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Suffield Special Publication No. 142 UNCLASSIFIED DEFENCE RESEARCH ESTABLISHMENT SUFFIELD RALSTON, ALBERTA SUFFIELD SPECIAL PUBLICATION NO. 142 PROCEEDINGS OF NMR IN DEFENCE SCIENCES 1990 SYMPOSIU M May 1991 !J NChA SI J-j~~ UF;FENCE RF?SEùARCN ES`l'AF3 L1S1`fiMEN1 SU FFlE1yD RALSTON ALBERTA I SU FFIEI.D SPECIAL PUBLICATION NO . 142 11R O(:[;1?[)INGS O F NMR IN 1) ET F,N(; E, SCIENCES 1990 SYMPOSIU M Octobcr 10-12, 1990 Defence Research I'stahlishmen t compilcc.l by C. A. Boulet waRNiNa 'The use of this information is permi tt ed suhject to recognition of pro{NietMy and patent rights' . IJNCI.ASS1FIFn UNCLAS4IFIE D i ABSTltAC7 ' Il In these proceedings, 11 papers from the NMR in Defence Sciences 1990 Symposium, held at the Defence Research Establishment Suffield from October 10-12, 1990, are presented . The papers cover a number of areas of defence sciences in ~-hich nuclear magnetic resonance (NMR) is an important instrumental method . Topics include the use of two dimensional NMR for characterization of defence related compounds, investigation of decontamination chemistry, and solid state NMR for the analysis o f materials . 1' It 1~,~;! 1 M a` Le compte rendu qui suit présente 11 études sur la RNM qui avaient été soumises dans le cadre du Symposium 1990 sur les sciences de la défense qui s'est tenu au Centre de recherches pour la défense -euffield du 10 au 12 octobre dernier. Ces études couvrent toute une gamme de domaines reliés aux sciences de la défense où la résonance nucléaire magnétique (RNM) joue un rôle important Les sujets traités comprennent l'usage de la RNM bidimensionnelle pour la caractérisation des composés à usage militaire, l'étude de la chimie de décontamination et la RNM en phase solide pour l'analyse des matériaux. UNCI.AS51F1Ell 1 ..JNCLA5SIFjED i i TABLE OF CONTENTS Abstract Table of Contents i i List of Registrants ii i Social and Scientific Schedule v 2D NMR Studies of the Indicat or Dye TBPE. G. W. Buchanan, J . W. Bovenkamp, and D. Thoraval. 1 Use of 2D NMR for the A , •.- ;r, nment of Structure of Defence Related Compounds. C. A . Boulet and A. S. I-'" ansen. 13 Search and Retrieval of r ;C NMR Data . D. A. Ross. ?.S Gas C"hromatof;raphy-Mass Spe:ctrometry : A Techniqu : for the Verificatio n of Chcmical Warfare Agents and Related Compounds. P. A. D'Af;ostino. 3 7 Kinetics and Mechanisms of the Ityclrolysis and Oxidation of III-) and VX. L. L. Szafranicc, W . T. Beaudry, D. K. Rohrbaugh, [ .. J. Szafraniec, J. R. Ward, and Y.-C. Yang. 52 Catalytic Oz-C)xid"tion of Alkyl Sulfides to Sulfoxides using I)ioxo-Ituthcniuni Porphyrins: a111 NMR Investigation, N . Rajapakse and B. R. .,ames. 65 'l'he Formation of Pyrophophosphates in the Oxidation of Phosphonothiolates . P. R. Leslie, W. T. Beaudry, L. L. Szafraniec, and D . K. Rohrbaugh . 75 NMR of Calixarenes . P. D. Beer, J . P. Martin and A. N . Trethewey . 85 Reactions of CW Agents in DS2 . W. T. Beaudry, L. L. Szafraniec, D. K. Rohrbaugh, and D. R. Leslie. 9 7 27A1 and rrB NQR of Ceramic Materials. C. Conner, J .-W. Chang, and A. Pines. 1 08 Solid-State NMR Study of Ambient Temperature Aging of Carbon Black-Filled Rubbers . D. E. Axelson, A. Sharma and J . Collyer. 11 9 S,,1NCL.A~SI FIED UN LQSS 1 FI I; D iii LIST OF REG ISTRANTS Dr. 1). E. Axelson Dr. P. A. D'Agostino President CBDS NMR Technologies Inc. I)efence Re search Establishment Suffield 132 Advanced Technology Center P.O. Box 4000 9650-20 Ave. Medicine Hat, AB CANADA 'I'IA $Kh 0 Edmonton, AB CANADA T6N 1G 1 Mr. A. S. Hansen Mr. W. T. Beaudry CI3I)S I US Army Chemical Research, Defence Research Establishment Suffield Development and Engineering Center P.O. Box 4000 Attn: SMCCR-RSC-P/William'I'. I3eauclry Medicine ilat, AB CANADATIA 81<6 Aberdeen Proving Groun d Maryland, 21010-5423 C)r. D . Ralph LeSli e USA )`latreials Research I .al7oratory I)efence. Science a ne1 l'c.chnol of,y Dr. C. A. 13cnilet C)rf;,tniiatir~ n Cf3I)S P.O. Box 5 0 Defence. Research Establishment Suffiel d Ascot Vale, V)C 3O3'2 P.O. Box 4000 A[1S'l'RAI,IA Medicine I lat, A13 CANADA TIA 8 K6 Dr . P. A. l,ockwoud 1)r. (;. W. I311chanari C'131)S I)chartmcnt of C'heniistry I)efencc: Research Istab1i5hnient Sufficld Carleton University P.O. Box 4000 Colonel By Drive Medicine I Iat, All C'ANA1)A 'l'lA SK 6 Ottawa, Ontario CANADA KIS 5f3fi Capt . C. Il . Pedersen "hhe Danish Defence Academy Dr. R . C'lr:wley P.O. Box 271 5 C[3DS 21 00 Koehenhavn OE Defence Research Establishment SLIffiCld I)I;NMAR K P.O . Box 4000 Medicine Hat, AB CANADA "T'IA 8K 6 C)r. G . Purclon C'(3DS Dr. C. Connor Defence Research Establishment Suffield Defence Research Establishment Pacific P.O. Box 4000 FMO Medicine flat, Af.3 CANADA T1A 8K6 Victoria, BC CANADA VOS 1130 SJNCLASS1 F1i j) UNCLASSIFIED iv Dr. Nimal Rajapakso Dr. V. V. Krishnamurthy Department of Chemist ry Senior Applications Chemist 2036 Main Mall Manager, Applications Laboratory University of British Columbia 25 Hanover Roa d Vancouver, B.C. CANADA Florham Park, New Jersey 07932 V6T 1 Y6 USA Mr. Deryck A. Ross DirectoratC Scientific Information Services Research and Devel opment Branch 101 Colonel By Drive Ottawa, Ontario, CANADA KIA OK2 Mrs. Linda Szafraniec US Army Chemical Research, Devel<7p ment and Engineering Center Attn : SMCCR-RS(`-P/Linda I.. Szafraniec Aberdeen Proving Ground Maryland, 21010-5423 US A Mr. Mogens Thornsen I )anish Civil Defence 11n,.ilytical-C:hernical E.aboratcyry U>>ivc;r5itetsparken 2 DK - 2100 Copenhaf;en 1)E:;NMAR K E)r. A. N . Trethewey CDD CDE Porton Down Salisbury, Wiltshire SP4 OJQ United Kingdom Mr. Bill Kenney Varian Canada Inc. 955 Green Valley Crescent Ottawa, Ontario CANADA K2C 3V4 u _-CLASSjFIED UNCI,ASSI fÂIF:;D v SOCIAL AND SCIENTIFIC SCHEDULfâ October 10, 1990 Îir,t,lg ,v n I..a•>c a ti o r► 0800 Pick-up at hotels Medicine Hat i .oclge Travelodge 0845 Registration DR1;S Building 1 0900 Welcoming Remarks large Conference Room Chief DRES, Symposium Chairman Building I 0930 PUNARY LECTURE LC R Dr. Krish Krishnarnrrrthy Varian USA 1015 Coffee 103 0 21) NM R IN I) E1,"►;N('1? SCIENCES Cs~W~ I3~~çt)~tn~►r~, J .W. I3ovenkanrp, U. 'I'hr>raval, anc) S . Fortier. Solvent 1)c}~cncJent "l'aut► rnreric I ;►luilihria in the Indicator I)ye 'I'IIP1; as EIrrcidaterl by 21) NMIt . (',A,.-,I3ojtkA and A.S . Hansen . Use of 21) NMR for the Assignment ►►f Structure of I)efencc 12rl :►tecl C'►rm p►runrls. 1230 I,unch C)fficers Mess 133 0 D.A . ltos, . Search and Rctrieva' of "C NMR Uata . 1415 RESEARCH 1)IRF.(:TIONS IN ( ."%V VE RIFIC'A"l'IO N P.A Io 1.)oj. The Chemical Weapons Convention . Implications for Chemical Defence Research . P.A . D'Agtastino. Gas Chronnatography-Mass Spectrometry : A Technique for the Verification of Chemical Warfare Agents and Related Compounds. 1630 Suds and Posters Officer's Mes s 1900 Return to H otels LJ N_C°'AS IS I"IF;D UNCLASSiFIED vi October 11, 1990 0800 Pick-up at hotels 0900 NMR STUDIES IN DECONTAMINATION CHEMISTRY Session chaired by Dr. G. Purdon L.L. Szafraniec, W.T. Beaudry, D.K. Rr>hrbaugh, L.J. Szafraniec, J.R. Ward, and Y.-C. Yang. Kinetics and Mechanisms of the 0 Hydrolysis and Oxidation of HD and VX . I N. Raiapakse and B.R. James. Catalytic 02-Oxidation of Alkyl Sulfides to Sulfoxides using Dioxo-Ruthenium Porphyrins: a ' FI NMR Investigation . 103() Coffee D.R . Lesl ie, W.T. Beaudry, L.L. Szafran;ec, and D. Rohrbaugh. The Formation of Pyruphophasphatrs in the Oxidation of Fhatiphonothiolates. AN, 'hrmligmçy, P.D. l3eer, and J .P. Martin. NMR of Calixareucs. 1230 Lunch 1330 NMR S'l'UDIES IN DECC)NTAMINA'I7C)N CHEMISTRY (contcl) . W.T. 13c Md_U, L.L. Szafraniec, D .K. Rohrbaugh, and D .R . l._e.,lie. Reactions of CW Agents in DS2. 1430 SOLID STATE NMR IN DEFENCE RELATED RESEARCH C. Conno, J.-W. Chang, and A. Pines. z?Al and L'B NQR of Ceramic Materials. .TZ,F,.AAgj=, A. Sharma, J. Collyer, and M . Scarrtntei1-Bullock. Solid-State NMR Study of Ambient Temperature Aging of Carbon Black-Filled Rubbers . 1615 Closing Remarks 1630 Return to }iotels 19()0 Banquet U,hICLASSIFif I3 UNCLAS 1EIED I 2D NMR STUDIL S OF THE INDICATOR DYE I BPE Gerald 1,'1 . Buchanan Ottawa-Carleton Chemistry Inst itute Department of Chemistry Carleton University, Ottawa, Canada K1 S 5B6 John W . Bovenkamp and Dominic Thoraval i Defence Research Establishment O ttawa Ottawa, Canada, K1A 0 Z2 Abstract For 3',3",5',5"-te'trabro mophonotphthalein ethyl ester (T13111-) in 1 :1 C.,O;)CI2'COC13 solution comploto tH and 13C NMR signal assignments have been made via 1 I 11 II COSY and I 1 f 1 3 C I jr 1 COR experi mo nts . The ctuinoic1~31 a nd phenolic intogri ties are, retained on the NMR tirnesca Io . By contrast for an acetone~ci6 Solution only 14 1JC resona nces are found and the colour of the soluti on changed from green to dark blue . 1 hc;se changes in acotono solution are attr ibuted to the loss of the phenol ic proton of TBPE and the exist ence.
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