interaction of acetonitrile with trifluoromethanesulfonic ... · interaction of acetonitrile with...
TRANSCRIPT
Interaction of Acetonitrile with Trifluoromethanesulfonic Acid: Unexpected Formation of a Wide Variety of Structures
George E. Salnikov, Alexander M. Genaev*, Vladimir G. Vasiliev, and Vyacheslav G. Shubin
Vorozhtsov Novosibirsk Institute of Organic Chemistry
Academician Lavrent’ev Ave., 9, Novosibirsk 630090, Russian Federation
e-mail: [email protected]
Electronic Supplementary Information
Table of content
MeCN-TfOH (1:14 m/m), products and their chemical shifts
Table 1 1H NMR spectra, Me region 1H NMR spectra, NH and CH regions 13C NMR spectrum, 192 h at r.t. 19F NMR spectrum, 192 h at r.t. 15N-1H correlations, 214 h at r.t.
MeCN-TfOH (1:2 m/m), products and their chemical shifts Table 2 1H NMR spectra, CH region 1H NMR spectra, NH region 13C NMR spectrum, 316 h at r.t. 15N-1H correlations, 316 h at r.t. CH3CN vs. CD3CN, 1H NMR spectra ESI-MS spectra
MeCN-TfOH (1:1 m/m), products and their chemical shifts
Table 4 1H and 13C NMR spectra
page S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S17 S18
MeCN-TfOH (4:1 m/m), products and their chemical shifts
Table 3 1H NMR spectra, CH region 1H NMR spectra, NH region 13C NMR spectrum, 214 h at r.t. ESI-MS spectra ESI-MS spectra (heavy ions)
MeCN-TfOH (17:1 m/m), products and their chemical shifts
Table 5 1H NMR spectra, CH region 1H NMR spectra, NH region
MeCN-TfOH (20:1 m/m), 1H NMR spectrum
13C NMR spectrum MeCN-TfOH (200:1 m/m), 1H NMR spectrum
page S19 S19 S20 S21 S22 S23 S25 S26 S26 S27 S28 S29 S30 S31
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Chemical shifts of MeCN, TfOH (molar ratio 1:14) and of the products of their interaction. 1H chemical shifts are given in italics, 13C in ordinary font, 15N in bold face. Here and further the chemical shifts of acetonitrile are in fact those of its mixture with the protonated form, the NMR signals are averaged due to a rapid exchange.
1
N
N
OH
H3C
H3C
H
HH 10.50
8.86
9.79
2.5824.8
2.61 dJ 0.7 Hz
138.0
150.8
180.9
171.0H3C C N
C NH2
H2N
H3C
2.662.0
2.3919.6
170.6
111.9 172.9
105.1
6.88
H3C4.078.9
2.8321.2 152.9
194.3
435
C
C NH2
TfO
H3C3.00 dJ 0.9 Hz
180.0154.2
10.129.76
2
O
Tf OH11.04119.3
1JCF 316.6 Hz 19F -71.019F -77.7
Tf OTf
119.11JCF 321 Hz
19F -73.36JF-F 0.85 Hz
Tf O
119.01JCF 320 Hz4JCF 1.1 Hz19F -74.85JFF 3.6 Hz
CF3
119.41JCF 274 Hz
19F -54.25JFF 3.6 Hz
O
OH
H
CH3HO
H
O
OH
H
CH3HO
CH3C
O
HN
O
O
H
CH3H3C
7 8 62.66 d0.8 Hz19.9
3.09 s29.6
2.66 d0.7 Hz21.4
3.11 s21.4
2.70 d1.0 Hz19.9
6.44 d2.1 Hz
6.87 dq2.1, 0.8 Hz
6.80 q0.7 Hz
6.89 q1.0 Hz
185.3
180.6
91.8
172.6 172.2
108.4
181.8
100.0171.4 177.9
106.0
159.0209.9
182.7 175.9
109.8
C OH
HO
H3C
21.6
21.5
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S3Table 1. Products of the interaction of MeCN with TfOH (mol. ratio 1:14). Given in italics are logarithms of diffusion coefficients (m2/s) derived from the DOSY spectra. Time (h) e MeCN 1а 2а 3а 4а 5а 6 7 8 sum Tf2O
b СF3OTf b 0.25 84.7 11.5 0.9 97.1 2.0 62.5 31.8 2.9 0.2 0.2 97.2 15 48 10 66.5 3.0 9.0 9.3 0.03 97.8 35 171 4.5 49.3 1.2 20.9 14.0 7.4 97.2 36 192
1H DOSY 3.8
-9.36 47.5 -9.56
1.0 -9.52
22.8 -9.42
13.8 -9.45
9.0 -9.45
0.4 -9.56
98.3 40.7
215 19F DOSY c
40.8 -9.24
1.5 -9.16
247 2.9 42.5 0.7 26.3 13.6 11.5 1.0 98.5 317+1/74º 1.3 23.2 0 37.7 20.0 5.3 4.4 1.5 2.3 95.6 36.6 4.5 335+3/74º 0 12.4 42.9 20 4.3 6.9 4.0 6.2 95.8 31.2 8.8 508+3/74º 10.5 42.8 20.6 3.7 7.3 4.2 7.3 96.4 1568+3/74º 1H DOSY d
5.7 -9.64
46.1 -9.53
24.3 -9.55
1.6 -9.55
7.3 -9.62
4.0 -9.60
8.6 -9.57
97.6 25.0 13.8
5572+3/74º 0.5 47.7 29.0 0 7.3 3.3 9.0 96.8 12 21.6 6287+3/74º
1H DOSY 0 47.2
-9.39 29.0 -9.43
7.0 -9.53
2.8 -9.47
9.1 -9.46
95.1 9.5 23.1
а Percentage of the acetonitrile turned into the corresponding product as determined from the 1Н NMR spectra. bMolar part (%) relative to the initial quantity of acetonitrile. cFor TfOH lg D = -9.37 (from 19F DOSY). d At –7 ºC. e In Fig. 1 of the paper an hour at 74 oC was set equal to 300 hours at room temperature
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S9Chemical shifts of MeCN, TfOH (molar ratio 1:2) and of the products of their interaction. 1H chemical shifts are given in italics, 13C in ordinary font, 15N in bold face.
N
N
N
CH2
H3C
H3C
NH
N
NH
CH3
H3C
H3C
12 11
H
H
H
H3C C N2.27
1.3
115.4 207.8
3.3223.2
177.7
221.5
12.20
11.72
129.0
5.0494.2
2.6820.7
167.6 158.2
141.4
1
N
N
OH
H3C
H3C
H
HH 10.63
8.85
9.93
2.4224.4
2.5020.7
134.0
151.2
176.8
170.3
C NH2
H2N
H3C2.3419.2
170.2105.4
7.027.07
3
NH
HN
N
H3C
H3C
157.6
2.7126.8
3.0119.7
170.9161.0
169.3
H
HO
CH3207.8
6.28
2.9522.6
96.3
170.2224.9
H
NCC
NH2
CH3
H2N
CH32.8521.5
147.7
139.6
172.4
10.95
14
9.299.83 H3C C2.69
20.6
192.6
4
OH
OH
15
Tf OH
N
N
NCH3
H3C
H3C 13
H
H
H
11.03
11.7989.9
2.0927.4
2.7219.2
164.6 163.1
141.1
OH
Tf OTf
119.519F -78.5
13.47
119.019F -72.9
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S10Table 2. Products of the interaction of MeCN with TfOH (mol. ratio 1:2).
Given in italics are logarithms of diffusion coefficients (m2/s) derived from the DOSY spectra.
Time (h) MeCN 12а 1а 13а 11а 4а 14а 3а 15а sum Tf2Ob
0.25 1H DOSYc
70.3 -9.60
12.9 -9.70
4.6 -9.66
4.6 -9.70
3.4 -9.70
0.3 0.3 96.4 2.6
2.5 30.5 33.4 12.4 8.0 7.3 1.2 1.0 93.7 23 7.6 46.5 19.2 6.4 11.0 2.4 1.9 94.9 9.7 26 6.7 47.3 19.5 6.2 11.3 2.5 2.1 0.0 95.5 72 2.8 50.9 19.8 4.0 12.0 3.3 2.4 0.8 0.0 96.0 169 1.3 53.6 18.3 12.5 3.8 2.5 1.9 1.5 95.4 316
1H DOSY 0.7
-10.02 48.1
-10.56 15.5
-10.19 11.1
-10.51 3.0 2.4
-10.52 3.2
-10.10 10.4
-10.50 94.4 7.9
1154 0.0 36.0 8.3 7.9 2.0 2.6 7.1 26.5 90.3 1394 33.8 7.2 7.7 1.9 2.9 8.0 28.5 90.0 6.2 2401 28.6 3.4 6.3 0.9 2.8 9.6 35.7 87.3
а Percentage of the acetonitrile turned into the corresponding product as determined from the 1Н NMR spectra. b Molar part (%) relative to the initial quantity of acetonitrile. c At –7ºC.
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ESI-MS spectra
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S16 MeCN-TfOH (1:2 m/m, 4000 h, 5 mg) in MeCN (1 ml) FIA , MeCN, 0.1ml/min, 4 µL , tune_low.m , ES 80-3000
84.040
124.083148.085
166.095
208.107
+MS, 0.5-0.5min #(28-31)
84.044
(CH3CN)COCH2, M+nH ,84.04
124.087
(CH3CN)3, M+nH ,124.09
166.097
(CH3CN)3COCH2, M+nH ,166.10
208.108
(CH3CN)3(COCH2)2, M+nH ,208.11
0.0
0.2
0.4
0.6
0.8
6x10Intens.
0.0
0.5
1.0
1.5
4x10
0
500
1000
1500
0.0
0.5
1.0
1.5
4x10
0.0
0.5
1.0
1.5
4x10
100 125 150 175 200 225 250 275 300 m/z
1 11+12
15
16
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S17 Chemical shifts of MeCN, TfOH (molar ratio 1:1) and of the products of their interaction. 1H chemical shifts are given in italics, 13C in ordinary font, 15N in bold face.
N
N
N
CH2
H3C
H3C
NH
N
NH
CH3
H3C
H3C
1211
H
H
H
H3C C N2.171.1
116.8 218.43.2322.9
177.2
222.6
12.69
12.21 129.54.9592.8
2.6118.7
167.2 158.8
142.5
N
N
N
CH3
H3C
H3C N
NH
N
H2C
CH3
CH3
17
H
H
H 2.1427.4
2.6719.2 2.95
22.4
4.0448.6
166.4
71.6173.4
171.5
11.31
12.23
139.7
152.6270.7
192.2
Tf OH119.6
19F -78.8
14.53
Table 4. Products of the interaction of MeCN with TfOH (mol. ratio 1:1).а Given in italics are logarithms of diffusion coefficients (m2/s) derived from the DOSY spectra.
Time (h) MeCN 12 11 17 Sum 0.25 92.5 4.5 1.2 0.0 98.2 0.4 88.1 7.6 2.0 0.0 97.7 5.4 52.5 33.9 8.4 0.2 95.0 24 30.1 46.6 11.8 4.8 93.3 96
1H DOSY 18.5
-10.38 42.5
-11.30 11.2
-11.19 18.7
-11.48 90.9
а Percentage of the acetonitrile turned into the corresponding product as determined from the 1Н NMR spectra.
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S19Chemical shifts of MeCN, TfOH (molar ratio 4:1) and of the products of their interaction. 1H chemical shifts are given in italics, 13C in ordinary font, 15N in bold face.
N
N
N
CH2
H3C
H3C
NH
N
N
CH3
H3C
H3C12 11
H3C C N1.930.7
117.3
239.7
2.9222.6
175.9
233.5129.5
4.7790.4
2.4617.9
166.3 159.4
144.1
H
H
12.83
H12.31
N
N
N
CH3
H3C
H3C N
NH
N
H2C
CH3
CH3
17
H
H
H 2.0026.8
2.5218.3
2.8221.8
3.8847.8
165.4
71.6172.3
177.5
11.39
12.21
140.4
152.6269.3
195.5
Tf OH119.4
19F -79.1
14.83
N
N
N
CH3
H3C
H3C N
NH+
N
H2C
CH3
18
H
H
H2.8421.8
172.5
177.3
270.2
N
N
N
CH3
CH3
H3C
H2C
H
H
H
2.0726.5
2.5418.4
4.0245.7
165.8
70.8
11.49
12.34
140.4
152.6
195.5
4.0148.4
174.0
71.2
2.0526.4
2.5418.4
165.8
11.49
12.34
152.6
140.4
270.2
Table 3. Products of the interaction of MeCN with TfOH (mol. ratio 4:1).а Given in italics are logarithms of diffusion coefficients (m2/s) derived from the DOSY spectra.
Time (h) MeCN 13 12 11 17 18 Sum MeCN 0.25 96.4 0.6 1.4 0.3 0 98.7 22 87.2 0 5.4 1.6 4.2 0 98.3 167 74.8 1.1 0.5 15.4 6.9 98.7 214
1H DOSY 72.7 -8.92
0.9 -9.73
0.4 15.3 -9.85
8.5 -9.98
97.7
672 64.5 0.3 12.1 18.4 95.3
а Percentage of the acetonitrile turned into the corresponding product as determined from the 1Н NMR spectra.
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17 18 18
ESI-MS spectra MeCN-TfOH (4:1 m/m, 5000 h, 5mg) in MeCN (1 mL) FIA, MeCN 0.1 ml/min, 2 µL , ES 100-3000
247.166
308.705
370.245 520.207643.287
793.248 916.325
+MS, 0.5-0.6min #(29-34)
247.167
(CH3CN)6, M+nH ,247.17
370.246
(CH3CN)9, M+nH ,370.25
520.206
(CH3CN)9OSO2HCF3, M+nH ,520.21
643.286
(CH3CN)12OSO2HCF3, M+nH ,643.29
793.246
(CH3CN)12(OSO2HCF3)2, M+nH ,793.25
916.325
(CH3CN)15(OSO2HCF3)2, M+nH ,916.33
0
2
4
5x10Intens.
0.0
0.5
1.0
1.54x10
0.0
0.5
1.0
1.54x10
0.0
0.5
1.0
1.54x10
0.0
0.5
1.0
1.54x10
0.0
0.5
1.0
1.54x10
0.0
0.5
1.0
1.54x10
200 300 400 500 600 700 800 900 1000 m/z
(MeCN)15H+H+
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1189.359
1339.316
1462.393
1735.423
+MS, 0.5-0.6min #(29-34)
1189.365
(CH3CN)18(OSO2HCF3)3, M+nH ,1189.37
1339.325
(CH3CN)18(OSO2HCF3)4, M+nH ,1339.33
1462.404
(CH3CN)21(OSO2HCF3)4, M+nH ,1462.40
1735.444
(CH3CN)24(OSO2HCF3)5, M+nH ,1735.44
0.0
0.5
1.0
4x10Intens.
0
500
1000
1500
0
500
1000
1500
0
500
1000
1500
0
500
1000
1500
1200 1400 1600 1800 2000 2200 m/z
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S25 MeCN-TfOH (4:1 m/m, 5000 h, 5mg) in MeCN (1 mL) FIA, MeCN, 0.1 ml/min, 4 µL,, tune_high.m , ES 200-10000 Heavy ions detection
2008.46
2131.53 2282.492405.55 2555.52 2679.57 2828.54
+MS, 0.4-0.7min #(26-40)
2008.48
(CH3CN)27(SO3HCF3)6, M+nH ,2008.48
2555.56
(CH3CN)33(SO3HCF3)8, M+nH ,2554.56
2678.64
(CH3CN)36(SO3HCF3)8, M+nH ,2677.64
0
1000
2000
3000
Intens.
0
500
1000
1500
0
500
1000
1500
0
500
1000
1500
2000 2200 2400 2600 2800 3000 3200 m/z
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S261H chemical shifts of MeCN, TfOH (molar ratio 17:1, 34 h at r.t.) and of the products of their interaction.
N
N
N
CH2
H3C
H3C
NH
N
N
CH3
H3C
H3C12 11
H3C C N1.89 2.43 H
H
H
N
N
N
CH3
H3C
H3C N
NH
N
H2C
CH3
CH3
17
H
H
H11.36
12.11
Tf OH19F -79.014.26
4.75
2.78
2.49
2.81
3.86
1.96
N
N
N
CH3
H3C
H3C 13
2.51d J 0.7 Hz
H
H
H
1.99
11.40
12.06 OH
NH2
HO
H3C2.30
8.758.55
Table 5. Products of the interaction of MeCN with TfOH (mol. ratio 17:1, 1 M TfOH).а
Time (h) MeCN 13 12 11 17 18 acetamide H+ Sum MeCN 3 99.2 0.42 0.22 0.02 0 0.02 99.8 34 95.9 0.32 0.33 0.35 2.43 0.10 0.13 99.5 74 94.8 0.19 0.15 0.19 3.43 0.32 0.16 99.2
а Percentage of the acetonitrile turned into the corresponding product as determined from the 1Н NMR spectra.
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