Interaction of Acetonitrile with Trifluoromethanesulfonic ... · Interaction of Acetonitrile with Trifluoromethanesulfonic Acid: Unexpected Formation of a Wide Variety of Structures
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
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
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
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.
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
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
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.
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.
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.
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.