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Electronic Supplementary Information
Fundamental chemistry of iodine; The reaction of di-iodine towards thiourea and its derivatives; formation of aminothiazoles and aminothiadiazoles through dicationic disulfides.
M. Biesiada [a,b], N. Kourkoumelis[c], M. Kubicki*[b], A. Owczarzak[b], V. Balas[a], S.K. Hadjikakou**[a]
[a]
Section of Inorganic and Analytical Chemistry, Department of Chemistry, University of
Ioannina, 45110 Ioannina, Greece; [b] Department of Chemistry, A. Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznań, Poland; [c] Medical Physics Laboratory, Medical School, University of Ioannina, Greece.
All correspondence should be addressed to: * Dr M Kubicki: e-mail:
[email protected]; tel +48-618291256 ** Professor Dr. S.K. Hadjikakou; e-mail:
[email protected]; tel. xx30-26510-08374; fax xx3026510-08786
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Free TU
9.0
8.8
8.6
8.4
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
5.2
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
5.2
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
5.2
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
6.0
5.8
5.6
5.4
5.2
1 prepared by reaction a
9.0
8.8
8.6
8.4
1 prepared by reaction b
9.0
8.8
8.6
8.4
1 prepared by reaction c1
9.0
8.8
8.6
8.4
Figure S1. 1H-NMR spectra of TU and 1 prepared by reactions a, b and c1 (Scheme 1) in DMSO-d 6
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Free TU 9.2
9.0
8.8
8.6
8.4
8.2
8.0
7.8
7.6
7.4
7.2
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6.8
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6.2
8.8
8.6
8.4
8.2
8.0
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7.6
7.4
7.2
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6.6
6.4
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8.4
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8.4
8.2
8.0
7.8
7.6
7.4
7.2
7.0
6.8
6.6
6.4
6.2
2 (Reaction c2)
9.2
9.0
4 (Reaction e1)
9.2
9.0
4 (Reaction f)
9.2
9.0
5 (Reaction e2)
9.2
9.0
Figure S2. 1H-NMR spectra of TU and 2, 4, 5 (Scheme 1) in DMSO-d 6
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Free MeTU
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
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1.5
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2.5
2.0
1.5
8 (Reaction i)
10.0
9.5
9.0
8 (Reaction k)
10.0
9.5
9.0
9 (Reaction mh)
10.0
9.5
9.0
Figure S3. 1H-NMR spectra of MeTU and 8, 9 in DMSO-d 6
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S4. Mid IR spectra of 1 (reactions a, b, c1)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S5. Mid IR spectra of 2 (reaction c2)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S6. Mid IR spectra of 3 (reaction d)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S7. Mid IR spectra of4 (reactions e1, f)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S8. Mid IR spectra of 5 (reaction e2)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S9. Mid IR spectra of 6 (reaction g)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S9. Mid IR spectra of 8 (reaction i, h)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S10. Mid IR spectra of 7 (reaction h)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Figure S11 Mid IR spectra of 9 (reaction m)
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
NL: 3.73E6 E11B_3_10_13_1310 03103354#1 RT: 0.01 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
151.01
100 90 Relative Abundance
80
170.97
70 60 50 40
117.02
30
107.03
139.00
20 10 0 100
159.06
131.00
77.81 102.13
182.98
202.91 214.09
151.01
234.88
90
NL: 8.68E5 C 2 H 7 N 4 S 2: C 2 H7 N4 S 2 pa Chrg 1
80 70 60 50 40 30 20
153.01
10 0
155.00 100
80
140
120
160 m/z
200
180
220
Figure S12. High Resolution Mass Spectrum (HRMS) of [(NH 2 ) 2 C-S-S-C(NH 2 )(=NH)]+ fragment in 1 (experimental (upper), simulated (bellow)). NL: 7.79E6 E11_r_3_10_13_130 726153314#1 RT: 0.02 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
120 170.97
Relative Abundance
100 80 139.00
60 40
107.03 129.05
20 66.76 79.01
102.13
117.02 131.19
146.97
163.03
179.00
202.94
120 170.03
100
NL: 8.66E5 C 2 H 8 N 4 S 2 H 2 O: C 2 H 10 N 4 S 2 O 1 pa Chrg 1
80 60 40 20
172.02 80
100
120
140 m/z
160
180
200
Figure S13. High Resolution Mass Spectrum (HRMS) of {[(NH 2 ) 2 C-S-S-C(NH 2 ) 2 ] H 2 O}+ fragment in 2 (experimental (upper), simulated (bellow)).
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
NL: 2.80E7
115.03
100
E34_3_10_13_13100 3103354[1]#1 RT: 0.00 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
Relative Abundance
80 60 40 20 0 100
131.00 157.08 73.72 115.98
240.93 245.07 213.10 282.98
353.26 381.29 427.30 NL: 8.69E5 CH 5 N 2 S +K: C 1H 5 N 2 S1K1 pa Chrg 1
80 60 40 20 122.98
0 100
150
200
250 m/z
300
450
400
350
Figure S14. High Resolution Mass Spectrum (HRMS) of {[(NH 2 ) 2 C=SH]}+ fragment in 3 (experimental (upper), simulated (bellow)).
NL: 5.59E6 E332_3_10_13_1310 03103354#1 RT: 0.02 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
170.97
100 90 Relative Abundance
80 70 60 50 40
139.00
30
151.01
20
169.09
10
131.00
0 100
148.99
159.06
172.97 182.98 170.03
202.94 NL: 8.66E5 c 2 h 10 n 4 s 2 O: C 2 H 10 N 4 S 2 O 1 pa Chrg 1
90 80 70 60 50 40 30 20
172.02
10 0
174.02 120
130
140
150
160 170 m/z
180
190
200
Figure S15. High Resolution Mass Spectrum (HRMS) of {[(NH 2 ) 2 C-S-S-C(NH 2 ) 2 ] H 2 O}+ fragment in 4 (experimental (upper), simulated (bellow)).
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Relative Abundance
NL: 1.89E6 E10_rac_3_10_13_13 1003103354[1]#1 RT: 0.00 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
120 151.01
100 80 60
139.00
117.02
107.03
145.05
40
153.01
113.59
20
108.99
0
159.06
129.05 138.36
119.02
NL: 8.68E5 C 2 H 7 N 4 S 2: C 2 H 7 N 4 S2 pa Chrg 1
120 151.01
100 80 60 40 20
153.01
0 110
130
120
150
140
157.00 160
m/z
Figure S16. High Resolution Mass Spectrum (HRMS) of [(NH 2 ) 2 C-S-S-C(NH 2 )(=NH)]+ fragment in 5 (experimental (upper), simulated (bellow)). NL: 6.72E7 E17_r_3_10_13_131 003103354#1 RT: 0.02 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
129.05
100 90 Relative Abundance
80 70 60 50 40
127.03
30 20 10
100.01 114.02
0 100
131.04 129.05
151.03
171.09
195.09 209.11
227.12
90 80
NL: 8.92E5 C 5 H 9 N 2 S: C 5 H9 N2 S 1 pa Chrg 1
70 60 50 40 30 20 10 0
133.04 80
100
120
140
160 m/z
180
200
220
Figure S17. High Resolution Mass Spectrum (HRMS) of [C 5 H 9 N 2 S]+ fragment in 8 (experimental (upper), simulated (bellow)).
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014
Relative Abundance
NL: 8.85E7 E13_r_3_10_13_131 003103354#1 RT: 0.01 AV: 1 T: FTMS + p ESI Full ms [50.00-2000.00]
145.05
100 80 60 40
104.01 182.16
20
147.05 129.05 145.05
0 100
185.11 236.07
287.08
353.26 381.29 427.26 NL: 8.95E5 C 4 H 9 N 4 S: C 4 H 9 N 4 S1 pa Chrg 1
80 60 40 20 147.05 0 100
150
200
250 m/z
300
350
400
Figure S18. High Resolution Mass Spectrum (HRMS) of [C 4 H 9 N 4 S]+ fragment in 9 (experimental (upper), simulated (bellow)).
