Article pubs.acs.org/IECR
N, N-Dichlorourethane: An Efficient Decontaminating Reagent for Sulfur Mustard, a Chemical Warfare Agent Ravindra Singh,† P.K. Gutch,*,† and Avik Mazumder‡ †
Synthetic Chemistry Division, Defence R&D Establishment, Jhansi Road, Gwalior 474 002 (MP), India Vertox Laboratory, Defence R&D Establishment, Jhansi Road, Gwalior 474 002 (MP), India
‡
ABSTRACT: An efficient and operationally simple method for chemical decontamination of sulfur mustard (HD) has been reported herein. A chlorine-bearing reagent N,N-dichlorourethane was developed to deactivate HD in aqueous (acetonitrile/ water, 80/20) medium. This decontamination reaction was monitored by gas chromatography−mass spectrometry and NMR spectroscopy. This reagent is highly efficient, stable, economical, and easy to synthesize and leads to instant decontamination of HD. The reaction was found to instantaneously and completely convert HD to innocent products at different temperatures (−20 to 40 °C).
1. INTRODUCTION Sulfur mustard1 (HD) and its analogues are persistent and highly toxic DNA alkylators. They cause severe blisters upon dermal contact. Hence, this class of compounds is referred to blistering agents. Due to their ability to injure or kill living beings they have been used as a weapon by state parties from World War I through the Iraq−Iran conflict.2 Due to ease of preparation and availability of the raw materials from industrial sources, they are also ideal candidates for the terrorist organizations. These potential threats are reflected by its inclusion among the list of chemicals restricted by the international treaty of chemical weapons convention (CWC), which has been in force since 29th April 1997, and restricts generation, production, stockpiling, proliferation, weaponization, and use of all enlisted chemical warfare agents (CWAs), their starting materials, and their degradation products. The CWC is implemented through its strict verification program3−5 of the Organization for Prohibition of Chemical Weapons (OPCW), The Hague, The Netherlands. Eradication of the existing stockpile of CWAs is a prime objective of OPCW. Decontamination is an important unavoidable technique for protection against chemical warfare agents. All experience confirms that the most important factor is time and high decontamination efficiency. The various methods have been reported for destruction of HD and its analogues. These include some elementary processes such as nucleophilic displacement, elimination, and oxidative pathways. The viable strategies make use of highly varied chemistry of these compounds, efficiency, and ease of implementation and the instantaneous conversion to innocuous end products. Among the various methods6−9 reported for the decontamination of HD, hydrolysis and oxidative methods are the most preferred. Among the other reported methods, hydrogenolysis, 10 oxidation with supercritical water,11 and electrochemical12 oxidation are noteworthy, although they have not achieved any practical utility to date. The practical utility of hydrolytic decontamination of HD is limited due to poor solubility of HD and inorganic bases in a common solvent. Solubility and rate of hydrolysis of HD © 2013 American Chemical Society
decreases appreciably when the reactions are carried out at low temperatures. Moreover, the toxic intermediates (formed during the reversible hydrolytic reactions) cause recurring toxicity. These factors are major impediments in the destruction of large quantity of HD. Although a number of reagents have been developed as decontaminants of these toxic compounds such as alkali2 and bleach solutions6 in aqueous and organic media, iodosocarboxylates,13 metal chelates,14 and oximino function-based reagents, only a few have “practical utility”. Most of these are expensive and nonbiodegradable.7,8 The industrially important inorganic15 and organic Nhaloamines16 contain halogen atom(s) directly attached to nitrogen (of an amine, imine, amide, or imide). The chemistry of chloramines and bromamines is diversified because they are positive halogen release agents. Owing to their easy handling, commercial availability, and high storage stability, the N-chloro amines act as and they have been extensively exploited for wide range of industrial applications as bleaches and disinfectants. Apart from these applications, intensive research has been carried out for chlorination, oxidation,17 water disinfection,18 antimicrobial activity,19 and other applications in synthetic organic chemistry. They have also been investigated for their microbicidal activity. The N-chloro compounds have also been reported20−28 for decontamination of chemical warfare agents. A variety of decontaminating agents have been reported over the years, however, most of them suffer from drawbacks such as the use of hazardous solvents and prolonged decontamination time due to poor miscibility with HD and small amount of active chlorine present in these compounds. Further, these reagents cannot be used on skin due to the toxicity of solvent and reagents. Our aim in this work is to generate a new cheap, easy-to-prepare, and stable decontaminant with higher active chlorine content. The target molecule should preferably be a Received: Revised: Accepted: Published: 4689
July 26, 2012 February 12, 2013 February 27, 2013 February 27, 2013 dx.doi.org/10.1021/ie301991q | Ind. Eng. Chem. Res. 2013, 52, 4689−4694
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liquid, and it should convert HD to innocuous products in less than one minute under homogeneous reaction conditions. Oxidative chlorination is the oldest and most widely used method for the decontamination of sulfur bearing CW agents. Oxidation reaction removes the lone pair on sulfur and forms sulfoxide and sulfone in aqueous medium. Introduction of chlorine at α-position reduces the toxicity and vesicant action of HD in an almost aprotic medium. Oxidation reactions are relatively faster than hydrolysis reactions. Owing to the presence of oxidizable bivalent sulfur, the oxidation of HD using organic chloramines is a promising method of decontamination.20−28 Oxidation reactions render the compound harmless to biological systems. Various agents7−12 have been used for decontamination of HD including hypochlorite,2,6 sodium,29 enzyme-based micro emulsion,30,31 zeolites,32 iodobenzoic acid complex,13 nanosize calcium oxide,33 titania nanotubes,34 peroxides,35 and alumina-supported fluoride reagents.36 We previously reported the use of N,N-dichlorourethane,20 for the decontamination of O,S-diethyl methylphosphonothiolate 20,21 (OSDEMP), a simulant of VX. In continuation of our previous studies20,23 here we explore the use of N,N-dichlorourethane as decontaminating reagent for the sulfur mustard.
2. EXPERIMENTAL SECTION 2.1. Materials and Methods. Acetonitrile, dichloromethane, and sodium sulfate of AR grade were purchased Scheme 1. Synthesis of N,N-Dichlorourethane
from SD. Fine-Chem Ltd., India. 2-Chloroethyl phenyl sulfide was purchased from Acros Chemicals. Ethyl carbamate, calcium hypochlorite, 3-trimethylsilyl propionic acid-d4 (TSP), chloroform-d1, and acetonitrile-d3 were purchased from Sigma-Aldrich Chemical Co., Milwaukee, USA. HD was prepared37 in house with average purity ∼99%. Purity was checked by GC and GC− MS. N,N-Dichlorourethane was prepared by one of our reported methods38 (Scheme 1), and active chlorine was determined by iodometric titration39 using sodium thiosulphate and found to be 44.4%. 2.2. Instruments Used and Conditions of Analysis. Identification of the products of the decontamination reaction was performed by GC−MS instrument (in EI mode) consisting of a 7890 Agilent GC coupled with 5975C mass selective detector (Agilent Technologies, San Jose, CA) in order. GC− MS experiments were carried out on BP-5 column (30 m × 0.250 mm 0.25 μm film thickness of the stationary phase) with the following temperature program: 80 °C for 2 min, followed by a linear gradient to 250 at 10 °C per minute and held at 250 °C for 5 min. The EI analysis was performed at 70 eV with ion source temperature at 200 °C and emission current of 400 μA. A Chemito (Nasik, India) make GC-FPD (S-mode) instrument was also used. The GC conditions used were as follows: column HP-5 (30 m × 0.250 mm, 0.25 μm film thickness of the stationary phase) with a temperature program of 50 °C for 2 min followed by a linear gradient to 250 at 10 °C min−1, and
Figure 1. Solvent suppressed NMR spectra of (a) HD (5 μL), (b) N,N-dichlorourethane (7.5 μL), (c) reaction mixture containing HD (5 μL) and N,N-dichlorourethane (7.5 μL). All NMR spectra were recorded at −20 °C in 400 μL CD3CN/D2O mixture (9:1) containing TSP taken in a stem coaxial insert. Field frequency locking and chemical shifts referencing was performed with the contents of the coaxial insert.
held at 250 °C for 5 min. The injector temperature was maintained at 250 °C while the transfer line was at 280 °C. All NMR spectra were recorded on 400-MHz Bruker AV II spectrometer equipped with a broadband inverse probe head. The variable temperature unit of the spectrometer was used for carrying out the reactions at −10, −5, 0, 10, 15, and 25 °C in 5mm NMR tubes. All the reactants and solvents were equilibrated for 10 min at the temperature at which the experiments were performed. Eight scans and four dummy scans were used for recording the solvent-suppressed spectra using Bruker presaturation pulse program zgpr. The data were Fourier transformed and processed with a Gaussian baseline correction function with a filter width of 1 ppm to suppress the residual solvent peak. 4690
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Scheme 2. Reaction of HD with N,N-Dichlorourethane in Aqueous Medium
Figure 2. (a) Gas chromatogram of pure HD and (b) gas chromatogram of HD after decontamination with N,N-dichlorourethane.
instrument. The samples were field frequency locked and referenced with respect to TSP dissolved in solvent mixture (9:1) taken in a stem coaxial insert. The reactions and the subsequent NMR experiments were carried out at the temperatures of −10, −5, 0, 10, 15, 25 °C. The reaction was found to proceed instantaneously even at −10 °C. To confirm the absence of HD in the products, chemical shifts and 3JH−H of the vicinal protons of the HD were observed in the 1H NMR spectra of the reaction mixture (Figure 1) immediately after the reaction and again after storage at room temperature for 24 h.
2.3. Decontamination of HD with N,N-Dichlorourethane in an Aqueous Medium. N,N-Dichlorourethane (1) (0.01 mol) was added to a stirred solution of HD (2) (0.01 mol) in 3 mL of CH3CN/H2O mixture (5:1). Aliquots were taken at different time intervals (up to 5 min) and extracted with dichloromethane (5 mL). The organic phase was analyzed for the residual HD and degradation products by GC-MS using HP-5 column. 2.4. Process for the Neutralization of HD in Aqueous Medium. The reaction was also studied by variable temperature 1H NMR spectroscopy (Figure 1). To 5 μL of HD dissolved in 400 μL of a mixture containing CD3CN/D2O (9:1) was added an aliquot of N,N-dichlorourethane (7.5 μL), and the contents were mixed on a vortex shaker momentarily before recording the spectra on the preconditioned NMR
3. RESULTS AND DISCUSSION Decontamination of HD was studied with N,N-dichlorourethane in aqueous medium (acetonitrile/water) at room temperature. This decontamination reaction was monitored 4691
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Figure 3. Mass spectrum of decontaminated products of HD.
products. The first step is chlorination of sulfide due to the electrophilic attack of chlorine on sulfur, generating sulfonium cation (a). Subsequently, nucleophilic displacement of chlorine by water with elimination of HCl from b produced corresponding bis(2-chloroethyl) sulfoxide (3). Further, αchlorination of sulfoxide (3) via intermediate c and d produced 2-chloroethyl-1,2-dichloroethylsulfoxide (4). On the basis of structures of the products and product composition, mechanism of the decomposition reaction in an aqueous medium was arrived at (Scheme 3). The conversion of HD into a series of oxidation and elimination products26 takes place. The first step is the electrophilic attack of chlorine on sulfur. This leads to chlorination of sulfide and generation of sulphonium cation a. Subsequent nucleophilic displacement of chlorine from a by water takes place with the elimination of hydrogen chloride via intermediate b leading to the formation of bis(2-chloroethyl) sulfoxide (3). Consequently, elimination of hydrogen chloride leads to the formation of 2-chloroethyl vinyl sulfoxide (c). Intermediate c can form 2-chloroethyl-1,2-dichloroethylsulfoxide (4) by two different pathways. Path A occurs via electrophilic-nucleophilc addition of chlorine to the double bond of 2-chloroethyl vinyl sulfoxide. Whereas if path B is followed, the in situ reaction of hydrogen chloride and Nchlorourethane generates a molecule of chlorine (1b). 1,2Addition of chlorine to the intermediate c leads to the formation of 2-chloroethyl-1,2-dichloroethylsulfoxide (4). HD bears oxidizable bivalent sulfur atom. Oxidation reaction removes the lone pair on sulfur and forms corresponding sulfoxide and α-chlorinated sulfoxide in an aqueous medium. This oxidation process yields products of varying but lower toxicity than that of the parent compound.40 N,N-Dichlorour-
by gas chromatography, and the decontamination products were analyzed by GC-MS in EI mode. The results are depicted in Scheme 2 and Figures 2 and 3 . The major product is bis(2chloroethyl)sulfoxide (3) and 2-chloroethyl 1,2-dichloroethyl sulfoxide (4). In this reaction, N,N-dichlorourethane (1) was converted into urethane (5). Decontamination of HD was studied with N,N-dichlorourethane in aqueous medium (acetonitrile:water) at different temperatures. The NMR studies indicated instantaneous decontamination of HD in the reaction mixture, even at −10 °C. The 1H NMR spectrum showed several overlapped resonances in the region of 3.0−6.0 ppm, which were absent in either of the reactants. These signals were attributed to the degradation products of HD formed after the reaction with N,N-dichlorourethane. The 1H spectrum clearly showed the absence of the vicinal methylene protons of HD (Figure 1a,c). Further, the COSY spectrum showed the absence of characteristic 3JH−H of the vicinal protons of HD. While performing the reactions and NMR experiments, the temperature chain was maintained for the reactants and the reaction mixture. No discernible changes were observed in these spectra when the sample was reanalyzed after storing at room temperature for 24 h. This was conclusive evidence that the reaction occurred instantaneously and no further change took place in the reaction mixture upon storage. The absence of sulfone (an over oxidation product of HD) was ascertained from CI-MS extracted ion chromatogram. On the basis of structures of the products and product compositions, a mechanism of the decomposition reaction in an aqueous medium was arrived at, as shown in Scheme 3; HD was converted26 into a series of oxidation and elimination 4692
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higher as compared to active chlorine content of chloramine-T (15.59%) and N,N′-dichloro-bis(2,4,6-trichlorophenyl)urea CC-2 (14.55%). The other advantages of N,N-dichlorourethanes are in terms of stability, effectiveness, cost, ease of synthesis, and instantaneous decontamination of HD as compared to other chloramines such as N-tert-butyl-N-chlorocyanamide,27a chloramine-T,28 and CC-2.22 Precursor of CC-2, i.e., phenyl urea, is costly, synthesis is tedious, a smaller amount of active chlorine content (14.55%) exists, and stability of CC-2 was found less stable as compared to N,N-dichlorourethane. It is reported2 that sodium hypochlorite is unstable at room temperature, and its active chlorine decreases with storage of time whereas N,Ndichlorourethane is highly stable up to 550 days at room temperature.
Scheme 3. Plausible Mechanism of Decontamination of HD in an Aqueous Medium
4. CONCLUSION In conclusion, the study reveals that N,N-dichlorourethane works as an excellent decontaminating agent against HD in aqueous medium at room temperature. This reagent has advantages over previously reported reagents22,28 in terms of effectiveness, stability, cost, ease of synthesis, and instantaneous decontamination of HD at different temperatures ranging from −10 to 25 °C.
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AUTHOR INFORMATION
Corresponding Author
*E-mail: pkgutch@rediffmail.com. Tel.:+91-751-2340245. Fax: +91-751-2341148. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We thank Prof. M. P. Kaushik, Director, and Dr. Devendra K. Dubey, Associate Director, DRDE Gwalior, for their interest, support, and encouragement in carrying out this work.
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REFERENCES
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Figure 4. Stability study of N,N-dichlorourethanes.
ethane, in which chlorine is directly attached to nitrogen, can generate positively charged chlorine which is an oxidizing species. The active chlorine content does not decrease with prolonged storage time. Presence of strong electron withdrawing (−O−CO−) group is expected to release positively charged chlorine, thereby facilating the decontamination reaction. 3.1. Stability Study of the Reagent. N,N-Dichlorourethane was prepared by our modified method and stored in glass vials at room temperature. Active chlorine was determined periodically by iodometric titration.39 It was observed that N,Ndichlorourethane was highly stable up to 550 days and active chlorine content was found to decrease marginally (from 100 (44.4%) to 92 (43.2%)) during this period (Figure 4). The additional advantage of N,N-dichlorourethane arises due to high amount of active chlorine content (44.94%). This is much 4693
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