There are three configurational isomers with this structure, that differ by the arrangement of the four C–C single bonds adjacent to the double bonds. Each pair of single bonds can be on the same side (cis,Z) or on opposite sides (trans,E) of the double bond's plane; the three possibilities are denoted cis,cis, trans,trans, and cis,trans; or (Z,Z), (E,E), and (Z,E). (Because of overall symmetry, trans,cis is the same configuration as cis,trans.)
Generally abbreviated COD, the cis,cis isomer of this diene is a useful precursor to other organic compounds and serves as a ligand in organometallic chemistry. It is a colorless liquid with a strong odor. [2][3] 1,5-Cyclooctadiene can be prepared by dimerization of butadiene in the presence of a nickel catalyst, a coproduct being vinylcyclohexene. Approximately 10,000 tons were produced in 2005.[4][5]
1,5-COD binds to low-valent metals via both alkene groups. Metal-COD complexes are attractive because they are sufficiently stable to be isolated, often being more robust than related ethylene complexes. The stability of COD complexes is attributable to the chelate effect. The COD ligands are easily displaced by other ligands, such as phosphines.
Extensive work has been reported on complexes of COD, much of which has been described in volumes 25, 26, and 28 of Inorganic Syntheses. The platinum complex is a precursor to a 16-electron complex of ethylene:
Pt(COD)2 + 3C2H4 → Pt(C2H4)3 + 2COD
COD complexes are useful as starting materials; one noteworthy example is the reaction:
The M(COD)2 complexes with nickel, palladium, and platinum have tetrahedral geometry, whereas [M(COD)2]+ complexes of rhodium and iridium are square planar.
^"AC1L1QCE - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 26 March 2005. Identification and Related Records. Retrieved 14 October 2011.
^Buehler, C.; Pearson, D. (1970). Survey of Organic Syntheses. New York: Wiley-Interscience.
^Shriver, D.; Atkins, P. (1999). Inorganic Chemistry. New York: W. H. Freeman and Co. ISBN 978-0-716-72873-3.
^Schiffer, Thomas; Oenbrink, Georg. "Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_205.pub2.
^Lee, H; Campbell, M. G.; Sánchez, R. H.; Börgel, J.; Raynaud, J; Parker, S. E.; Ritter, T. (2016). "Mechanistic Insight Into High-Spin Iron(I)-Catalyzed Butadiene Dimerization". Organometallics. 35 (17): 2923–2929. doi:10.1021/acs.organomet.6b00474.
^Soderquist, John A.; Negron, Alvin (1998). "9-Borabicyclo[3.3.1]nonane Dimer". Organic Syntheses.; Collective Volume, vol. 9, p. 95
^Díaz, David; Converso, Antonella; Sharpless, K. Barry; Finn, M. G. (2006). "2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold" (PDF). Molecules. 11 (4): 212–218. doi:10.3390/11040212. PMC6148556. PMID 17962753.
^Schunn, R.; Ittel, S. (2007). "Bis(1,5-Cyclooctadiene)Nickel(0)". Inorganic Syntheses. pp. 94–98. doi:10.1002/9780470132593.ch25. ISBN978-0-470-13259-3. {{cite book}}: |journal= ignored (help)
^Crascall, L; Spencer, J. (2007). "Olefin Complexes of Platinum". Inorganic Syntheses. pp. 126–132. doi:10.1002/9780470132593.ch34. ISBN978-0-470-13259-3. {{cite book}}: |journal= ignored (help)
^Whitesides, George M.; Goe, Gerald L.; Cope, Arthur C. (1969). "Irradiation of cis,cis-1,5-cyclooctadiene in the presence of copper(I) chloride". J. Am. Chem. Soc. 91 (10): 2608–2616. doi:10.1021/ja01038a036.
^Boeckh, Dieter; Huisgen, Rolf; Noeth, Heinrich (1987). "Preparation and conformation of (E,E)-1,5-cyclooctadiene". J. Am. Chem. Soc. 109 (4): 1248–1249. doi:10.1021/ja00238a046.
^Stöckmann, Henning; Neves, André A.; Day, Henry A.; Stairs, Shaun; Brindle, Kevin M.; Leeper, Finian J. (2011). "(E,E)-1,5-Cyclooctadiene: a small and fast click-chemistry multitalent". Chem. Commun. 47 (25): 7203–5. doi:10.1039/C1CC12161H. PMID 21611648.
August 24, 2023
cyclooctadiene, cycloocta, diene, cyclic, hydrocarbon, with, chemical, formula, c8h12, specifically, namespreferred, iupac, name, cycloocta, diene, identifierscas, number, y1552, y5259, y17612, model, jsmol, interactive, imageabbreviations, codbeilstein, refer. Cycloocta 1 5 diene is a cyclic hydrocarbon with the chemical formula C8H12 specifically CH2 2 CH CH 2 1 5 Cyclooctadiene NamesPreferred IUPAC name Cycloocta 1 5 diene 1 IdentifiersCAS Number 111 78 4 Y1552 12 1 Z Z Y5259 71 2 Z E Y17612 50 9 E E Y3D model JSmol Interactive imageAbbreviations 1 5 CODBeilstein Reference 20365421209288 Z Z ChemSpider 7843 N74815 Z Z Y18520443 Z E Y19971660 E E YECHA InfoCard 100 003 552EC Number 203 907 1MeSH 1 5 cyclooctadienePubChem CID 813582916 Z Z 5364364 Z E 5702534 E E RTECS number GX9560000 GX9620000 Z Z UNII 1E1VVD385Z YUN number 2520CompTox Dashboard EPA DTXSID0026888InChI InChI 1S C8H12 c1 2 4 6 8 7 5 3 1 h1 2 7 8H 3 6H2 b2 1 8 7 YKey VYXHVRARDIDEHS QGTKBVGQSA N YInChI 1 C8H12 c1 2 4 6 8 7 5 3 1 h1 2 7 8H 3 6H2 b2 1 8 7 Key VYXHVRARDIDEHS QGTKBVGQBMSMILES C1CC CCCC C1PropertiesChemical formula C 8H 12Molar mass 108 184 g mol 1Appearance Colorless liquidDensity 0 882 g mLMelting point 69 C 92 F 204 KBoiling point 150 C 302 F 423 KVapor pressure 910 PaRefractive index nD 1 493ThermochemistryHeat capacity C 198 9 J K 1 mol 1Std molarentropy S 298 250 0 J K 1 mol 1Std enthalpy offormation DfH 298 21 27 kJ mol 1Std enthalpy ofcombustion DcH 298 4 890 4 884 MJ mol 1HazardsGHS labelling PictogramsSignal word DangerHazard statements H226 H304 H315 H317 H319 H334Precautionary statements P261 P280 P301 P310 P305 P351 P338 P331 P342 P311Flash point 32 to 38 C 90 to 100 F 305 to 311 K Autoignitiontemperature 222 C 432 F 495 K Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references There are three configurational isomers with this structure that differ by the arrangement of the four C C single bonds adjacent to the double bonds Each pair of single bonds can be on the same side cis Z or on opposite sides trans E of the double bond s plane the three possibilities are denoted cis cis trans trans and cis trans or Z Z E E and Z E Because of overall symmetry trans cisis the same configuration ascis trans Generally abbreviated COD the cis cis isomer of this diene is a useful precursor to other organic compounds and serves as a ligand in organometallic chemistry It is a colorless liquid with a strong odor 2 3 1 5 Cyclooctadiene can be prepared by dimerization of butadiene in the presence of a nickel catalyst a coproduct being vinylcyclohexene Approximately 10 000 tons were produced in 2005 4 5 Contents 1 Organic reactions 2 Metal complexes 3 E E COD 4 ReferencesOrganic reactions EditCOD reacts with borane to give 9 borabicyclo 3 3 1 nonane 6 commonly known as 9 BBN a reagent in organic chemistry used in hydroborations COD adds SCl2 or similar reagents to give 2 6 dichloro 9 thiabicyclo 3 3 1 nonane 7 8 The resulting dichloride can be further modified as the diazide or dicyano derivative in a nucleophilic substitution aided by anchimeric assistance Metal complexes EditSelected metal 1 5 COD complexes Bis cyclooctadiene nickel 0 Crabtree s catalyst The complex Rh2 COD 2Cl2 Co 1 5 cyclooctadiene cyclooctenyl Dichloro 1 5 cyclooctadiene palladium cyclooctadiene iridium chloride dimer Dichloro 1 5 cyclooctadiene platinum1 5 COD binds to low valent metals via both alkene groups Metal COD complexes are attractive because they are sufficiently stable to be isolated often being more robust than related ethylene complexes The stability of COD complexes is attributable to the chelate effect The COD ligands are easily displaced by other ligands such as phosphines Ni COD 2 is prepared by reduction of anhydrous nickel acetylacetonate in the presence of the ligand using triethylaluminium 9 1 3 Ni C5H7O2 2 3 2COD 2Al C2H5 3 Ni COD 2 2Al C2H5 2 C5H7O2 C2H4 C2H6The related Pt COD 2 is prepared by a more circuitous route involving the dilithium cyclooctatetraene 10 Li2C8H8 PtCl2 COD 3C7H10 Pt C7H10 3 2LiCl C8H8 C8H12 Pt C7H10 3 2COD Pt COD 2 3C7H10Extensive work has been reported on complexes of COD much of which has been described in volumes 25 26 and 28 of Inorganic Syntheses The platinum complex is a precursor to a 16 electron complex of ethylene Pt COD 2 3C2H4 Pt C2H4 3 2CODCOD complexes are useful as starting materials one noteworthy example is the reaction Ni COD 2 4CO Ni CO 4 2CODThe product Ni CO 4 is highly toxic thus it is advantageous to generate it in the reaction vessel upon demand Other low valent metal complexes of COD include cyclooctadiene rhodium chloride dimer cyclooctadiene iridium chloride dimer and Fe COD CO 3 and Crabtree s catalyst The M COD 2 complexes with nickel palladium and platinum have tetrahedral geometry whereas M COD 2 complexes of rhodium and iridium are square planar E E COD Edit E E COD synthesis Stockmann et al 2011 The highly strained trans trans isomer of 1 5 cyclooctadiene is a known compound E E COD was first synthesized by George M Whitesides and Arthur C Cope in 1969 by photoisomerization of the cis cis compound 11 Another synthesis double elimination reaction from a cyclooctane ring was reported by Rolf Huisgen in 1987 12 The molecular conformation of E E COD is twisted rather than chair like The compound has been investigated as a click chemistry mediator 13 References Edit AC1L1QCE Compound Summary PubChem Compound USA National Center for Biotechnology Information 26 March 2005 Identification and Related Records Retrieved 14 October 2011 Buehler C Pearson D 1970 Survey of Organic Syntheses New York Wiley Interscience Shriver D Atkins P 1999 Inorganic Chemistry New York W H Freeman and Co ISBN 978 0 716 72873 3 Schiffer Thomas Oenbrink Georg Cyclododecatriene Cyclooctadiene and 4 Vinylcyclohexene Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a08 205 pub2 Lee H Campbell M G Sanchez R H Borgel J Raynaud J Parker S E Ritter T 2016 Mechanistic Insight Into High Spin Iron I Catalyzed Butadiene Dimerization Organometallics 35 17 2923 2929 doi 10 1021 acs organomet 6b00474 Soderquist John A Negron Alvin 1998 9 Borabicyclo 3 3 1 nonane Dimer Organic Syntheses Collective Volume vol 9 p 95 Bishop Roger 9 Thiabicyclo 3 3 1 nonane 2 6 dione Organic Syntheses Collective Volume vol 9 p 692 Diaz David Converso Antonella Sharpless K Barry Finn M G 2006 2 6 Dichloro 9 thiabicyclo 3 3 1 nonane Multigram Display of Azide and Cyanide Components on a Versatile Scaffold PDF Molecules 11 4 212 218 doi 10 3390 11040212 PMC 6148556 PMID 17962753 Schunn R Ittel S 2007 Bis 1 5 Cyclooctadiene Nickel 0 Inorganic Syntheses pp 94 98 doi 10 1002 9780470132593 ch25 ISBN 978 0 470 13259 3 a href Template Cite book html title Template Cite book cite book a journal ignored help Crascall L Spencer J 2007 Olefin Complexes of Platinum Inorganic Syntheses pp 126 132 doi 10 1002 9780470132593 ch34 ISBN 978 0 470 13259 3 a href Template Cite book html title Template Cite book cite book a journal ignored help Whitesides George M Goe Gerald L Cope Arthur C 1969 Irradiation of cis cis 1 5 cyclooctadiene in the presence of copper I chloride J Am Chem Soc 91 10 2608 2616 doi 10 1021 ja01038a036 Boeckh Dieter Huisgen Rolf Noeth Heinrich 1987 Preparation and conformation of E E 1 5 cyclooctadiene J Am Chem Soc 109 4 1248 1249 doi 10 1021 ja00238a046 Stockmann Henning Neves Andre A Day Henry A Stairs Shaun Brindle Kevin M Leeper Finian J 2011 E E 1 5 Cyclooctadiene a small and fast click chemistry multitalent Chem Commun 47 25 7203 5 doi 10 1039 C1CC12161H PMID 21611648 Retrieved from https en wikipedia org w index php title 1 5 Cyclooctadiene amp oldid 1171817274, wikipedia, wiki, book, books, library,
