materials and bioengineering, kansai university, suita ...€¦ · compounds 3a1, 3b1,2, 3c1,2,...
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Electronic Supplementary Information
Surfactant-free single-nano-sized colloidal Cu nanoparticles for use as an
active catalyst of Ullmann-coupling reaction
Yuto Isomura,a Takashi Narushima,b Hideya Kawasaki,a Tetsu Yonezawab and
Yasushi Obora*a
a Department of Chemistry and Materials Engineering, Faculty of Chemistry,
Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan b Division of Materials Science and Engineering, Faculty of Engineering, Hokkaido
University, Sapporo, Hokkaido 060-8628, Japan.
E-mail: [email protected]
Table of Contents
S2: General
S2-6: Experimental details
S6: References
S7: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3a.
S8: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3b.
S9: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3c.
S10: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3d.
S11: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3e.
S12: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3f.
S13: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3g.
S14: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3h.
S15: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3i.
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S2
General
GLC analysis was performed with a flame ionization detector using a 0.22 mm×25
m capillary column (BP-5). 1H and 13C NMR were measured at 400 and 100 MHz,
respectively, in CDCl3 with Me4Si as an internal standard. The products were
characterized by 1H NMR, 13C NMR, and GC-MS. The yields of products were
estimated from the peak areas based on the internal standard technique using GC.
All starting materials were commercially available and used without any purification.
CuCl2 was obtained from Wako Chemical Co. All solvents and other regents were
obtained from Wako Chemical Co, TCI and ALDRICH and were used without further
purification.
Compounds 3a1, 3b1,2, 3c1,2, 3d1,2, 3e2, 3f2, 3g2, 3h1, 3i1 were reported previously.
Experimental details
Preparation of Cu NPs. A solution of 15 L of 0.1 M aqueous CuCl2 was added to 15
mL of N, N-dimethylformamide (DMF) that had been preheated to 140 oC, and the
DMF solution was refluxed in a 140 oC oil bath with stirring for 8 h. The surfactant-free
copper nanoparticles (Cu NPs) were obtained as the 0.1 mM Cu NPs in DMF. After
vacuum evaporation of excess solvent, the residue was redissolved in selected solvents
such as methanol, acetonitrile (MeCN), and N-methylpyrrolidone (NMP) for the TEM
measurement and the Ullmann O-Arylation.
Preparation of 0.01 mM Cu NPs in DMF (10-3 mol %)
The DMF solution of 1 mL of the prepared 0.1 mM Cu NPs was added to 10 mL of
DMF, and the solution of 0.01 mM Cu NPs in DMF was prepared.
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Photophysical property. Fluorescence excitation and emission spectra were obtained
on a JASCO FP-6200 fluorospectrophotometer. at UV excitation of 350 nm (Figure S1)
Figure S1. Photoluminescene emission spectra of DMF-protected Cu NPs.
Figure S2. The high-magnification TEM image of Cu NPs showed that the crystal
lattice fringes are 0.2 nm apart, which agrees with the d value of the (111) planes of the
metallic Cu crystal. Bar : 3nm.
0
200
400
600
800
1000
1200
1400
1600
350 400 450 500 550 600
PL
Inte
nsi
ty (
a.u.
)
Wavelength (nm)
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S4
X-ray photoelectron spectroscopy (XPS). X-ray photoelectron spectra were recorded
with a Quantera SXM spectrometer (Physical Electronics, Inc.) using the
monochromatic Al Kα line at 1486.7 eV. The base pressure was approximately 2 × 10-8
Torr. To compensate for charging effect, binding energies were referenced to C 1s at
284.7 eV of hydrocarbon.
9309409509609700
200
400
600
800
1000
1200
1400
1600
1800
Binding Energy (eV)
Inte
nsity
(arb
. uni
ts)
Cu2p932.0 eV
934.4 eV
Figure S3. XPS spectrum of dried Cu NCs
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Transmission electron microscopy (TEM). A drop of Cu NPs dispersed in methanol
was placed on a carbon-coated Cu grid, and HR-TEM (high resolution TEM) image was
obtained with a Hitachi H-9500 at an acceleration voltage of 300 kV. The raw
magnification of the image was 1,000,000.
Dynamic Light Scattering (DLS). A Nanoparticle analyser model SZ-100 with a
100mW laser and an interference optical filter at wavelength of 532nm (HORIBA,
Japan) was used to perform dynamic light scattering for samples 200 L (40 mM
solution in DMF) in volume . The DLS measurement was performed at 25 oC.
A typical reaction procedure for Cu NPs catalyzed Ullmann O-Arylation of 1a with
2a (Table 1, entry 2)
A mixture of iodobenzene 1a (306 mg, 1.5 mmol), 3, 5-dimethylphenol 2a (122 mg,
1.0 mmol), Cs2CO3 (652 mg, 2.0 mmol) and 0.1 mM Cu NPs in DMF (1 mL) as a
catalyst was stirred at 140 oC for 24 h under Ar. The conversions and yields of products
were estimated from peak areas based on an internal standard (tridecane) using GC and
the product 3a was obtained in quantitative yield. The product 3a was isolated by
column chromatography (230-400 mesh silica gel, n-hexane / ethyl acetate = 20 / 1) in
88% yield (174 mg). The highest turnover frequency was achieved 450 for 1 h.
Figure S4. Time course for Ullmann O-Arylation reaction
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S6
A typical procedure for the catalyst-reusing sequence in the Cu NPs-catalyzed
model reaction
After the reaction was performed under the conditions of entry 2, Table 1, iodobenzene
1a (306 mg, 1.5 mmol), 3, 5-dimethylphenol 2a (122 mg, 1.0 mmol) and Cs2CO3 (652
mg, 2.0 mmol) were added to the reaction mixture. It was used next catalytic sequence
under the same reaction conditions as first cycle.
Figure S5. Depiction of the catalyst-reusing
Table S1. Catalyst-reusing
Cycle 1st 2nd 3rd
Yield (%)a >99 51 18 a GC yields (based on 2a) were determined by average of three runs.
References
(1) H. J. Cristau, P. P. Cellier, S. Hamada, J. –F. Spindler and M. Taillefer, Org. Lett., 2004, 6, 913.
(2) A. B. Naidu, E. A. Jaseer and G. Sekar, J. Org. Chem. 2009, 74, 3675.
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3a
PPM
8 6 4 2 0
PPM
200 175 150 125 100 75 50 25 0
O
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3b
PPM
10.0 7.5 5.0 2.5 0.0 -2.5
PPM
200 175 150 125 100 75 50 25 0
O
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3c
PPM
12.5 10.0 7.5 5.0 2.5 0.0 -2.5
PPM
200 175 150 125 100 75 50 25 0
O
OMe
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3d
O
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3e
PPM
10.0 7.5 5.0 2.5 0.0 -2.5
PPM
200 150 100 50 0
O
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S12
3f
PPM
10.0 7.5 5.0 2.5 0.0 -2.5
PPM
200 175 150 125 100 75 50 25 0
O
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S13
3g
PPM
8 6 4 2 0
PPM
200 175 150 125 100 75 50 25 0
O
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S14
3h
PPM
2.5 10.0 7.5 5.0 2.5 0.0 -2.
PPM
200 150 100 50 0
O
MeO
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S15
3i
PPM
2.5 10.0 7.5 5.0 2.5 0.0 -2.5
PPM
200 175 150 125 100 75 50 25 0
O
F3C
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