Scheme 2.

Dissociation of MPA
The Chemical Weapons Convention (CWC) bans the production. storage, and the use of chemical weapons, and signatories of the CWC agree to destroy any stockpiles they may have. To monitor destruction activities, especially chemical neutraliztion, and to ensure compliance with the CWC, chemical analysis is used. Methyiphosphonic acid (MPA) is the ultimate and common hydrolysis product of the organophosphorus nerve agents VX, RVX, sarin (GB). soman (GD), and cyclosarin (GF), and has measured pKl values of 2.33 to 2.38 and pK2 value of 7.1 to 7.76. Though the effect is not generally large in 'H-NMR, it is known that a variety of factors such as solvent can affect the chemical shift. This study began by determining the effect of increasing amounts of sodium deuteroxide (NaOD) on the chemical shift in the 'lT-NMR spectrum of MPA in D20.
Figure3

161
'S
_______________ ____________________ Figure 1.

Ii U) 12
r 6)

NeOD d,1 . Ne CO
. Ne CO (4pE Pyrd,neJ _____

H3C Chemical Shift as Function of pH

IS
-

onstant
Pyr:d e.2

0 o H.C-P-OH pH'-2.3 H C-P--OH OH

0 H.C-P-0

'3
15 0 2 4 6 pH 6 10 12 14

pH

10

'2

14

18 175

Scheme 1. Hydrolysis of G and V-Agents to MPA

0 H,C P F GB R' - sopropvl GD: R' pmacolyl GF R' cyc1ohexi 0 H0C P OR' H3C OR 0 0 - H3C P OR - H,C P OH OH OH MPA

H1C Chemical Shift 4S Function of Equiv ants NaOD Added

I
tO

l 3 ___________________________ 12
11 ____________________

Figsire4. H3C-P Coupling Constant as

17

Function of Equivalents NaOD Added

ms
6) 1: C)
U

15 15

_______________________________
0 55 1 15 2 25 3 35

RESULTS I As the MPA solution became more alkaline, the amount of shielding of the methyl protons increased as indicated by the chemical shift decreasing from 1.47 ppm to 1.08 ppm. This decrease in chemical shift tvas linear as the amount of NaOD added reached 1.5 equivalents of the MPA and then was unchanged. Also observed was a change in the H3C-P coupling constant from about 17.1 Hz to 15.6 Hz though it did not quite follow the same overall pattern. With Na1CO1. a continual change in chemical shift occurs while the H1C-P coupling constant changes in stages. With pyridine-d5. the chemical shift decreased linearly but after 0.75 molar equivalents were added, the trend re ersed, probably as a result of the increasing organic content of the solution. In this case, the magnitude of coupling constant did not exhibit consistent behavior.

05

15

25

35

MoIr EqoK HoOD to MPA

Mobor Eqolv. HoOD to MPA

0 P OH
15 14

SC,CH2NR2

SC,CHNR

j751
N1,
_____________ ______ ____

18

I
______________________________

CONCLUSIONS

Figure 5.

\'X R isopropyl: R' ethsl R'SX Rethy..R' isobutvl

1
12

H1C Chemical Shift as Function of Equrs ants Na,CO Added iS

17 165 16

I
______ p

Figure 6. H3C-P Coupling Constant as Function of Equivalents Na2CO4 Added

11

_____

155 IS

EXPERIMENTAL

05

15

25

35

05

15

25

35

Mob, Equbo. Ne2CO3 to MPA

MONO Equi No2CO3 to MPA

Instrumentation: Varian Gemini NMR Spectrometer operating at 300 MHz. Reagents: MPA. D20, D20 with 0.75% TSP, 30 % NaOD in D20, pyridine-d5, and Na2CO3 were purchased from Aldrich, lnitial concentration of MPA was 0.0200 to 0.0203 g per 750 FL of D20. Bases were added in increments of 0.25 equivalents (NaOD: 4.9 FL: pyridine-d6: 4.2 FL; Na2CO-,: 13.3 FL).
15 14 Figure 8. 18 175

The chemical shift of the methyl protons of MPA in D20 behaved in a predictable but different maimer as increasing amounts of the bases NaOD, Na2CO3, and pyridine-d5 were added. The H3C-P coupling constants exhibited more erratic behavior under the same conditions. The effects observed with pyridine-d1 may result from the increasing organic content of the solution. This data shows that there is a significant matrix effect on the chemical shift and coupling constant of MPA and that 'H-NMR spectroscopy alone may not provide a high-confidence identification of MPA in neutralized nerve agent solutions. In situations where the confidence is not great, spiking experiments or other analysis methods may be required to confirm its identity.

Figure 7.

113C Chemical Shift as Function of Equivanss Pyridine-d Added

U
iS

1 3 _____________________________
12
11 ____________________

H1C-P Coupling Constant as Function of Equivalents Pyridine-d, Added

g'

__________________

16 __________ 155

_______

C)
0 CS 1 15 2 25 3 35

15 0 05 1 15 2 25 3 35
Motor Eqobv. Pyrid,oe.di to MPA

Motor Equbo. Pyndlno.d5 to MPA

2003 Joint Service Scientific Conference on Chemical and Biological Deft use Research. I '-20 November 2003, Baltzmorc, ,'IID