Examination of the Hydroperoxidolysis of a VX Model...
Transcript of Examination of the Hydroperoxidolysis of a VX Model...
![Page 1: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/1.jpg)
Joshua M. Blechle & Erin L. FutrellFaculty Mentor
Dr. Eric V. Patterson
Examination of theHydroperoxidolysis of a
VX Model Compound
![Page 2: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/2.jpg)
VX Facts
• Discovered by various groups in1952-53
• It is mistaken by the body to beacetylcholine, a neurotransmitter thatcauses muscles to contract
• Previous research has shown that VX isbest neutralized by an attack ofhydroperoxide
![Page 3: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/3.jpg)
Model VX-Compound
O-ethyl S-2-[(diisoproylamino)ethyl]methylphosponothiolate (VX)
O,S-dimethylmethylphosphonothiolate
![Page 4: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/4.jpg)
Previous Research
![Page 5: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/5.jpg)
Oxygen Transfer
• This shift was found to be the pathwayrequiring the least energy
• This, however, is suspect since thetransfer is so unusual
• The goal of this research is to learn moreabout the oxygen transfer and determineits likelihood
![Page 6: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/6.jpg)
Theory
• MPWB1K/6-31+G(d,p) Provides accurate representation of
energies and geometries (quantum)
• Standard quantum chemical resultsare obtained at 0 K
• Thermal energy can be considered byemploying classical moleculardynamics
![Page 7: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/7.jpg)
ADMP Calculations
• Atom-Centered Density Matrix Propagation Treats electrons quantum-mechanically, but
nuclei classically
U is the energy from the quantum calculationGenerates a thermal potential energy surface
!
F = ma = mdv
dt= m
d2x
dt2
= "#
#rU
![Page 8: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/8.jpg)
Gas and Solution Phases
• A gas-phase reaction can have a potential energy surface (PES) thatis very different from the PES of the same reaction in solution
![Page 9: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/9.jpg)
Motivation
• Previous study employed gas-phasegeometries
• Current study employs gas-phaseconditions as well as aqueous conditions.
• Solvation could have significant impact onresults
![Page 10: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/10.jpg)
Gas Phase Results
• The observed outcomes of gas phase TBP Direct P-S cleavage Rearrangement with loss of water Rearrangement with loss of OH group
(possibly additional water)• Only the TBP product was previously
predicted• Suggests a more complicated PES than
originally thought
![Page 11: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/11.jpg)
Trigonal Bipyramidal
To view movie:http://jade6.truman.edu/movies/tbr.mov
![Page 12: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/12.jpg)
Direct P-S Bond Cleavage
To view movie:http://jade6.truman.edu/movies/ps.mov
![Page 13: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/13.jpg)
Formation of H2O
To view movie:http://jade6.truman.edu/movies/water.mov
![Page 14: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/14.jpg)
Gas Phase Summary
One Hundred completed trajectories:
Transition State
TBP
16.0% (16)
H2O45.0% (45)
P-S
33.0% (33)
OH
6.0% (6)
![Page 15: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/15.jpg)
Aqueous Phase Results
• Stationary point calculations have ledto an acceptable transition state
• Frequency calculations were used topinpoint the most stable geometry
• From this, subsequent ADMPcalculations can be performed
• This will follow the same procedure asthe gas phase
![Page 16: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/16.jpg)
Aqueous Transition State
• This is the optimized geometry from whichADMP calculations will start
![Page 17: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/17.jpg)
Goals for the Future
• Using the constructed aqueoustransition state, determine theexistence of the oxygen transfer
• Continue to collect aqueous phasedata using ADMP calculations
• Use combined data to confirm mostprobable mechanism for thehydroperoxidolysis of VX
![Page 18: Examination of the Hydroperoxidolysis of a VX Model …discus/muccc/muccc10/MUCCC10-BlechleFutrell.pdfJoshua M. Blechle & Erin L. Futrell Faculty Mentor Dr. Eric V. Patterson Examination](https://reader033.fdocuments.in/reader033/viewer/2022060721/6081afb5c218e30e27387237/html5/thumbnails/18.jpg)
References andSpecial Thanks
• References Seckute, J.; Menke, J.L.; Emnett, R.J.;
Patterson, E.V.; Cramer, C.J. J. Org. Chem.2005, 70(22), 8649-8660.
• Special Thanks To Dr. Patterson, our faculty mentor,
who has given us this wonderfulopportunity.