoate, and the aromatic electrophilic substitution reaction in acidic media [8, 9]. Symmetric triarylmethanes (TAMs) were prepared by the treatment of electrophilic reagents such as triethyl orthoformate or chloroform with arene nucleophiles [10, 11].

Recently, an efficient synthesis of unsymmetrical triarylmethanes has been reported by Friedel-Crafts reaction of aromatic nucleophiles with heteroarylcarbinols [12]. Werbel et al. have reported a facile method for the synthesizing of triarylmethane by the catalytic hydrogenation of the diaryl ketone and the subsequent treatment of the carbinol with aryl amines and HCl [13].

The selective condensation of oxophilic metal phenolates with an aromatic aldehyde at the ortho position of the starting phenol has been utilized in the synthesizing of a 2,2′-di-hydroxy triphenylmethane, another TAM derivative [7].

Development of methods using heteropolyacids (HPAs) as catalysts for fine organic synthetic processes related to fine chemicals, such as flavors, pharmaceuticals, and food industries have been under attention in the last decade. The catalysts based on HPAs have many advantages over liquid acid catalysts. They are not corrosive and environmentally benign, presenting fewer disposal problems. Solid HPAs have attracted much attention in organic synthesizing owing to easy workup procedures, easy filtration, and minimization of cost and waste generation because of reusing and recycling of the catalysts [14, 15].

Newly some books and papers have been published which show that the synthesizing of compounds has been accelerated by ultrasound irradiation. In comparison with the traditional methods, this method is more convenient and easier to work up [16, 17].

Herein, we report a simple method for synthesizing of hydroxytriarylmethane derivatives from reaction of 2-sulfobenzoeic anhydride with phenols in the presence of catalytic amounts of H₁₄[NaP₅W₃₀O₁₁₀], H₄SiW₁₂O₄₀ and H₃PW₁₂O₄₀, under ultrasonic irradiation (Scheme 1).

Scheme 1: Synthesis of hydroxytriarylmethane derivatives.

2. Experimental

2.1. Chemicals and Apparatus

All the chemicals were obtained from Merck, Fluka, and Aldrich Companies and were used without further purification. Melting points were measured using Thermo-Fisher Scientific. IR spectra were recorded by Bruker tensor 27, FT-IR Spectrophotometer. All ¹H NMR and ¹³C NMR spectra were recorded on a Bruker 400 MHZ Spectrophotometer. Chemical shifts are reported in parts per million (ppm), using tetra methyl silane (TMS) as an internal standard. The microanalyses for C and H were performed on Perkin-Elmer elemental analyzer. The ultrasonic apparatus was the cleaning bath Wiseclear 770 W (Seoul, Korea). The operating frequency was 40 kHz and the output power was 200 W, estimated calorimetrically. The reaction flasks were located in the maximum energy area in the water bath, where the surface of reactants (reaction vessel) was slightly lower than the surface level of the water, and the addition or removal of water which controlled the temperature of the water bath. The temperature of the water bath was controlled at 55–65°C. Silica-supported Preyssler nanoparticles were prepared according to [18].

2.2. General Procedure

A mixture of 2-sulfobenzoeic anhydride (20 mmol), phenol derivatives (60 mmol), and catalytic amount of heteropolyacid (0.03 mmol) in 10 mL CH₃CN was irradiated under ultrasound at 55–65°C for required reaction time. The progress of the reaction was monitored by TLC. When the reaction was completed, the catalyst was filtered off, the solvent was evaporated under vacuum, and the product was poured into 100 mL NaOH 10%. Then, the solution was acidified by HCl. The precipitate was collected under filtration. All products were identified by their physical and spectroscopic data (Tables 1 and 2).

Table 1: Physical and spectral data of the compounds (a–f).

Entry
Product
Structure
1H NMR (DMSO, ppm)
IR (, cm⁻¹)
% Analysis Calc (Found)
m.p. (°C)

1
a

6.33–8.06 (m, 14H, OH, SO₃H, Ar–H)
3441, 1662, 1676
C: 64.40 (64.22), H: 3.95 (4.09)
296-297

2
b

2.09 (s, 3H, CH₃), 2.48 (s, 3H, CH₃), 6.07–8.10 (m, 12H, OH, SO₃H, Ar–H)
3433, 1667, 1671
C: 65.97 (66.28), H: 4.71 (5.01)
—

3
c

1.90 (s, 3H, CH₃), 2.34 (s, 3H, CH₃), 5.92–8.13 (m, 12H, OH, SO₃H, Ar–H)
3438, 1666, 1678
C: 65.97 (65.75), H: 4.71 (4.96)
247-248

4
d

6.25–7.98 (m, 12H, OH, SO₃H, Ar–H)
3427, 1665, 1677
C: 44.53 (44.78), H: 2.34 (2.59)
225–227

5
e

6.29–8.11 (m, 12H, OH, SO₃H, Ar–H)
3421, 1668, 1680
C: 53.90 (54.22), H: 2.84 (3.09)
256–258

6
f

6.37–8.01 (m, 10H, OH, SO₃H, Ar–H)
3425, 1664, 1678
C: 34.03 (33.81), H: 1.49 (1.29)
266–269 (decom)

Table 2: 13C NMR data of the compounds (a–f).

Entry
Product
13C NMR (ppm)

1
a
100.2, 117.4, 120.7, 123.9, 125.7, 126.1, 126.8, 131.5, 135.1, 136.6, 145.8, 148.2, 155.9, 158.1, 183.4

2
b
20.4, 21.6, 98.61, 99.5, 120.2, 120.4, 124.6, 126.0, 127.1, 127.4, 127.8, 129.6, 130.7, 133.8, 134.9, 137.4, 146.1, 152.0, 154.3, 155.2, 181.9

3
c
14.2, 17.5, 93.2, 100.2, 118.9, 120.6, 121.1, 124.7, 126.7, 127.5, 127.7, 127.9, 128.7, 129.9, 134.2, 136.1, 145.3, 147.1, 156.8, 157.3, 179.5

4
d
80.1, 96.3, 110.0, 115.9, 124.3, 124.6, 125.9, 126.9, 127.5, 127.6, 127.9, 131.0, 134.5, 137.7, 144.5, 150.0, 150.7, 161.1, 173.9

5
e
83.2, 98.8, 119.4, 122.2, 123.1, 124.8, 126.1, 126.9, 127.4, 127.5, 127.8, 130.5, 132.0, 134.1, 145.9, 150.0, 154.3, 155.6, 175.3

6
f
78.9, 115.9, 120.0, 123.9, 127.4, 127.6, 128.4, 129.0, 135.6, 141.1, 147.7, 148.2, 156.0, 170.1, 173.3

2.3. Recycling of the Catalyst

After filtration of the catalyst, it could be recycled, washing it with diethylether in each case. The recovered catalyst could be dried and reused for the next reaction with only a modest loss in activity. The catalyst has been recovered and reused for six times in reactions. The obtained results are summarized in Table 3.

Table 3: Recyclability of H₁₄[NaP₅W₃₀O₁₁₀].

Entry
Phenol
Yield (%)a/Run

1
2
3
4
5
6

1
phenol
95
93
90
88
86
84

2
m-cresol
96
93
91
88
86
85

3
o-cresol
95
92
91
89
87
84

4
2-bromophenol
93
90
87
86
84
82

5
2-Chlorophenol
94
91
90
88
85
83

6
2,6-dibromophenol
94
92
89
87
86
85

aIsolated yields.

3. Results and Discussions

The progress of reaction 2-sulfobenzoeic anhydride with phenols was monitored by TLC and reported yields were based on isolated products. The results showed that the highest yield of the products was achieved when H₁₄[NaP₅W₃₀O₁₁₀] was used as the catalyst.

Comparison of the catalysts in Tables 4 and 5 showed that H₁₄[NaP₅W₃₀O₁₁₀] is the catalyst of choice. Comparison of supported and nonsupported Preyssler catalyst showed that, in all cases, the supported Preyssler catalyst was less active than the nonsupported one. One plausible interpretation of this observation is that, in supported type, there are polyanion-support interactions of an acid-base nature. Some protons of the polyacid and some basic sites of the support (e.g., hydroxyl groups) can interact. This would lead to diminished availability of hydrogens because of this extra ionic interaction [19]. Interestingly, this behavior is similar to that of Keggin heteropolyacids. However, when H₃[PW₁₂O₄₀] or H₄[SiW₁₂O₄₀] were used instead of H₁₄[NaP₅W₃₀O₁₁₀] the yield of product was slightly decreased.

Table 4: The reaction of o-cresol and 2-sulfobenzoeic anhydride in the presence of different catalyst at 140°C (time of reaction 60 min).

Entry
Catalyst
Yielda (%)

1
H₄SiW₁₂O₄₀
65

2
H₃PW₁₂O₄₀
68

3
H₁₄[NaP₅W₃₀O₁₁₀]
72

4
H₁₄[NaP₅W₃₀O₁₁₀]/SiO₂
35

5
H₂SO₄
58

6
ZnCl₂
44

aIsolated yield.

Table 5: The reaction of o-cresol and 2-sulfobenzoeic anhydride in the presence of different catalysts at 55–65°C under ultrasonic irradiation (time of reaction 15 min).

Entry
Catalyst
Yielda (%)

1
H₄SiW₁₂O₄₀
87

2
H₃PW₁₂O₄₀
90

3
H₁₄[NaP₅W₃₀O₁₁₀]
95

4
H₁₄[NaP₅W₃₀O₁₁₀]/SiO₂
26

5
H₂SO₄
31

6
ZnCl₂
12

aIsolated yield.

The results point out that the catalytic effectiveness may be enhanced as the number of tungsten atoms (or the number of protons) is increased. Both possibilities stand to reason. In addition, the large anion also provides many “sites” on the oval-shaped molecule that are likely to render the catalyst effectiveness. Interestingly, the comparison of Preyssler heteropolyacid, with its exclusive properties, with Keggin heteropolyacids, ZnCl₂, and H₂SO₄ showed that the activity for H₁₄[NaP₅W₃₀O₁₁₀] is the most. The compression of efficiency of heteropolyacids has been carried out. The results are shown in Table 6. It is clear that H14 [NaP₅W₃₀O₁₁₀] gave the better yields than others. The catalytic activity is increased in the following order: H₁₄[NaP₅W₃₀O₁₁₀] > H₃[PW₁₂O₄₀] > H₄[SiW₁₂O₄₀].

Table 6: Comparison of efficiency of H₄SiW₁₂O₄₀, H₃PW₁₂O₄₀, and H₁₄[NaP₅W₃₀O₁₁₀] in synthesis of hydroxytriarylmethane derivatives under ultrasonic irradiation.

Entry
Phenol
Catalyst
Yield (%)a

1
phenol
H₄SiW₁₂O₄₀
86

2
phenol
H₃PW₁₂O₄₀
90

3
phenol
H₁₄[NaP₅W₃₀O₁₁₀]
91

4
m-cresol
H₄SiW₁₂O₄₀
88

5
m-cresol
H₃PW₁₂O₄₀
90

6
m-cresol
H₁₄[NaP₅W₃₀O₁₁₀]
94

7
o-cresol
H₄SiW₁₂O₄₀
87

8
o-cresol
H₃PW₁₂O₄₀
90

9
o-cresol
H₁₄[NaP₅W₃₀O₁₁₀]
95

10
2-bromophenol
H₄SiW₁₂O₄₀
85

11
2-bromophenol
H₃PW₁₂O₄₀
91

12
2-bromophenol
H₁₄[NaP₅W₃₀O₁₁₀]
94

13
2-chlorophenol
H₄SiW₁₂O₄₀
83

14
2-chlorophenol
H₃PW₁₂O₄₀
88

15
2-chlorophenol
H₁₄[NaP₅W₃₀O₁₁₀]
92

16
2,6-dibromophenol
H₄SiW₁₂O₄₀
84

17
2,6-dibromophenol
H₃PW₁₂O₄₀
86

18
2,6-dibromophenol
H₁₄[NaP₅W₃₀O₁₁₀]
90

aIsolated yield.

Phenols with electron withdrawing groups gave hydroxytriarylmethane derivative in low yields. To show the merit of this method, reaction has been performed using the same catalyst repeatedly under classical heating condition. As it is shown under heating condition the higher reaction time is required. The results are shown in Tables 7 and 8.

Table 7: Synthesis of hydroxytriarylmethane derivatives using H₁₄[NaP₅W₃₀O₁₁₀] under ultra sonic irradiation.

Entry
Phenol
Time (min)
Yield (%)a

1
phenol
20
91

2
m-cresol
20
94

3
o-cresol
15
95

4
2-bromophenol
25
94

5
2-chlorophenol
30
92

6
2,6-dibromophenol
40
90

aIsolated yield.

Table 8: Synthesis of hydroxytriarylmethane derivatives using H₁₄[NaP₅W₃₀O₁₁₀] under heating condition.

Entry
Phenol
Time (min)
Yield (%)a

1
phenol
90
69

2
m-cresol
75
61

3
o-cresol
60
72

4
2-bromophenol
120
63

5
2-chlorophenol
120
58

6
2,6-dibromophenol
150
54

aIsolated yield.

As ultrasound generated intense turbulence and microscale liquid circulation currents, uniform mixing at microlevel has occurred and the mass transfer resistances have been eliminated [20]. This explanation can justify the shorter reaction time observed for reactions under ultrasonic condition.

This catalyst retained its activity over six consecutive runs (Table 3).

4. Conclusion

We developed a new method using heteropolyacids under ultrasonic irradiation for synthesis of hydroxytriarylmethanes. The short reaction times, high yields, reusability of catalyst, and easy work up procedure are some advantages of this method.

Acknowledgment

The author thanks Payame Noor University (PNU) of Kerman for the financial support.

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