1,5-Cyclooctadiene

changed changed 477206505 1,5-Cyclooctadiene.svg correct ?? 100 Skeletal formula of 1,5-cyclooctadiene 1,5-cyclooctadiene-ED-3D-balls.png correct ?? 100 Ball and stick model of 1,5-cyclooctadiene Cycloocta-1,5-diene AC1L1QCE - Compound Summary https://pubchem.ncbi.nlm.nih.gov/compound/8135 PubChem Compound National Center for Biotechnology Information 14 October 2011 USA 26 March 2005 Identification and Related Records 1,5-COD 111-78-4 correct CAS correct ?? 1552-12-1 (Z,Z) correct ?? 5259-71-2 (Z,E) correct ?? 17612-50-9 (E,E) correct FDA 1E1VVD385Z 8135 82916 (Z,Z) 5364364 (Z,E) 5702534 (E,E) 7843 changed chemspider 74815 correct chemspider (Z,Z) 18520443 correct chemspider (Z,E) 19971660 correct chemspider (E,E) 203-907-1 2520 1,5-cyclooctadiene GX9560000 GX9620000 (Z,Z) 2036542 1209288 (Z,Z) C1CC=CCCC=C1 1S/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7- correct chemspider 1/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7- VYXHVRARDIDEHS-QGTKBVGQSA-N correct chemspider VYXHVRARDIDEHS-QGTKBVGQBM 8 12 Colorless liquid 0.882 g/mL 204 423 910 Pa 1.493 21–27 kJ mol−1 −4.890 – −4.884 MJ mol−1 250.0 J K−1 mol−1 198.9 J K−1 mol−1 flame health hazard DANGER 226 304 315 317 319 334 261 280 301+310 305+351+338 331 342+311 32 to 38 222 1,5-Cyclooctadiene (also known as cycloocta-1,5-diene) is a cyclic hydrocarbon (a cycloalkene) with the chemical formula C8H12, specifically [\s(CH2)2\sCH\dCH\s]2. 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. 1,5-Cyclooctadiene can be prepared by dimerization of butadiene in the presence of a nickel or iron catalyst, a coproduct being vinylcyclohexene. Approximately 10,000 tons were produced in 2005. Organic reactions COD reacts with borane to give 9-borabicyclo[3.3.1]nonane, commonly known as 9-BBN, a reagent in organic chemistry used in hydroborations: 450px COD adds SCl2 (or similar reagents) to give 2,6-dichloro-9-thiabicyclo[3.3.1]nonane: 450px|2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, synthesis and reactions The resulting dichloride can be further modified as the diazide or dicyano derivative in a nucleophilic substitution aided by anchimeric assistance. COD is used as an intermediate in one of the syntheses of disparlure, a gypsy moth pheromone. 10.1002/anie.197800471 Synthesis of Disparlure by Kolbe Electrolysis 1978 Klünenberg Helmut Schäfer Hans J. Angewandte Chemie International Edition in English 17 47–48 Metal complexes 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. Ni(COD)2 is prepared by reduction of anhydrous nickel acetylacetonate in the presence of the ligand, using triethylaluminium [Ni(C5H7O2)2]3 + 2COD + 2Al(C2H5)3 → Ni(COD)2 + 2Al(C2H5)2(C5H7O2) + C2H4 + C2H6 The related Pt(COD)2 is prepared by a more circuitous route involving the dilithium cyclooctatetraene: Li2C8H8 + PtCl2(COD) + 3C7H10 → [Pt(C7H10)3] + 2LiCl + C8H8 + C8H12 Pt(C7H10)3 + 2COD → Pt(COD)2 + 3C7H10 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: Ni(COD)2 + 4CO → Ni(CO)4 + 2COD The 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 thumb|600px|none|E,E-COD synthesis (Stöckmann 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. Irradiation of cis,cis-1,5-cyclooctadiene in the presence of copper(I) chloride George M. Whitesides George M. Whitesides Gerald L. Goe Arthur C. Cope Arthur C. Cope J. Am. Chem. Soc. 1969 91 10 2608–2616 10.1021/ja01038a036 Another synthesis (double elimination reaction from a cyclooctane ring) was reported by Rolf Huisgen in 1987. Preparation and conformation of (E,E)-1,5-cyclooctadiene Dieter Boeckh Rolf Huisgen Rolf Huisgen Heinrich Noeth J. Am. Chem. Soc. 1987 109 4 1248–1249 10.1021/ja00238a046 The molecular conformation of (E,E)-COD is twisted rather than chair-like. The compound has been investigated as a click chemistry mediator. (E,E)-1,5-Cyclooctadiene: a small and fast click-chemistry multitalent Henning Stöckmann André A. Neves Henry A. Day Shaun Stairs Kevin M. Brindle Finian J. Leeper Chem. Commun. 2011 47 25 7203–5 10.1039/C1CC12161H 21611648 Related compounds Dibenzocyclooctatetraene References 30em Buehler C. Pearson D. Survey of Organic Syntheses https://archive.org/details/surveyoforganics00bueh registration Wiley-Interscience New York 1970 Shriver D. Atkins P. Inorganic Chemistry https://archive.org/details/inorganicchemist00shri registration W. H. Freeman and Co. New York 1999 978-0-716-72873-3 9 95 1998 9-Borabicyclo[3.3.1]nonane Dimer John A. Soderquist Alvin Negron cv9p0095 Roger Bishop 9 692 CV9P0692 9-Thiabicyclo[3.3.1]nonane-2,6-dione Mechanistic Insight Into High-Spin Iron(I)-Catalyzed Butadiene Dimerization Organometallics 2016 35 2923–2929 10.1021/acs.organomet.6b00474 Lee H Campbell M. G. Sánchez R. H. Börgel J. Raynaud J Parker S. E. Ritter T. 17 2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold Molecules 2006 11 212–218 http://www.mdpi.org/molecules/papers/11040212.pdf 10.3390/11040212 Díaz David Converso Antonella Sharpless K. Barry Finn M. G. 4 17962753 6148556 free Schunn R. Ittel S. Inorganic Syntheses Bis(1,5-Cyclooctadiene)Nickel(0) 2007 28 10.1002/9780470132593.ch25 94–98 978-0-470-13259-3 Thomas Schiffer Georg Oenbrink Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene 10.1002/14356007.a08_205.pub2 Crascall L Spencer J. Inorganic Syntheses Olefin Complexes of Platinum 10.1002/9780470132593.ch34 28 2007 126–132 978-0-470-13259-3 Category:Cycloalkenes Category:Dienes Category:Ligands Category:Eight-membered rings Category:Foul-smelling chemicals