Interaction of Acetonitrile with Trifluoromethanesulfonic ... · Interaction of Acetonitrile with Trifluoromethanesulfonic Acid: Unexpected Formation of a Wide Variety of Structures

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


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


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)


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

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

S2

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


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


S4


S5


S6


S7


S8


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


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.


S11


S12


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S14


S15

ESI-MS spectra


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


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.


S18


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



S20


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S23

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+


S24

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


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


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



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Interaction of Acetonitrile with Trifluoromethanesulfonic ... · Interaction of Acetonitrile with Trifluoromethanesulfonic Acid: Unexpected Formation of a Wide Variety of Structures