5-Chloro-2-norbomene

Acetophenone Hydrogen chloride Magnesium 5-Chloro-2-norbomene Piperidine hydrochloride Formaldehyde ... 

Butoxynorbomadiene provides a convenient route to 7-sub-stituted norbomenes and norbomadienes including anti-7-nor-bomenol,2 7-norbomadienyl acetate,2 7-norbomadienol,2 7-chloro-norbomadiene, 7-methylnorbomadiene, and 7-phenylnorbor-... 

The results of the olefin oxidation catalyzed by 19, 57, and 59-62 are summarized in Tables VI-VIII. Table VI shows that linear terminal olefins are selectively oxidized to 2-ketones, whereas cyclic olefins (cyclohexene and norbomene) are selectively oxidized to epoxides. Cyclopentene shows exceptional behavior, it is oxidized exclusively to cyclopentanone without any production of epoxypentane. This exception would be brought about by the more restrained and planar pen-tene ring, compared with other larger cyclic nonplanar olefins in Table VI, but the exact reason is not yet known. Linear inner olefin, 2-octene, is oxidized to both 2- and 3-octanones. 2-Methyl-2-butene is oxidized to 3-methyl-2-butanone, while ethyl vinyl ether is oxidized to acetaldehyde and ethyl alcohol. These products were identified by NMR, but could not be quantitatively determined because of the existence of overlapping small peaks in the GC chart. The last reaction corresponds to oxidative hydrolysis of ethyl vinyl ether. Those olefins having bulky (a-methylstyrene, j8-methylstyrene, and allylbenzene) or electon-withdrawing substituents (1-bromo-l-propene, 1-chloro-l-pro-pene, fumalonitrile, acrylonitrile, and methylacrylate) are not oxidized. 

Cyclothiazide Cyclothiazide is 1,1-dioxide 3,4-dihydro-3-(5-norbomen-2-yl)-6-chloro-27f-l,2,4-benzothiadiazin-7-sulfonamide (21.3.12) [32-34],... 

Acetoxylchlorination of norbomene (75), followed by skeletal rearrangement of 76 in an excess of Q1CI2, gives exo-2-chloro-syn-7-acetoxynorbornane (77). This is a good synthetic method for yyn-7-norbomenol (78) [67]. Similarly, the brendane... 

Cyclobutanes from the addition of 1-chloro-l-fluoroethylene to chlorotrifluoro- or tetrafluoro-ethylene, of 2-fluoropropene to tetrafluoroethylene, and of 1-chloro-2,2-difluoroethylene to vinyl fluoride or propene have been claimed to be anaesthetics. Diels-Alder addition of cyclopentadiene to acids of the type, trans-RpCHiCH COaH (Rf = CHaF, CHFa, CFs, C2F5, or n-CsFv) and a number of related esters and other derivatives, at 25 °C, results in predominant formation of adduct witii an endo fluoroalkyl group. The addition of cyclopentadiene to the 1,1-difluoroethylenes, CFalCFa, CFa CF CFs, CFa CCla, CFa C(CF3)2, CFaiCCl-CFaCl, and CFa.CFH has been recorded and the fiee-radical bromina-tion of the resulting norbomenes studied. Buta-1,3-diene and trifluorovinyl-sulphur pentafluoride yield essentially a mbcture of cis- and rmns-cyclobutanes (116), with little or no cyclohexene formation the olefin resembles perfluoropropene which yields ca. 5% of cyclohexene, in this respect. Perfluoroindene, which adds... 

Stille and co-workers devised an elegant method for attaching cyclopentadienyl ligand onto polystyrenes. Thus, reaction of p-styryl-MgBr with norbomen-7-one gave syn-7-(p-styryl)norbom-2-en-7-ol, which was converted into 7-chloro-7-(p-styryl)norbom-2-ene. Polymerization of this compound with styrene and divinylbenzene gave polymers... 

MPR)TPP)C0 epoxidized a variety of alkenes with Cl2pyNO as oxidant, the chloro system giving higher yields (56-98%) with Ru (8.6 wt.%.) oxidant substrate = 1 14(X) KXX), in benzene, atr. t. for 24 h. Cw-stilbene and norbomene yield exclusively cM-epoxides. In contrast, with the M-41(m) system, the Ru((4-Cl)i 4-MPR)TPP)CO polymer oxidized frani-stilbene and rra j-P-methylstyrene to the corresponding trans epoxides in 90 and 86 % yields, respectively. Several alkenes were oxidized catalytically for the first time with high selectivity 3,4-dihydronaphthalene yielded 62% epoxide. 

Hydrosilylation of norbornadiene (nbd) by chloro- or alkyl-hydrosilanes in the presence of Pd- or Mo-catalysts [178, 179] led to the corresponding silylnor-bornenes. Norbornenes with ethane spacer between bicyclic nuclear and silicon atom can be synthesized by hydrosilylation of 5-vinyl-2-norbomene [180],... 

The unsubstituted "1-norbomene" was nevertheless generated by alkyllithium-mediated iodo/lithium permutation from l-iodobicyclo[2.2.1]heptanes bearing at the 2-endo- or 2-exo-position a bromo or chloro substituent and ensuing lithium halide elimination. When the reaction is carried out in the presence of furan at -60 °C, always the same endo/exo mixture of Diels-Alder cycloadducts is obtained irrespective of what starting material is employed(Scheme 1-216). " This corroborates the intermediacy of the short-lived species 274. 

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