Formation of octachlorostyrene during the synthesis of chromium(iii) chloride

Article abstract of DOI:10.1080/10587250216178

Octachlorostyrene has been recovered from the reaction tube, along with previously reported hexachlorobenzene, during the synthesis of CrCl₃ from Cr₂O₃ and CCl₄ at high temperature. The region in the reaction tube where the octachlorostyrene was found, namely upstream from the Cr₂O₃ held at 890°C, suggests that this molecule is formed at a temperature below 890°C and that it decomposes if raised to that temperature. A low gas flow was used in this experiment, allowing products to diffuse countercurrently. Copyright

Full text of DOI:10.1080/10587250216178

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Formation of
Octachlorostyrene During the
Synthesis of Chromium(Iii)
Chloride
a
a
a
P. Mataruse , B. Yuknis , B. Mcdonald , G. Booth
a
a
b
,
D. A. Cleary & B. Twamley
a
Department of Chemistry , Gonzaga University ,
Spokane , WA , 99258
b
University of Idaho , Moscow , ID , 83844
Published online: 18 Oct 2010.
To cite this article: P. Mataruse , B. Yuknis , B. Mcdonald , G. Booth , D. A. Cleary
&
B. Twamley (2003) Formation of Octachlorostyrene During the Synthesis of
Chromium(Iii) Chloride, Molecular Crystals and Liquid Crystals, 392:1, 69-74, DOI:
0.1080/10587250216178
1
To link to this article: http://dx.doi.org/10.1080/10587250216178
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Mol. Cryst. Liq. Cryst., Vol. 392, pp. 69–74
Copyright # 2003 Taylor & Francis
1542-1406/03 $12.00+.00
DOI: 10.1080/15421400390193909
FORMATION OF OCTACHLOROSTYRENE DURING
THE SYNTHESIS OF CHROMIUM(III) CHLORIDE
P. Mataruse, B. Yuknis, B. McDonald, G. Booth,
and D. A. Cleary*
Department of Chemistry, Gonzaga University,
Spokane, WA 99258
B. Twamley
University of Idaho, Moscow, ID 83844
Octachlorostyrene has been recovered from the reaction tube, along with pre-
viously reported hexachlorobenzene, during the synthesis of CrCl
and CCl at high temperature. The region in the reaction tube where the
octachlorostyrene was found, namely upstream from the Cr
3 2 3
from Cr O
4
ꢀ
O
2 3
held at 890 C,
ꢀ
suggests that this molecule is formed at a temperature below 890 C and that it
decomposes if raised to that temperature. A low gas flow was used in this
experiment, allowing products to diffuse countercurrently.
Keywords: octachlorostyrene, synthesis, countercurrent formation
INTRODUCTION
Hexachlorobenzene and octachlorostyrene have attracted considerable
attention recently because they have been detected in fish and water
around areas where metals are produced [1–3]. The US Environmental
Protection Agency’s Office of Pollution Prevention and Toxics administers
the Persistent Bioaccumulative and Toxic (PBT) Chemical Program [4].
Hexachlorobenzene and octachlorostyrene are two of several com-
pounds for which the agency is developing national action plans. Other
PBTs include PCBs, DDT, and alkyllead compounds. The presence of
Received 13 June 2002; accepted 5 August 2002.
The authors gratefully acknowledge the National Science Foundation (DMR-0102149 and
CHE-0077972) for its support of this research. The Bruker (Siemens) SMART CCD diffraction
facility was established at the University of Idaho with the assistance of the NSF-EPSCoR
program and the M. J. Murdock Charitable Trust, Vancouver, WA, USA.
*Corresponding author. Fax: 509-323-5718; E-mail: cleary@ganzaga.edu
69

7
0
P. Mataruse et al.
octachlorostyrene in the environment is particularly interesting given that
it is not manufactured commercially. Little is known about octachloro-
styrene, but its similarity to hexachlorobenzene has led regulators to
assume octachlorostyrene has toxic effects similar to hexachlorobenzene
[
5–7]. Our interest in these compounds comes from the unexpected
observation of octachlorostyrene formation during the synthesis of chro-
mium(III) chloride from chromium(III) oxide. We followed a modified
procedure described by Angelici in his book Synthesis and Technique in
Inorganic Chemistry [8]. Stevenson and Rudman reported in this journal a
detailed study of the variety of products produced when processing chro-
mium(III) oxide with CCl at high temperature [9]. We observed essentially
4
the same behavior reported by them, with the exception that we observed
the formation of an additional product, octachlorostyrene, along with hexa-
chlorobenzene. An important feature about this observation is where in the
reaction tube the octachlorostyrene was observed. The purpose of this
communication is to report our observation of the presence of octachloro-
styrene when CrCl is produced from Cr O and CCl at high temperature.
3
2
3
4
EXPERIMENTAL PROCEDURE
Synthesis
Chromium(III) oxide was prepared from ammonium dichromate by igniting
a small pile (2.44 g, 9.67 mmol) of ammonium dichromate. The green fluffy
oxide (chromium(III) oxide) was separated from the unreacted orange
dichromate by washing with hot deionized water several times and filtering.
ꢀ
The oxide was dried at 110 C for 30 min. The oxide was transferred to an
open-ended quartz reaction tube which was inserted into a quartz flow
tube. The flow tube was placed in a tube furnace and the system was
purged with nitrogen gas. The nitrogen gas used in the purge was bubbled
through a reservoir of carbon tetrachloride. The tube furnace was brought
ꢀ
from room temperature to 890 C in 3 h. The N /CCl purge was continued
2
4
for 2 h. The furnace was then turned off and the sample allowed to cool
while still under the N /CCl gas flow. When the reaction tube had returned
to room temperature, it was removed from the furnace. In addition to the
2
4
III
expected formation of the desired product—Cr Cl (purple crystals)
3
downstream from the green oxide—colorless needle-shaped crystals
formed at both ends of the reaction tube outside the furnace.
DSC Analysis
The melting point of the colorless needle-shaped crystals formed down-
stream was determined using a Perkin-Elmer DSC 7 differential scanning

Formation of Octachlorostyrene
71
ꢀ
calorimeter. A sample of these needles (997 mg) was heated from 180 C to
ꢀ ꢀ
2
45 C at 10 C/min.
GC/MS Analysis
The gas chromatographic/mass spectrometric (GC/MS) analysis was per-
formed on a Hewlett-Packard 5890 Series II Plus gas chromatograph with a
Hewlett-Packard 5972 Series mass selective detector. A 4 mL sample was
ꢀ
ꢀ
ꢀ
ꢀ
heated from 60 C to 100 C at 20 C/min followed by heating at 30 C/min to
ꢀ
3
25 C. The column was 30 meters long with a 250 mm inside diameter and
was coated on the inside with 0.25 mm of 5% crosslinked methylsilicone. A
helium purge was used with a flow rate of 1.3 mL/min.
Single Crystal Structural Analysis
Crystals of octachlorostyrene were removed from the flask and covered
with a layer of hydrocarbon oil. A suitable crystal was selected, attached to
a glass fiber, and placed in the low-temperature nitrogen stream [10]. Data
were collected at 203(2) K using a Bruker/Siemens SMART 1K instrument
˚
(
Mo Ka radiation, l ¼ 0.71073 A) equipped with a Siemens LT-2A low
ꢀ
temperature device. Data were measured using omega scans of 0.3 per
frame for 30 s, and a half sphere of data was collected. A total of 1471
˚
frames were collected with a final resolution of 0.84 A. The first 50 frames
were recollected at the end of data collection to monitor for decay. Cell
parameters were retrieved using SMART [11] software and refined using
SAINTPlus [12] on all observed reflections. Data reduction and correction
for Lp and decay was performed using the SAINTPlus software. Absorption
corrections were applied using SADABS [13]. The structure was solved by
2
direct methods and refined by least squares method on F using SHELXTL
[
14]. The structure was solved in the space group P2(1)/c (#14) by analysis
of systematic absences. All atoms are refined anisotropically. No decom-
position was observed during data collection. Details of the data collection
and refinement are given in Table 1.
RESULTS
The crystals recovered downstream from the furnace began melting at
ꢀ ꢀ
2
26 C, and had a melting peak with a full width at half maximum of 0.75 C.
The GC/MS analysis revealed this product to be essentially pure hexa-
chlorobenzene. The GC/MS analysis, using the same parameters, of the
crystals formed upstream of the furnace revealed a mixture of hexa-
chlorobenzene and octachlorostyrene. The total ion chromatogram from

7
2
P. Mataruse et al.
TABLE 1 Crystal Data and Structure Refinement for Octachlorostyrene
Compound
Formula (fw)
T (K)
Octachlorostyrene
Cl (379.71)
203(2)
C
8
8
Crystal system
Space group
Unit cell dimensions
Monoclinic
P2(1)/c
˚
a ¼ 7.5618(16) A
˚
ꢀ
b ¼ 10.237(2) A, ꢀ ¼ 93.323(4)
˚
c ¼ 16.887(4) A
3
V (A ), Z
˚
1305.8(5), 4
1.931
1.690
ꢁ3
D (calcd) (g cm
)
ꢁ1
Absorption coefficient (mm
F(000)
Crystal size (mm)
)
736
0.3660.0660.03
2.33 to 25.00
ꢁ
range for data collection (deg)
ꢀ
Completeness to theta
Index ranges
94.1% (25.00 )
ꢁ8 ꢂ h ꢂ 8, ꢁ12 ꢂ k ꢂ 10, ꢁ19 ꢂ l ꢂ 20
6632
Reflections collected
Independent reflections
Absorption correction
Max. and min. transmission
Data / restraints / parameters
2159 [R(int) ¼ 0.0467]
Empirical
0.9511 and 0.5814
2159 / 0 / 145
1.083
2
Goodness-of-fit on F
Final R indices [I > 2ꢂ(I)]
R indices (all data)
Largest diff. peak and hole
R1 ¼ 0.0641, wR2 ¼ 0.1471
R1 ¼ 0.1097, wR2 ¼ 0.1773
ꢁ
3
˚
0.692 and ꢁ0.518 e.A
the upstream sample showed two peaks with retention times of 12.72 min
and 13.90 min. The relative areas were 100(hexachlorobenzene) to
9
.4(octachlorostyrene). The mass spectrum for each peak contained the
parent ion (m/z ¼ 284 for hexachlorobenzene and m/z ¼ 380 for octa-
chlorostyrene) expected for the given stoichiometry along with the
required isotopic pattern for species containing such a number of chlorine
atoms. A single crystal X-ray diffraction analysis of one of the crystals also
confirmed it to be octachlorostyrene. The results of the crystal analysis are
given in Table 1.
The observed space group and unit cell dimensions are consistent with
the previously published single crystal data for octachlorostyrene, which
was solved and refined in the non-standard setting of P2(1)/a [15].
DISCUSSION
Hexachlorobenzene has been observed previously during the synthesis of
chromium(III) chloride from chromium(III) oxide [9]. In the present

Formation of Octachlorostyrene
73
case, octachlorostyrene was also produced with hexachlorobenzene.
Octachlorostyrene has been prepared previously by chlorination of a
solution of 1,3-dichloro-2-vinylbenzene in CCl , following by addition of
4
SbCl5 [16]. It has also been prepared as a byproduct (20%) in the
chlorination of n-propylbenzene, again using CCl4 as the solvent [17].
Incidents of octachlorostyrene in the environment have been attributed
to waste products from electrolytic chlorine production [18]. In the
present example, it is interesting to note where the hexachlorobenzene
and octachlorostyrene were found in the reaction tube. Hexa-
chlorobenzene was found, as in the work of Stevenson and Rudman, at
the exit of the reaction tube. In addition, hexachlorobenzene was also
found at the entrance of the reaction tube, upstream from where the
Cr O was placed. The octachlorostyrene was only found upstream, and
2
3
it deposited as separate needle-like crystals among the more abundant
hexachlorobenzene crystals. This suggests that wherever it is formed in
the reaction tube, it survives only if it diffuses to the cooler upstream
portion of the reaction tube. We used a very low gas flow rate in our
experiments. This may explain how octachlorostyrene was able to dif-
fuse against the N /CCl gas flow direction.
2
4
REFERENCES
[
1] Sandau, C. D., Meerts, I. A. T. M., Letcher, R. J., McAlees, A. J., Chittim, B., Brouwer, A., &
Norstrom, R. J. (2000). Environmental Science and Technology, 34, 3871–3877.
2] van den Brink, N. W., & de Ruiter-Dijkman, E. M. (1997). Antarctic Science, 9, 414–417.
3] Jørgensen, E. H., Burkow, I. C., Foshaug, H., Killie, B., & Ingebrigtsen, K. (1997). Comp.
Biochem. Physiol., 118C, 311–318.
[
[
[
[
[
[
[
[
4] US Environmental Protection Agency. (2001). 2000 PBT Program Accomplishments,
EPA-742-R-01-003, November 2001.
5] Seld e´ n, A. I., Floderus, Y., Bodin, L. S., Westberg, H. B., & Thunell, S. (1999). Archives of
Environmental Health, 54, 248–253.
6] Seld e´ n, A. I., Nygren, Y., Westberg, H. B., & Bodin, L. S. (1997). Occupational and
Environmental Medicine, 54, 613–618.
7] Smith, A. G., Carthew, P., Francis, J. E., & Ingebrigtsen, K. (1994). Cancer Letters, 81,
145–150.
8] Angelici, R. J. (1986). Synthesis and Technique in Inorganic Chemistry. 2nd ed. Mill
Valley, CA: University Science Books.
9] Rudman, R., & Stevenson, C. (1994). Mol. Cryst. Liq. Cryst., 240, 105–111.
[10] Hope, H. (1995). Prog. Inorg. Chem., 41, 1.
[11] Bruker. (1997-1998). SMART: Bruker Molecular Analysis Research Tool, v.5.059.
Madison, WI: Bruker AXS.
[
[
12] Bruker. (1999). SAINTPlus: Data Reduction and Correction Program. Madison, WI:
Bruker AXS.
13] Sheldrick, G. M. (1999). SADABS v.2.01: An Empirical Absorption Correction Pro-
gram. Madison, WI: Bruker AXS Inc.

7
4
P. Mataruse et al.
[14] Sheldrick, G. M. (1998). SHELXTL: Version 5.10, Structure Determination Software
Suite. Madison, WI: Bruker AXS Inc.
[15] Huffman, J. C., Kaminsky, R., & Hites, R. A. (1984). Proc. Indiana Acad. Sci., 93,
145–147.
[16] Bieniek, D., & Korte, F. (1978). Chemosphere, 7(9), 729–730.
[17] Ruetman, S. H. (1975). Synthesis, 6, 382–384.
[18] Kaminsky, R., Kaiser, K. L. E., & Hites, R. A. (1983). J. Great Lakes Res., 9, 183–189.