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Supporting Information
Method for derivatization and detection of Chemical Weapons Convention related sulfur
chlorides via electrophilic addition with 3-hexyne
D. Raghavender Goud, Deepak Pardasani, Ajay Kumar Purohit, Vijay Tak, Devendra Kumar Dubey*
Vertox Laboratory, Defence Research and Development Establishment, Jhansi road, Gwalior-474002, India.
E-mail: [email protected]
Contents
1. Figure S1: GC-MS total ion chromatograms showing peaks of reaction products by the reaction of
sulfur dichloride with a) 1-Hexene; b) Cyclohexene and c) Divinyl sulfide
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2. Figure S2: GC-MS total ion chromatograms showing peaks of reaction products by the reaction of
sulfur dichloride with a)1- Hexyne and b) 3-Hexyne
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3. Figure S3: EI-MS spectra and fragmentation pattern of sulfur dichloride derivative
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4. Figure S4: EI-MS spectra and fragmentation pattern of sulfur monochloride derivative
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5. Figure S5: Calibration curve of Relative response Vs concentration of Sulfur dichloride in the range
of 10 to 100 µg/mL
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6. Figure S6: Calibration curve of Relative response Vs concentration of Sulfur monochloride in the
range of 10 to 500 µg/mL
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7. Figure S7: 1H NMR spectra of sulfur monochloride derivative
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8. Figure S8: 1H NMR spectra of sulfur dichloride derivative
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9. Figure S9: 13C NMR spectra of sulfur dichloride derivative
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10. Figure S10: 13C NMR spectra of sulfur monochloride derivative
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11. Figure S11: GC-MS total ion chromatogram representing the identification of sulfur chlorides
(10 µg/ml) by derivatization with 3-hexyne in the presence of sulfur mustard (100 µg/ml) in acetonitrile.
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S
a)
Cl
Cl
S
Cl
Cl
Cl
S
a)
)
b)
S
S
Cl Cl
Cl
b)
Cl
c)
S
S
S
Cl
S
Cl
Cl
S
Cl
Figure SI (1): GC-MS total ion chromatograms showing peaks
of reaction products by the reaction of sulfur dichloride with
a) 1-Hexene; b) Cyclohexene and c) Divinyl sulfide
Figure SI (2): GC-MS total ion chromatograms showing peaks
of reaction products by the reaction of sulfur dichloride with
a) 1-Hexyne and b) 3-Hexyne
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Figure SI (1) shows the total ion chromatograms of reactions of sulfur dichloride with 1-hexene, cyclohexene and divinyl
sulfide. Figure SI (1a) shows total ion chromatogram of reaction of SCl 2 with 1-hexene which shows three major
diastereomeric peaks at retention times 10.61, 10.85, and 11.05 minutes corresponding to m/z value of molecular ion 270 of
addition product. Minor diastereomeric peaks at 9.98, 10.08, 10.21 and 10.32 minutes corresponding to m/z value of
molecular ion 234 are formed by the elimination of HCl from addition products. Figure SI (1b) shows the total ion
chromatogram of reaction of SCl2 with symmetric alkene like cyclohexene, which results in a broad peak at 11.93 minutes
due to the merging of diastereomeric peaks with m/z value of molecular ion 266 corresponding to the addition product.
Another broad peak was observed at 11.08 minutes with m/z value of molecular ion 230 corresponding to the products
resulted from the elimination of HCl from addition product. Similarly, dialkenes like divinyl sulfide, (figure SI (1c)) gives
two diastereomeric peaks resulting from addition reaction at 8.98 and 9.36 minutes with m/z value of molecular ion 188.
Two additional diasteromeric peaks resulted from the elimination of HCl from the addition product at 7.63, 7.98 minutes
with m/z value of molecular ion 152. From these results it was concluded that alkenes are not suitable reagents for the
derivatization of CWC related sulfur chlorides. Because these derivatives have isomers and multiple products which limits
the quantification and sensitivity.
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Figure SI (3): EI-MS spectra and fragmentation pattern of sulfur dichloride derivative
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Figure SI (4): EI-MS spectra and fragmentation pattern of sulfur monochloride derivative
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0.8
14
y = 0.007x - 0.064
R² = 0.991
Relative response
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Relative response
y = 0.022x - 0.331
R² = 0.992
12
0.4
0.2
10
8
6
4
2
0.0
0
-2
0
20
40
60
80
100
120
Concentration of SCl2
Figure SI (5): Calibration curve of
Relative response Vs
concentration of Sulfur dichloride in the range of 10 to 100 µg/mL
0
100
200
300
400
Concentration of S2Cl2
500
600
Figure SI (6): Calibration curve of Relative response Vs concentration
of Sulfur monochloride in the range of 10 to 500 µg/mL
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Figure SI (7): 1H NMR spectra of sulfur monochloride derivative
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Figure SI (8): 1H NMR spectra of sulfur dichloride derivative
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Figure SI (9): 13C NMR spectra of sulfur dichloride derivative
Figure SI (10): 13C NMR spectra of sulfur monochloride derivative
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Sulfur mustard
DPS
SCl2 Derivative
S2Cl2 Derivative
Figure SI (11): GC-MS total ion chromatogram representing the identification of sulfur chlorides (10
µg/ml) by derivatization with 3-hexyne in the presence of sulfur mustard (100 µg/ml) in acetonitrile.