Dichloroacetylene
|
|
|
|
Names
|
IUPAC name
Dichloroethyne
|
Other names
DCA, dichloroethyne
|
Identifiers
|
|
|
|
|
ChemSpider
|
|
ECHA InfoCard
|
100.149.197
|
|
|
RTECS number
|
|
UNII
|
|
|
|
InChI=1S/C2Cl2/c3-1-2-4
Key: ZMJOVJSTYLQINE-UHFFFAOYSA-N
InChI=1/C2Cl2/c3-1-2-4
Key: ZMJOVJSTYLQINE-UHFFFAOYAO
|
|
Properties
|
|
C
2
Cl
2
|
Molar mass
|
94.927
[1]
|
Appearance
|
colorless oily liquid
[1]
|
Odor
|
disagreeable, sweetish
|
Density
|
1.26 g/cm
3
|
Melting point
|
?66 to ?64 °C (?87 to ?83 °F; 207 to 209 K)
|
Boiling point
|
33 °C (91 °F; 306 K) explodes
|
|
insoluble
|
Solubility
|
soluble in
acetone
,
ethanol
,
ether
|
Hazards
|
Occupational safety and health
(OHS/OSH):
|
Main hazards
|
explosive, potential carcinogen
[1]
|
GHS
labelling
:
|
|
|
|
H200
,
H319
,
H330
,
H335
,
H351
,
H370
,
H372
,
H373
|
|
P260
,
P261
,
P264
,
P270
,
P271
,
P280
,
P284
,
P304+P340
,
P310
,
P312
,
P320
,
P321
,
P337+P313
,
P403+P233
,
P405
,
P501
|
NIOSH
(US health exposure limits):
|
|
none
[1]
|
|
Ca C 0.1 ppm (0.4 mg/m
3
)
[1]
|
|
Ca (N.D.)
[1]
|
Related compounds
|
|
Acetylene
,
Dibromoacetylene
,
Difluoroacetylene
,
Diiodoacetylene
|
Except where otherwise noted, data are given for materials in their
standard state
(at 25 °C [77 °F], 100 kPa).
|
Chemical compound
Dichloroacetylene
(
DCA
) is an
organochlorine compound
with the formula C
2
Cl
2
.
[2]
It is a colorless, explosive liquid that has a sweet and "disagreeable" odor.
[3]
Production
[
edit
]
Dichloroacetylene was first synthesized from
trichloroethylene
by E. Ott, W. Ottemeyer and K. Packendorff in 1930.
[2]
Ether solutions of dichloroacetylene are relatively stable, and such solutions can be safely generated by the
dehydrochlorination
of trichlorethylene. A popular procedure uses
potassium hydride
as the base:
[4]
- Cl
2
C=CHCl + KH → ClC≡CCl + KCl + H
2
A trace of methanol is required.
It has also been generated (and used in situ) using
lithium diisopropylamide
under anhydrous conditions
[5]
as well as
potassium hydroxide
.
[6]
Dichloroacetylene can occur and be stable in
air
at concentrations of up to 200 parts per million if certain other compounds, such as ether, with which it forms an azeotrope (boiling point of 32 °C), and trichloroethylene,
[7]
are also present.
[8]
Adventitious routes
[
edit
]
It is a
by-product
in the production of
vinylidene chloride
.
[9]
For instance, it can be formed from
trichloroethylene
.
[10]
[11]
It is also possible to produce dichloroacetylene from trichloroethylene at low concentrations by running the trichloroethylene through
nitrogen
at 120 °C in the presence of dry
potassium hydroxide
.
[12]
Reactions
[
edit
]
Dichloroacetylene reacts with
oxygen
to give
phosgene
:
[12]
- ClC≡CCl + O
2
→ Cl
2
CO +
CO
Dichloroacetylene, being electrophilic, adds nucleophiles, such as
amines
:
- ClC≡CCl + R
2
NH → Cl(H)C=CCl(NR
2
)
Biological role and toxicity
[
edit
]
Dichloroacetylene causes
neurological
disorders,
[9]
among other problems.
[13]
[14]
Studies on male
rats
and
rabbits
have shown that inhalation of dichloroacetylene can cause
tubular necrosis
,
focal necrosis
, and other nephrotoxic effects. Additionally, the rabbits that were given dichloroacetylene experienced
hepatotoxic
and
neuropathological
effects. Inhalation of dichloroacetylene also causes
benign tumors
of the
livers
and
kidneys
of rats. The chemical also caused increased instances of
lymphomas
.
[9]
It also causes
weight loss
in animals.
[13]
3.5% of a dose of dichloroacetylene remains in the
corpses
of male
Wistar rats
.
[9]
The
LC50s
of
mice
exposed to dichloroacetylene are 124 parts per million for a 1-hour exposure by inhalation and 19 parts per million for a 6-hour exposure by inhalation.
[12]
The chemical is ingested primarily through
glutathione
-dependent systems.
Glutathione
also reacts with it.
Hepatic
and
renal
glutathione S-transferases serve as
catalysts
to this reaction. While dichloroacetylene is
nephrotoxic
in rats, it does not show any signs of nephrotoxicity in humans.
[7]
Dichloroacetylene has
mutagenic
effects on
Salmonella typhimurium
.
[9]
The maximum safe concentration of dichloroacetylene in
air
is 0.1
parts per million
.
[15]
It is unsafe to store dichloroacetylene in close proximity to
potassium
,
sodium
, or
aluminium
powder
.
[3]
Like trichloroethylene, dichloroacetylene is metabolized to S-(1,2-dichlorovinyl)-
L
-cysteine (DCVC)
in vivo
.
[16]
[17]
According to the
Department of Transportation
, it is forbidden to
ship
dichloroacetylene.
[3]
Additional reading
[
edit
]
See also
[
edit
]
References
[
edit
]
- ^
a
b
c
d
e
f
NIOSH Pocket Guide to Chemical Hazards.
"#0188"
.
National Institute for Occupational Safety and Health
(NIOSH).
- ^
a
b
Henning Hopf; Bernhard Witulski (1995). "Functionalized Acetylenes in Organic Synthesis - The Case of the 1-Cyano- and the 1-Halogenoacetylenes". In Stang, Peter J.; Diederich, Francois (eds.).
Modern Acetylene Chemistry
. Weinheim: VCH. pp. 33?66.
doi
:
10.1002/9783527615278.ch02
.
ISBN
9783527615261
.
- ^
a
b
c
Pohanish, Richard P. (2011),
Sittig's Handbook of Toxic and Hazardous Chemicals and Carcinogens
, William Andrew,
ISBN
9781437778694
[
page needed
]
- ^
Denis, Jean Noel; Moyano, Albert; Greene, Andrew E. (1987). "Practical synthesis of dichloroacetylene".
The Journal of Organic Chemistry
.
52
(15): 3461?3462.
doi
:
10.1021/jo00391a059
.
- ^
"Dichlorovinylation of an Enolate: 8-Ethynyl-8-Methyl-1,4-Dioxaspiro[4.5]Dec-6-Ene".
Organic Syntheses
.
64
: 73. 1986.
doi
:
10.15227/orgsyn.064.0073
.
- ^
Siegel, J.; Jones, Richard Arvin.; Kurlansik, L. (1970). "Safe and Convenient Synthesis of Dichloroacetylene".
The Journal of Organic Chemistry
.
35
(9): 3199.
doi
:
10.1021/jo00834a090
.
- ^
a
b
Valacchi, Giuseppe; Davis, Paul A., eds. (January 1, 2008),
Oxidants in Biology: A Question of Balance
,
Springer Science+Business Media
,
ISBN
9781402083990
[
page needed
]
- ^
Proceedings
, Aerospace Medical Research Laboratory, 1966
[
page needed
]
- ^
a
b
c
d
e
"Dichloroacetylene"
(PDF)
,
IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans
,
39
: 369?78, 1986,
PMID
3465694
- ^
John T. James; Harold L. Kaplan; Martin E. Coleman (1996),
B5 Dichloroacetylene
,
doi
:
10.17226/5435
,
hdl
:
2060/19970023991
,
ISBN
978-0-309-05629-8
, retrieved
July 3,
2013
- ^
Greim, H; Wolff, T; Hofler, M; Lahaniatis, E (1984), "Formation of dichloroacetylene from trichloroethylene in the presence of alkaline material--possible cause of intoxication after abundant use of chloroethylene-containing solvents",
Archives of Toxicology
,
56
(2): 74?7,
doi
:
10.1007/bf00349074
,
PMID
6532380
,
S2CID
19576314
- ^
a
b
c
Reichert, D.; Ewald, D.; Henschler, D. (1975), "Generation and inhalation toxicity of dichloroacetylene",
Food and Cosmetics Toxicology
,
13
(5): 511?5,
doi
:
10.1016/0015-6264(75)90004-8
,
PMID
1201833
- ^
a
b
Dichloroacetylene
, November 18, 2010
, retrieved
July 3,
2013
- ^
Dichloroacetylene
, retrieved
July 3,
2013
- ^
Hazardous Material Fact Sheet
(PDF)
, April 1997
, retrieved
July 4,
2013
- ^
Purich, Daniel L., ed. (September 15, 2009),
Advances in Enzymology and Related Areas of Molecular Biology, Amino Acid Metabolism
, John Wiley & Sons,
ISBN
9780470123973
[
page needed
]
- ^
Kanhai, Wolfgang; Dekant, Wolfgang; Henschler, Dietrich (January 1989). "Metabolism of the nephrotoxin dichloroacetylene by glutathione conjugation".
Chemical Research in Toxicology
.
2
(1): 51?56.
doi
:
10.1021/tx00007a009
.
eISSN
1520-5010
.
ISSN
0893-228X
.
PMID
2519231
.