Supplementary Information Behaviour of iprit carbonate analogues in solventless reactions
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Supplementary Information Behaviour of iprit carbonate analogues in solventless reactions Fabio Aricò, Serena Evaristo, Pietro Tundo Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2014
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SUPPORTING INFORMATION 1 H NMR, 13 C NMR, GC-MS spectra and HRMS analysis of Bis-(2-ethylcarbonate)ethyl sulfide S2 GC-MS spectrum of the reaction of several nucleophiles with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 12-23 (entry 1-7, Table 2) S5
1 H NMR spectrum of methyl 2-(4-bromophenoxy)ethyl sulfide 12
S15
1 H NMR,
13 C NMR, GC-MS spectra and HRMS analysis of 4-[2-(methylthio)ethoxy]benzonitrile 13 S16 1
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1 H NMR,
13 C NMR, GC-MS spectra and HRMS analysis of 1,4-bis-[2-(methylthio)ethoxy]benzene 15 S20 1 H NMR,
13 C NMR, GC-MS spectra of 1,4-bis-[2-(methylthio)ethoxy]benzene 16
1 H NMR,
13 C NMR, GC-MS spectra and HRMS analysis of 2,2’-[2-(methylthio)ethoxy]biphenyl 18 S25 1
13 C NMR, GC-MS spectra of 2-[2-(methylthio)ethoxy]-2'-methoxybiphenyl 19
S28
GC-MS spectrum of the reaction of p-cyanophenol with several mustard carbonates 2-5 – Product identification 12-23 (entry 1-4, Table 3)
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1 H NMR,
13 C NMR, GC-MS spectra and HRMS analysis of 4-[2-(phenylthio)ethoxy]benzonitrile 24 S34 1
13 C NMR, GC-MS spectra and HRMS analysis of 4-[3-(methylthio)propoxy]benzonitrile 25 S37 1 H NMR,
13 C NMR, GC-MS spectra and HRMS analysis of 4-[4-(methylthio)butoxy]benzonitrile 26 S40 1
13 C NMR spectra and HRMS analysis of Bis[2-(4-cyanophenoxy)ethyl]sulfide 27
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1 H NMR spectrum of Bis-(2-ethylcarbonate)ethyl sulfide 7 O O O S O O O
13 C NMR spectrum of Bis-(2-ethylcarbonate)ethyl sulfide 7
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GC-MS spectrum of Bis-(2-ethylcarbonate)ethyl sulfide 7
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HRMS analysis of Bis-(2-ethylcarbonate)ethyl sulfide 7
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GC-MS spectrum of the reaction of 4-bromophenol with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 12 (entry 1, Table 2)
OCH 3 Br Chemical Formula: C 7 H 7 BrO Exact Mass: 185,97 Molecular Weight: 187,03 OCH
3 Br OCH 2 CH 2 SCH 3 Br 1 (residual) S7
GC-MS spectrum of the reaction of p-cyanophenol with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 13 (entry 2, Table 2)
OCH 3 CN 1-bromo-4-methoxybenzene Chemical Formula: C 8 H
NO Exact Mass: 133,05 Molecular Weight: 133,15 OCH
3 CN OCH 2 CH 2 SCH 3 CN 1 (residual) S8
GC-MS spectrum of the reaction of p-cyanophenol with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 13 (entry 3, Table 2)
OCH 2 CH 2 SCH 3 CN OCH 3 CN 1 (residual) 1 decomposition OCH
3 CN 1-bromo-4-methoxybenzene Chemical Formula: C 8 H 7 NO Exact Mass: 133,05 Molecular Weight: 133,15 S9
GC-MS spectrum of the reaction of β-naphtol with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 14 (entry 4, Table 2)
OCH 3 Chemical Formula: C 11 H
O Exact Mass: 158,07 Molecular Weight: 158,20 OCH
2 CH 2 SCH 3 OCH 3 unidentified products unidentified products
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GC-MS spectrum of the reaction of hydroquinone with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 15, 16, 17 (entry 5, Table 2)
OCH 2 CH 2 SCH 3 OCH 2 CH 2 SCH 3
Unidentified product
OCH 2 CH 2 SCH
3 OCH
3 16 Residual
Reagents OCH
3 OCH
3 17 OCH
3 OCH
3 17 Chemical Formula: C 8 H
O 2 Exact Mass: 138,07 Molecular Weight: 138,16 S11
GC-MS spectrum of the reaction of biphenyl-2,2'-diol with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 18, 19, 20 (entry 6, Table 2)
O O S S 18 O O S 19 O O 20 O O 20 Chemical Formula: C 14 H
O 2 Exact Mass: 214,10 Molecular Weight: 214,26 S12
GC-MS spectrum of the reaction of phenylsulfonyl)acetonitrile with 2-(methylthio)ethyl methyl carbonate 1 – Product identification 21, 22, 23 (entry 7, Table 2)
S CN O O CH 3 CH 3 23 Chemical Formula: C 10 H
NO 2 S Exact Mass: 209,05 Molecular Weight: 209,26 S CN
O CH 3 CH 3
S CN
O CH 2 CH 2 SCH 3 CH 3 22 S CN O O CH 2 CH 2 SCH 3 CH 2 CH 2 SCH 3
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GC-MS spectrum of the reaction of phenylsulfonyl)acetonitrile with 2-(methylthio)ethyl methyl carbonate 1
S CN O O CH 2 CH 2 SCH 3 CH 2 CH 2 SCH 3
Chemical Formula: C 14 H 19 NO 2 S 3 Exact Mass: 329,06 Molecular Weight: 329,50 S CN O O CH 2 CH 2 SCH 3 CH 3 22 Chemical Formula: C 12 H
NO 2 S 2 Exact Mass: 269,05 Molecular Weight: 269,38
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1 H NMR spectrum of methyl 2-(4-bromophenoxy)ethyl sulfide 12 2.0
2.2 2.4
2.6 2.8
3.0 3.2
3.4 3.6
3.8 4.0
4.2 4.4
4.6 4.8
5.0 5.2
5.4 5.6
5.8 6.0
6.2 6.4
6.6 6.8
7.0 7.2
7.4 f1 (ppm)
-20 0 20 40 60 80 100 120
140 160
180 200
220 240
260 280
300 320
340 Br O S CH 3
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1 H NMR spectrum of 4-[2-(methylthio)ethoxy]benzonitrile 13 1.8 2.0
2.2 2.4
2.6 2.8
3.0 3.2
3.4 3.6
3.8 4.0
4.2 4.4
4.6 4.8
5.0 5.2
5.4 5.6
5.8 6.0
6.2 6.4
6.6 6.8
7.0 7.2
7.4 7.6
7.8 8.0
f1 (ppm) 0 50 100 150
200 250
300 350
400 450
O S CH 3 N
13 C NMR spectrum of 4-[2-(methylthio)ethoxy]benzonitrile 13 1 6
8 3 2 .8 5 6 7 .7 6 1 0 4 .3 1 1 1 5 .2 4 1 1 9 .1 0 1 3 4 .0 4 1 6 1 .7 8
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GC-MS spectrum of 4-[2-(methylthio)ethoxy]benzonitrile 13
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HRMS analysis of 4-[2-(methylthio)ethoxy]benzonitrile 13
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1 H NMR spectrum of methyl 2-(naphthalen-2-yloxy)ethyl sulfide 14 O S
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1 H NMR spectrum of 1,4-bis-[2-(methylthio)ethoxy]benzene 15 2.0 2.2
2.4 2.6
2.8 3.0
3.2 3.4
3.6 3.8
4.0 4.2
4.4 4.6
4.8 5.0
5.2 5.4
5.6 5.8
6.0 6.2
6.4 6.6
6.8 7.0
7.2 7.4
f1 (ppm) -20
0 20 40 60 80 100 120 140
160 180
200 220
240 260
280 300
O S CH 3 O S C H 3 13 C NMR spectrum of 1,4-bis-[2-(methylthio)ethoxy]benzene 15 1 6 .5 7 3 3 .4 7 6 8 .4 2 1 1 5 .9 7 1 5 3 .2 2
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GC-MS spectrum of 1,4-bis-[2-(methylthio)ethoxy]benzene 15
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HRMS analysis of 1,4-bis-[2-(methylthio)ethoxy]benzene 15
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1 H NMR spectrum of 4-[2-(methylthio)ethoxy]anisole 16
13C NMR spectrum of 4-[2-(methylthio)ethoxy]anisole 16
OCH
2 CH 2 SCH 3 OCH 3 16 S24
GC-MS spectrum of 4-[2-(methylthio)ethoxy]anisole 16
OCH
2 CH 2 SCH 3 OCH 3 16 Chemical Formula: C 10 H
O 2 S Exact Mass: 198,07 Molecular Weight: 198,28 S25
1 H NMR spectrum of 2,2’-[2-(methylthio)ethoxy]biphenyl 18
13 C NMR spectrum of 2,2’-[2-(methylthio)ethoxy]biphenyl 18 1 6 .3 5 3 3 .3 4 6 9 .0 3 1 1 2 .6 6 1 2 0 .9 8 1 2 8 .7 2 1 3 1 .8 1 1 5 6 .3 7
GC-MS spectrum of 2,2’-[2-(methylthio)ethoxy]biphenyl 18 O O S S S26
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HRMS analysis of 2,2’-[2-(methylthio)ethoxy]biphenyl 18
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1 H NMR spectrum of 2-[2-(methylthio)ethoxy]-2'-methoxybiphenyl 19
13 C NMR spectrum of 2-[2-(methylthio)ethoxy]-2'-methoxybiphenyl 19
O O S S29
GC-MS spectrum of 2-[2-(methylthio)ethoxy]-2'-methoxybiphenyl 19
O O S
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GC-MS spectrum of the reaction of p-cyanophenol with 2-(phenylthio)ethyl carbonate 2 – Product identification 24 (entry 1, Table 3)
OCH 3 CN Chemical Formula: C 8 H 7 NO Exact Mass: 133,05 Molecular Weight: 133,15 OCH
3 CN carbonate 2 2 decomposition 24 O S NC S31
GC-MS spectrum of the reaction of p-cyanophenol with ethyl 2-(phenylthio)ethyl carbonate 3 – Product identification 24 (entry 2, Table 3)
O S
carbonate 3 3 decomposition 24 O S NC Chemical Formula: C 15 H
NOS Exact Mass: 255,07 Molecular Weight: 255,33
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GC-MS spectrum of the reaction of p-cyanophenol with ethyl 3-(Methylthio)propyl methyl carbonate 4 – Product identification 25 (entry 3, Table 3)
carbonate 4 OCH 3 CN Chemical Formula: C 8 H 7 NO Exact Mass: 133,05 Molecular Weight: 133,15 OCH
3 CN O S NC
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GC-MS spectrum of the reaction of p-cyanophenol with ethyl 4-(methylthio)butyl methyl carbonate 5 – Product identification 26 (entry 4, Table 3)
OCH 3 CN Chemical Formula: C 8 H 7 NO Exact Mass: 133,05 Molecular Weight: 133,15 carbonate 5 OCH 3
26 O NC S S34
1 H NMR spectrum of 4-[2-(phenylthio)ethoxy]benzonitrile 24 3.0 3.2
3.4 3.6
3.8 4.0
4.2 4.4
4.6 4.8
5.0 5.2
5.4 5.6
5.8 6.0
6.2 6.4
6.6 6.8
7.0 7.2
7.4 7.6
7.8 f1 (ppm)
-20 0 20 40 60 80 100 120
140 160
180 200
220 240
260 280
300 O S N
13 C NMR spectrum of 4-[2-(phenylthio)ethoxy]benzonitrile 24 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105
110 115
120 125
130 135
140 145
150 155
160 165
f1 (ppm) 0 200 400 600
800 1000
1200 1400
1600 1800
2000 2200
2400 2600
2800 3000
O S N
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GC-MS spectrum of 4-[2-(phenylthio)ethoxy]benzonitrile 24
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HRMS analysis of 4-[2-(phenylthio)ethoxy]benzonitrile 24
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1 H NMR spectrum of 4-[3-(methylthio)propoxy]benzonitrile 25 2.0 2.2
2.4 2.6
2.8 3.0
3.2 3.4
3.6 3.8
4.0 4.2
4.4 4.6
4.8 5.0
5.2 5.4
5.6 5.8
6.0 6.2
6.4 6.6
6.8 7.0
7.2 7.4
7.6 f1 (ppm)
-20 0 20 40 60 80 100 120
140 160
180 200
220 240
260 280
300 320
340 O S CH 3 N 13 C NMR spectrum of 4-[3-(methylthio)propoxy]benzonitrile 25 10 20 30 40 50 60 70 80 90 100 110
120 130
140 150
160 f1 (ppm)
0 200
400 600
800 1000
1200 1400
1600 1800
2000 2200
2400 2600
2800 3000
3200 3400
C H 3 S O N
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GC-MS spectrum of 4-[3-(methylthio)propoxy]benzonitrile 25
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HRMS analysis of 4-[3-(methylthio)propoxy]benzonitrile 25
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1 H NMR spectrum of 4-[4-(methylthio)butoxy]benzonitrile 26
S O
13 C NMR spectrum of 4-[4-(methylthio)butoxy]benzonitrile 26 20 30 40 50 60 70 80 90 100 110
120 130
140 150
160 f1 (ppm)
0 200
400 600
800 1000
1200 1400
1600 1800
2000 2200
2400 2600
2800 3000
3200 3400
3600 3800
4000 C H 3 S O N
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GC-MS spectrum of 4-[4-(methylthio)butoxy]benzonitrile 26
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HRMS analysis of 4-[4-(methylthio)butoxy]benzonitrile 26
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1 H NMR spectrum of Bis[2-(4-cyanophenoxy)ethyl]sulfide 27 3.0 3.2
3.4 3.6
3.8 4.0
4.2 4.4
4.6 4.8
5.0 5.2
5.4 5.6
5.8 6.0
6.2 6.4
6.6 6.8
7.0 7.2
7.4 7.6
7.8 f1 (ppm)
-10 0 10 20 30 40 50 60 70 80 90 100 110 120
130 140
150 160
170 180
190 200
210 O S O N N 13 C NMR spectrum of Bis[2-(4-cyanophenoxy)ethyl]sulfide 27 30 40 50 60 70 80 90 100
110 120
130 140
150 160
170 f1 (ppm)
0 100
200 300
400 500
600 700
800 900
1000 1100
1200 1300
1400 1500
1600 1700
1800 1900
2000 2100
2200 2300
2400 O S O N N
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HRMS analysis of Bis[2-(4-cyanophenoxy)ethyl]sulfide 27
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