Büro
für Altlastenerkundung und Umweltforschung
Dr. Rainer Haas
Stadtwaldstr. 45a, D-35037 Marburg, Tel.: 06421/93084, Fax: 06421/93073
email: haasr@gmx.net
Chemical reactions of chlorovinylarsines (Lewisite)
2. Reaction of 2-Chlorovinylarsine dichloride (Lewisite I) with Alcohols
Rainer Haas1, Alfred Krippendorf2
1: Buero fuer Altlastenerkundung und Umweltforschung, Stadtwaldstrasse 45a, D-35037 Marburg, Germany
2: Hazard Control Ltd., Versuchsfeld Trauen, D-29328 Fassberg, Germany
Translation, original article was published in UWSF - Z Umweltchem. Oekotox. 10 (3) 141-142 (1998), ecomed publishers D-86899 Landsberg, Germany
Abstract
2-Chlorovinylarsine dichloride (Lewisite I) react by room temperature quickly with alcohols in an equilibrium reaction to yield 2-Chlorovinylarsine chloridether and bisether. The reactions are not quantitative. The ethyl and propyl ether are not stable. The ether were identified with mass spectrometry.
Key words: analysis, arsenical compounds, chemical warfare agents, cwa, chemical reactions, chlorovinlyarsine dichloride, lewisite
1 Experimental
2-Chlorovinylarsine dichloride, Lewisite I (CAS-No. 541-25-3) was derivatizied with the following alcohols: methanol (MeOH), ethanol (EtOH), 1-propanol (1PrOH), 2-propanol (2PrOH), 1-butanol (1BuOH), 2-butanol (2BuOH), 1-pentanol (1PeOH), 2-pentanol (2PeOH), 3-pentanol (3-PeOH), 1-hexanol (1HexOH), 2-hexanol (2-HexOH), 1-heptanol (1HepOH), 2-heptanol (2HepOH), 3-heptanol (3-HepOH), 1-octanol (1OcOH), 2-octanol (2OcOH) and 3-octanol (3OcOH).
For the derivatization procedures acetonic solutions of Lewisite I 76 µg/ml and of the different alcohols with 40 mg/ml were used. Derivatizations were done in 1.4 ml vials by a temperature of 20°C.
For the separation of the Lewisite I-alcohol derivatives a gas chromatograph HP 5890 with HP 7673 autosampler and electronic capture detector (ECD) was used. Analysis were done under the following chromatographic conditions:
column: capillary column DB 5, length 30 m, thickness 0.25 mm
carrier gas: nitrogen
column temperature: initial 100°C (1 min), 10°C/min to 230°C, 230°C (6 min)
injector temperature: 250°C
detector temperature: 300°C
injection volume: 1 µl.
Three minutes after adding of alcohols analysis were started, continously repeated during three days and sometimes repeated during the next three weeks (stabilization control). Identifications of the derivatives were done by gas chromatography/mass spectrometry (GC/MS).
3 Results and discussion
2-Chlorovinylarsine dichloride reacts upon alcohols like
Cl(CH=CH)AsCl2 + ROH --> Cl(CH=CH)AsCl(OR) + HCl + ROH -->
Cl(CH=CH)As(OR)2 + 2 HCl
by creating 2-Chlorovinylarsine chloridether and 2-Chlorovinylarsine bisether. This products can be detected with gas chromatography and electron capture detector (GC/ECD).
The reaction rate could not be detected, because Lewisite I could not be detected with gas chromatography.
There are retention times (Rt) and relative intensity of the peaks (Area) of Chlorovinylarsine chloridether (1) and Chlorovinylarsine bisether (2) shown in table 1.
Table 1: Retention times (Rt) and relative intensity of the Chlorovinylarsine chloridether (1) and Chlorovinylarsine bisether (2)
|
alcohol |
Rt 1 |
Rt 2 |
Area 1 |
Area 2 |
|
|
min |
min |
mV*min |
mV*min |
|
MeOH |
3,76 |
4,19 |
0,47 |
1,16 |
|
EtOH |
4,89 |
4,99 |
not stable |
|
|
1PrOH |
5,99 |
7,19 |
not stable |
|
|
2PrOH |
5,28 |
5,75 |
not stable |
|
|
1BuOH |
7,30 |
9,63 |
1,61 |
1,61 |
|
2BuOH |
6,58 |
8,26 |
3,20 |
0,94 |
|
1PeOH |
8,64 |
11,98 |
1,43 |
1,69 |
|
2PeOH |
7,77 |
10,35 |
2,68 |
1,53 |
|
3PeOH |
7,84 |
10,48 |
2,82 |
0,88 |
|
1HexOH |
10,03 |
14,24 |
1,57 |
2,20 |
|
2HexOH |
9,03 |
12,52 |
2,23 |
2,00 |
|
3HexOH |
8,91 |
12,20 |
1,29 |
0,74 |
|
1HepOH |
11,34 |
16,65 |
1,38 |
2,82 |
|
2HepOH |
10,29 |
14,53 |
2,09 |
2,59 |
|
3HepOH |
10,12 |
14,11 |
2,81 |
2,05 |
|
1OcOH |
12,63 |
20,20 |
1,15 |
3,75 |
|
2OcOH |
11,51 |
16,86 |
1,50 |
3,15 |
|
3OcOH |
11,34 |
16,21 |
2,52 |
2,78 |
|
13Pdiol |
6,25 |
--- |
2,10 |
--- |
The ethyl- and propyl ether are not stable. They decomposite during 72 hours to undetectable products. With the other alcohols a stable equilibrium between chloridether and bisether is obtained. The equilibrium concentrations are reached in 30 min. The reactions products are stable.
With gas chromatography/mass spectrometry the following derivatives were identified:
2-Chlorovinylarsine chloridmethylether and bismethylether from methanol
2-Chlorovinvlarsine chloridbutylether and bisbutylether from butanol
2-Chlorovinylarsine chloridpentylether and bispentylether from pentanol
2-Chlorovinylarsine chloridheptylether and bisheptylether from heptanol
2-Chlorovinylarsine chloridoctylether and bisoctylether from octanol.
From a mixture of Lewisite I and different alcohols all possible products were created. From a mixture of Lewisite I, alcohols and thiols only the more stable Dichlorodivinylarsine thioether were detected.
3 Literature
Haas, R., Schmidt, T.C., Steinbach, K., v.Loew, E.: Gaschromatographische Bestimmung von Arsenkampfstoffen und Umwandlungsprodukten. Fachtagung Ruestungsaltlasten (Grundwassersanierung), Munster 7./8.10.97