Electronic Supplementary Material (ESI) for Dalton Transactions.
This journal is © The Royal Society of Chemistry 2014
Electronic Supplementary Information
Syntheses
and
structures
of
copper
3-(6-(1H-pyrazol-1-yl)pyridin-2-yl)pyrazol-1-ide
and
complexes
their
of
excellent
performance in the syntheses of nitriles and aldehydes
Da-Wei Tan,a Jing-Bo Xie,a Qi Li,a Hong-Xi Li,a,* Jun-Chi Li,a Jian-Ping Langa,b*
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
P. R. China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 210032, P. R. China
S1
Table of Contents
Figure S1. One-dimensional chain (extended along the b axis) formed via H-bonding interactions in 4.··S4
Figure S2. The calculated isotope pattern (top) and the observed patterns (below) of the
[{(Cu(NO3))(μ-pzpypz)}2 + NO3 + 2CH3CN]+ cation in the positive-ion ESI mass spectrum of 1.··········S4
Figure S3. The calculated isotope pattern (top) and the observed patterns (below) of the
[CuClO4(pzpypzH)CuOCH3(pzpypz)]+ cation in the positive-ion ESI mass spectrum of
2.················S4
Figure S4. The calculated isotope pattern (top) and the observed patterns (below) of the
[{Cu2(μ-SO4)(μ-pzpypz)2} + HSO4 + 2MeOH + 4H2O + CH3CN]+ cation in the positive-ion ESI mass
spectrum of 3.·············································································································S5
Figure S5. The calculated isotope pattern (top) and the observed patterns (below) of the
[{(CuI)(μ-pzpypz)}2 + I + 3H2O + 4CH3CN]+ cation in the positive-ion ESI mass spectrum of 5.··········S5
The
1
13
H and
C NMR data of benzonitrile, 2-methylbenzonitrile, 3-methylbenzonitrile,
4-methylbenzonitrile,
2-methoxybenzonitrile,
4-chlorobenzonitrile,
4-nitrobenzonitrile,
3-cyanopyridine,
2-thiophenecarbonitrile,
3-methoxybenzonitrile,
4-methoxybenzonitrile,
3,4-(methylenedioxy)benzonitrile,
benzaldehyde,
1-naphthonitrile,
2-methylbenzaldehyde,
3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde,
4-methoxybenzaldehyde, 4-chlorobenzoic aldehyde, 4-nitrobenzaldehyde, 3-pyridinecarboxaldehyde,
2-thenaldehyde··········································································································S6
The 1H and 13C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethanone····························S8
The
1
H and
13
C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-3-(dimethylamino)prop-
2-en-1-one················································································································S9
The 1H and 13C NMR spectra of 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine·····················S10 The 1H and 13C NMR spectra of the product benzonitrile····················································S11
The 1H and 13C NMR spectra of the product 2-methylbenzonitrile·········································S12 The 1H and 13C NMR spectra of the product 3-methylbenzonitrile·········································S13 The 1H and 13C NMR spectra of the product 4-methylbenzonitrile········································S14 The 1H and 13C NMR spectra of the product 2-methoxybenzonitrile······································S15 The 1H and 13C NMR spectra of the product 3-methoxybenzonitrile······································S16 The 1H and 13C NMR spectra of the product 4-methoxybenzonitrile·····································S17 S2
The 1H and 13C NMR spectra of the product 4-chlorobenzonitrile·········································S18 The 1H and 13C NMR spectra of the product 4-nitrobenzonitrile··········································S19 The 1H and 13C NMR spectra of the product 1-naphthonitrile··············································S20 The 1H and 13C NMR spectra of the product 3,4-(methylenedioxy)benzonitrile·························S21 The 1H and 13C NMR spectra of the product 3-cyanopyridine··············································S22 The 1H and 13C NMR spectra of the product 2-thiophenecarbonitrile·····································S23
The 1H and 13C NMR spectra of the product benzaldehyde··················································S24 The 1H and 13C NMR spectra of the product 2-methylbenzaldehyde······································S25 The 1H and 13C NMR spectra of the product 3-methylbenzaldehyde······································S26 The 1H and 13C NMR spectra of the product 4-methylbenzaldehyde·····································S27 The 1H and 13C NMR spectra of the product 2-methoxybenzaldehyde···································S28 The 1H and 13C NMR spectra of the product 3-methoxybenzaldehyde···································S29 The 1H and 13C NMR spectra of the product 4-methoxybenzaldehyde··································S30 The 1H and 13C NMR spectra of the product 4-chlorobenzoic aldehyde··································S31 The 1H and 13C NMR spectra of the product 4-nitrobenzaldehyde·······································S32
The 1H and 13C NMR spectra of the product 3-pyridinecarboxaldehyde································S33 The 1H and 13C NMR spectra of the product 2-thenaldehyde··············································S34 S3
Figure S1. One-dimensional chain (extended along the b axis) formed via H-bonding
interactions in 4.
690.06
690
691
692
693
694
695
696
m/z
Figure S2. The calculated isotope pattern (top) and the observed patterns (below) of the
[{(Cu(NO3))(μ-pzpypz)}2 + NO3 + 2CH3CN]+ cation in the positive-ion ESI mass spectrum of
1.
773.07
774
776
m/z
778
Figure S3. The calculated isotope pattern (top) and the observed patterns (below) of the
[CuClO4(pzpypzH)CuOCH3(pzpypz) + 3MeOH]+ cation in the positive-ion ESI mass
spectrum of 2.
S4
756.04
756
757
758
759
760
761
m/z
Figure S4. The calculated isotope pattern (top) and the observed patterns (below) of the
[{Cu2(μ-SO4)(μ-pzpypz)2} + HSO4 + 2MeOH + 4H2O + CH3CN]+ cation in the positive-ion
ESI mass spectrum of 3.
893.06
891
892
893
894
895
896
m/z
Figure S5. The calculated isotope pattern (top) and the observed patterns (below) of the
[{(CuI)(μ-pzpypz)}2 + I + 3H2O + 4CH3CN]+ cation in the positive-ion ESI mass spectrum of
5.
S5
benzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 7.47 (t, J = 8.0Hz, 1H), 7.60 (d, J = 8.0Hz, 1H), 7.64 (d,
J = 8.0Hz, 2H). 13C NMR (100 MHz, CDCl3, ppm): δ 112.2, 118.6, 128.9, 132.0, 132.6.
2-methylbenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 2.53 (s, 3H), 7.26 (d, J = 8.0Hz, 1H), 7.31 (t, J
= 8.0Hz, 1H), 7.47 (t, J = 8.0Hz, 1H), 7.56 (d, J = 8.0Hz, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 20.2,
112.4, 117.9, 126.0, 130.0, 132.2, 132.4, 141.6.
3-methylbenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 2.37 (s, 3H), 7.34 (t, J = 8.0Hz, 1H), 7.41 (t, J
= 8.0Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 20.8, 111.8, 118.7, 128.7, 132.1, 133.4, 138.8.
4-methylbenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 2.42 (s, 3H), 7.27 (d, J = 8.0Hz, 2H), 7.52 (d,
J = 8.0Hz, 2H). 13C NMR (100 MHz, CDCl3, ppm): δ 21.7, 109.1, 119.0, 129.7, 131.9, 143.6.
2-methoxybenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 2.53 (s, 3H), 7.27 (t, J = 8.0Hz, 1H), 7.31 (t,
J = 8.0Hz, 1H), 7.48 (t, J = 8.0Hz, 1H), 7.57 (t, J = 8.0Hz, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 20.2,
112.4, 117.9, 126.0, 130.0, 132.2, 132.4, 141.6.
3-methoxybenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 3.83 (s, 3H), 7.13 (d, J = 8.0Hz, 2H), 7.23 (d,
J = 8.0Hz, 1H), 7.37 (t, J = 8.0Hz, 1H).
13
C NMR (100 MHz, CDCl3, ppm): δ 55.3, 112.9, 116.6, 118.6,
119.1, 124.2, 130.1, 159.4.
4-methoxybenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 3.86 (s, 3H), 6.95 (d, J = 8.0Hz, 2H), 7.58 (d,
J = 8.0Hz, 2H). 13C NMR (100 MHz, CDCl3, ppm): δ 55.5, 103.9, 114.7, 119.2, 133.9, 162.8.
4-chlorobenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 7.47 (d, J = 8.0Hz, 2H), 7.61 (d, J = 8.0Hz,
2H). 13C NMR (125 MHz, CDCl3, ppm): δ 110.7, 117.9, 129.6, 133.3, 139.4.
4-nitrobenzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 7.89 (d, J = 8.0Hz, 2H), 8.35 (d, J = 8.0Hz, 2H).
13
C NMR (125 MHz, CDCl3, ppm): δ 116.7, 118.2, 124.2, 133.4, 150.0.
3,4-(Methylenedioxy)benzonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 6.08 (s, 2H), 6.87 (d, J = 8.0Hz,
1H), 7.02 (s, 1H), 7.21 (d, J = 8.0Hz, 1H). 13C NMR (125 MHz, CDCl3, ppm): δ 102.1, 104.8, 109.0, 111.2,
118.8, 128.0, 147.9, 151.4.
1-naphthonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 7.47 (t, J = 8.0Hz, 1H), 7.58 (t, J = 8.0Hz, 1H),
7.64 (t, J = 8.0Hz, 1H), 7.86 (t, J = 8.0Hz, 2H), 8.02 (d, J = 8.0Hz, 1H), 8.19 (d, J = 8.0Hz, 1H). 13C NMR
(125 MHz, CDCl3, ppm): δ 110.0, 117.8, 124.8, 127.3, 128.4, 128.5, 132.1, 132.4, 132.7, 133.1.
3-cyanopyridine: 1H NMR (400 MHz, CDCl3, ppm): δ 7.49 (t, J = 8.0Hz, 1H), 8.02 (d, J = 8.0Hz, 1H),
8.86 (s, 1H), 8.92 (s, 1H). 13C NMR (75 MHz, CDCl3, ppm): δ 109.8, 116.3, 123.5, 139.1, 152.2, 152.7.
2-thiophenecarbonitrile: 1H NMR (400 MHz, CDCl3, ppm): δ 7.75 (s, 3H). 13C NMR (100 MHz, CDCl3,
S6
ppm): δ 109.2, 113.9, 127.3, 132.4, 137.1
benzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 7.50 (t, J = 8.0Hz, 2H), 7.60 (t, J = 8.0Hz, 1H), 7.86
(d, J = 8.0Hz, 2H), 9.99 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 129.1, 129.8, 134.6, 136.5, 192.5.
2-methylbenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 2.66 (s, 3H), 7.25 (d, J = 8.0Hz, 1H), 7.35 (t,
J = 8.0Hz, 1H), 7.47 (t, J = 8.0Hz, 1H), 7.79 (d, J = 8.0Hz, 1H), 10.26 (s, 1H). 13C NMR (100 MHz, CDCl3,
ppm): δ 19.9, 126.3, 131.8, 132.1, 133.7, 134.2, 140.6, 192.8.
3-methylbenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 2.41 (s, 3H), 7.39 (t, J = 8.0Hz, 2H), 7.66 (s,
2H), 9.96 (s, 1H).
13
C NMR (100 MHz, CDCl3, ppm): δ 21.2, 127.2, 128.9, 130.0, 135.3, 136.5, 138.9,
192.6.
4-methylbenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 2.44 (s, 3H), 7.33 (d, J = 8.0Hz, 2H), 7.77 (t,
J = 8.0Hz, 2H), 9.96 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 21.2, 71.8, 127.9, 129.1, 135.3, 137.3.
2-methoxybenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 3.89 (s, 3H), 6.95-7.01 (m, 2H), 7.53 (t, J
= 8.0Hz, 1H), 7.80 (d, J = 8.0Hz, 1H), 10.45 (s, 1H).
13
C NMR (125 MHz, CDCl3, ppm): δ 55.3, 111.4,
120.3, 124.5, 128.0, 135.7, 161.5, 189.4.
3-methoxybenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 3.06 (s, 3H), 7.13-7.16 (m, 1H), 7.33-7.43
(m, 3H), 9.94 (s, 1H). 13C NMR (125 MHz, CDCl3, ppm): δ 55.3, 112.0, 121.3, 123.3, 129.9, 137.7, 160.0,
191.9.
4-methoxybenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 3.73 (s, 3H), 6.86 (d, J = 12.0Hz, 2H),
7.69 (d, J = 12.0Hz, 2H), 9.73 (s, 1H).
13
C NMR (125 MHz, CDCl3, ppm): δ 55.2, 114.0, 129.6, 131.6,
164.2, 190.4.
4-chlorobenzoic aldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 7.53 (d, J = 12.0Hz, 2H), 7.83 (d, J =
12.0Hz, 2H), 9.99 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 129.5, 130.9, 134.7, 141.0, 190.9.
4-nitrobenzaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 8.09 (d, J = 8.0Hz, 2H), 8.41 (d, J = 12.0Hz,
2H), 10.17(s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 124.3, 130.5, 140.1, 151.1, 190.4.
3-pyridinecarboxaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 7.51-7.54 (m, 1H), 8.20 (d, J = 8.0Hz,
1H), 8.87 (d, J = 8.0Hz, 1H), 9.11 (d, J = 4.0Hz, 1H), 10.15 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ
124.0, 131.3, 135.7, 151.7, 154.5, 190.8.
2-thenaldehyde: 1H NMR (400 MHz, CDCl3, ppm): δ 7.21-7.24 (m, 1H), 7.77-7.80 (m, 2H), 9.96 (d, J =
4.0Hz, 1H). 13C NMR (125 MHz, CDCl3, ppm): δ 128.2, 134.9, 136.3, 143.7, 182.8.
S7
The 1H and 13C NMR spectra of 1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)ethanone
25.6
77.4
77.0
76.6
115.9
108.1
126.9
142.3
139.6
151.6
150.5
199.0
S8
1
13
The
H
and
C
NMR
1-(6-(1H-pyrazol-1-yl)pyridin-2-yl)-3-(dimethylamino)prop-2-en-1-one
spectra
of
S9
The 1H and 13C NMR spectra of 2-(1H-pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine 9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0 4.5 4.0
f1 (ppm)
S10
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
The 1H and 13C NMR spectra of the product benzonitrile
S11
7.58
7.56
7.49
7.48
7.46
7.32
7.30
7.28
7.26
7.24
2.53
0.98
1.00
1.00
0.97
3.05
The 1H and 13C NMR spectra of the product 2-methylbenzonitrile S12
S13
20.8
77.3
77.0
76.7
111.8
128.9
128.7
118.7
138.9
133.4
3.00
2.94
1.00
2.37
7.43
7.41
7.39
7.36
7.34
7.32
The 1H and 13C NMR spectra of the product 3-methylbenzonitrile 21.7
77.3
77.0
76.7
109.1
119.0
131.9
129.7
143.6
3.00
1.91
1.98
2.42
7.54
7.52
7.28
7.26
The 1H and 13C NMR spectra of the product 4-methylbenzonitrile S14
The 1H and 13C NMR spectra of the product 2-methoxybenzonitrile 101.1
111.1
116.2
120.5
134.2
133.3
160.8
S15
S16
55.3
77.3
77.0
76.7
124.2
119.1
118.6
116.6
112.9
130.1
159.4
3.83
0.97
0.93
1.87
3.00
-0.00
7.39
7.37
7.35
7.29
7.24
7.22
7.14
7.12
The 1H and 13C NMR spectra of the product 3-methoxybenzonitrile The 1H and 13C NMR spectra of the product 4-methoxybenzonitrile S17
2.00
2.01
7.62
7.60
7.48
7.46
7.29
-0.00
The 1H and 13C NMR spectra of the product 4-chlorobenzonitrile S18
-0.04
7.26
7.90
7.88
2.00
2.00
8.36
8.33
The 1H and 13C NMR spectra of the product 4-nitrobenzonitrile 77.2
77.0
76.8
118.2
116.7
124.2
133.4
149.9
S19
1.00
1.03
2.10
1.04
1.06
1.13
0.01
8.20
8.18
8.03
8.01
7.89
7.86
7.84
7.66
7.64
7.62
7.60
7.58
7.56
7.49
7.47
7.45
7.26
The 1H and 13C NMR spectra of the product 1-naphthonitrile S20
77.2
77.0
76.8
109.0
104.7
102.1
118.7
128.0
151.4
147.9
2.00
0.96
0.95
0.98
-0.00
6.08
7.29
7.22
7.20
7.02
6.88
6.86
The 1H and 13C NMR spectra of the product 3,4-(methylenedioxy)benzonitrile S21
7.51
7.49
7.48
7.33
1.02
8.03
8.01
1.00
1.00
1.00
8.92
8.86
8.85
The 1H and 13C NMR spectra of the product 3-cyanopyridine S22
160
155
150
145
140
7.26
135
130
125
120 115 110
f1 (ppm)
S23
77.3
77.0
76.7
109.2
113.9
127.3
137.1
2-氰基噻吩-碳谱
132.4
3.00
7.75
The 1H and 13C NMR spectra of the product 2-thiophenecarbonitrile
105
100
95
90
85
80
75
70
2.03
1.01
2.00
7.87
7.85
7.62
7.60
7.58
7.52
7.50
7.48
7.30
1.00
9.99
The 1H and 13C NMR spectra of the product benzaldehyde 230
210
190
170
150
130
77.8
77.5
77.2
192.5
tdw-2-c400
13C OBSERVE
136.5
134.6
129.8
129.1
110
f1 (ppm)
S24
90
80
70
60
50
40
30
20
10
0
10.26
7.80
7.78
7.49
7.47
7.45
7.37
7.35
7.33
7.26
7.24
2.66
0.92
0.98
1.02
0.95
0.97
3.00
The 1H and 13C NMR spectra of the product 2-methylbenzaldehyde 邻甲基苯甲醛-碳谱
210
190
170
150
130
110
90
f1 (ppm)
S25
80
70
60
50
40
30
20
10
0
S26
21.2
77.4
77.0
76.7
138.9
136.5
135.3
130.0
128.9
127.2
192.6
9.96
7.66
7.65
7.41
7.39
7.37
2.41
1.00
2.01
1.99
3.09
The 1H and 13C NMR spectra of the product 3-methylbenzaldehyde S27
21.2
77.4
77.0
76.7
71.8
137.3
135.3
129.1
127.9
7.34
7.32
7.25
2.44
3.00
7.78
7.76
1.98
1.99
9.96
0.97
The 1H and 13C NMR spectra of the product 4-methylbenzaldehyde 3.89
2.99
1.97
7.81
7.79
7.55
7.53
7.51
7.30
7.01
6.99
6.97
6.95
1.00
0.99
1.00
10.45
The 1H and 13C NMR spectra of the product 2-methoxybenzaldehyde S28
The 1H and 13C NMR spectra of the product 3-methoxybenzaldehyde 240
220
200
180
160
140
120
100
f1 (ppm)
S29
80
55.3
77.2
77.0
76.8
137.7
129.9
123.3
121.3
112.0
191.9
CARBON_01
160.0
60
40
20
0
7.22
6.87
6.84
3.73
1.08
0.91
3.05
7.70
7.67
1.03
0.92
1.00
9.73
The 1H and 13C NMR spectra of the product 4-methoxybenzaldehyde 240
220
200
180
160
140
120
100
f1 (ppm)
S30
80
55.2
77.2
77.0
76.8
114.0
131.6
129.6
190.4
CARBON_01
164.2
60
40
20
0
7.84
7.82
7.53
7.51
7.26
1.97
1.95
1.00
9.99
The 1H and 13C NMR spectra of the product 4-chlorobenzoic aldehyde S31
77.4
77.1
76.8
151.1
140.1
130.5
124.3
190.4
8.42
8.39
8.10
8.08
2.02
2.00
7.27
10.17
1.00
The 1H and 13C NMR spectra of the product 4-nitrobenzaldehyde
S32
The 1H and 13C NMR spectra of the product 3-pyridinecarboxaldehyde S33
The 1H and 13C NMR spectra of the product 2-thenaldehyde S34