Silk Road forums
Discussion => Newbie discussion => Topic started by: NeoLex on October 03, 2013, 12:56 am
-
Im calling for a violent revolution agaisnt our masters lets show them that we are SICK AND TIRED OF THEIR ZIONIST BULLSHIT.Throw bombs into their houses kill the cops hang the lawyers
Here is a recipe for a Chemical weapon:
arks: Sulfur mustard (2,20-dichloroethyl sulfide; bis-(2-chloroethyl) sulfide; CAS#
505-60-2) was introduced during WWI as a blister agent (vesicant). Although often called ‘‘HD’’
(distilled sulfur mustard) today, it also has been known as ‘‘Lost,’’ ‘‘S-Lost,’’ ‘‘Yellow Cross,’’ ‘‘H’’
(a cruder form of sulfur mustard), ‘‘HS,’’ and ‘‘Yperite.’’ It is one member of a class of compounds
known as mustards that generally bear a heteroatom (Z) separated from a leaving group (L) by two
atoms, that is, contain the Z-(CH2)2-L fragment. Sulfur mustard has the structural formula
ClCH2CH2SCH2CH2Cl. Nitrogen mustards, where Z¼N, have been considered as anticancer
drugs and CWAs but are not now considered as likely chemical warfare or terrorist threats. They
are not discussed in this chapter.
Physical Properties: Sulfur mustard (mustard gas) is a colorless oil with bp of 2278C, mp of
148C, molecular dipole moment 1.78 D (hexane), and molecular mass of 159. It normally is
encountered as an impure, pale yellow–brown, odoriferous liquid. The color generally deepens
with increasing amounts of impurity. HD has a vapor density of 5.4 relative to air and a vapor
pressure of 0.072 mm Hg at 208C. As a liquid, it is slightly denser than water (1.27 g=mL at 208C). It
is miscible in typical organic solvents (e.g., carbon tetrachloride, acetone or chloroform) but has a
lower solubility in water (0.092 g=100 g at 228C) (Sidell et al., 1998; Somani, 1992).
Chemistry: There are several routes to sulfur mustard. The first production of sulfur mustard in
reasonable yield is often credited to Meyer (1886). A second route (Levinstein process) produces
elemental sulfur as a contaminant in the mustard. The Steinkopf synthesis of sulfur mustard involves
S(CH2CH2OH)2. (Steinkopf et al., 1920).
The reactions of sulfur mustard are dominated by its heteroatoms. First, divalent sulfur is a good
nucleophile and encourages SN reactions (Whitman, 1995a). Sulfur’s location b to a good leaving
group (chlorine) leads to neighboring group participation (Eliel and Wilen, 1994) and, hence, to
episulfonium ion formation. This internal nucleophilic displacement is favored by entropic factors.
The resulting episulfonium ion possesses substantial small-ring strain and is equally prone to ring
opening at either ring carbon. Using water as an external nucleophile, repetition eventually affords a
diol
Protonated Thiodiglycol
hemi-mustard
⊕
⊕ ⊕
24 Chemical Warfare Agents: Chemistry, Pharmacology, Toxicology, and Therapeutics
Structural variations that hinder episulfonium ion formation or sulfur nucleophilicity reduce
activity. Thus, S(C(O)CH2Cl)2 is reported to show little vesicant behavior (Sartori, 1939).
Mustard is denser than water, not very water soluble, and hydrolyzes rather slowly in cold
water. Thus, it can remain a threat for sometime in bodies of water even though it ultimately
hydrolyzes to the relatively safe thiodiglycol. Depending on specific conditions, the hydrolysis also
can produce 1,4-thioxane (O(CH2CH2)2S), 2-(vinylthio)ethanol (CH2¼CHSCH2CH2OH), and a
variety of other compounds, some in quite minor amounts (D’Agostino and Provost, 1985). For
example, mustard can react with thiodiglycol to form, depending on concentrations, mono- or
disulfonium ions. One example in which the product is hazardous follows (Yang et al., 1992; Munro
et al., 1999).
If the external nucleophile is attached to a chain, then two consecutive attacks on HD lead to
cross-linking of two chains.
Nu = nucleophilic
center
Cross-linked chains
S(CH2CH2Cl)2
Nu Nu NuCH2CH2SCH2CH2Nu
Molecules with more extensive separation between sulfur and leaving groups, such as chlorine
(e.g., Cl(CH2)6S(CH2)6Cl), behave like simple aliphatic halides (or sulfides) since three-membered
ring (episulfonium ion) formation is no longer possible. One convenient method for verifying the
formation of an episulfonium ion intermediate involves isotopic carbon labeling. Since this ion is
symmetric, it would ultimately lead to a nearly 1:1 distribution of an appropriately placed label,
something not observed in a direct displacement.
SR
Sulfides, including HD, undergo oxidation at sulfur. Initial oxidation produces a sulfoxide,
whereas further oxidation produces a sulfone (below). Oxidants include hydrogen peroxide, peroxyacids,
nitric acid, permanganate ion, ozone, dinitrogen tetroxide, and dichromate ion. Oxides of
mustard are not as volatile as mustard. This may help to explain why British air raid shelters were
sometimes ‘‘painted’’ using the oxidant calcium hypochlorite (Ca(OCl)2). ‘‘Episulfonium’’ ion
formation is less likely in the sulfoxide of HD than in HD itself.
Chemistry of Chemical Warfare Agents 25
Sulfide Sulfoxide Sulfone
Titanium dioxide and iron oxide particles (anatase TiO2 and ferrihydrite) have been explored as
‘‘detoxification’’ materials for threat agents including HD and nerve agents (soman and VX).
(Kleinhammes et al., 2005; Ohtani et al., 1987). TiO2 was found to be the more rapidly acting
against HD and was able to convert HD into nontoxic materials with 99% effectiveness. Kinetic data
for reactions involving both oxides and three threat agents at 258C are provided. Analyses focused
on the disappearance of threat agents, and identification of products was not provided. The authors
claim that these oxides are more reactive than AP-MgO (Stengl et al., 2005; Kopeer et al., 1999).
Chloramine B oxidizes HD to its sulfoxide via an intermediate containing an S–N bond
(Whitman, 1995b).
S N
Strong bases (e.g., alkoxide) can dehydrochlorinate mustard and its sulfoxide and sulfone,
converting one or both of their 2-chloroethyl fragments to vinyl groups.
Didehydrohalogenation of HD is reported to be complete within 1 min at room temperature
using CH3OCH2CH2O as the base (Beaudry et al., 1992). This is a ‘‘component’’ of the decontaminating
solution known as DS2 (a mixture of diethylene triamine, ethylene glycol monomethyl
ether, and sodium hydroxide). Nanosize particles of calcium oxide have been shown to dehydrohalogenate
HD (Wagner et al., 2000b).
Although anhydrous mustard is not a substantial corrosion threat to most metals, hydrolysis
forms hydrochloric acid and does contribute to mustard’s corrosive behavior. An interesting pmr
and gas chromatograph–mass spectrometry (GC–MS) study of the hydrolysis of HD has been
reported (Logan and Sartori, 2003). In this work, it was shown that hydrolysis (D2O at 228C) had
a half-life of approximately 7 min, but that in the presence of sodium chloride, the half-life
increased to approximately 24 min. These results are consistent with those reported by Bartlett and
Swain (1949).
Sulfur mustard has been shown to react with nucleic acid components and the N7-guanine
adduct studied by several techniques (Rao et al., 2002).