CA1224800A - Chemical warfare simulant - Google Patents
Chemical warfare simulantInfo
- Publication number
- CA1224800A CA1224800A CA000471084A CA471084A CA1224800A CA 1224800 A CA1224800 A CA 1224800A CA 000471084 A CA000471084 A CA 000471084A CA 471084 A CA471084 A CA 471084A CA 1224800 A CA1224800 A CA 1224800A
- Authority
- CA
- Canada
- Prior art keywords
- simulant
- chemical
- ethyl
- nerve
- nerve gas
- 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.)
- Expired
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT
The invention disclosed is a chemical substance, 2-(diisopropylamino)ethyl dimethylthiocarbamate. This substance exhibits utility as a simulant for use in place of VX nerve gas in decontamination studies.
The invention disclosed is a chemical substance, 2-(diisopropylamino)ethyl dimethylthiocarbamate. This substance exhibits utility as a simulant for use in place of VX nerve gas in decontamination studies.
Description
This invention relates to a novel simulator of a chemical warfare agent.
~ ore particularly, this invention relates to a chemical which may be used to simulatè nerve aas in an improved manner durin~ decontamination procedures.
Difficulties of a technical and administrative nature prevent the use of nerve nas in research, development, and testing procedures due to the hazards involved. ~urrent safety and security re~ulations which govern the use of toxic chemical warfare agents preclude most research, development, and testing of nerve aas such dS VX in ~ost la~oratories. For exa~ple, no outdDor testing may be done ~ith the actual nerve aas itsel f. Thus, in order to facilitate che~ical defense research, develop~ent, testin~ and evaluation, it is vital to have an inventory of che~ical simulants for such nerve gas for s~ecific purposes. It can be seen where simulants are vital to sustained progress ;n the improvement of our defensive posture relative chemical warfare. As one can see, simulants are use~ in every major area of the research operation of chem~cal warfare agents. They are necessary in everp stage of the life cycle of a system from conception through basic research, development, testing, evaluation an~ training.
To date, the only compound used to mimic the chemical behavior of VX is O-ethyl S-ethyl methylDhosphonothiolate. Howe~er, the solubility and reactivity of this compound preclude the valid performance study of VX at varying pH levels.
It is known that each of the areas of study in testing and evaluation set their own parameters relative the experimental or operating stages. These parameters dictate what properties are essential for an effective slmulant in the areas under study. In the past, experimenters had to use their individual judgement in selecting simulants and, many times, a simulator was a material which was used because it was readily available or because of prior use in another stage of the cycle. Many times, the material used for one specific purpose was not altogether satisfactory for a second speclfic purpose because of its properties.
There has been a long standing need in the research cnmmunity of chemical defense for a catalog of co~pnunds which might be used as simulants for specific chemical agents under specific conditions particular decomposition or decontamination. In particular, a search for a slmulant of VX under decontamination studies is extremely important.
It is therefore an object of this in~ention to provide a simulant for VX
nerve gas for use in research, development, evaluation and testing of chemically active liguid decontaminants.
Another object is to provide a simulator of YX which is safe to use hut mimics the physical and chemical properties of the cited dangerous tnxic agent itself.
Other objects and many of the attendant advantages of this invention will become rore apparent to thos~ skilled ;n the art from a reading of the detailed specification which follows.
~ 2 ~2Z4800 In general, the simulator of VX must be liquid, should have a solubil~ty similar to YX, and in solut~on should be destroyed by ox~datlon and hydrolysis in a manner and rate si~ilar to VX. Thus the three main properties of a simulant are state, solubility, and reactivity. However, a fourth requirement of a decreased amount of toxicity when compared to VX is highly important.
We have found that the chemical 2-(diisopropylam~no)ethyl dimethylthiocarbamate is the preferred stimulant for use ln place of VX nerve gas in decontamination studies.
The formula for this simulator is, viz.
lo ~CH3~ \ / CH3
~ ore particularly, this invention relates to a chemical which may be used to simulatè nerve aas in an improved manner durin~ decontamination procedures.
Difficulties of a technical and administrative nature prevent the use of nerve nas in research, development, and testing procedures due to the hazards involved. ~urrent safety and security re~ulations which govern the use of toxic chemical warfare agents preclude most research, development, and testing of nerve aas such dS VX in ~ost la~oratories. For exa~ple, no outdDor testing may be done ~ith the actual nerve aas itsel f. Thus, in order to facilitate che~ical defense research, develop~ent, testin~ and evaluation, it is vital to have an inventory of che~ical simulants for such nerve gas for s~ecific purposes. It can be seen where simulants are vital to sustained progress ;n the improvement of our defensive posture relative chemical warfare. As one can see, simulants are use~ in every major area of the research operation of chem~cal warfare agents. They are necessary in everp stage of the life cycle of a system from conception through basic research, development, testing, evaluation an~ training.
To date, the only compound used to mimic the chemical behavior of VX is O-ethyl S-ethyl methylDhosphonothiolate. Howe~er, the solubility and reactivity of this compound preclude the valid performance study of VX at varying pH levels.
It is known that each of the areas of study in testing and evaluation set their own parameters relative the experimental or operating stages. These parameters dictate what properties are essential for an effective slmulant in the areas under study. In the past, experimenters had to use their individual judgement in selecting simulants and, many times, a simulator was a material which was used because it was readily available or because of prior use in another stage of the cycle. Many times, the material used for one specific purpose was not altogether satisfactory for a second speclfic purpose because of its properties.
There has been a long standing need in the research cnmmunity of chemical defense for a catalog of co~pnunds which might be used as simulants for specific chemical agents under specific conditions particular decomposition or decontamination. In particular, a search for a slmulant of VX under decontamination studies is extremely important.
It is therefore an object of this in~ention to provide a simulant for VX
nerve gas for use in research, development, evaluation and testing of chemically active liguid decontaminants.
Another object is to provide a simulator of YX which is safe to use hut mimics the physical and chemical properties of the cited dangerous tnxic agent itself.
Other objects and many of the attendant advantages of this invention will become rore apparent to thos~ skilled ;n the art from a reading of the detailed specification which follows.
~ 2 ~2Z4800 In general, the simulator of VX must be liquid, should have a solubil~ty similar to YX, and in solut~on should be destroyed by ox~datlon and hydrolysis in a manner and rate si~ilar to VX. Thus the three main properties of a simulant are state, solubility, and reactivity. However, a fourth requirement of a decreased amount of toxicity when compared to VX is highly important.
We have found that the chemical 2-(diisopropylam~no)ethyl dimethylthiocarbamate is the preferred stimulant for use ln place of VX nerve gas in decontamination studies.
The formula for this simulator is, viz.
lo ~CH3~ \ / CH3
2 _, N-CH -CH -S-C-N
~ 3~2 2 2 ~ CH3 The table I which follows sets forth a comparison of the physical and chemical properties of this simulator as compared to YX.
TABLE I
Cited YX Simulator For ula267.4 232.4 Point 298C 320 Dens;ty-25C 1.008qlCm3 0.978g/Cm3Yiscosity-25C 9.96 cP 9.75 cP
SolubiliOty in 0.11M/liter O.nl5M/liter Hydrolysis 40 hours @ pH10 60 hours @ pH10 ToxicitY 500,0nO M~lsec~l 17M~lsec~l .
~22~8()0 As seen in Table 1, the properties of a necessary si~ulant in place of YX
are shown. It has been found that a8 a result of this comparison, the simulant of thls invention could replace YX in various studies which have to be ~ade. In particular, the simulant besides havin~ properties, which are substantially e~uivalent to that;of VX, is less tox~c th~n the nerve gas and could be used to study decontam~nation procedures. As shown, the s~ulant has no significant anti-cholinesterate properties which make it less dangerous.
Thus, a low tox kity substltute has been found for YX.
PREPARATIO~I
The simulant 2-(diisopropylaminol ethyl dimethylthiocarbamate is prepared from equimolar a~ounts of dimethylcarbamayl chloride and 2-- [diisopropylamino)ethanethiol hydrochlorid~. The latter two chemicals are refluxed for about 2D hours ~n a five-fold molar excess of pyridine. The pyridine is evaporated, and the residue dissolved in chloroform. Th~s solution ls washed with dilute sodium hydroxide solution, dried o~Yer magnesium sulfate, and the chloroform is evaporated under vacuum. The product is then purified by vacuum distillation, and ~s collected at 118 - 120C at .55 torr. The distillate, a colorless liquid, was confirmed as a pure compound by nmr spectroscopy, elemental analysis, and gas chromatography.
COMPARISnN
REACTIQN TO AQUEO~S HYPOCHLORlTE
In separate experiments, the simulant of this ~nvention and VX nerve gas were reacted with a five-fold ~olar excess of sodiu~ N, N-dichloroisocyanurate in water. At intervals of two to ten ~inutes, al~quots of each of the materials were re~oved and analyzed iodi~etrically for active ch~orine concentration.
VX nerve gas un~er the above reaction conditions, consumed chlorine in two ki~etically distinct processes. In the first f~lY minutes, there was a ~2248t)~
rapid consumption of ahout 1.5 mole equivalent of hypochlorite per mol of VX
ner~e gas. This was followed by a slower but nearly l~near consumption of chlorine over a substantially two hour period.
The chlorine consumption of the simulant of this ~nvention followed a similar two-stage pattern when compared to VX. During the period of 15 minutes to 60 minutes after miKing, their re~ative chlorine consumptions are within lQ percent of each other.
In comparison, VX is a liquid, so is the si~ulant of this invention. V~
could never be ~imicked by a solid. VX and the cited si~ulant of this invention have similar solubilities in water and both are pH dependent in similar ways. Once in solution, VX nerve gas may be destroyed by oxidation or hydrolysis, and such is the chemical reactivity of the s~mulant of this invention.
There has been a long-standing need in the chemical defense research community for a simulant which would satisfactDrily m1mlc the physical and chemical properties of YX. The slmulant of this invention has been prepared and its physical properties, slow hydrolysis, and behavior toward hypochlorite make this a suitable simulant for VX. The homologues of the simulant of this invention do rot exhibit the desired propert~es. The cited simulant of this invention may be added to a catlog of compounds which may be used as si~ulants for specific agents under specific conditions. For exa~ple, the simlllant o~
this invention may be used in the testing of che~ically active liguid decontaminants in place of YX for research, development, test, and evaluation of new systems.
~YPOCHLnRITE OXIDATION
Sodium N, N-dichloroisocyanurate (Fichlor reagent) was used in the comparison of the hypochtorite oxidation reaction. When YX was added to an unbuffered solution of the Fichlor reagent in water at a S molar excess relative VX, there was an i~m~diate reactiDn. h'ithin I minute, the YX was destroyed. The data for the simulant in Fichlor exhibited a similar 12248~)0 pattern. There was an initial rapid burst of chloring consumption ~y the simulant wh~ch was followed by a slower steady-state consumption. The correlation of VX and simulant relative Kinetics is highly satisfactory for the lntended purpose of test~ng and eva~uatlon of the decontam~natlon procedure.
.
~ 3~2 2 2 ~ CH3 The table I which follows sets forth a comparison of the physical and chemical properties of this simulator as compared to YX.
TABLE I
Cited YX Simulator For ula267.4 232.4 Point 298C 320 Dens;ty-25C 1.008qlCm3 0.978g/Cm3Yiscosity-25C 9.96 cP 9.75 cP
SolubiliOty in 0.11M/liter O.nl5M/liter Hydrolysis 40 hours @ pH10 60 hours @ pH10 ToxicitY 500,0nO M~lsec~l 17M~lsec~l .
~22~8()0 As seen in Table 1, the properties of a necessary si~ulant in place of YX
are shown. It has been found that a8 a result of this comparison, the simulant of thls invention could replace YX in various studies which have to be ~ade. In particular, the simulant besides havin~ properties, which are substantially e~uivalent to that;of VX, is less tox~c th~n the nerve gas and could be used to study decontam~nation procedures. As shown, the s~ulant has no significant anti-cholinesterate properties which make it less dangerous.
Thus, a low tox kity substltute has been found for YX.
PREPARATIO~I
The simulant 2-(diisopropylaminol ethyl dimethylthiocarbamate is prepared from equimolar a~ounts of dimethylcarbamayl chloride and 2-- [diisopropylamino)ethanethiol hydrochlorid~. The latter two chemicals are refluxed for about 2D hours ~n a five-fold molar excess of pyridine. The pyridine is evaporated, and the residue dissolved in chloroform. Th~s solution ls washed with dilute sodium hydroxide solution, dried o~Yer magnesium sulfate, and the chloroform is evaporated under vacuum. The product is then purified by vacuum distillation, and ~s collected at 118 - 120C at .55 torr. The distillate, a colorless liquid, was confirmed as a pure compound by nmr spectroscopy, elemental analysis, and gas chromatography.
COMPARISnN
REACTIQN TO AQUEO~S HYPOCHLORlTE
In separate experiments, the simulant of this ~nvention and VX nerve gas were reacted with a five-fold ~olar excess of sodiu~ N, N-dichloroisocyanurate in water. At intervals of two to ten ~inutes, al~quots of each of the materials were re~oved and analyzed iodi~etrically for active ch~orine concentration.
VX nerve gas un~er the above reaction conditions, consumed chlorine in two ki~etically distinct processes. In the first f~lY minutes, there was a ~2248t)~
rapid consumption of ahout 1.5 mole equivalent of hypochlorite per mol of VX
ner~e gas. This was followed by a slower but nearly l~near consumption of chlorine over a substantially two hour period.
The chlorine consumption of the simulant of this ~nvention followed a similar two-stage pattern when compared to VX. During the period of 15 minutes to 60 minutes after miKing, their re~ative chlorine consumptions are within lQ percent of each other.
In comparison, VX is a liquid, so is the si~ulant of this invention. V~
could never be ~imicked by a solid. VX and the cited si~ulant of this invention have similar solubilities in water and both are pH dependent in similar ways. Once in solution, VX nerve gas may be destroyed by oxidation or hydrolysis, and such is the chemical reactivity of the s~mulant of this invention.
There has been a long-standing need in the chemical defense research community for a simulant which would satisfactDrily m1mlc the physical and chemical properties of YX. The slmulant of this invention has been prepared and its physical properties, slow hydrolysis, and behavior toward hypochlorite make this a suitable simulant for VX. The homologues of the simulant of this invention do rot exhibit the desired propert~es. The cited simulant of this invention may be added to a catlog of compounds which may be used as si~ulants for specific agents under specific conditions. For exa~ple, the simlllant o~
this invention may be used in the testing of che~ically active liguid decontaminants in place of YX for research, development, test, and evaluation of new systems.
~YPOCHLnRITE OXIDATION
Sodium N, N-dichloroisocyanurate (Fichlor reagent) was used in the comparison of the hypochtorite oxidation reaction. When YX was added to an unbuffered solution of the Fichlor reagent in water at a S molar excess relative VX, there was an i~m~diate reactiDn. h'ithin I minute, the YX was destroyed. The data for the simulant in Fichlor exhibited a similar 12248~)0 pattern. There was an initial rapid burst of chloring consumption ~y the simulant wh~ch was followed by a slower steady-state consumption. The correlation of VX and simulant relative Kinetics is highly satisfactory for the lntended purpose of test~ng and eva~uatlon of the decontam~natlon procedure.
.
Claims (2)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for simulating the behaviour of VX nerve gas, which comprises employing 2-(diisopropylamino)ethyl dimethylthio-carbomate as VX nerve gas simulant.
2. The method of claim 1, wherein said 2-(diisopropylamino)-ethyl dimethylthiocarbomate has the following properties, viz:
a) molecular weight of 232.4, b) boiling point of 320°C, c) density of 0.978 g/cm3 at 25°C, d) viscosity of 9.75 cP at 25°C, e) solubility in water of 0.015M at 25°C, and f) hydrolysis in t ? greater than 60 hours at pH10.
a) molecular weight of 232.4, b) boiling point of 320°C, c) density of 0.978 g/cm3 at 25°C, d) viscosity of 9.75 cP at 25°C, e) solubility in water of 0.015M at 25°C, and f) hydrolysis in t ? greater than 60 hours at pH10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58269784A | 1984-02-23 | 1984-02-23 | |
| US582,697 | 1984-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224800A true CA1224800A (en) | 1987-07-28 |
Family
ID=24330162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000471084A Expired CA1224800A (en) | 1984-02-23 | 1984-12-27 | Chemical warfare simulant |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1224800A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2729234C1 (en) * | 2020-01-27 | 2020-08-05 | Федеральное государственное бюджетное учреждение "33 Центральный научно-исследовательский испытательный институт" Министерства обороны Российской Федерации | Use of triethanolamine as a simulator of fluorescent properties of o-ethyl-s-2-diisopropylaminoethyl methylphosphonate |
-
1984
- 1984-12-27 CA CA000471084A patent/CA1224800A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2729234C1 (en) * | 2020-01-27 | 2020-08-05 | Федеральное государственное бюджетное учреждение "33 Центральный научно-исследовательский испытательный институт" Министерства обороны Российской Федерации | Use of triethanolamine as a simulator of fluorescent properties of o-ethyl-s-2-diisopropylaminoethyl methylphosphonate |
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| MKEX | Expiry |