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Fundamental chemistry of iodine; The reaction of di-iodine towards thiourea and its derivatives; formation of aminothiazoles and aminothiadiazoles through ...
Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2014

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

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7.4

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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

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8.0

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2 (Reaction c2)

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9.0

4 (Reaction e1)

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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

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8 (Reaction i)

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8 (Reaction k)

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9 (Reaction mh)

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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

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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)).