Preparation of Carbon Nanotube-Supported α-Fe O @CuO ...

Supporting Information for:

Preparation of Carbon Nanotube-Supported α-Fe2O3@CuO

Nanocomposite: A Highly Efficient and Magnetically Separable Catalyst

in Cross-Coupling of Aryl Halides with Phenols 5

Dariush Saberi,a Mehdi Sheykhan,

b Khodabakhsh Niknam,

c and Akbar Heydari

a,*

aChemistry Department, Tarbiat Modares University, P.O. Box 14155-4838 Tehran, Iran, Fax: (+98)-21- 82883455; phone:

(+98)-21-82883444; email: heydar [email protected]

10 bChemistry Department, Guilan University, P.O.Box 41335-1914 Rasht, Iran

cChemistry Department, Faculty of Sciences, Persian Gulf University, Bushehr, 75169, Iran

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Table of Content

Experimental

Preparation of carbon nanotube-supported α-Fe2O3

Synthesis of Carbon nanotube-supported α-Fe2O3@CuO nanoparticles

Recyclability test of Catalyst

Spectrum Information of diarylether derivatives

1H NMR and

13C NMR Spectrum of diarylether derivatives

Electronic Supplementary Material (ESI) for Catalysis Science & TechnologyThis journal is © The Royal Society of Chemistry 2013

mailto:a@

S2

Experimental

All reagents were purchased from commercial suppliers and used without further purification. Multi

wall carbon nanotubes used in this work incorporate 3.06 wt% of OH with an external diameter 10-20

nm, internal diameter 5-10 nm and approximate length of 30 micrometres. All experiments were

carried out under argon. Catalysts were characterized using spectroscopic techniques (FTIR, XRD, 5

BET, BJH, ICP, VSM, SEM and TEM). FT-IR spectra were obtained over the region 400-4000 cm-1

with NICOLET IR100 FT-IR with spectroscopic grade KBr. Powder XRD spectrum was recorded at

r.t by a Philips X’pert 1710 diffractometer using Cu Kα (α = 1.54056 Å) in Bragg-Brentano geometry

(θ-2θ). The BET specific surface area, pore volume and average pore size were determined by physical

adsorption of N2 at −196 °C in an automatic volumetric system using Belsorp instrument. ICP analysis 10

was accomplished using a VISTA-PRO, CCD simultaneous ICP analyser.Magnetic properties of

catalyst were obtained by homemade VSM. SEM image was observed using SEM (Philips XL 30 and

S-4160) with gold coating equipped with energy dispersive X-ray spectroscopy (EDX). TEM

measurements were carried out at 120 kV (Philips, model CM120).NMR1H and

13C NMR spectra were

recorded on a BrukerAvance (DRX 500 MHz) and BrukerUltrashield (400 MHz) in pure deuterated 15

CDCl3 solvent with tetramethylsilane (TMS) as internal standards.

Preparation of carbon nanotube-supported α-Fe2O3

FeSO4•7H2O (1.00 g, 3.6 mmol) was dissolved into 10 mL distilled water and then multiwall carbon

nanotubes (0.200 g) were added into solution. The complex was sonicated for 5 min, and then

hydrogen peroxide (30 mL, 30%) was dripped slowly into the above complex with vigorous stirring 20

and refluxed at 353 K for 4 h. The black complex was collected by decantation, washed with distilled

water, and subsequently treated in an oven at 393 K for 12 h. This resulting nanocomposite

(CNT@Fe(OH)3.xH2O) was then exposed to argon atmosphere at 450 °C giving rise to a carbon

nanotube-supported α-Fe2O3 compound.


S3

Synthesis of Carbon nanotube-supported α-Fe2O3@CuO nanoparticles

To a magnetically stirred mixture of Cu(OAc)2.H2O (0.4 g, 2.2 mmol) in deionized water (100 mL),

carbon nanotube-supported α-Fe2O3 (0.4 g) was added and then the solution was heated to 100 °C.

After hydrolysis and crystallization for 5 h, the black precipitate formed in the solution was

magnetically decanted, washed repeatedly with distilled water and absolute ethanol, and dried in air at 5

room temperature.

Recyclability test of Catalyst

Upon completion of the first reaction between iodobenzene and phenol to afford a quantitative yield of

the corresponding aryl ether (92% yield), the catalyst was recovered by external magnet, washed with

H2O and ethanol and oven dried at 80 °C overnight. A new reaction was then performed with fresh 10

solvent and reactants under identical conditions.

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S4

Spectroscopic data of products:

Diphenyl ether.Following the general procedure using phenol (94 mg, 1mmol) and iodobenzene (0.05

mL, 0.5 mmol) provided 156.6 mg (92% yield) of the coupling product as a colorless liquid after

purification by flash chromatography (pentane) of the crude oil.

O

5

1H NMR (CDCl3, 500 MHz) δ 7.05 (d, J= 7.75 Hz, 4H), 7.13 (t, J=7.35, 2H), 7.37 (t, J=7.55 Hz, 4H),

13C NMR (CDCl3, 125 MHz) δ 118.9, 123.2, 129.7, 157.3

All spectral data correspond to those given in the literature

4-Methoxyphenyl phenyl ether. Following the general procedure using 4-Methoxyphenol (124 mg, 10

1mmol) and iodobenzene (0.05 mL, 0.5mmol) provided 180 mg (90% yield) of the coupling product

as a colorless liquid after purification by flash chromatography (pentane) of the crude oil.

O

OMe 1H NMR (CDCl3, 400 MHz) δ 3.73 (s, 3H), 6.78-6.82 (m, 2H), 6.85-6.92 (m, 4H), 6.96 (t,J= 7.32 Hz, 15

1H), 7.22 (t,J= 7.32 Hz, 2H);

13CNMR (CDCl3, 100 MHz) δ 55.8, 114.9, 115.0, 117.7, 121.0, 122.4, 129.6, 129.8, 155.8;


4-Nitrophenyl phenyl ether. Following the general procedure using 4-Nitrophenol (139mg, 1mmol) 20

and iodobenzene (0.05 mL, 0.5 mmol) provided 157 mg (73% yield) of the coupling product as a

yellow solid after purification by flash chromatography (8:2 pentane/DCM) of the crude oil.

O

NO2


S5

1H NMR (CDCl3, 400 MHz) δ 6.89-6.93 (m, 2H), 7 (d, J=7.84 Hz, 2H), 7.17 (t, J=7.56 Hz, 1H), 7.34

(t, J= 7.6Hz, 2H), 8.10 (d, J=9.36 Hz, 2H);

13C NMR (CDCl3, 100 MHz) δ 117.1, 120.6, 125.5, 126, 130.4, 142.6, 154.7, 163.4;


5

4-Methylphenyl phenyl ether. Following the general procedure using 4-Methylphenol (100 mg,

1mmol) and iodobenzene (0.05 mL, 0.5 mmol) provided 175 mg (95% yield) of the coupling product

as a colorless liquid after purification by flash chromatography (pentane) of the crude oil.

O

Me 10 1H NMR (CDCl3, 400 MHz): δ＝2.26 (s, 3H), 6.84 (d, J= 8.56 Hz, 2H), 6.91 (d, J=8.56 Hz, 2H), 6.99

(t, J=7.56 Hz, 1H), 7.06 (d, J=8.1 Hz, 2H),7.24 (t,J=7.56 Hz, 2H),

13C NMR (CDCl3, 100 MHz): δ＝20.7, 118.3, 119.1, 122.8, 129.7, 130.2, 132.9, 154.7, 157.8


15

4-Bromophenyl phenyl ether. Following the general procedure using 4-Bromophenol (173 mg, 1

mmol) and iodobenzene (0.05 mL, 0.5 mmol) provided 149 mg (60% yield) of the coupling product as

a colorless liquid after purification by flash chromatography (pentane) of the crude oil.

O

Br 20 1H NMR (CDCl3, 400 MHz): δ＝ 6.79-6.83 (m, 2H), 6.93 (d, J=7.56 Hz, 2H), 7.05 (t, J=7.56 Hz, 1H),

7.27 (t, J=7.57 Hz, 2H),7.33-7.37 (m, 2H),

13C NMR (CDCl3, 100 MHz): δ＝115.6, 119.0, 120.4, 123.7, 129.9, 130.2, 132.7, 156.6, 156.7


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S6

4-Ethylphenyl phenyl ether. Following the general procedure using 4-Ethylphenol (122 mg, 1

mmol) and iodobenzene (0.05 mL, 0.5 mmol) provided 178 mg (90% yield) of the coupling product as

a colorless liquid after purification by flash chromatography (pentane) of the crude oil.

O

Et 5 1H NMR (CDCl3, 400 MHz): δ＝ 1.16 (t, J=7.56 Hz, 3H), 2.56(q, J=7.56 Hz, 2H), 6.87 (d,J=8.32 Hz,

2H), 6.91 (d,J=7.84Hz, 2H),7.00 (t, J=7.32 Hz, 1H), 7.09 (d, J= 8.56 Hz, 2H), 7.27 (t, J= 7.32 Hz,

2H),

13C NMR (CDCl3, 100 MHz): δ＝15.8, 28.2, 118.4, 119.1, 122.8, 129.0, 129.7, 139,3, 154,9, 157,76.

All spectral data correspond to those given in the literature 10

3,5-Dimethylphenyl phenyl ether. Following the general procedure using 3,5-Dimethylphenol (122

mg, 1 mmol) and iodobenzene (0.05 mL, 0.5 mmol) provided 168 mg (85% yield) of the coupling

product as a colorless oil after purification by flash chromatography (pentane) of the crude oil.

15

O

1H NMR (CDCl3, 400 MHz) δ= 2.20 (s, 6H), 6.56 (s, 2H), 6.67 (s, 1H), 6.92 (d, J=7.56 Hz, 2H), 7.01

(t, J=7.32 Hz, 1H), 7.23-7.27 (m, 2H),

13C NMR (CDCl3, 100 MHz) δ= 21.3, 116.6, 118.9, 123, 124.9, 129.7, 139.6, 157.1, 157.4

20

2-Naphthyl phenyl ether. Following the general procedure using 2-naphthol (144 mg, 1mmol) and

iodobenzene (0.05 mL, 0.5 mmol) provided 209 mg (95% yield) of the coupling product as a Pale

yellow colored solid after purification by flash chromatography (pentane) of the crude oil.

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S7

O

1H NMR (CDCl3, 400 MHz) δ＝7 (d, J= 7.56, 2H), 7.06 (t,J=7.56 Hz, 1H), 7.17-7.39 (m, 6H), 7.62 (d,

J=7.8 Hz, 1H), 7.73-7.77 (m, 2H),

13C NMR (CDCl3, 100 MHz):＝114.1, 119.2, 120.0, 123.5, 124.7, 126.5, 127.1, 127.8, 129.8, 129.9, 5

130.2, 134.3, 155.1, 157.2.


2-Methylphenyl phenyl ether. Following the general procedure using Phenol (94 mg, 1 mmol) and 2-10

iodotoluene(0.064 mL, 0.5 mmol) provided 129 mg (70% yield) of the coupling product as a

Colorlessliquidafter purification by flash chromatography (pentane) of the crude oil.

O

Me

1H NMR (CDCl3, 400 MHz) δ= 2.17 (s, 3H), 6.82-6.84 (m, 3H), 6.95-7.01 (m, 2H), 7.1 (t, J= 6.28 Hz, 15

1H), 7.17-7.24 (m, 3H);

13C NMR (CDCl3, 100 MHz) δ= 16.2, 117.3, 119.8, 122.3, 124.0, 127.1, 129.7, 131.5, 131.46, 154.6,

157.8;


20

3-Methylphenyl phenyl ether. Following the general procedure using phenol (94 mg, 1 mmol) and

3-bromotoluene (0.06 mL, 0.5 mmol) provided 133 mg (72% yield) of the coupling product as a

colorless liquid after purification by flash chromatography (pentane) of the crude oil

OMe

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1H NMR (CDCl3, 500 MHz) δ 2.35 (s, 3H), 6.78-6.85(m, 2H), 6.90-6.94 (m, 1H), 7.00-7.03 (m, 2H),

7.11 (t,J= 7.4 Hz, 1H), 7.22 (t, J= 7.85 Hz, 1H), 7.33-7.37 (m, 2H);

13C NMR (CDCl3, 125 MHz) δ 21.5, 116.0, 119.0, 119.7, 123.2, 124.2, 129.6, 129.8, 140.1, 154.3,

157.5;

All spectral data correspond to those given in the literature 5

3-Pyridine phenyl ether. Following the general procedure using phenol (94 mg, 1 mmol) and 3-

iodopyridine (102 mg, 0.5 mmol) provided 128 mg (75% yield) of the coupling product as a colorless

oil after purification by flash chromatography (pentane) of the crude oil

10

N

O

1H NMR (CDCl3, 500 MHz) δ 7.03 (d, J = 8.4 Hz, 2H), 7.16 (t, J = 7.4, 1H), 7.22-7.30 (m, 2H), 7.38

(t,J= 8.3, 2H), 8.37 (br s, 1H), 8.42 (brs, 1H);

13C NMR (CDCl3, 125 MHz) δ 119, 121.3, 124, 125, 130, 141, 144, 157.3, 157.5;

15

5-Pyrimidine phenyl ether. Following the general procedure using phenol (94 mg, 1 mmol) and 5-

bromopyrimidine (79 mg, 0.5 mmol) provided 129 mg (75% yield) of the coupling product as a white

solid crystal after purification by flash chromatography (pentane) of the crude oil

N

N

O

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1H NMR (CDCl3, 500 MHz) δ 7.06 (t, J = 8.35 Hz, 2H), 7.41- 7.44 (m, 3H), 8.48(s, 2H), 8.97 (s, 1H);

13C NMR (CDCl3, 125 MHz) δ 119.1, 123.2, 130.3, 144.4, 147.0, 153.2, 175.2;

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Diphenyl ether


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4-Methoxyphenyl phenyl ether

2011-08-25-ejt-25.010.esp

16 14 12 10 8 6 4 2 0 -2 -4

Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

3.091.973.961.052.00

7.2

389 7.2

206

6.9

200

6.8

973

6.8

172

6.7

945

6.7

857

3.7

261

2011-08-26-ejt-25.011.esp

260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40


-0.1

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

155.8

524

129.7

739

129.6

454

122.4

447

121.0

138

117.7

115

114.9

872

114.9

413

77.5

159

77.1

948

76.8

738

55.8

128

5


S11

4-Nitrophenyl phenyl ether

2011-08-23-ejt-7.010.esp

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

2.022.011.082.012.00

8.1

219

8.1

137

8.0

903

8.0

821

7.3

674

7.3

484

7.3

276

7.1

890

7.1

701

7.1

518

7.0

169

7.0

144

6.9

948

6.9

375

6.9

293

6.9

060

6.8

978

2011-08-23-ejt-7.011.esp

165 160 155 150 145 140 135 130 125 120 115


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

163.4

109

154.6

875

142.6

068

130.3

609

125.9

671

125.4

718

120.5

918

117.0

878

5


S12

4-Methylphenyl phenyl ether


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4-Bromophenyl phenyl ether NikD3 2011-08-24-ejt-32.010.esp

7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 6.70 6.65


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0N

orm

alized Inte

nsity

1.921.961.002.001.95

7.3

751

7.3

669

7.3

499

7.3

443

7.3

361

7.2

976

7.2

787

7.2

573

7.1

879

7.0

757

7.0

568

7.0

385

6.9

396

6.9

207

6.8

337

6.8

261

6.8

091

6.8

034

6.7

952

2011-08-24-ejt-32.011.esp

155 150 145 140 135 130 125 120 115


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

156.7

147

156.5

679 132.6

909

129.9

115

123.7

381

120.4

450

119.0

508

115.6

109

5


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4-Ethylphenyl phenyl ether

2011-08-25-ejt-27.010.esp

16 14 12 10 8 6 4 2 0 -2 -4


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

3.262.001.931.971.042.022.00

7.2

654

7.2

471

7.1

027 7.0

813 6.8

809

6.8

601

2.5

940

2.5

751

2.5

562

2.5

373

1.4

935

1.1

878

1.1

689

1.1

500

2011-08-25-ejt-27.011.esp

260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

157.7

604

154.8

801

139.3

320

129.6

730

129.0

584

119.0

875

118.4

362

77.3

691

77.0

481

76.7

270

28.1

840

15.7

915

5


S15

3,5-Dimethylphenyl phenyl ether

2011-08-25-ejt-26.010.esp

16 14 12 10 8 6 4 2 0 -2 -4


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

6.121.940.991.961.012.00

7.2

715

7.2

533

7.2

318

6.9

337

6.5

599

2.2

088

1.4

864

2011-08-25-ejt-26.011.esp

260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

157.4

210

157.1

458

139.6

072

129.6

822

123.0

043

118.8

673

116.6

108

77.3

783

77.0

572

76.7

362

21.3

502

5


S16

2-Naphthyl phenyl ether

2011-08-24-ejt-34_2.010.esp

7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

1.941.006.221.001.99

7.7

703

7.7

564

7.7

482

7.7

369

7.6

335 7.6

140

7.3

972

7.3

940

7.3

795

7.3

770

7.3

474

7.3

442 7.3

272 7.3

146

7.2

950

7.2

932

7.2

749

7.2

408

7.2

352

7.2

062

7.1

778

7.1

747

7.0

864

7.0

675

7.0

492

7.0

114

6.9

925

2011-08-24-ejt-34.011.esp

260 240 220 200 180 160 140 120 100 80 60 40 20 0 -20 -40


0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

157.1

825

155.1

003

134.3

420

130.1

683

129.8

564

126.5

450

124.7

196

120.0

231

119.1

608

114.0

882

77.3

783

77.0

572

76.7

454

5

10


S17


5


S18


5


S19

3-Pyridine phenyl ether

5


S20

5-Pyrimidine phenyl ether

5


Preparation of Carbon Nanotube-Supported α-Fe O @CuO ...

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