2-adamantanecarboxylic acid

Hydroxy-1-adamantanecarboxylic acid reacts exothermally with FAR to give 3-fluoro 1 adamantanoyl fluoride, which, after treatment with ammonium hydroxide, yields 3 fIuoro-1 adamantanecarboxamide [79] (equation 50)... 

An interesting appetite suppressant very distantly related to hexahydroamphetamines is somanta-dine (24). The reported synthesis starts with conversion of 1-adamantanecarboxylic acid (20) via the usual steps to the ester, reduction to the alcohol, transformation to the bromide (21), conversion of the latter to a Grignard reagent with magnesium metal, and transformation to tertiary alcohol 22 by reaction with acetone. Displacement to the fomiamide (23) and hydrolysis to the tertiary amine (24) completes the preparation of somantadine [6]. 

As an alternative purification procedure, the checkers have esterified the crude acid by refluxing it for 2 hours with three times its weight of methanol and 2 ml. of 98% sulfuric acid. The solution is poured into 10 volumes of water and extracted with the minimum amount of chloroform required to give a clean separation of layers. The chloroform solution is washed with water, dried over calcium chloride, and distilled from a Claisen flask with an indented neck. Methyl 1-adamantanecarboxylate is collected at 77-79° (1 mm.) m.p. 38-39°. Hydrolysis of the ester with the calculated amount of 1A potassium hydroxide followed by acidification yields 1-adamantanecarboxylic acid m.p. 175-176.5° 90% overall recovery. 

Adamantanecarboxylic acid can be prepared by carboxyla-tion of 1-adamantanol3 or 1-bromoadamantane3,4 by formic acid and 96% sulfuric acid by carboxylation of adamantane by formic acid, 2-butyl alcohol, and 96% sulfuric acid 5 and by carboxylation of adamantane by formic acid and 130% sulfuric acid. ... 

In contrast, the fluorescence spectra of the parent y-cyclodextrins (compounds y-CD1, y-CD2, y-CD3, y-CD4) exhibit both monomer and excimer bands in the absence of guests because the cavity is large enough to accommodate both fluorophores (Figure 10.38). The ratio of excimer and monomer bands changes upon guest inclusion. The ratio of the intensities of the monomer and excimer bands was used for detecting various cyclic alcohols and steroids (cyclohexanol, cyclo-dodecanol, i-borneol, 1-adamantanecarboxylic acid, cholic acid, deoxycholic acid and parent molecules, etc.). 

A further use of the system is to mediate the reaction of adamantane with carbon monoxide and oxygen to form 1-adamantanecarboxylic acid . When long-wavelength light (>300 nm) is used, hydroperoxides efficiently generate hydroxyl radicals without the use of metal ions and would be an extremely useful source of hydroxyl radicals, particularly in the design of DNA-cleaving molecules . ... 

A solution of 21.7 g (0.11 mole) 1-adamantanecarboxylic acid chloride in 100 ml ether was added to a solution of 19.4 g (0.22 mole) 2-dimethylaminoethanol in 200 ml ether. The reaction mixture was stirred overnight at room temperature. Then additional 15.0 g (0.17 mole) 2-dimethylaminoethanol was added and the reaction mixture again stirred overnight. The reaction mixture was poured into 300 ml water and treated with 20 ml of 10% NaOH solution. From the ether layer was recovered 23.0 g of 2-dimethylaminoethyl 1-adamantanecarboxylate as oil. 

The only example of a twisted cuboctahedron was reported by Kimura and coworkers [159]. Cuboctahedron 63 was obtained by the 4 4 self-assembly of fris(Znn-cyclen) complex 61 with trianionic trithiocyanurate (TCA3-, 62) upon guest encapsulation and was characterized both in the solid state and in solution (Fig. 33). Suitable guests are lipophilic organic molecules of matching size, such as, ([D4]-2,2,3,3)-3-(trimethylsilyl)propionic acid (TSP), 1-adamantanecarboxylic acid, 2,4-dinitrophenol (2,4-DNP), adamantine (ADM), or the tetra-n-propylammonium (TPA) cation. 

Alkyl radicals that formed from alkanes under the action of various radical-like species can react rapidly not only with molecular oxygen, but can also be trapped by carbon monoxide. In this case, carboxylic acids can be obtained. Thus adamantane has been recently converted into 1-adamantanecarboxylic acid as the main product (Scheme II.7) [50]. N-Hydroxyphthalimide was used for this transformation as an efficient radical catalyst. The reaction occurs under mild conditions (CO pressure up to 15 atm and temperature below 100 °C) and gives l-adamantanecarboxyUc acid with selectivity 56% and conversion 75%. 

Weickenmeier and Wenz [84] investigated the inclusion complex formation of poly[(N-vinyl-2-pyrrolidone)-co-(maleic acid)] modified with j8-CD moieties with 1-adamantanamine and with 1-adamantanecarboxylic acid by isothermal titration calorimetry. They reported 1 1 inclusion complexes between -CD moieties and adamantane derivatives with relatively large binding constants (ca. 3-5 x 10 M ). 

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