Octachloropropane

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Octachloropropane
Octachloropropane.png
Names
Preferred IUPAC name
Octachloropropane
Other names
Propane octachloride, Perchloropropane
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/C3Cl8/c4-1(5,2(6,7)8)3(9,10)11
    Key: QQAHAGNPDBPSJP-UHFFFAOYSA-N
  • C(C(Cl)(Cl)Cl)(C(Cl)(Cl)Cl)(Cl)Cl
Properties
C3Cl8
Molar mass 319.63 g·mol−1
Melting point 160 °C (320 °F; 433 K)[1]
Hazards
Lethal dose or concentration (LD, LC):
[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Octachloropropane or perchloropropane is the chemical compound with elemental formula C3Cl8 and structural formula Cl3C−CCl2−CCl3. Its molecule has a simple chain of three carbon atoms connected by single bonds, with chlorine atoms filling their remaining bonds. It is a chlorocarbon, specifically the third simplest perchloroalkane. It can be described as a derivative of propane C3H8, with all hydrogen atoms replaced by chlorine.

Octachlorpropane is a clear white crystalline solid at room temperature, with hexagonal crystal structure. It is easily deformed by mechanical stress, without losing its crystal structure—like a metal.[3][4][1]

History[edit]

Synthesis and characterization of octachloropropane was reported in 1875 by Krafft and Merz.[5] Its remarkable crystal growth and deformation properties were noted by McCrone in 1949.[6][7][8] Its use as a model for crystal deformation of minerals was pioneered by Win D. Means, Marc W. Jessel and others in the 1980s.[9][1]

Production[edit]

Octachloropropane can be obtained by reacting partially chlorinated propane with iodine trichloride (as in the original synthesis by Krafft and Merz), or with chlorine at high pressure or with activation by light. The temperature must be close to but below 200 °C, since at higher temperatures further reaction with chlorine gives carbon tetrachloride and hexachloroethane instead.[5]

Chemistry[edit]

Octachloropropane treated with aluminum in diethyl ether affords several unsaturated perchlorocarbons, by way of hexachloropropene (C3Cl6, Cl3C−CCl=CH2).[10] For instance,

C3Cl8 + 2/3 Al 2/3 AlCl3 + C3Cl6
2 C3Cl6 + 4/3 Al 4/3 AlCl3 + C6Cl8 (three isomers)
2 C3Cl6 + 2 Al 2 AlCl3 + C6Cl6 (two isomers)

The products were identified as

α-C6Cl6: colorless, m. p. 148 °C.
β-C6Cl6: red, m. p. 155 °C

with conjectured structures CCl≡C−CCl=CCl−CCl=CCl2 or CCl2=CCl−C≡C−CCl=CCl2, and

α-C6Cl8: b. p. 105-110 °C at 0.1 torr.
β-C6Cl8: m. p. 71 °C.
γ-C6Cl8: m. p. 183 °C.

which were claimed to be cis/trans isomers and atropisomers of CCl2=CCl−CCl=CCl−CCl=CCl2 (octachloro(1,3,5)hexatriene).[10]

Applications[edit]

Crystalline plasticity model[edit]

Octacholopropane is used by geologists and metallurgists as a model to study the plastic deformation of crystalline minerals and rocks under stress. The large individual crystalline grains (0.1-1.0 mm diameter) are distinguishable with a polarized light microscope at moderate magnification, and generally retain their size and approximate aspect ratio as the material undergoes shear strain.[4][3][11] The grains will spontaneously arise from the quenched solid, in minutes or hours, even at room temperature.[1]

The material's flow driven by stress can be followed by embedding in it small amounts of fine inert particles, such as grit 1000 abrasives; the particles apparently do not affect the grain evolution and deformation.[4][3][11] Camphor (with rhombohedral crystal structure) was previously proposed for this use.[12]

Metal separation[edit]

Octachlorpropane reacts with niobium pentoxide and tantalum pentoxide at atmospheric pressure yielding the corresponding chlorides. It also reacts with titanium dioxide, if the other two oxides are present. This reaction, followed with distillation of the titanium tetrachloride at about 225 °C, could be an effective way to remove TiO2 from mixtures of those oxides.[13]

Pesticide[edit]

Octachloropropane has been commercialized as a snail killer with the brand name HRS-1622, although it was not found to be very effective.[14]

Octachloropropane was found to be highly toxic to larvae of the housefly, with an efficiency comparable to decachlorobutane and hexachlorobenzene (BHC). Unlike the latter, it is somewhat volatile and thus effective even without physical contact with the solid.[15]

Environmental concerns[edit]

Octachloropropane was detected as a relatively minor item among dozens of highly chlorinated and perchlorinated hydrocarbons present as contaminants in the carbon tetrachloride produced from methanol by a plant in China,[16] and also in the condensed waste from etching aluminum films in an integrated circuit factory.[17]

See also[edit]

References[edit]

  1. ^ a b c d Paul D. Bons, Mark W. Jessel, Lynn Evans, Terence Barr, and Karl Stüwe (2001) "Modeling of anisotropic grain growth in minerals" Tectonic Modeling: A Volume in Honor of Hans Ramberg; Geological Society of America Memoir, volume 193. 276 pages. ISBN 9780813711935
  2. ^ "Hexachloroethane". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. ^ a b c Mark W. Jessell and G. S. Lister (1991): "Strain localization behaviour in experimental shear zones". Pure and Applied Geophysics, volume 137, page 421–438. doi:10.1007/BF00879043
  4. ^ a b c Win D. Means and Jin-Han Ree (1988): "Seven types of subgrain boundaries in octachloropropane". Journal of Structural Geology, volume 10, issue 7, pages 765-770. doi:10.1016/0191-8141(88)90083-1
  5. ^ a b F. Asinger (196662): Paraffins: Chemistry and Technology. Revised English edition of German original published in 1956. 920 pages. ISBN 9781483146621
  6. ^ W. C. McCrone (1949): "Boundary migration and grain growth". Discussions of the Faraday Society, volume 5, pages 158-166.
  7. ^ W. C. McCrone and P. T. Cheng (1949): "Grain growth in octachloropropane". Journal of Applied Physics, volume 20, pages 230–231
  8. ^ P. A. Beck (1949): "Comments on grain growth in octachloropropane". Journal of Applied Physics, volume 20, page 231.
  9. ^ Win D. Means (1983): "Microstructure and micromotion in recrystallization flow of octachloropropane: A first look". Geologische Rundschau, volume 71, pages 511-528. doi:10.1007/BF01822080
  10. ^ a b A. Roedig (1948): "Über die Synthese einiger Polychlorpolyene und die Atropisomerie der Oktachlorhexatriene". Experientia, volume 4, pages 305–307 doi:10.1007/BF02164460
  11. ^ a b Mark Jessel (1996): "Analogue Modelling at the University at Albany, State University of New York" (1996): Online collection of videos created by Youngdo Park, Jin-Han Ree, and Win D. Means. Accessed on 2020-07-03.
  12. ^ J. L. Urai, F. J. Humphreys, and S. E. Burrows (1980): "In-situ studies of the deformation and dynamic recrystallization of rhombohedral camphor". Journal of Materials Science, volume 15, pages 1231–1240. doi:10.1007/BF00551812
  13. ^ R. H. Atkinson, Joseph Steigman, and C. F. Hiskey (1952): "Analytical chemistry of niobium and tantalum. Chlorination of titania and distillation separation from niobium and tantalum". Analytical Chemistry, volume 24, issue 3, pages 484–488. doi:10.1021/ac60063a013
  14. ^ E. A. Seiffer and H. F. Schoof (197): "Tests of 15 experimental molluscicides against Australorbis glabratus". Public Health Reports, volume 82, issue 9, pages 833–839. PMID 4963721 PMC 1920017
  15. ^ K. R. S. Ascher and Z. H. Levinsox (1954): "Chemicals affecting the preimaginal stages of the housefly. III. Contact toxicity for third stage larvae of some chlorinated hydrocarbons deposited on adsorbent surfaces.". Rivista di Parassitologia, Volume 15, issue 1, pages 57-61. ISSN 0035-6387
  16. ^ Lifei Zhang, Wenlong Yang, Linli Zhang, Xiaoxiu Li (2015): "Highly chlorinated unintentionally produced persistent organic pollutants generated during the methanol-based production of chlorinated methanes: A case study in China". Chemosphere, volume 133, pages 1-5. doi:10.1016/j.chemosphere.2015.02.044
  17. ^ Peggy Müller, Thomas Stock, Siegfried Bauer, and Ilona Wolff (2002): "Genotoxicological characterisation of complex mixtures: Genotoxic effects of a complex mixture of perhalogenated hydrocarbons". Mutation Research/Genetic Toxicology and Environmental Mutagenesis, volume 515, issues 1–2, pages 99-109 doi:10.1016/S1383-5718(02)00005-0
  18. ^ Stephen W. Tobey and Robert. West (1964): "Hexachlorocyclopropane". Journal of the American Chemical Society, volume 86, issue 1, pages 56–61. doi:10.1021/ja01055a014