© The Royal Society of Chemistry 2000
Supplementary Data
Reaction of VX and GD with Gaseous Ozone
George W. Wagner,*,a Philip W. Bartram,a Mark D. Brickhouse,b Theresa R. Connell,c William
R. Creasy,c Vikki D. Henderson,a Joseph W. Hovanec,a Kevin M. Morrissey,c John R. Stuffc and
Barry R. Williamsc
a
Research and Technology Directorate, U.S. Army Edgewood Chemical and Biological Center,
Aberdeen Proving Ground, MD 21010-5423
b
Geo-Centers, Inc., Gunpowder Branch Box 68, Aberdeen Proving Ground, MD 21010-0068;
Current address: Hercules, Inc., Wilmington, DE 19894-0001
c
EAI Corporation, 1308 Continental Dr., Abingdon, MD 21009
Figure S-1 31P NMR spectra for: (top) VX-NO in CH3CN; (middle) VX-NO/CH3CN added to
acetonitrile extract of the 2.0 h reaction of neat VX with dry ozone; (bottom) acetonitrile extract
of the 2.0 h reaction of neat VX with dry ozone (immediately before the addition of VX-NO/
CH3CN). Besides VX-NO, the top spectrum contains residual VX (left peak). In the middle
spectrum, the appearance of the VX-NO peak is accompanied by an appropriate increase in the
VX peak (left-most peak). Considerable peak shifting occurs owing to matrix/solvent effects,
but the relative positions remain unchanged. The VX-NO peak is not coincident with any
detectable peak.
2
Figure S-2 31P NMR spectra for: (top) authentic compound 2 in CH3CN; (middle) 2 (neat)
added to aged acetonitrile extract of the 2.0 h reaction of neat VX with humidified ozone;
(bottom) aged acetonitrile extract of the 2.0 h reaction of neat VX with humidified ozone
immediately before the addition 2. Shifting of the peak for 2 occurs on addition to the extract
owing to matrix/solvent effects, but product peaks in the extract remain unshifted. The peak for
2 is coincident with a small, but detectable peak in the bottom spectrum. The coincident peak
was much larger in the fresh sample, but diminished over time.
3
Figure S-3 Liquid Chromatogram with extracted ion chromatograms of initial part of a gradient
run of the VX/ozone reaction mass, showing a peak for 125 (EMPA, 7) and 102
(diisopropylamine)
Ion 125.00 (124.50 to 125.70): W1125B1.D
Ion 102.00 (101.50 to 102.70): W1125B1.D
Abundance
3500
3000
125
2500
102
2000
1500
1000
500
0
Time-->
2.00
4.00
6.00
8.00
10.00
12.00
14.00
Figure S-4 Liquid chromatogram with extracted ion chromatograms of the final part of a
gradient run of the VX/ozone reaction mass, showing the M+H+ which are labelled
Ion 226.00 (225.50 to 226.70): W1125B1.D
Ion 240.00 (239.50 to 240.70): W1125B1.D
Ion 254.00 (253.50 to 254.70): W1125B1.D
Ion 268.00 (267.50 to 268.70): W1125B1.D
Ion 130.00 (129.50 to 130.70): W1125B1.D
Ion 282.00 (281.50 to 282.70): W1125B1.D
Abundance
6500
6000
5500
5000
4500
4000
226
3500
3000
268
2500
282
2000
130
1500
240
1000
254
500
Time-->
0
16.00
17.00
18.00
19.00
20.00
4
21.00
22.00
23.00
Figure S-5 Liquid chromatogram with extracted ion chromatograms of the isocratic run using
method B of the VX/ozone reaction mass, showing the M+H+ peaks which are labelled
Ion 226.00 (225.50 to 226.70): W1202A2.D
Ion 240.00 (239.50 to 240.70): W1202A2.D
Ion 254.00 (253.50 to 254.70): W1202A2.D
Ion 268.00 (267.50 to 268.70): W1202A2.D
Ion 130.00 (129.50 to 130.70): W1202A2.D
Abundance
5500
5000
4500
4000
3500
226
3000
130
2500
268
254
2000
268
1500
1000
500
Time-->
0
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
Figure S-6 Liquid chromatogram UV absorption trace for 210 nm of the same isocratic run as in
Figure S-5
LC Chromatogram: W1202A2.D
Abundance
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
200000
0
Time-->
2.00
4.00
6.00
8.00
10.00
5
12.00
14.00
16.00
18.00
Figure S-7 GC-IRD/MS chromatogram obtained for the derivatized VX/ozone extract showing
peaks for compounds 6, 7 (off scale), 1, VX, 4, 2, and 3.
T IC : 7 4 8 3 A .D
A b und a nce
7
4 .0 4 4 .5 0
450000
5 .5 7
9 .3 7
1
6
4
3 .6 9
400000
1 2 .9 2
2
5 .6 2
350000
4 .6 0
300000
3
1 3 .1 0
1 3 .3 1
6 .2 6
6 .7 6
250000
200000
5 .9 1
6 .2 16 .5 6
150000
VX
100000
3 .0 0
5 .0 0
4 .7 4
1 1 .1 3
1 0 .2 9
8 .4 7
50000
T im e -->
0
3 .0 0
4 .0 0
5 .0 0
6 .0 0
7 .0 0
8 .0 0
9 .0 0
1 0 .0 0
1 1 .0 0
1 2 .0 0
1 3 .0 0
Figure S-8 GC-IRD/MS-EI Data for N,N-diisopropylformamide (6)
NAME: N,N-Diisopropylformamide
CAS: 2700-30-3
ABBR: DIF
MW: 129.12
MOLECULAR FORMULA: C7H15NO
O
H C N
M a s s
s p e c t ra l
A b u n d a n c e
d if f e r e n c e
(1 6 4 -* )
(-)
Peak 8 ( 3.64 : 3.67 ) Ref. ( 3.4 : 3.54 ) of F:\HPCHEM\1\DATA\MISC\7483A.D
1698.87
7 2
1 2 0 0 0 0
.04
1 1 0 0 0 0
1 0 0 0 0 0
4 0 0 0 0
4 4
1 2 9
3 0 0 0 0
8 6
0
4000
1 1 4
Ver A.00.02
2 0 0 0 0
4 1
5 8
1 0 0 0 0
m /
1 0 0
5 4
6 8
1 1 1
6 2 1
8 29 2
7 3
1 0 3
1
1
4
47
9
9
0
z -->
3 04 05 06 07 08 09 0
1 01
011
021
031
04 0
6
3000
2000
Wavenum ber (cm -1)
1000
616.794
.01
5 0 0 0 0
851.387
776.269
730.396
6 0 0 0 0
1423.01
1373.88
1281.9
1209.36
1156.31
1109.45
1039.39
.02
7 0 0 0 0
2944.12
2887.08
2801.87
2751.86
Absorbance
8 0 0 0 0
2979.31
.03
9 0 0 0 0
O
NAME: O-ethyl S-[2-(isopropylamino)ethyl]
methylphosphonothioate
CAS: TBD
ABBR: Isopropyl-VX
MW: 225.10
MOLECULAR FORMULA: C8H20NO2PS
N
O P S
H
CH3
0
7
5
0
0
0
7
0
0
0
0
6
5
0
0
0
6
0
0
0
0
5
5
0
0
0
5
0
0
0
0
4
5
0
0
0
4
0
0
0
0
3
5
0
0
0
3
0
0
0
0
2
5
0
0
0
2
0
0
0
0
1
5
0
0
0
1
0
0
0
0
5
0
0
0
t
7
2
r a
l
d
i f
f
e
r e
n
c
e
( *
- *
)
( - )
Peak 22 ( 9.28 : 9.34 ) Ref. ( 8.96 : 9.18 ) of F:\HPCHEM\1\DATA\MISC\7483A.D
8
5
.015
2972.24
.01
7
2941.75
4000
4
z
1469.04
1383.96
1663.87
2840.02
3000
2000
Wavenum ber (cm -1)
1000
4
1
1
8
0
0
7
8
1
0
- - >
4
0
6
0
8
0
1
0
1
0
1
2
2
1
0
3
61
1
4
91
5
5
1
0
6
3
1 1
6
1
0
7
8
1
1
8
2
3
9
9
2
0
0
1
72
6
2
0
0
2
2
4
0
Figure S-10 GC-IRD/MS-EI data for Authentic O-ethyl S-[2-(isopropylamino)ethy]
methylphosphonothioate (1).
O
NAME: O-ethyl S-[2-(isopropylamino)ethyl]
methylphosphonothioate
CAS: NA
ABBR: Isopropyl-VX
MW: 225.10
MOLECULAR FORMULA: C8H20NO2PS
N
O P S
H
CH3
S c a n 1 0 5 5 ( 1 0 . 2 9 5 m in ) : N B 8 5 P O 8 A . D
Peak 8 ( 10.17 : 10.27 ) Ref. ( 9.62 : 10.03 ) of D:\DJM\NB85PO8A.D
(-)
1040.04
A b u n d a n c e
7 2
8 5
1 8 0 0 0 0
.02
1 7 0 0 0 0
7 0 0 0 0
6 0 0 0 0
4000
4 0 0 0 0
Ver A.00.02
3 0 0 0 0
4 4
4 2
1 0 7
5 6
1 3 9
1 6 7
1 0 0 0 0
m / z -->
889.052
0
5 0 0 0 0
2 0 0 0 0
657.546
.005
8 0 0 0 0
2619.57
9 0 0 0 0
1470.65
1384.09
1 0 0 0 0 0
9 5
1 1 3
2 1 0
1 2 6
1 5 5
0
4 0
6 0
8 0
1 0 0
1 2 0
1 4 0
1 6 0
1 6 8
1 8 0
1 8 0
2 22 24 6
2 0 0
2 2 0
7
3000
2000
Wavenum ber (cm -1)
727.05
.01
1 1 0 0 0 0
769.382
1 2 0 0 0 0
1251.86
1 3 0 0 0 0
1300.39
.015
1 4 0 0 0 0
2941.55
1 5 0 0 0 0
946.947
1 6 0 0 0 0
2837.75
/
3210.73
0
9
Ver A.00.02
5
m
3330.26
.005
769.218
727.025
0
c
653.786
0
e
1040.09
0
p
946.847
8
s
889.206
s
e
1251.75
s
c
1299.7
a
n
1172.02
M
a
1171.29
1091.87
d
2972.18
n
3774.53
u
Absorbance
b
Absorbance
A
Figure S-9 GC-IRD/MS-EI data for O-ethyl S-[2-(isopropylamino)ethyl]
methylphosphonothioate (1)
1000
Figure S-11 GC/MS-EI data for TMS derivative of 1: O-ethyl S-[2-(N-isopropyl-Ntrimethylsilylamino)ethyl] methylphosphonothioate.
O
NAME: O-ethyl S-[2-(N-isopropyl-Ntrimethylsilylamino)ethyl] methylphosphonothioate
CAS: TBD
ABBR:
MW: 297.13
MOLECULAR FORMULA: C11H28NO2PSSi
N
O P S
TMS
CH3
A
b
u
n
d
a
n
M
a
c
e
3
2
0
0
3
0
0
0
2
8
0
0
2
6
0
0
2
4
0
0
2
2
0
0
2
0
0
0
1
8
0
0
1
6
0
0
1
4
0
0
1
2
0
0
1
0
0
0
8
0
0
6
0
0
4
0
0
2
0
0
s
m
/
z
s
p
7
e
8
2
c
t r a
l
d
i f f e
r e
n
c
e
( * - * )
( - )
5
IR spectrum
not obtained
4
0
- - >
s
3
1
5
8
1
9
4
0 6
0 8
0
1
01
1
7 1
2
31 95
6
3
7
1
1
8 32 1
1 9 7
2
2
2
3
4
9
0
2 2
6
7
1
22
0 10 2 10 4 10 6 10 8 20 0 20 2 20 4 20 6 20 8
9
7
0
Figure S-12 GC-IRD/MS-EI data for O-ethyl S-[2-(N,N-diisopropylamino)-2-oxoethyl]
methylphosphonothioate (2)
O
N
O P S
O
CH3
s p e c t ra l
d if f e r e n c e
(* -* )
(-)
Peak 26 ( 13.02 : 13.06 ) Ref. ( 12.15 : 12.64 ) of F:\HPCHEM\1\DATA\MISC\7483A.D
1039.44
9 8
.002
1 0 0 0 0
1 8 1
1 5 3
5 8
0
1 0 8
1 2 8
3000
4 4
Ver A.00.02
1 6 7
1 9 2
4
21
127
93
26
5212
6 8
9 1
4 06 08 0
1 01
021
041
061
082
002
022
042
062
08 0
8
2000
Wavenum ber (cm -1)
1000
588.73
947.546
890.773
1439.43
1377.01
.004
2940.25
4 3
1 5 0 0 0
0
m / z -->
Absorbance
1 4 1
1213.25
2976.04
.006
2 5 0 0 0
5 0 0 0
1321.69
1251.59
.008
3 0 0 0 0
2 0 0 0 0
1666.15
8 6
771.962
726.934
M a s s
A b u n d a n c e
NAME: O-ethyl S-[2-(N,N-diisopropylamino)-2oxoethyl] methylphosphonothioate
CAS:
ABBR: 2-acetamido-VX
MW: 281.12
MOLECULAR FORMULA: C11H24NO3PS
Figure S-13 GC-IRD/MS-EI data for O-ethyl S-[2-(N-acetyl-N-isopropylamino)ethyl]
methylphosphonothioate (3)
N
O P S
C
CH3
M a ss
A b u nd a n c e
O
CH3
s p e c t ra l d if f e re n c e
(* -* ) (-)
Peak 27 ( 13.22 : 13.27 ) Ref. ( 12.15 : 12.64 ) of F:\HPCHEM\1\DATA\MISC\7483A.D
1676.22
O
NAME: O-ethyl S-[2-(N-acetyl-N-isopropylamino)ethyl]
methylphosphonothioate
CAS:
ABBR: VX-acetamide
MW: 267.11
MOLECULAR FORMULA: C10H22NO3PS
7 2
1039.91
.01
5 0 00 0
4 5 00 0
.008
.002
1 5 00 0
3632.67
2 0 00 0
3000
7 0
1 1 4
1 0 8
5 0 00 4 2
0
m / z -->
0
8 5
4 3
1 0 00 0
591.186
947.828
889.561
1304.09
1250.96
2944.31
2 5 00 0
771.577
727.478
.004
1 2 7
1406.51
3 0 00 0
.006
1170.19
3 5 00 0
2980.52
Absorbance
4 0 00 0
2000
Wavenum ber (cm -1)
1000
Ver A.00.02
2 2 4
14
6 7
1 5
2 1 0
5
1 6
19
8 3 2 22
2
6 7
73
245
4 06 08 0
1 01
021
041
061
082
002
022
042
062
08 0
Figure S-14 GC-IRD/MS-EI data for O-ethyl S-[2-(N-formyl-N-isopropylamino)ethyl]
methylphosphonothioate (4)
O
O P
N
S
C
H
CH3
s p e c t ra l
O
d if f e r e n c e
(* -* )
(-)
Peak 25 ( 12.78 : 12.89 ) Ref. ( 12.19 : 12.64 ) of F:\HPCHEM\1\DATA\MISC\7483A.D
1 1 3
.02
1702.18
M a s s
A b u n d a n c e
NAME: O-ethyl S-[2-(N-formyl-Nisopropylamino)ethyl] methylphosphonothioate
CAS:
ABBR: VX-formamide
MW: 253.09
MOLECULAR FORMULA: C9H20NO3PS
3 0 0 0 0
5 8
.015
2 5 0 0 0
8 5
1 2 5
5 0 0 0
m /
0
z -->
4 1
1039.53
947.847
889.361
0
4 3
3000
66 7
1
11440
2 2 4
Ver A.00.02
2 5 3
1 9 4
2 1 0
1 8
11
9 7
2 4 3
4 06 08 0
1 01
021
04 1
061
082
002
02 2
04 0
9
2000
Wavenum ber (cm -1)
1000
630.9
1 0 0 0 0
770.54
727.307
.005
1296.75
1 0 0
1406.4
1 5 0 0 0
1248.89
.01
1167.38
1129.37
2 0 0 0 0
2979.84
2943.35
2854.98
2783.42
Absorbance
7 2
Figure S-15 GC-AED phosphorus specific chromatogram for diluted, derivatized acetonitrile
extract of VX/ozone reaction
AED2 A, Phosphorus 178 of OZONE\023F0101.D
Counts
1000
800
600
400
200
0
6
8
10
12
14
16
18
20
22
24
min
Figure S-16 GC/MS-EI total ion chromatogram of the diluted, derivatized acetonitrile extract of
the VX/ozone reaction
Abundance
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
Time-->0
4.00
6.00
8.00
10.00
12.00
14.00
10
16.00
18.00
20.00
22.00
Figure S-17 (A) EI, (B) CH4-CI, and ( C) NH3-CI MS for the first peak of the triplet shown in
Figure S-16 (identified as compound 4).
Abundance
(C)
1000000
500000
m/z-->
88
60
80
148 165176 194 212 224233
105114 126 146
100 120 140 160 180 200 220 240
Abundance
m/z-->
Abundance
400000
60
85 100
80
100
79
72
200000
m/z-->
60
80
100
100
299
300
130141
148 167 181 194 210 226 240 254 268 282 294
120 140 160 180 200 220 240 260 280
(A)
113
58
271
272
260 280
(B)
114
5000000
254
125
120
224
146
167
154
181 194 210
233 253261
140 160 180 200 220 240 260
280 295
280
Figure S-18 (A) EI, (B) CH4-CI, and ( C) NH3-CI MS for the second peak of the triplet shown
in Figure S-16 (identified as compound 2).
Abundance
800000
600000
400000
200000
m/z-->
Abundance
1500000
1000000
500000
m/z-->
Abundance
200000
100000
m/z-->
(C)
60
84
80
282
100 113 128 144 159
161 176 191 204 219 236 248 268 286 300
100 120 140 160 180 200 220 240 260 280
(B)
282
141
181
158 172
84 100 113 128
198
204 222 240
296
247 266
60
80
100 120 140 160 180 200 220 240 260 280
86
141 (A)
98
153
181
107
128
58 70
168
194 210 226236 253 267 282 295
60
80
100 120 140 160 180 200 220 240 260 280
11
Figure S-19 (A) EI, (B) CH4-CI, and ( C) NH3-CI MS for the third peak of the triplet shown in
Figure S-16 (identified as compound 3).
Abundance
150000
100000
50000
m/z-->
Abundance
4000000
2000000
m/z-->
268
(C)
128
86 98
80
100
60
119
120
128
86 99 114
80
100 120
60
Abundance
300000
200000
100000 56
m/z-->
60
72
127
79
95
80
100
114
120
162 179190 204
146 160
226 243
245
140 160 180 200 220 240 260
285
286
280
(B)
296
141 156167 180 197 210 224234 252 268
275
140 160 180 200 220 240 260 280
(A)
139 154 167 181 196 210 224 240
244
267
272 288
140 160 180 200 220 240 260 280
12