1- Adamantyl bromide

Adamantyl bromide [768-90-1] M 215.1, m 117-119", 118", 119.5-120". If coloured, dissolve in CCI4, wash with H2O, treat with charcoal, dry (CaCl2), filter, evap to dryness. Dissolve in a small volume of MeOH and cool in a C02/trichloroethylene bath and collect the crystals. Sublime at 90-100°/water pump vacuum. [Chem Ber 92 1629 1959 J Am Chem Soc 83 2700 1961.]... 

Figure 11. Correlation of solvolytic rate constants for 1-adamantyl bromide (45, X = Br) at 25° and Y. (From Raber et al., 1970, and reproduced by permission of the American Chemical Society.)...

A direct and satisfactory procedure for tertiary alkyl-alkynyl coupling has been developed by Negishi and Baba, who used trialkynylaluminums readily obtainable from the corresponding alkynyllithiums and anhydrous AICI3 [92]. For instance, tris(l-hexynyl)aluminum underwent a remarkably clean reaction with 1-adamantyl bromide to produce cross-coupled product 96 in 96 % yield. It is noteworthy that the reaction enables novel geminal alkyl-alkynylation of ketones this reaction should find a considerable application in natural product synthesis (Sch. 60). 

Heating 5-methylpyrazol-3-one 11 with 1-adamantyl bromide 27 at 150 °C afforded 2-adamantylpyrazol-3-one 28, whereas at 200 °C 4-adamantylpyrazol-3-one 29 was obtained (99BSB735) (Scheme 9). 

H20 (1.4) > TFE (1.0) toward An-C=CMe2 and H20 (0.9) TFE (1.0) for its o-methoxy analogue. The former order is reasonable in terms of nu-cleophilicities of both species. The nearly similar reactivities of TFE and H20 are somewhat surprising, but they do not differ much from the kTFE/kH20 values calculated for the solvolysis of 1-adamantyl bromide and t-BuCl (78). 

Adamantyl bromide heated 20 min. at 100° with excess coned, ethereal methyl-magnesium bromide in an aerosol pressure bottle -> 1-methyladamantane. Y ... 

Alkyl halides, excepting alkyl fluorides, can be reduced under electrochemical conditions in aprotic solvents. For example, 1-adamantyl bromide can be reduced to... 

Both 1-adamantyl bromide and l-bromobicyclo[2,2,2]octane react rapidly with trimethylaluminium, even at — 70 °C, to give good yields of the bridgehead methyl derivatives 1-bromonorbomane is inert under these conditions. Likewise, coupling of the 1-adamantyl and 1-bicyclo-octyl bromides with MeMgBr gave satisfactory yields of the methyl derivatives, whereas 1-bromonorbornane did not react. It has been... 

---