Title of Invention

"A COMPOSITION FOR INSTANT DECONTAMINATION OF SULFUR MUSTARD AND PROCESS OF PREPARATION THEREOF"

Abstract The present invention relates to a composition for instant decontamination of sulfur mustard and process of preparation, comprising N-chlorocyanamide (NCC) derivatives, the said composition is capable to decontaminate the highly toxic organosulfur compounds.
Full Text A COMPOSITION FOR INSTANT DECONTAMINATION OF SULFUR MUSTARD AND PROCESS OF PREPARATION THEREOF
FIELD OF INVENTION
The present invention relates to a composition for instant decontamination of sulfur mustard (SM) comprising a mixture of N-chlorocyanamides(NCC) & its derivatives with polar solvent system, wherein the said composition provide desired effect, while being exposed with sulfur mustard.
BACKGROUND AND PRIOR ART
Neutralization of chemical and biological organosulfur agents on a large scale, i.e., across large areas or on major pieces of equipment is particularly difficult to achieve. Application of large amounts of decontamination composition does not solve a large scale contamination problem. With the large-scale dispersion of the decontamination composition, effective contact between the decontamination composition and organosulfur agents decreases. Spreading a large amount of decontamination composition in an area allows the decontamination composition to absorb into ground, or seep away on equipment, without neutralization of the organosulfur agent. Saturation of the area with decontamination composition does not ensure reaction with the organosulfur agent, that may require mechanical agitation to effectuate the decontamination composition with the organosulfur agent. Scrubbing by personnel, to provide mechanical agitation, once the decontamination composition has been applied may expose the personnel to both the decontamination composition and the organosulfur compound, presenting a serious safety hazard. Additionally, the decontamination composition may prove hazardous to personnel and equipment, regardless of the amount of original organosulfur agent contamination. In an effort to neutralize small amounts of contamination over a large area, the saturation of the large area with decontamination composition may increase environmental damage to the
area, increase equipment damage, or inhibit mission completion beyond that of the effects of the organosulfur agent itself.
The US patent No.4,874,532 discloses use of super tropical bleach (STB) as decontaminate, which is a white powder containing about 30 percent available chlorine in the form of calcium hypochlorite. STB may be used either as a dry mix or as an aqueous slurry to decontaminate exterior surfaces and ground that has become contaminated with chemical toxic agents. STB deteriorates with time and accordingly must be replaced every few years. Further, STB is more soluble in aqueous media than in organic media and, therefore, is less effective as a decontamination agent against
toxic organic chemical substances that are disseminated in an aqueous medium.
Decontamination Solution (DS2) is also one of the decontamination composition which is currently used against a variety of organosulfur compounds containing agents. DS2 contains 70% diethylenetriamine, 28% ethylene glycol monomethyl ether and 2% sodium hydr&xide. However, the said composition is extremely corrosive, and providing handling difficulties.
One another decontamination compositions have also been disclosed in U.S. Pat. Nos. 5,760,089 and 5,859,064. The said patents disclose quaternary ammonium compound based decontamination compositions that are based on solutions of benzyltrimethylammonium chloride or benzyltriethylammonium chloride, and use a ratio of approximately 100:1 decontamination composition to organosulfur agent. As such, the decontamination compositions are limited to in their ability to decontaminate relatively large areas of contamination.
Yet another decontamination composition has been disclosed in US Patent 5,607,979. The said patent discloses the reactive decontaminants such as 1,3,4,6 tetrachloro-7,8-diphenyl-2,5-diimino glycouril coded as S-330 was mixed with perfluorinated ether and evaluated as a reactive decontaminant against sulfur mustard. The disadvantages of this system are the use of uneconomical and decomposes with in 2-3 weeks at room temperature in presence of even little bit of moisture. (E.H. Bran, J.Appl.Toxicol.1999,
19 S47; O. Koper, E.Lucas, K.J. Klabunde, J. Appl. Toxicol. 1999, 19, S59). Another disadvantage of this system is that it is not fast acting which is the prime requirement of any decontaminant.
Foam use to knock-down chemical vapors and biological particulates has been disclosed in U.S. Pat. No. 5,864,767 to Drumgoole et al. The said patent reveals an inflatable, portable apparatus having an aqueous foam for substantially mitigating the effects of an explosively deployable chemical, biological and/or radiological agent within the substantially defined area. Drumgoole discloses that decontamination compounds can be added to the foam to allow chemical, biological and/or radiological neutralization in situ. However, these decontamination compounds are limited to the relatively small areas only.
Methods for decontamination of organosulfur agents also include physical removal of organosulfur compounds from contaminated site can be carried out using adsorbent like Fuller's earth and detergent / soap solutions. However, they are simply, adsorbed at the surface of adsorbent not destroyed and need further chemical treatment for complete detoxification, and hence are not considered as reliable means.
Also, chemical decontamination of organosulfur agent can be carried out using reactive component as disclosed in (Yang Y.C. Chem. Ind. 1995, May 1, 334), (Yang Y.C. Baker J.A.; WardJ.R. Chem. Rev. 1992, 92, 1729; R.P. Seiders, US Patent H3 66, 1987; and Govan Noram, Int.Patent A62D3/00 & Eur. Patent A62D3/00E, 1998; Yang Y.C. Szfraniec L.L. Beaudry W.T., Davis F.A. Proceedings of the 1998 US Army CRDEC -SP-013, Aberdeen Proving Ground Maryland August 1989, Vol 1). However, these known methods use compositions which have certain undesirable properties, including corrosiveness, flammability, toxicity, instability, not economic and require prolonged reaction time. Additionally, many decontaminants degrade upon exposure to water and carbon dioxide, requiring that these solutions be prepared and used the same day they are needed.
A need exists for a decontamination of organosulfur agent which is noncorrosive, nontoxic, nonflammable, stable, and environmentally safe. It is also required that substance can be applied directly to a contaminated area to destroy/detoxify the chemical agents which can then be washed, swept, or vacuumed away. In addition, the substance must be capable of being effectively applied to a surface or items. As a result, substance must be fluid enough to be quickly and easily applied to surfaces.
Keeping in view the hazards of organosulfur agent, their decontamination is of paramount importance. It is required on the field, in laboratories, production and storage plants, and destruction sites. Of the various known organosulfur mustard, sulphur mustard is potential fatal.vesicant that damages skin, eyes, and respiratory track Blood-forming tissues (marrow, lymph nodes and spleen) and particularly sensitive to cytotoxic alkylating properties of mustard. There are no specific antidotes for SM toxicity and it is a challenge even today in organosulfur agent scenario. Since SM is highly lipophilic and gets absorbed very quickly after contact with skin, the best way of protection from SM is to decontaminate it instantaneously after contact with skin without causing any damage to delicate human skin. This stringent requirement of decontaminant was successfully met by developing N-chlorocyanamide based composition that deactivate the topically applied SM instantaneously without causing any irritation or harm to the skin. Keeping in view the requirement of N-tert-butyl-N-chlorocyanamide, this substance was produced in gram quantity by making use of indigenously and commonly available chemicals such as amines, cyanogens bromide, tert-butanol and chlorine gas.
OBJECTIVES OF THE INVENTION
The primary objective of the present invention is to provide a composition for instant decontamination of sulfur mustard comprising a mixture of N-chlorocyanamides & its derivatives with polar solvent system in a ratio of 1:3 to 1:20, wherein 1% by weight of the said composition provide desired effect, while being exposed with 2 to 10% by weight of sulfur mustard.
Yet another objective of the invention is to explore most suitable N-chlorocyanamides derivatives having low vapour pressure, high chemical reactivity against sulfur mustard stable under normal conditions and posses good chlorine content.
Still another objective of the invention is to use of reaction conditions for the decontaminant of sulphur mustard and its stimulants such as use of appropriate solvent system in making the compositions, temperature, and time.
Yet another objective of the invention is to develop a cost effective, non toxic, stable decontaminant for sulfur mustard, which can be prepared from indigenously and commonly available chemicals.
Yet another objective of the invention is to develop N-chlorocyanamide based compositions that deactivated the topically applied sulfur mustard instantaneously and without causing any irritation or harm to the skin.
Still another objective of the invention is that the composition can be applied directly to a contaminated area to destroy/detoxify the chemical agents which can then be washed, swept or vacuumed away.
Yet another objective of the invention is use of components in the method of manufacture of the composition that are not flammable or corrosive.
STATEMENT OF THE INVENTION
Accordingly, the present invention relates to a composition for instant decontamination of sulfur mustard comprising a mixture of N-chlorocyanamides & its derivatives with polar solvent system in a ratio of 1:3 to 1:20, wherein 1% by weight of the said
composition provide desired effect, while being exposed with 2 to 10% by weight of sulfur mustard.
Also, present invention relates to a process of instant decontamination of sulfur mustard by using the said the composition, comprising the steps of:
a) allowing to react the said composition with sulfur mustard in a ratio of 1:2 to 1:10 at a temperature in the range of-20°C to 50°C; and obtaining a solid product,
b) extracting the product of step (a) by mixing with water and dichloromethane and evaporating the same.
c) obtaining the product of step (b) as mixture of sulfoxide compound and cyanamide derivative.
d) separating the cyanamide derivative from the product of step(c) in presence of dichloromethane/petroleum ether at a temperature 40 to 60°C, in a ratio of 3:7, for obtaining decontaminated sulfoxide derivative compound.
SUMMARY OF THE INVENTION
The organosulfur agents are required on the field, in laboratories, production and storage plants, and destruction sites. Of the various known organosulfur agents, sulphur mustard is potential fatal vesicant that damages skin, eyes, and respiratory track. Since SM is highly lipophilic and gets absorbed very quickly after contact with skin, the best way of protection from SM is to decontaminate it instantaneously after contact with skin without causing any damage to delicate human skin. Accordingly, the present invention provides an instant composition for decontaminating sulfur mustard. The said composition deactivate the topically applied SM instantaneously by reacting with sulfur mustard, without causing any irritation or harm to the skin.
DETAILED DESCRIPTION OF THE INVENTION
Accordingly, the present invention relates to a composition for instant decontamination of sulfur mustard comprising a mixture of N-chlorocyariamides & its derivatives with polar solvent system in a ratio of 1:3 to 1:20, wherein 1% by weight of the said
composition provide desired effect, while being exposed with 2 to 10% by weight of sulfur mustard.
One embodiment of the present invention, wherein the derivative of N-chlorocyanamides are selected from the group comprising N-methyl-N-chlorocyanamide, N-ethyl-N-chlorocyanamide, N-propyl-N-chlorocyanamide, N-isopropyl-N-chlorocyanamide, N-butyl-N-chlorocyanamide, N-tert-butyl-N-
chlorocyanamide, N-cyclohexyl-N-chlorocyanamide, N-phenyl-N-chlorocyanamides, N-benzyl-N-chlorocyanamides.
In one another embodiment of the present invention, wherein the solvent system comprising a mixture of one or more polar solvent which are selected from the group comprising methanol, ethanol, n-butanol, water, n-propanol,l,4-
dioxane,tetrahydrofuran,acetone,acetonitrile,dimethylsulfoxide,dimethylformamide.
Yet another embodiment of the present invention, wherein the solvent system is a mixture of acetonitrile and water in a ratio of 1:5 to 5:1.
A further embodiment of the present invention relates to a process of instant decontamination of sulfur mustard by using the said the composition, comprising the steps of:
a) allowing to react the said composition with sulfur mustard in a ratio of 1:2 to 1:10 at a temperature in the range of-20°C to 50°C; and obtaining a solid product,
b) extracting the product of step(a) by mixing with water and dichloromethane and evaporating the same.
c) obtaining the product of step(b) as mixture of sulfoxide compound and cyanamide derivative.
d) separating the cyanamide derivative from the product of step(c) in presence of dichloromethane/petroleum ether at a temperature 40 to 60°C,in a ratio of 3:7, for obtaining decontaminated sulfoxide derivative compound.
Accordingly to the present invention provides a organosulfur agent decontamination composition having N-chlorocyanamides as a reactive component in noncorresive, nontoxic, nonflammable composition systems. The decontaminant is nonflammable and nontoxic and does not degrade significantly over time after exposure to air and moisture. The decontaminant contain N-chlorocyanamides as an active moiety. As defined herein, NCC has general structure given below. Chlorine atom in NCC is chemically bonded to nitrogen atom that makes chlorine atom positive in nature. Moreover, electron-withdrawing group (-CN) also attached to same nitrogen atom which further enhance the positive chlorine donating power of NCC irrespective of alkyl/aryl group attached to nitrogen atom.
(Formula Rempved)
Where R includes Me,Et, Pr, z'-Pr, Butyl, t-Butyl, Cyclohexyk Phenyl, Benzyl sunsstituent also chemically bonded to nitrogen. All NCC derivatives do not match with the requirement of an efficient decontaminant. Some of these suffer either from poor yield or reactivity of NCC and instability at room temperature for long duration. Among these N-tertbutyl-N-chlorocynamide was found to be most suitable and all required properties to behave as an excellent decontaminants. After selection of suitable NCC derivatives another important parameter is to select solvent system. For this, a nonflammable, nontoxic, noncorrosive solvent has always been a better choice. Using a mixed acetonitrile-water solution, their different ratio was investigated to optimized the reaction conditions and we reach to concklusion that 6:4 of acetonitrile:water was the most suitable composition to bring about the decontamination. NCC derivatives based composition in mixed acertonitrile (6:4) was highly reactive to decontaminate organosulfur agent instantaneously. The decontamination of organosulfur agent of this invention was also evaluated from a ranges of temperature stating from -10°C to 50°C. This composition works effectively at both temperatures at same rate.
Advantageously, a acetonitrile water-based decontaminant of the invention, stored under ambient Conditions, showed no changes in its infrared spectrum over a
period of 100 days also appeared unchanged, when exposed to a range of temperatures of 5-115 0F. These tests indicate that the compositions are stable. Further, none of the components used in these compositions are listed as flammable or corrosive.
Thus, the decontaminant compositions of the invention are believed to be stable, nontoxic and useful in detoxifying/neutralizing a variety of organosulfur agent, including organosulfur agents such as mustard gas and organophosphorus agents such as the nerve agents. Decontamination is effected by applying a decontaminant of the invention to the contaminated material, equipment, personnel, or the like. Such application may be spraying, showering, washing or other suitable means. The amount of decontaminant required under field conditions can be readily determined by the person having skill in the art.
The advantages of the disclosed invention are thus attained in an economical, practical and facile manner. While preferred embodiments and example configurations have been shown and described, it is to be understood that various further modifications and additional configurations will be apparent to those skilled in the art. It is intended that the specific embodiments and configurations herein disclosed are illustrative of the preferred and best modes for practicing the invention, and should not be interpreted as limitations on the scope of the invention.
EXAMPLE 1
Preparation of the decontaminant
A dried solution containing 0.28 mol of cyanogen bromide in 350 mL of anhydrous ether was cooled at 0 °c /and tert-butyl amine was added slowly with the help of dropping funnel. When 1.8 mol of amine/ mol of cyanogen bromide have been added (2 h), a precipitate of amine hydrobromide was removed by Alteration. This filtrate was washed with water (2 X 100 mL) and solution was evaporated to make one-half of its total volume. The solution containing tert-butyl cyanamide is converted to N-tert-butyl-N-chlorocyanamide as follows:
The resulting solution was diluted with 75 mL of carbon tetrachloride in flask cooled to 0 °c, treated with theoretical amount of tert-butyl hypochlorite in 30 mL of carbon tetrachlorideand allowed to warm at room temperature. The yellow solution was evaporated, and residue was distilled to afford the product, bp 53.5 (8 mm), IR (KBr): 2216 cm-1 (NCN) and weak band at 2082 cm-1. The positive chlorine of N-tert-butyl-N-chlorocyanamide was checked by standard iodometric titration it was found to be 26.54 % (theoretical value 26.76 %).
EXAMPLE 2
Process for the neutralization of Sulfur Mustard
N-tert-butyl-N-corocyanamide (1.0 mmol) was added slowly to a stirred solution of SM (1.0 equiv.) in mixed acetonitrile-water solution (1:1) (10. ml). The reaction was carried out at two different temperatures (-10 and 35°C)and monitored by gas chromatography. After completion of reaction, water was added to the reaction mixture and product was extracted with dichloromethane (3 x 10 ml). Organic layer was washed with water (2x10 ml) and dried over anhydrous Na2SO4. On evaporation of the solvent on rotavapour, mixture of sulfoxides and t-butyl cyanamide was obtained. The sulfoxide was separated from tert-butyl cyanamide by recrystallization method using DCM/petroleum ether (40-60 °C) (3:7).
EXAMPLE 3
Process for the preparation of sulfoxides
To a stirred solution of N-t-butyl-N-chlorocyanamide (1.0 mmol), in a mixed acetonitrile-water solution (1:1), sulfide (1.0 equiv.) was added. The reaction was carried out at room temperature and was monitored by TLC. After completion of reaction, water (50 ml) was added to the solution, which was then extracted with DCM, dried over anhydrous Na2SO4. On evaporation of the solvent on rotavapour gave mixture of sulfoxide and t-butyl cyanamide (bp 53-54 °C / 8 mmHg). The pure sulfoxide was obtained either by recrystallization in DCM/petroluem ether (40-60 °C) (in case of solid products) or distillation (in case of liquid products).
ADVANTAGES
1. An instant decontamination of sulfur mustard to sulfoxide at room temperature.
2. Compositions having N-chlorocyanamides is also used to detoxify organphosphorus agents particularly those which is having -S- linkages
3. Compounds having N-chlorocyanamides {R-N(CIXCN)} moiety is useful in converting organic sulfides to respective sulfoxides chemoselectively.
4. The said composition is non-inflammable and non-toxic and does not degrade significantly over time after exposure to air and moisture.
5. The instant composition is also non-corrosive, stable and environmentally safe.
6. The said composition instantaneously deactivates the topically applied sulfur mustard without causing any irritation or harm to the skin.
7. The neutralization of organosulfur agents is achieved immediately.
8. Since chlorine atom is released as positive ion in the process, hence less amount of said composition is required for neutralization.









We Claim:
1. A composition for instant decontamination of sulfur mustard comprising a mixture of N-chlorocyanamides and/or its derivatives with polar solvent system such as herein described, in a ratio of 1:3 to 1:20, wherein 1% by weight of the said composition provide desired effect, while being exposed with 2 to 10% by weight of sulfur mustard.
2. The composition as claimed in claim 1, wherein the derivative of N-chlorocyanamides are selected from the group comprising N-methyl-N-chlorocyanamide, N-ethyl-N-chlorocyanamide, N-propyl-N-chlorocyanamide, N-isopropyl-N-chlorocyanamidc, N-butyl-N-chlorocyanamide, N-tert-butyl-N-chlorocyanamidc, N-cyclohexyl-N-chlorocyanamide, N-phenyl-N-chlorocyanamides, N-benzyl-N-chlorocyanamidcs.
3. The composition as claimed in claim 2, wherein the N-chlorocyanamide derivative is N-tert-butyl-n-chlorocyanamide.
4. The composition as claimed in claim 1, wherein the solvent system comprising a mixture of one or more polar solvent which are selected from the group comprising methanol, ethanol, n-butanol, water, n-propanol, 1,4-methanol, tetrahydrofuran, acetone, acetonitrile, dimethylsulfoxide, dimethylformamide.
5. The composition as claimed in claim 4, wherein the solvent system is a mixture of acetonitrile and water in a ratio of 1:5 to 5:1.
6. A process of instant decontamination of sulfur mustard by using the composition as claimed in ciaim 1, comprising the steps of:
a. allowing to react the said composition with sulfur mustard in a ratio of 1:2 to 1:10 at a
temperature in the range of-20°C to 50°C; and obtaining a solid product;
b. extracting the product of step (a) by mixing with water and dichloromcthanc and
evaporating the same,
c. obtaining the product of step (b) as mixture of sulfoxide compound and cyanamide
derivative,
d. separating the cyanamide derivative from the product of step (c) in presence of dichloromethane/petroleum ether at a temperature 40 to 60° C, in a ratio of 3:7, for obtaining decontaminated sulfoxide derivative compound.

Documents:

1515-DEL-2006-Abstract-(07-03-2011).pdf

1515-del-2006-abstract.pdf

1515-DEL-2006-Claims-(07-03-2011).pdf

1515-del-2006-Claims-(21-04-2011).pdf

1515-del-2006-claims.pdf

1515-DEL-2006-Correspondence Others-(18-08-2011).pdf

1515-DEL-2006-Correspondence-Others-(07-03-2011).pdf

1515-del-2006-Correspondence-Others-(21-04-2011).pdf

1515-del-2006-correspondence-others-1.pdf

1515-del-2006-correspondence-others.pdf

1515-DEL-2006-Description (Complete)-(07-03-2011).pdf

1515-del-2006-description (complete).pdf

1515-del-2006-form-1.pdf

1515-del-2006-form-18.pdf

1515-del-2006-form-2.pdf

1515-del-2006-form-3.pdf

1515-del-2006-form-5.pdf

1515-DEL-2006-GPA-(07-03-2011).pdf


Patent Number 248422
Indian Patent Application Number 1515/DEL/2006
PG Journal Number 28/2011
Publication Date 15-Jul-2011
Grant Date 13-Jul-2011
Date of Filing 27-Jun-2006
Name of Patentee DIRECTOR GENERAL ,DEFENCE RESEARCH & DEVELOPMENT ORGANISATION
Applicant Address MINISTRY OF DEFENCE, GOVT. OF INDIA, ROOM NO. 38, B-WING, DRDO BHAWAN, RAJAJI MARG, NEW DELHI
Inventors:
# Inventor's Name Inventor's Address
1 VINOD KUMAR DEFENCE RESEARCH & DEVELOPMENT ESTABLISHMENT, JHANSI ROAD, GWALIOR-474002
2 MAHABIR PARSHAD KAUSHIK DEFENCE RESEARCH & DEVELOPMENT ESTABLISHMENT, JHANSI ROAD, GWALIOR-474002
PCT International Classification Number A61K
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA