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The synthesis of the title compounds with substituents R=Alkyl, Cl, H by reaction of COT2? with RPCl2 at ?70°C is described. 相似文献
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9-Thiabicyclo[6.1.0]nona-2,4,6-triene was oxidized at ?15 to ?20°C with sodium periodate in a methanol-water medium. The major isolated product was established as 3a,7a-dihydrobenzo[b]thiophene--1-oxide, which is best explained as arising from intramolecular cycloaddition of a thionin oxide intermediate. 相似文献
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Treatment of the title compound (1a) with potassium in liquid ammonia at ca ?33° immediately afforded the benzylcyclooctatetraene dianion (4a) which, upon quenching with iodine-pentane, gave benzylcyclooctatetraene (5) as the only isolable product. In contrast, treatment of1a with potassium amide in liquid ammonia at ?69° initially afforded the 9-phenylmethylenecyclooctatrienyl anion (6a) as a short-lived intermediate which was then converted to the α-aminobenzylcyclooctatetraene dianion (7a). These results, coupled with the observation that cis-bicyclo[6.1.0]nona-2,4-diene (12) in potassium amide-liquid ammonia affords the cis-bicyclo[6.1.0]nonadienyl anion (8b) which then slowly opens to the methylcyclooctatetraene dianion (4b) at ?12°, lead to the conclusion that4a is produced by a reductive cleavage of1avia a radical anion or dianion. 相似文献
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The reaction of diiron nonacarbonyl with cis-bicyclo[6.2.0]deca-2,4,6-triene in ether at room temperature produces several products which are separable by chromatography on alumina. Compound (A), C10H12Fe2(CO)6, obtained in 23% yield, is shown by PMR and IR spectra to have the FeFe bonded Fe2(CO)6 group attached to the triene portion of the starting bicyclotriene. Compound (B), C10H12Fe(CO)3, obtained both from the initial reaction and by heating (A) in refluxing toluene; is the Fe(CO)3 adduct of tricyclo[4.4.0.02.5]deca-7,9-diene, a molecule which has not been isolated in the free state. Compound (C), also obtained on pyrolysis of (A) in minute yield, has not yet been characterized. Compound (D), C10H12Fe2(CO)6, from the original reaction, in small yield, appears to have separate Fe(CO)3 groups bonded to the olefinic portions of a C10H12 monocycle, but spectral data alone do not allow a complete specification of the structure. 相似文献
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9-Chlorobicyclo[6.1.0]non-l(9)-ene ( 4 ), a 2-chlorinated 1,3-fused cyclopropene, is synthesized and isolated from the dehalogenation of the l-bromo-9,9-dichlorobicyclo[6.1.0]nonane, itself derived from cyclooctene. Compound 4 undergoes ring opening reaction to generate cyclooctenyl chlorocarbene ( 9 ) which reacts with water via conjugate addition and ipso-addition to give ( E )-2-(chloromethylene)cyclooctanol ( 7 ) and cyclooctene-l-carboxaldehyde ( 8 ), respectively. The conjugate addition of 9 with water is more favorable than the ipso-addition by 3:1. Compound 4 , which is stable at ?25 °C for weeks without any decomposition, reacts with oxygen to produce 2-chlorocyclonon-2-enone ( 12 ) via the ring-opening reaction adduct, vinyl alkylcarbene 10 . 相似文献