Cyclooctatetraene

1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy. 1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy. Unlike benzene, C6H6, cyclooctatetraene, C8H8, is not aromatic, although its dianion, C8H2−8 (cyclooctatetraenide), is. Its reactivity is characteristic of an ordinary polyene, i.e. it undergoes addition reactions. Benzene, by contrast, characteristically undergoes substitution reactions, not additions. 1,3,5,7-Cyclooctatetraene was initially synthesized by Richard Willstätter in Munich in 1905 using pseudopelletierine as the starting material and the Hofmann elimination as the key transformation: Willstätter noted that the compound did not exhibit the expected aromaticity. Between 1939 and 1943, chemists throughout the US unsuccessfully attempted to synthesize COT. They rationalized their lack of success with the conclusion that Willstätter had not actually synthesized the compound but instead its isomer, styrene. Willstätter responded to these reviews in his autobiography, where he noted that the American chemists were 'untroubled' by the reduction of his cyclooctatetraene to cyclooctane (a reaction impossible for styrene). During World War 2, Walter Reppe at BASF Ludwigshafen developed a simple, one-step synthesis of cyclooctatetraene from acetylene, providing material identical to that prepared by Willstätter. Any remaining doubts on the accuracy of Willstätter's original synthesis were resolved when Arthur C. Cope and co-workers at MIT reported, in 1947, a complete repetition of the Willstätter synthesis, step by step, using the originally reported techniques. They obtained the same cyclooctatetraene, and they subsequently reported modern spectral characterization of many of the intermediate products, again confirming the accuracy of Willstätter's original work. Early studies demonstrated that COT did not display the chemistry of an aromatic compound. Then, early electron diffraction experiments concluded that the C-C bond distances were identical. However, X-ray diffraction data from H. S. Kaufman demonstrated cyclooctatetraene to adopt several conformations and to contain two distinct C–C bond distances. This result indicated that COT is an annulene with fixed alternating single and double C-C bonds. In its normal state, cyclooctatetraene is non-planar and adopts a tub conformation with angles C=C−C = 126.1° and C=C−H = 117.6°. The point group of cyclooctatetraene is D2d. In its planar transition state, the D4h transitional state is more stable than the D8h transitional state due to the Jahn–Teller effect. Richard Willstätter's original synthesis (4 consecutive elimination reactions on a cyclooctane framework) gives relatively low yields. Reppe's synthesis of cyclooctatetraene, which involves treating acetylene at high pressure with a warm mixture of nickel cyanide and calcium carbide, was much better, with chemical yields near 90%: COT can also be prepared by photolysis of barrelene, one of its structural isomers, the reaction proceeding via another isolable isomer, semibullvalene. COT derivatives can also be synthesised by way of semibullvalene intermediates. In the sequence illustrated below, octaethylcyclooctatetraene (C8Et8) is formed by thermal isomerisation of octaethylsemibullvalene, itself formed by copper(I) bromide mediated cyclodimerisation of 1,2,3,4-tetraethyl-1,4-dilithio-1,3-butadiene.