USOO8722956B2 (12) United States Patent (10) Patent No.: US 8,722,956 B2 BrOWn et al. (45) Date of Patent: *May 13, 2014 (54) KIT FOR DECOMPOSING (56) References Cited ORGANOPHOSPHORUS COMPOUNDS U.S. PATENT DOCUMENTS (75) Inventors: R. Stanley Brown, Kingston (CA); 3,079.346 A 2f1963 Jackson Alexei A. Neverov, Kingston (CA); 3,725,269 A 4, 1973 Wolverton Josephine S. W. Tsang, Kingston (CA) 4,337,368 A * 6/1982 Pytlewski et al.............. 588,316 4,602,994. A * 7/1986 Pytlewski et al... 208,262.1 (73) Assignee: Queen's University at Kingston, 4,874,526 A * 10/1989 Grade et al. .................. 210,697 Kingston, ON, CA (US) 5,859,064 A 1/1999 Cronce 6.479,723 B1 * 1 1/2002 Malhotra et al. .............. 588,316 (*) Notice: Subject to any disclaimer, the term of this (Continued) patent is extended or adjusted under 35 U.S.C. 154(b) by 254 days. FOREIGN PATENT DOCUMENTS This patent is Subject to a terminal dis DE 2994.58 4f1992 claimer. EP O906773 A1 4f1999 (Continued) (21) Appl. No.: 13/012,269 OTHER PUBLICATIONS (22) Filed: Jan. 24, 2011 Harrison et al.; The Chemistry of Organophosphorous Chemical (65) Prior Publication Data Warefare Agents; PATAI's Chemistry of Functional Groups; 2009.* US 2011 FO253580-A1 Oct. 20, 2011 (Continued) Related U.S. Application Data Primary Examiner — Guinever Gregorio (63) Continuation of application No. 1 1/713,805, filed on (74) Attorney, Agent, or Firm — Angela Lyon; Carol Mar. 5, 2007, now Pat. No. 7,875,739, which is a Miernicki Steeg continuation of application No. 10/798,880, filed on Mar. 12, 2004, now Pat. No. 7,214,836. (57) ABSTRACT (60) Provisional application No. 60/453.762, filed on Mar. Methods and kits for decomposing organophosphorus com 12, 2003. pounds in non-aqueous media at ambient conditions are (51) Int. C. described. Insecticides, pesticides, and chemical warfare BOI. 23/00 (2006.01) agents can be quickly decomposed to non-toxic products. The A62D 3/38 (2007.01) method comprises combining the organophosphorus com A62D 3/00 (2006.01) pound with a non-aqueous solution, preferably an alcohol, A62D 3/30 (2007.01) comprising metalions and at least a trace amount of alkoxide (52) U.S. C. ions. In a first preferred embodiment, the metal ion is a lan USPC ............ 588/300; 588/320:588/313; 502/302 thanum ion. In a second preferred embodiment, the metalion is a transition metal. (58) Field of Classification Search None See application file for complete search history. 30 Claims, 10 Drawing Sheets g La3. QJLa 3. (EIOP-0Ar Pt 34 N La3. CAr O- o1 Yo-sp^ CH, ch, R (OEt) -phosphate C t i).6.Yo oA -6La y af N." heriiCHO1 Y(OEtz her(EIO: OA Hc-'n?Eo-OAf US 8,722.956 B2 Page 2 (56) References Cited Khan, A., et al. “Strong Zn" and Co'Catalysis of the Methanolysis of Acetyl Imidazole and Acetyl Pyrazole'. Can. J. Chem. 77: 1005 U.S. PATENT DOCUMENTS 1008 (1999). 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Nature. 177: 392–393 (1956). * cited by examiner U.S. Patent May 13, 2014 Sheet 2 of 10 US 8,722,956 B2 S H CHOH H n r / S 3 p Hoo--och,OCH CN d YoCH,N -- to OCH ( e. -- NO2 Figure 1C {Cu°12laneNsfoCH.) 0.03 0.00 0.0000 0.0005 0.0010 0.0015 La(OTf), M Figure 2 U.S. Patent May 13, 2014 Sheet 3 of 10 US 8,722,956 B2 5 6 7 8 9 10 11 Figure 3 U.S. Patent May 13, 2014 Sheet 4 of 10 US 8,722,956 B2 La2(OCH3)2 La2(OCH3)4 OOOO8 0.0006 N OOOO4 : Figure 4 U.S. Patent May 13, 2014 Sheet 5 of 10 US 8,722,956 B2 O f 2 3 4. 5 6 Cu(OTf)2total, mM Figure 6 U.S. Patent May 13, 2014 Sheet 6 of 10 US 8,722,956 B2 100 8 n 60 40 O.O 0.5 1.0 1.5 Cu(OTf)2total, m Figure 7 600 5OO 4 O O 3 O O 2 O O (NaOMe), mM Figure 8 U.S. Patent May 13, 2014 Sheet 7 of 10 US 8,722,956 B2 Zn(OTf), mM Figure 9A 750 Zn(OTf)2), mM Figure 9B U.S. Patent May 13, 2014 Sheet 8 of 10 US 8,722,956 B2 1.OC 9 0.75 s OSO is 0.25 O.OO O 250D 5000 7500 10000 Time, sec Figure 10 50 40 s E 30 s 20 10 O O 0.5 10 15 2.0 Equivalents of NaOMe.