EP0906773A1 - Dekontaminierungmittel - Google Patents

Dekontaminierungmittel Download PDF

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Publication number
EP0906773A1
EP0906773A1 EP98402407A EP98402407A EP0906773A1 EP 0906773 A1 EP0906773 A1 EP 0906773A1 EP 98402407 A EP98402407 A EP 98402407A EP 98402407 A EP98402407 A EP 98402407A EP 0906773 A1 EP0906773 A1 EP 0906773A1
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EP
European Patent Office
Prior art keywords
neutralization
type
composition
oxime
decontamination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98402407A
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English (en)
French (fr)
Inventor
Eric Le Guevel
Gilles Moutiers
François Terrier
Luc Villien
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Direction General de lArmement DGA
Gouvernement de la Republique Francaise
Original Assignee
Delegation Generale pour lArmement
Gouvernement de la Republique Francaise
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Publication date
Application filed by Delegation Generale pour lArmement, Gouvernement de la Republique Francaise filed Critical Delegation Generale pour lArmement
Publication of EP0906773A1 publication Critical patent/EP0906773A1/de
Withdrawn legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides

Definitions

  • the present invention relates to decontamination by neutralization of environments contaminated with neurotoxic organophosphorus compounds, such as organophosphates and organophosphonates. Neutralization transforms the compound toxic into a harmless compound.
  • organophosphorus compounds such as organophosphates and organophosphonates.
  • Organophosphate cholinesterase inhibitor compounds are used especially as pesticides and insecticides (for example paraoxon, parathion) in agriculture and also as potential war toxics, which block so irreversible nerve transmission by covalently binding to acetylcholinesterase.
  • organophosphonates have the following general formula:
  • BNPP O-bis (4-nitrophenyl) phenylphosphonate
  • R ' 4-NO 2 -ArO
  • R Ar
  • L 4-NO 2 -ArO.
  • War toxics are listed as toxic agents G by inhalation (soman, sarin, tabun) or percutaneous toxic agents V (VX, VG).
  • VX O-ethyl, S-2- (diisopropylaminoethyl) methyl thiolophosphonate
  • L SCH 2 CH 2 N (iPr) 2
  • R CH 3
  • R ' EtO
  • Very basic formulations were used: sodium carbonate, soda aqueous or alcoholic, alcoholic potash to destroy compounds organophosphates toxic to phosphonic acids.
  • a formulation developed by the American army, DS2 has the following composition: 70% diethylenetriamine (DETA), 28% monomethyl ether of ethylene glycol and 2% sodium hydroxide. These formulations are very aggressive. Other less aggressive formulations have proven effective: hydroxamic acids, phenols and polyphenols, hydrates aldehyde, amines including monoethanolamine. Other authors have been interested in oximes, for example 2-PAM in the form of pyridinium chloride 2- [hydroxyimino) methyl] -1-methyl in the article by C.D. Bedford, M. Miura, J.C.
  • Formulations based on the use of highly oxidizing media have also been developed: chloramine B, chlorine, bleach, Fichlor (sodium N, N'-dichloroisocyanurate), curox or oxone (triple potassium permonosulfate salt), water oxygenated, tert-butyl hydroperoxide, perborates and aryl peracids and aliphatics in general.
  • chloramine B chlorine, bleach, Fichlor (sodium N, N'-dichloroisocyanurate), curox or oxone (triple potassium permonosulfate salt), water oxygenated, tert-butyl hydroperoxide, perborates and aryl peracids and aliphatics in general.
  • Fichlor sodium N, N'-dichloroisocyanurate
  • curox or oxone triple potassium permonosulfate salt
  • water oxygenated tert-butyl hydroperoxide
  • perborates perborates
  • Patent FR 2 676 368 discloses a neutralization composition consisting in an aqueous solution at pH between 7 and 10 of monoperoxyphthalate magnesium hexahydrate (MPPM) containing a surfactant ammonium salt quaternary substituted by alkyl radicals, but this composition turns out unstable at pH close to neutral, preparation should be done a few minutes before use.
  • MPPM monoperoxyphthalate magnesium hexahydrate
  • the most of the formulations proposed for mild neutralization are based on the use of basic reagents with pKa greater than or equal to 9, such as various ions phenate, hydroxamate, oximate or even alcoholate introduced in the form of salts alkaline.
  • basic reagents with pKa greater than or equal to 9, such as various ions phenate, hydroxamate, oximate or even alcoholate introduced in the form of salts alkaline.
  • the pH of the formulations is on average 2 to 3 units above physiological pH.
  • Some of them even use solvents or non-aqueous cosolvents or ingredients (chelating agents, surfactants, macrocycles) whose intrinsic properties are by their nature intended to strengthen the basicity of reagents.
  • the subject of the invention is therefore a composition for decontamination by neutralization of media contaminated with organophosphorus toxic agents, in particular of type G or V, characterized in that it comprises an oxime / oximate buffer solution of pK a between 7.5 and 8.6.
  • the concentration of oxime is equal to the concentration of oximate.
  • Figures la and 1b are graphs of Brönsted (log of the speed constant as a function of pKa) describing the results obtained by studying hydrolysis reactions catalyzed by various oximate reagents in aqueous solution.
  • Figure la concerns a toxic G, soman, and Figure 1b the BNPP.
  • reactivity less than a factor of 2
  • pKa oximes of the order of 8 strongly ionized at physiological pH and pKa oximes greater than 9
  • Figures la and 1b also illustrate the fact that all phenate anions have a significantly lower nucleophilic reactivity than that of the reagents oximates of the same basicity. Also, due to this extra-reactivity, the oximates alkalines of pKa of the order of 8 have, at physiological pH conditions, a potential nucleophile greater than or equal to that of all alkali metal oxime or phenol salts used so far.
  • the nucleophilic behavior of the oximate anion is superior to that of phenates, and is believed to reach a maximum in the pH 7.5 to 8.6 range, which remains unchanged with an increase in the basicity of the medium.
  • This behavior had already observed with an electrophile with a carbon center (acetate of paranitrophenyl or PNPA) by F. Terrier, P. MacCormack, E. Kizilian, J-C. Hallé, P. Demerseman, F. Guir, C. Lion in J. Chem. Soc. Perkin Trans. 2, 1991, 153, but there was nothing to suggest that it could also concern electrophiles with a center phosphorus.
  • 2-PAM 2-pyridinium aldoxime
  • EXAMPLE 1 DESTRUCTION OF SALIN AND SOMAN BY OXIMATE 2-PYRIDINIUM ALDOXIME
  • the speed of the overall hydrolysis reaction is too high (half-reaction time less than 10 seconds) so that the destruction of toxic substances can be studied kinetically by following the appearance of the F - ions released by a potentiometric assay method using a fluorine indicating electrode.
  • the concentrations of HEPES, sarin and 2-PAM are respectively 10 -1 mole / liter, 10 -3 mole / liter, 4 x 10 -3 mole / liter.
  • the rate constant k has been determined per unit of concentration (mole / l): 5.3 mol -1 ls -1 as well as the half-reaction time in HEPES: 170 seconds.
  • the speed constant and therefore the half-reaction time corresponding to the experimental pseudo-first order conditions brought into play in the proposed formulation were calculated and are respectively 5.3 x 10 -2 s - 1 and 13 s.
  • the concentrations of HEPES, soman and 2-PAM are respectively 10 -1 mole / liter, 10 -3 mole / liter, 4 x 10 -3 mole / liter.
  • the rate constant k has been determined per unit of concentration (mole / l): 1.5 mol -1 1 s -1 as well as the half-reaction time in HEPES : 500 s.
  • the speed constant and therefore the half-reaction time corresponding to the experimental pseudo-first order conditions brought into play in the proposed formulation were calculated and are respectively 1.5 x 10 -2 s - 1 and 46 s.
  • the speed of hydrolysis has also been confirmed here by measuring the the rate constant k of the reactions under experimental conditions allowing to get lower speeds.
  • non-nucleophilic exteriors such as TAPS or 3- [tris (hydroxymethyl) methylamino] -1-propane acid sulfonic at a value of 8.30, the concentration of oximate ion, active form of the formulations, can be reduced, which slows down the hydrolysis.
  • the concentrations of TAPS, sarin and CEB 1574 are respectively 10 -1 mole / liter, 10 -3 mole / liter, 2 x 10 -3 mole / liter.
  • the rate constant k has been determined per unit of concentration (mole / l): 8.2 mol -1 ls -1 as well as the half-reaction time in the TAPS: 100 s.
  • the concentrations of TAPS, soman and CEB 1574 are respectively 10 -1 mole / liter, 10 -3 mole / liter, 2 x 10 -3 mole / liter.
  • the rate constant k has been determined per unit of concentration (mole / l): 2 mol -1 1 s -1 as well as the half-reaction time in the TAPS: 300 s .
  • the reaction is rapid (half-reaction time of the order of 120 s) and the efficiency of the formulation is greater than that involving the oxidizing reagent MPPM under similar concentration and pH conditions.
  • MPPM requires an external buffer, for example KHCO 3 / KOH in equimolar mixture.
  • the MPPM concentration is 1.4 mole / l for a VX concentration of 0.14 mole / l.
  • the major advantage of the proposed formulations is the rapid destruction of toxic under mild conditions suitable for effective neutralization of physiological tissues, without generating products which in turn present toxicity notable.
  • Efficiency can be increased by increasing the concentration of oximate used as a buffer.
  • Any other pKa oxime between 7.5 and 8.5 can be substituted for 2-PAM or CEB 1574 without compromising efficiency.
  • dioximes described in patent FR 2 605 631 such as toxogonin (1,3-bis [4- (hydroxyimino) methyl-1-pyridino] -2-oxopropane) in the form of dichloride, TMB 4 (1,3-bis [4- (hydroxyimino) methyl-1-pyridino] propane) in the form of dibromide.
  • Dioxime known as R-665 (1,5-bis [2-hydroxyiminomethyl 1-methyl] -3-pyridino-1,5dioxopentane) also suitable as iodide.
  • oximes having both a good affinity for the enzyme and a good ability to cross the blood-brain barrier.
  • the kinetic measurements are simple because no organic co-solvent or additive promoting complexation is not involved, and the cost of implementation is low.
  • the formulation according to the invention also allows the neutralization of other organophosphorus compounds, including parathion and DFP (diisopropylphosphorofluoridate).

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP98402407A 1997-10-02 1998-09-30 Dekontaminierungmittel Withdrawn EP0906773A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9712251 1997-10-02
FR9712251A FR2769234B1 (fr) 1997-10-02 1997-10-02 Composition de decontamination

Publications (1)

Publication Number Publication Date
EP0906773A1 true EP0906773A1 (de) 1999-04-07

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FR (1) FR2769234B1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10010373C1 (de) * 2000-03-02 2002-02-21 Bundesrep Deutschland Hautentgiftungsmittel gegen Haut- und Nervenkampfstoffe
US7214836B2 (en) 2003-03-12 2007-05-08 Queen's University At Kingston Method of decomposing organophosphorus compounds
WO2009094098A3 (en) * 2008-01-22 2010-04-08 E-Z-Em, Inc. Method and formulation for neutralizing toxic chemicals and materials
US8772197B2 (en) 2007-08-17 2014-07-08 Massachusetts Institute Of Technology Compositions for chemical and biological defense
AU2012233058B2 (en) * 2008-01-22 2014-12-11 Emergent Protective Products Canada Ulc Method and formulation for neutralizing toxic chemicals and materials
RU2540582C1 (ru) * 2013-08-20 2015-02-10 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") Способ переработки токсичных отходов, образующихся при уничтожении фосфорорганического отравляющего вещества типа vx

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110240306B (zh) * 2019-05-30 2021-12-14 西安建筑科技大学 一种降低含有机磷农药废水毒性的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3135761A (en) * 1959-04-28 1964-06-02 Jr Brennie E Hackley Bis quaternary oximes
GB1098128A (en) * 1965-03-08 1968-01-03 Ciba Ltd Injectable solutions of 1-alkyl-2-pyridinium-aldoxime salts
DE2844667A1 (de) * 1978-10-13 1980-04-17 Battelle Institut E V Mittel zur dekontamination von mit phosphorhaltigen giftgasen und pestiziden verunreinigten gegenstaenden und koerperteilen
FR2605631A1 (fr) * 1986-10-24 1988-04-29 France Etat Armement Sels doubles de di (hydroxyiminomethyl-pyridyloxy)-w, w' alcanes; leur procede de preparation et leur utilisation a titre therapeutique et/ou prophylactique
US5075297A (en) * 1983-11-22 1991-12-24 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government Broad spectrum chemical decontaminant system
WO1992007627A1 (en) * 1990-11-02 1992-05-14 Her Majesty The Queen As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government Metal oximate polyethylene glycols chemical decontaminant system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3135761A (en) * 1959-04-28 1964-06-02 Jr Brennie E Hackley Bis quaternary oximes
GB1098128A (en) * 1965-03-08 1968-01-03 Ciba Ltd Injectable solutions of 1-alkyl-2-pyridinium-aldoxime salts
DE2844667A1 (de) * 1978-10-13 1980-04-17 Battelle Institut E V Mittel zur dekontamination von mit phosphorhaltigen giftgasen und pestiziden verunreinigten gegenstaenden und koerperteilen
US5075297A (en) * 1983-11-22 1991-12-24 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government Broad spectrum chemical decontaminant system
FR2605631A1 (fr) * 1986-10-24 1988-04-29 France Etat Armement Sels doubles de di (hydroxyiminomethyl-pyridyloxy)-w, w' alcanes; leur procede de preparation et leur utilisation a titre therapeutique et/ou prophylactique
WO1992007627A1 (en) * 1990-11-02 1992-05-14 Her Majesty The Queen As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government Metal oximate polyethylene glycols chemical decontaminant system

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ARCH. TOXICOL. (1992), 66(3), 211-15 CODEN: ARTODN;ISSN: 0340-5761, 1992 *
BIOCHEM. PHARMACOL. (1969), 18(2), 419-27 CODEN: BCPCA6, 1969 *
CHEMICAL ABSTRACTS, vol. 117, no. 23, 7 December 1992, Columbus, Ohio, US; abstract no. 225768, WASER, P. G. ET AL: "Interaction of obidoxime with sarin in aqueous solution" XP002071446 *
CHEMICAL ABSTRACTS, vol. 70, no. 17, 28 April 1969, Columbus, Ohio, US; abstract no. 76069, HARRIS, LARREL W. ET AL: "Effects of 2-pyridinium aldoxine methochloride and atropine in relation to elevation of blood pH in soman -poisoned dogs" XP002071447 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10010373C1 (de) * 2000-03-02 2002-02-21 Bundesrep Deutschland Hautentgiftungsmittel gegen Haut- und Nervenkampfstoffe
US8722956B2 (en) 2003-03-12 2014-05-13 Queen's University At Kingston Kit for decomposing organophosphorus compounds
US7214836B2 (en) 2003-03-12 2007-05-08 Queen's University At Kingston Method of decomposing organophosphorus compounds
US7875739B2 (en) 2003-03-12 2011-01-25 Queen's University At Kingston Method of decomposing organophosphorus compounds
US8772197B2 (en) 2007-08-17 2014-07-08 Massachusetts Institute Of Technology Compositions for chemical and biological defense
AU2008348284C1 (en) * 2008-01-22 2012-11-29 Emergent Protective Products Canada Ulc Method and formulation for neutralizing toxic chemicals and materials
RU2495697C2 (ru) * 2008-01-22 2013-10-20 Е-З-Ем, Инк. Способ и рецептура для нейтрализации токсичных химикатов и материалов
US20130281538A1 (en) * 2008-01-22 2013-10-24 E-Z-Em, Inc. Method and Formulation for Neutralizing Toxic Chemicals and Materials
AU2008348284B2 (en) * 2008-01-22 2012-08-02 Emergent Protective Products Canada Ulc Method and formulation for neutralizing toxic chemicals and materials
WO2009094098A3 (en) * 2008-01-22 2010-04-08 E-Z-Em, Inc. Method and formulation for neutralizing toxic chemicals and materials
AU2012233058B2 (en) * 2008-01-22 2014-12-11 Emergent Protective Products Canada Ulc Method and formulation for neutralizing toxic chemicals and materials
CN105344058A (zh) * 2008-01-22 2016-02-24 E-Z-Em有限公司 中和杀虫剂的方法和制剂
US9604085B2 (en) 2008-01-22 2017-03-28 Emergent Protective Products Canada Ulc Method and formulation for neutralizing toxic chemicals and materials
RU2540582C1 (ru) * 2013-08-20 2015-02-10 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ") Способ переработки токсичных отходов, образующихся при уничтожении фосфорорганического отравляющего вещества типа vx

Also Published As

Publication number Publication date
FR2769234A1 (fr) 1999-04-09
FR2769234B1 (fr) 1999-11-26

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