Title of Invention

"COMPOSITION FOR DECONTAMINATING CHEMICAL WARFARE AGENT AND A PROCESS OF PREPARATION THEREOF"

Abstract

The present invention relates to compositions for decontamination of toxic chemical agents such as nerve agents and blistering agents. The composition comprises of an N-chlorobezamide derivative and a solvent system. The N-chlorobenzamide derivative of general formula A : wherein if X;= Cl, NO2, CH3, OCH3, F, Jhen X & X"= H, if X"= CI then X" and X = H,C1 if X"&X"= CI, then X = H The solvent system of present invention comprises of an active ingredient and optionally a solvent. The active ingredient is selected from a group of Acetonitrile, Toluene, DMSO, CC14,CHC13 and DMF and the said solvent is water. The present invention also pertains to cost effective method of obtaining such composition.

Full Text

FIELD OF INVENTION The present invention relates to the development of a decontaminant against toxic agents such as blistering agents and nerve agents . More particularly, the present invention relates to the development of a decontaminant against sulphur mustard (SM), the developed decontaminant is reactive, stable, easy to synthesise and for which the precursors are easily available. More particularly, the present invention relates to development of industrially viable one pot procedure for the production of N-Chloro benzamide derivative , which is to be used as key ingredient in the development of chemical decontaminant against sulphur mustard. PRIOR ART Decontamination of toxic agents is required in case of chemical attack by adversaries or terrorists. Decontamination is one of the important combating activities (detection , protection and decontamination) against toxic agents. Decontamination of toxic agents is achieved either by physically removing the toxic substances from contaminated surfaces (materials in the field like vehicles, buildings, equipments etc. and living objects) or by chemically converting them into relatively less or non-toxic substances (R. Trapp, 'The detoxification and Natural Degradation of Chemical Warfare Agents' Stockholm International Peace Research Institute, SIPRI, Taylor & Francis, London and Philadelphia 1985). For physical removal of toxic agents from contaminated site, adsorbents like Fuller's earth (native aluminium silicate) and detergent / soap solutions are used. Since these decontaminants do not detoxify the toxic agents, hence are not considered as reliable means. Second major problem of physical decontaminants is their safe disposal. Physical decontaminants themselves get contaminated during decontamination operation; their subsequent safe disposal requires further treatment to neutralise the toxic agents. Another problem of physical decontaminants is secondary contamination, which is caused by the ensuing desorption of adsorbed toxic agents. Yet another problem of physical decontaminants like washing solutions is spreading of contaminated area, since during washing operation the solution is spread over contaminated surface. Chemical deactivation of Toxic agents with reactive decontaminants is a better choice of decontamination (Yang Y.C. Chem. Ind. 1995, May 1, 334). Currently used reactive-decontaminants include nucleophilic/base-amine mixtures and bleach formulations. (Yang Y.C.; Baker J.A.; WardJ.R. Chem. Rev. 1992, 92, 1729; R.P.Seiders, US Patent H366, 1987; and Govan Norman, Int.Patent A62D3/00 & Eur. Patent A62D3/00E, 1998; Yang Y.C, Szfraniec L.L., Beaudry W.T., Davis F.A. Proceedings of the 1988 US Army CRDEC-SP-013, Aberdeen Proving Ground Maryland August 1989, Vol 1 ). These formulations are although effective in decontaminating the toxic agents cannot be used as personal protective formulation because, they are highly corrosive and toxic, hence best suited for material decontamination only. Consequently, there was need to develop safe and effective decontamination formulation against toxic agents for human application. A requirement for a topical skin protectant (TSP) to protect skin from toxic agents was immediately recognised following the introduction of these agents in World War I. Although several creams and ointments were made but none of them was effective in deactivating the toxic agents. Just prior to and during World War II, a concentrated effort to develop ointments for protection from sulphur mustard was made at the chemical warfare service in Edgewood Arsenal, Maryland USA. Which resulted in development of M-5 ointment but it left room for improvement. For several years, research concentrated to introduce active ingredients like alkalies, chelators, sorbents etc into polyethylene based formulations. However, none of them provided the required protection (D.K L iu, R.W. Wannemacher, T.H.Snider, T.L.Hayes, J.Appl. Toxicol 1999, 19, 541) and CC-2 (N,N-dichloro bis (2,4,6 trichlorophenyl) urea (D.K.Dubey, R.C.Malhotra, R Vaidyanathaswamy, R Vijayaraghavan, J.Org.Chem. 1999,64, 8031) have also been discovered. Recently, two compounds have been used as active ingredients in the formulations made to protect human skin from sulphur mustard. A substance coded as S-330 (1,3,4,6-tetrachloro-7,8-diphenyl-2,5-diiminoglycoluril) (JC.Speck Jr. US Patent No 5607,979, 1997) was mixed with perfluorinated ethers and evaluated as a reactive decontaminant against sulphur mustard (M.L.Shih, W.D.Korte, J.R.Smith, L.L.Szfraniec , J.Appl.Toxicol. 1999, 19, S89). But the main disadvantages of this system are use of uneconomic and non-ecofriendly per fluorinated compound as base material and S-330 decomposes within 2-3 weeks at room temperature in presence of even little moisture (E.H.Brau, J.Appl.Toxicol. 1999, 19, S47; O.Koper, E.Lucas, KJ.Klabunde J.Appl.Toxicol. 1999, 19, S59). Another disadvantage of this system is that it is not very fast acting, which is the prime requirement of any decontaminant. Moreover, many decontaminants degrade upon exposure to moisture and air. Among of these decontaminant, hypochlorite and DS2 (diethylenetriaminers 70% + ethylene glycol, monoethyl ether 28% & 2%sodium hydroxide) are generally used for decontamination of mustard, but there are some disadvantages in using bleach as a decontaminant as a large amount of bleach is required for the oxidation of the agents and most importantly bleach is corrosive to many surfaces and in cold weather bleach is not effective.DS2 is also used for decontamination. But DS2 is corrosive to skin, painted surfaces, plastics, rubber and leather materials. The currently used method for decontamination of Mustard is oxidation with caustic solutions of hypochlorite, while effective for the most part but injurious to metals, plastic, clothing and human skin. A need exists for a decontamination of toxic chemical agents which is non-corrosive, non-toxic, non-flammable, stable and environmentally safe. It is also required that a substance can be applied directly to a contaminated area to destroy/detoxify the chemical agents which can then be washed swept, or vaccumed away. In addition, the substance must be capable of being effectively applied to surface or items. As a result, substance must be fluid enough to be quickly and easily applied to surfaces. NEED FOR THE INVENTION Keeping in view the hazards of toxic chemical agents, their decontamination is of paramount importance. It is required on the battlefield, laboratories, production and storage plants, destruction sites and more importantly in case of sabotage and usage of toxic chemical agent as by the terrorists. Of the various known such toxic chemical agents is Sulphur Mustard (SM) which is an alkylating agent, and is a potent incapacitant and lethal in large quantities. Sulphur Mustard causes serious blisters on the skin upon contact, and it is cytotoxic and radiomimetic . There are no specific antidotes for SM toxicity and it is a challenge even today in chemical warfare 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. The stringent requirement of decontaminant was successfully met by developing substituted N-Chloro benzamides are envisaged as decontaminants against SM owing to their high oxidation potential and stability , Generally ,the organic chloroamines are considered as potent decontaminants against Sulphur Mustard ; N-chlorobenzamides are of particular interest as their lipophilicity (i.e. the miscibility with SM) and oxidation potential (i.e. reactivity against SM) and stability can be manipulated by aptly placing in benzene ring. . Thus keeping in view the requirement, variety of substituted N-chloro benzamide derivatives were tested as decontaminant against SM, and a commercially viable method was developed for their production. OBJECTS OF THE INVENTION An objective of the present invention is to develop a cost effective, non-toxic, stable decontaminant for chemical toxic agents, which can be prepared from indigenously and commonly available chemicals. The main objective of the present invention is to explore most suitable N- Chlorobenzamide derivative having low vapour pressure, high chemical reactivity against chemical toxic agents particularly Sulphur mustard , stable under normal conditions and possess good chlorine content. Another objective of the present invention is to optimise the reaction conditions for the decontaminant of toxic agents such as sulphur mustard and its stimulants such as use of appropriate solvent system in making the formulations, temperature, and time. Yet another objective of present invention is to develop a cost effective and one pot process for the process for production of N -Chlorobenzamide derivatives, Still another objective of this invention is to optimise the pH of reaction of N-chlorination of chlorobenzamide derivatives . The main object of the present invention is to develop an aqueous and aprotic condition for N-Chloro benzamide derivatives as decontaminant for toxic agents such as Sulphur Mustard that rapidly detoxifies (with t1/2 less than a minute). STATEMENT OF THE INVENTION To achieve these objectives, in the present invention electrophilic chlorination of amide group of benzamide using suitable chlorinating agent is proposed. Thus the decontaminant composition of the present invention is a composition comprising of an N chlorobenzamide derivative of general formula A: (Formula Removed) wherein if X'= CI, NO2, CH3, OCH3, F, Jhen X & X"= H, if X"= Cl then X' and X = H,C1 ifX'*&X'= Cl, then X = H and a solvent system. Further the present invention also pertains to a method of preparing such decontaminant system. The method comprising chlorinating benzamide derivative of formula B (Formula Removed) wherein if X'= CI, NO2, CH3, OCH3, F, Jhen X & X"= H, if X",= Cl then X' and X = H,C1 if X" & X'= CI then X = H with a chlorinating agent in an acidic medium followed by extracting with an organic solvent and drying in the presence of a hygroscopic agent to obtain the N chlorinated Benzamide derivative and further mixing it in a solvent system to obtain the decontaminant composition of the present invention. Detailed Description of the invention The present invention provides a toxic agent decontamination compositions having N-chloro benzamide as a reactive component in non-corrosive, non-toxic, non-flammable formulation systems. The decontaminant is non-flammable and non-toxic and does not degrade significantly over time after exposure to air and moisture . The decontaminant of the present invention is effective against chemical toxic agents such as organophophorous agents particularly those which is having -S- linkage such as VX. It was found that Compounds having N-Chlorobenzamide {0=C-N- Cl) moiety are very useful to bring about many organic transformations via oxidation, elimination followed by hydrolysis. In an aspect of the present invention it was found that the initial attack of positive chlorine from N-chloro benzamide at sulphur atom of toxic agents generate sulphonium cation that further reacts with water to give sulfoxide and hydrogen chlorite gas. The reagent work effectively and instantaneously with the range from -20°C to 50°C. As discussed earlier the substituted N-Chlorobenzamides are envisaged as decontaminants against Sulphur Mustard owing to their high oxidation potential and stability . Generally ,the organic chloroamines are considered as potent decontaminant against Sulphur Mustard, N- chloro-benzamides are of particular interest as their lipophilicity (i.e. the miscibility with SM) and oxidation potential (i.e. reactivity against SM) and stability can be manipulated by aptly placing in benzene ring. The decontaminant contain N-chloro benzamide as an active moiety. As defined herein, N-Chloro benzamide derivatives have general structure A as given below. Chlorine atom in N-Chloro benzamide is chemically bonded to nitrogen atom that makes chlorine atom positive in nature. Moreover electron-withdrawing group (C=0) also attached to same nitrogen atom and chlorine group present in aromatic ring which further enhance the positive chlorine donating power of N-Chloro benzamide derivatives. (Formula Removed) wherein if X'= CI, NO2, CH3, OCH3, F, Jhen X & X"= H, if X"= Cl then X' and X = H,C1 if X" & X' = Cl, then X = H The N-chlorobenzamide derivatives are selected from the group of 4-chloro N-chlorobenzamide, 2-chloro N-chlorobenzamide, 2, 4, 6-trichloro-N-chlorobenzamide, 2, 4 -dichloro N-chlorobenzamide, 4 - methoxy N-chloro benzamide, 4-methyl N-chloro benzamide ,4-nitro N-chlorobenzamide, 2-Fluro-N-chlorobenzamides and 4-Fluro-N-chlorobenzamide. In order to obtain the N-chloro benzamide derivatives of present invention benzamide derivatives of formula B were chlorinated with a suitable chlorinating agent. (Formula Removed) wherein if X'= CI, N02, CH3, OCH3, F, jhen X & X"= H, if X"= CI then X: and X = H,C1 if X" & X' = Cl then X = H Further to obtain the composition of the present invention these derivatives were mixed in a solvent system. The chlorination of benzamide derivatives of formula B was carried out with chlorinating agents in acidic medium. The organic acidic medium is most suitable for this reaction .The most preferred organic solvent of the present invention is glacial acetic acid. The N chlorination of benzamide derivatives can be achieved using various chlorinating reagents such as Cl2, NaOCl, CaOCl2 and tert-butyl hypochlorite. But the best results are obtained when N-chlorination of benzamide was carried out using NaOCl in glacial acetic acid medium as it is mild reagent and does not affect the -CO group of benzamide which is sensitive to another chlorinating agent and furthermore reaction of benzamide with NaOCl is very fast. Moreover, the reaction does not require any base to scavenge the proton released from benzamide as the oxygen of chlorinating agent picks it up after donating the positive chlorine to benzamide. (Formula Removed) wherein if X'= Cl, N02, CH3, OCH3, F, Jhen X & X"= H, if X"= Cl then X' and X = H,C1 If X^&X'- Cl then X = H However the chlorination of benzamide with the chlorinating agents is to be carried out at low temperature in the range of 0°C to 5°C to minimise the possibility of formation of side reaction. After addition of chlorinating agents in solution of benzamide derivatives of formula B in acidic medium is to be cooled and stirred, solution of amide is very rapid and completion of reaction takes place with the formation of precipitate of N-chloro benzamide derivative. This precipitate is insoluble in reaction mixture and can be easily removed by filtration or extraction by using volatile organic solvents. Further to obtain the composition of the present invention the thus obtained N-chlorobenzamide derivative is mixed in a suitable solvent system . After obtaining suitable N-Chlorobenzamide derivatives another important parameter that is to be selected is solvent system. The solvent system comprises of an active ingredient and optionally a solvent. The active ingredient is selected from the group comprising of acetonitrile ,toluene, DMSO , CC14, CHCI3 and DMF . The solvent of the solvent system is water. However the preferable solvent system of the present invention is an acetonitrile-water solution. N-Chlorobenzamide derivative based composition to bring about the decontamination in both mixed active ingredient with solvent and pure active ingredient are found to be highly reactive to decontaminate chemical warfare agent instantaneously. The ratio of the said N benzamide derivative to said solvent system is in the range of 1: 5 to 1:10 w/v. The mixed solutions can be made in different concentrations in the range of 1:1 to 9:1 (v/v ) of the active ingredient in water respectively. All these different ratios were investigated to optimize the reaction conditions. The preferable ratio of 9:1 of acetonitrile : water was found most suitable formulations to bring about the decontamination. The preferable solvent system of present invention is acetonitrile water solution in varied ratio and pure acetonitrile as aprotic medium. Various ratios were applied to bring the formation of non-toxic sulfoxide. A ratio of 9:1 of acetonitrile : water was found to be most suitable for the purpose. Role of water is to provide oxygen in order to convert Sulphur Mustard to sulfoxide. The process for obtaining the decontaminant composition of present invention comprising the steps of: a) adding the benzamide derivative of formula B, (Formula Removed) wherein if X'= CI, NO2, CH3, OCH3, F, then X & X"= H, if X"= Cl then X' and X = H,C1 if X"&X'= Cl, then X = H in an organic acid medium followed by adding a chlorinating agent to the above mixture at a temperature in the range of 0 to 5°C . ; b) extracting the N chloro benzamide derivative from the reaction mixture of step (a) using an organic solvent. ; c) drying the N chloro benzamide derivative as obtained in step b) over an hygroscopic agent. ; d) adding the N chloro benzamide derivative as obtained in step c to a solvent system in the ratio of 1:5 to 1:10 at room temperature to obtain the decontaminant composition. As discussed above the solvent system comprises of an active ingredient and optionally a solvent .The active ingredient is selected from the group comprising of Acetonitrile ,Toluene, DMSO , CC14, CHC13 and DMF and said solvent is water. The chlorinating agent such as chlorine, sodium hypochlorite, calcium hypochlorite and ter-butyl hypochlorite are used in present invention for chlorination of the benzamide derivetaive. The acidic medium in the process is prepared by using an organic acid. The most preferred organic acid to be used is glacial acetic acid. Chlorinating agents such as chlorine, sodium hypochlorite, calcium hypochlorite and ter-butyl hypochlorite are used for chlorination of the Benzamide derivatives for obtaining N-chlorobenzamides in the present invention. The organic solvents such as dichloromethane, chloroform, ether and acetonitrile are used in the process of present invention for extraction of N chloro benzamide derivatives The hygroscopic agents such as anhydrous sodium sulphate, anhydrous calcium carbonate and calcium chloride are used for drying the N chlorobenzamide derivative of present invention. .The hygroscopic agents used in the above process preferably is anhydrous sodium sulphate. The ratio of the chlorobenzamide derivative to the acidic medium is perferably 1:3. The temperature range for performing step a in the above process is 0°C to 5°C . Further preferably the ratio of the said benzamide derivative to said chlorinating agent solution is 1: 10 to 1:15. Compounds of the present invention convert Sulphur Mustard to corresponding sulfoxide and sulfone in aqueous medium. The decontamination of CW agent of this invention was also evaluated from a range of temperature starting from -10°C to + 50°C. This formulation works effectively within this temperature range at same rate. (Formula Removed) wherein if X'= Cl, NO2, CH3, OCH3, F, then X & X"= H, if X"= Cl then X' and X = H,C1 if X"& X' = Cl, then X = H Further the decontaminant composition of the present invention was tested under storage conditions. Advantageously, an acetonitrile water based decontaminant of the invention, stored under ambient conditions, showed no changes in its infra-red spectrum over a period of 120 days also appeared unchanged, when exposed to a range of temperature of-10°C - 50°C. These tests indicate that the formulations are stable. Further, none of the components used in these compositions are listed as flammable or corrosive. The decontaminant of the present invention is effective against chemical toxic agents such as organophophorous agents and organosulfur agents particularly those which are having -S-linkage such as VX. Thus, the decontaminant compositions of the invention are believed to be stable, nontoxic and useful in detoxifying / neutralizing a variety of chemical warfare agents including Organosulfur agents such as mustard gas (HD) and orgnophosphosphorus agents such as the nerve agents termed VX. Decontamination is effected by applying a decontaminant of the invention to the contaminated material, equipment, personnel, or the like. Such applications 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. These examples illustrate the preferred methods for preparing and applying the decontaminant of the invention. These examples are illustrative and do not limit the scope of the invention. Although the invention has been described in detail with reference to a preferred embodiment it is to be understood that the above description of the present invention is susceptible to considerable modification, variations and adaptations by those skilled in the art, such modification are intended to be considered to be within the scope and spirit of the present invention. The present invention is further illustrated through the foregoing non limiting examples Example 1 Preparation of the decontaminant A solution containing of 20g of 4-Chloro benzamide in 60ml of glacial acetic acid at 2°C and freshly prepared 220 mL 13 % sodium hypochlorite was added slowly with the help of dropping funnel upto 1-2 hrs and pH of solution was maintain acidic and product was extracted with 90 ml of dichloromethane and dried over anhydrous Na2SO4. On evaporation of the solvent on rota vapour, product was identified by IR and NMR. Yield was 89%.and M.P 112°C.The positive chlorine of 4-chloro N-chloro benzamide was checked by standard iodometry titration it was found to be 18.40% (theoretical value 18.51 %) Example 2 Process for the neutralization of Sulphur Mustard in aqueous medium 2.5 mmol of 4-Chloro-N-Chloro benzamide was added slowly in mixed in 5 ml of acetonitrile - water solution .The acetonitrile water solution was prepared in ratio of 9:1 . The reaction was carried out at room temperature i.e 35°C. SM was added to this solution slowly and with stirring and the reaction was monitored by Gas chromatography using FPD Sulphur mode as detector. After completion of reaction water was added to the reaction mixture and product was extracted with dichloromethane (3 x 20ml) and dried over anhydrous Na2SO4. On evaporation of the solvent on rota vapour, mixtures of products were identified by GC-MS. Example 3 Process for the neutralization of Sulphur Mustard in aprotic medium 3 mmol of 4-Chloro-N-Chloro benzamide was added slowly to a stirred solution of in 5 ml acetonitrile . The reaction was carried out at room temperature i.e at 35°C. SM was added slowly to the above decontaminant solution and reaction was monitored by Gas chromatography Gas chromatography using FPD Sulphur mode as detector. After completion of reaction mixtures of products were identified by GC-MS. WE CLAIMS :- 1. A decontaminant composition comprising an N-chlorobenzamide derivative of general formula A: (Formula Removed) wherein if X'= CI, NO2, CH3 ,OCH3, F, Jhen X & X"= H, if X"= Cl then X' and X = FLC1 If X" & X'= Cl then X = H and a solvent system in the ratio of 1:5 to 1:10 . 2. The composition as claimed in claim 1 wherein the N-chlorobenzamide derivative is selected from the group of 4-chloro N-chlorobenzamide, 2-chloro N- chlorobenzamide, 2, 4, 6-trichloro-N-chlorobenzamide, 2, 4-dichloro N -chlorobenzamide, 4 - methoxy N-chloro benzamide, 4-methyl N-chloro benzamide ,4-nitro N-chlorobenzamide, 2-Fluro-N-chlorobenzamides and 4-Fluro-N-chlorobenzamide. 3. The composition as claimed in claim 1 wherein the solvent system comprises of an active ingredient and optionally a solvent wherein said active ingredient is selected from the group comprising of Acetonitrile ,Toluene, DMSO , CCU, CHC13 and DMF and said solvent is water. 4. The composition as claimed in claim 3 wherein the ratio of the said active ingredient to said solvent is in the range of 1:1 to 9:1 in the said solvent system. 5. The composition as claimed in claim 1 wherein the said N-chlorobenzamide derivative is 4 - chloro N-chloro benzamide. 6. The composition as claimed in claim 1, wherein the said solvent system is a solution of acetonitrile in water in the ratio of 9:1. 7. A process for preparation of the composition as claimed in claim 1, wherein the said process comprises the steps of: a) adding the benzamide derivative of formula B, (Formula Removed) wherein if X'= CI, NO2, CH3, OCH3, F, then X & X"= H, if X"= Cl then X' and X = H,C1 if X" & X' = Cl, then X = H in an acidic medium followed by adding a chlorinating agent to the above mixture at a temperature in the range of 0 to 5°C wherein the said chlorinating agent is preferably selected from the group of chlorine, sodium hypochlorite, calcium hypochlorite and ter-butyl hypochlorite ; b) extracting the N-chloro benzamide derivative from the reaction mixture of step (a) using an organic solvent wherein the said organic solvent is preferably selected from the group of dichloromethane, chloroform, ether and acetonitrile.; c) drying the N-chloro benzamide or a derivative thereof as obtained in step b) over an hygroscopic agent wherein the said hygroscopic agent is preferably selected from the group of anhydrous sodium sulphate, anhydrous calcium carbonate and calcium chloride d) adding the N-chloro benzamide derivative as obtained in step c to a solvent system in the ratio of 1:5 to 1:10 at room temperature to obtain the decontaminant composition wherein the said solvent system comprises of an active ingredient and optionally a solvent, wherein said active ingredient is selected from the group comprising of Acetonitrile ,Toluene, DMSO , CC14, CHC13 and DMF and said solvent is water. 8. The process as claimed in claim 7, wherein the said acidic medium is prepared using an organic acid preferably glacial acetic acid. 9. The process as claimed in claim 7, wherein pH in step a is maintained in range of 4 to 7. 10. The process as claimed in claim 7, wherein the ratio of the said benzamide derivative to the acidic medium is 1:3. 11. The process as claimed in claim 7, wherein the ratio of the said benzamide derivative to said chlorinating agent solution is 1: 10 to 1:15. 12. The composition as claimed in any of the preceding claims wherein the said composition is used to decontaminate chemical toxic agents. 13. A decontaminant composition, substantially as hereinbefore described with reference to the foregoing description and examples. 14. A method for preparation of a decontaminant composition, substantially as hereinbefore described with reference to the foregoing description and examples.

Documents:

57-del-2009-Abstract-(13-03-2014).pdf

57-del-2009-abstract.pdf

57-del-2009-Claims-(13-03-2014).pdf

57-del-2009-claims.pdf

57-del-2009-Correspondence Others-(13-03-2014).pdf

57-DEL-2009-Correspondence-Others-(30-09-2009).pdf

57-del-2009-correspondence-others.pdf

57-del-2009-description (complete).pdf

57-del-2009-form-1.pdf

57-DEL-2009-Form-18-(16-01-2008).pdf

57-del-2009-Form-2-(13-03-2014).pdf

57-del-2009-form-2.pdf

57-DEL-2009-Form-26-(30-09-2009).pdf

57-del-2009-form-3.pdf

57-del-2009-form-5.pdf