Chemistry:Dicyclopentadiene

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Dicyclopentadiene[1]
Stereo wireframe model of dicyclopentadiene.
endo‑Dicyclopentadiene (left) exo‑Dicyclopentadiene (right)
Ball and stick model of dicyclopentadiene
Ball-and-stick model of endo‑Dicyclopentadiene
Names
IUPAC name
Tricyclo[5.2.1.02,6]deca-3,8-diene
Other names
1,3-Dicyclopentadiene, Bicyclopentadiene, 3a,4,7,7a-Tetrahydro-1H-4,7-methanoindene
  • endo isomer: (3aR*,4S*,7R*,7aS*)-
  • exo isomer: (3aS*,4S*,7R*,7aR*)-
Identifiers
3D model (JSmol)
Abbreviations DCPD
1904092
ChemSpider
EC Number
  • 201-052-9
KEGG
MeSH Dicyclopentadiene
RTECS number
  • PC1050000
UNII
UN number UN 2048
Properties
C10H12
Molar mass 132.20 g/mol
Appearance Colorless, crystalline solid[2]
Odor camphor-like[2]
Density 0.978 g/cm3
Melting point 32.5 °C (90.5 °F; 305.6 K)
Boiling point 170 °C (338 °F; 443 K)
0.02%[2]
Solubility very soluble in ethyl ether, ethanol
soluble in acetone, dichloromethane, ethyl acetate, n-hexane, toluene
log P 2.78
Vapor pressure 180 Pa (20 °C)[2]
Hazards
NFPA 704 (fire diamond)
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineHealth code 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
3
1
1
Flash point 32 °C (90 °F; 305 K)
503 °C (937 °F; 776 K)
Explosive limits 0.8%-6.3%[2]
NIOSH (US health exposure limits):
PEL (Permissible)
 none[2]
REL (Recommended)
 TWA 5 ppm (30 mg/m3)[2]
IDLH (Immediate danger)
 N.D.[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Dicyclopentadiene, abbreviated DCPD, is a chemical compound with formula C
10H
12. At room temperature, it is a white brittle wax, although lower purity samples can be straw coloured liquids. The pure material smells somewhat of soy wax or camphor, with less pure samples possessing a stronger acrid odor. Its energy density is 10,975 Wh/l. Dicyclopentadiene is a co-produced in large quantities in the steam cracking of naphtha and gas oils to ethylene. The major use is in resins, particularly, unsaturated polyester resins. It is also used in inks, adhesives, and paints.

The top seven suppliers worldwide together had an annual capacity in 2001 of 179 kilotonnes (395 million pounds).

DPCD was discovered as a C
10H
12 hydrocarbon among the products of pyrolysis of phenol by Henry Roscoe, who didn't identify the structure (that was made during the following decade) but accurately assumed that it was a dimer of some C
5H
6 hydrocarbon.[3]

History and structure

For many years the structure of dicyclopentadiene was thought to feature a cyclobutane ring as the fusion between the two subunits. Through the efforts of Alder and coworker, the structure was deduced in 1931.[4]

The spontaneous dimerization of neat cyclopentadiene at room temperature to form dicyclopentadiene proceeds to around 50% conversion over 24 hours and yields the endo isomer in better than 99:1 ratio as the kinetically favored product (about 150:1 endo:exo at 80 °C).[5] However, prolonged heating results in isomerization to the exo isomer. The pure exo isomer was first prepared by base-mediated elimination of hydroiodo-exo-dicyclopentadiene.[6] Thermodynamically, the exo isomer is about 0.7 kcal/mol more stable than the endo isomer.[7] The exo isomer also has a lower reported melting point of 19°C.[8] Both isomers are chiral.

Dicyclopentadiene formation.png

Reactions

Above 150 °C, dicyclopentadiene undergoes a retro-Diels–Alder reaction at an appreciable rate to yield cyclopentadiene. The reaction is reversible and at room temperature cyclopentadiene dimerizes over the course of hours to re-form dicyclopentadiene. Cyclopentadiene is a useful diene in Diels–Alder reactions as well as a precursor to metallocenes in organometallic chemistry. It is not available commercially as the monomer, due to the rapid formation of dicyclopentadiene; hence, it must be prepared by "cracking" the dicyclopentadiene (heating the dimer and isolating the monomer by distillation) shortly before it is needed.

The thermodynamic parameters of this process have been measured. At temperatures above about 125 °C in the vapor phase, dissociation to cyclopentadiene monomer starts to become thermodynamically favored (the dissociation constant Kd = [cyclopentadiene]2 / [dicyclopentadiene] > 1). For instance, the values of Kd at 149 °C and 195 °C were found to be 277 and 2200, respectively.[9] By extrapolation, Kd is on the order of 10–4 at 25 °C, and dissociation is disfavored. In accord with the negative values of ΔH° and ΔS° for the Diels–Alder reaction, dissociation of dicyclopentadiene is more thermodynamically favorable at high temperatures. Equilibrium constant measurements imply that ΔH° = –18 kcal/mol and ΔS° = –40 eu for cyclopentadiene dimerization.[10]

Dicyclopentadiene polymerizes. Copolymers are formed with ethylene or styrene. The "norbornene double bond" participates.[11] Using ring-opening metathesis polymerization a homopolymer polydicyclopentadiene is formed.

Hydroformylation of DCP gives the dialdehyde called TCD dialdehyde (TCD = tricyclodecane). This dialdehyde can be oxidized to the dicarboxylic acid and to a diol. All of these derivatives have some use in polymer science.[12]

Hydrogenation of dicyclopentadiene gives tetrahydrodicyclopentadiene (C10H16), which is a component of jet fuel JP-10,[13] and rearranges to adamantane[14][15] with aluminium chloride or acid at elevated temperature.

Adamantane synthesis.png

References

  1. ↑ Merck Index, 11th Edition, 2744
  2. ↑ 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 NIOSH Pocket Guide to Chemical Hazards. "#0204". National Institute for Occupational Safety and Health (NIOSH). https://www.cdc.gov/niosh/npg/npgd0204.html. 
  3. ↑ Levandowski, B. J.; Raines, R. T. (2021). "Click Chemistry with Cyclopentadiene". Chemical Reviews 121 (12): 6777–6801. doi:10.1021/acs.chemrev.0c01055. PMID 33651602. 
  4. ↑ Roberts, John D.; Sharts, Clay M. (2011). "Cyclobutane Derivatives from Thermal Cycloaddition Reactions". Organic Reactions. pp. 1–56. doi:10.1002/0471264180.or012.01. ISBN 978-0471264187. 
  5. ↑ Xu, Rui; Jocz, Jennifer N.; Wiest, Lisa K.; Sarngadharan, Sarath C.; Milina, Maria; Coleman, John S.; Iaccino, Larry L.; Pollet, Pamela et al. (2019-09-05). "Cyclopentadiene Dimerization Kinetics in the Presence of C5 Alkenes and Alkadienes". Industrial & Engineering Chemistry Research 58 (50): 22516–22525. doi:10.1021/acs.iecr.9b04018. ISSN 0888-5885. 
  6. ↑ Bartlett, Paul D.; Goldstein, Irving S. (1947-10-01). "exo-Dicyclopentadiene". Journal of the American Chemical Society 69 (10): 2553. doi:10.1021/ja01202a501. ISSN 0002-7863. 
  7. ↑ Narayan, Adithyaram; Wang, Beibei; Nava Medina, Ilse Belen; Mannan, M. Sam; Cheng, Zhengdong; Wang, Qingsheng (2016-11-01). "Prediction of heat of formation for exo-Dicyclopentadiene" (in en). Journal of Loss Prevention in the Process Industries 44: 433–439. doi:10.1016/j.jlp.2016.10.015. ISSN 0950-4230. 
  8. ↑ Jamróz, Małgorzata E; Gałka, Sławomir; Dobrowolski, Jan Cz (September 2003). "On dicyclopentadiene isomers". Journal of Molecular Structure: THEOCHEM 634 (1–3): 225–233. doi:10.1016/S0166-1280(03)00348-8. 
  9. ↑ Wilson, Philip J.; Wells, Joseph H. (1944-02-01). "The Chemistry and Utilization of Cyclopentadiene.". Chemical Reviews 34 (1): 1–50. doi:10.1021/cr60107a001. ISSN 0009-2665. 
  10. ↑ Lenz, Terry G.; Vaughan, John D. (1989-02-01). "Employing force-field calculations to predict equilibrium constants and other thermodynamic properties for the dimerization of 1,3-cyclopentadiene". The Journal of Physical Chemistry 93 (4): 1592–1596. doi:10.1021/j100341a081. ISSN 0022-3654. 
  11. ↑ Li, Xiaofang; Hou, Zhaomin (2005). "Scandium-Catalyzed Copolymerization of Ethylene with Dicyclopentadiene and Terpolymerization of Ethylene, Dicyclopentadiene, and Styrene". Macromolecules 38 (16): 6767. doi:10.1021/ma051323o. Bibcode: 2005MaMol..38.6767L. 
  12. ↑ Kohlpaintner, Christian; Schulte, Markus; Falbe, Jürgen; Lappe, Peter; Weber, Jürgen (2008). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_321.pub2. 
  13. ↑ "Combustion Chemistry". The University of Utah. https://chem.utah.edu/directory/anderson/research-group/CombustChem.php. 
  14. ↑ Schleyer, Paul von R.; Donaldson, M. M.; Nicholas, R. D.; Cupas, C. (1973). "Adamantane". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=cv5p0016. ; Collective Volume, 5, pp. 16 
  15. ↑ Hönicke, Dieter; Födisch, Ringo; Claus, Peter; Olson, Michael (2002). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_227. 

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