Paper
Organic & Biomolecular Chemistry
breakdown experiments, using GB and VX, was performed on
a Bruker 400 MHz spectrometer. Deuterated acetonitrile was
Acknowledgements
used as NMR solvent for all experiments. An internal reference, The authors would like to thank the Defence Science and
% H PO in deuterium oxide (0.0 ppm, singlet), sealed in a Technology Laboratory (Dstl) for funding. Glasgow University
glass capillary, was used in all P NMR experiments unless mass spectrometry service. DJA thanks the EPSRC for a
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stated otherwise.
Fellowship (EP/L021978/1).
The synthesis of methyl paraoxon and lithium methyl
4
-nitrophenyl phosphate is reported in the ESI.†
Breakdown studies
Notes and references
The reactions involving the CWAs, GB, and VX, were carried
out under the same conditions as with MP. All reactions with
GB and VX were carried out at Dstl by trained personnel using
appropriate care and equipment due to the lethal toxicity of
the agents.
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Variation in water content, with TMG as base. MP (3 µL,
.0168 mmol, 1 equivalent) was added to a water (1, 5, 10, 25,
0, 150, 300, 600, or 800 equivalents) solution containing TMG
0
5
871.
5
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(
5 equivalents). The resulting solution was stirred in a vial at
room temperature for 24 hours. After such time, CD CN (ca.
.5 mL) was added and the solution transferred to an NMR
tube, fitted with a glass capillary (containing 1% H PO as
internal standard). The P [ H] NMR was recorded within
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hour of transfer of the solution.
Reaction of TMG, MTBD, or DBU with MP, in absence of
water. The base, TMG, MTBD, or DBU, (2 equivalents) was
9
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added to a vial prior to the addition of MP (3 µL, 0.0168 mmol,
1
equivalent). The resulting solution was stirred in a vial at
room temperature for 24 hours. After such time, CD CN (ca.
.5 mL) was added and the solution transferred to an NMR
tube, fitted with a glass capillary (containing 1% H PO as
internal standard). The P[ H] NMR was recorded within
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hour of transfer of the solution from the vial.
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Screening of bases. The base (8.8 equivalents) was dissolved
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in a water/deuterated acetonitrile mixture (0.5 mL, 1 : 1 v/v). To
this solution, MP (3 µL, 0.0168 mmol, 1 equivalent) was
added. The solution was transferred to an NMR tube, fitted
1
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3 4
with a glass capillary (containing 1% H PO as internal stan-
3
1
1
dard). P [ H] NMR was recorded within the first hour for
each sample. Further monitoring of the reaction solution was
carried out until complete conversion was achieved, estab-
lished by the disappearance of the MP peak at −4.5 ppm.
Variation in TMG or MTBD content, in excess water. MP
1
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3
(3 µL, 0.0168 mmol, 1 equivalent) was added to a water/CD CN
1
1
1
2
2
2
solution (0.5 mL, 1 : 1 v/v) containing either TMG (1.0, 2.5, 5.0,
or 9.0 equivalents) or MTBD (1.0, 2.5, 5.0, or 9.0 equivalents).
The resulting solution was stirred in a vial at room tempera-
ture for 24 hours. After such time, the solution was transferred
to an NMR tube, fitted with a glass capillary (containing 1%
2
1
3
1
1
3 4
H PO as internal standard). The P[ H] NMR was recorded
within 1 hour of transfer of the solution from the vial.
23, 6519–6525.
Conflicts of interest
2 X. Han, V. K. Balakrishnan, G. W. vanLoon and E. Buncel,
There are no conflicts to declare.
Langmuir, 2006, 22, 9009–9017.
9290 | Org. Biomol. Chem., 2018, 16, 9285–9291
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