Adamantane amination

Capping of inclusion complex with adamantane amine... 

A mixture consisting of the step 2 product and a solution of adamantane amine (0.13 g), benzotriazol-l-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate (0.38 g), and 0.14 ml of diisopropylethylamine dissolved in 50 ml of anhydrous dimethylformamide was shaken and then placed into a refrigerator overnight. Thereafter 50 ml of methanol was added and the mixtures stirred, centrifuged, and the supernatant discarded. This solid was washed twice with 100 ml of dimethyl formamide (DMF)/methanol, 1 1, followed by washing with 100 ml of methanol and... 

FIGURE 16.9 The antiviral adamantane amines amantadine 22 and rimantadine 23. 

Extensive investigations have been performed related to the synthesis of new adamantane derivatives with better therapeutic actions and less adverse effects. For example, it has been proved that adamantylamino-pyrimidines and -pyridines are strong stimulants of mmor necrosis factor-a (TNF-a) [132]. TNF is a substance that can improve the body s namral response to cancer by killing cancer cells. Another example is 1,6-diaminodiamantane [87], which possesses an antitumor and antibacterial activity. Also, many derivatives of aminoadamantanes have antiviral activity like 3-(2-adamantyl) pyrolidines with two pharmacophoric amine groups, which have antiviral activity against influenza-A virus [133]. 

The condensation reactions described above are unique in yet another sense. The conversion of an amine, a basic residue, to a neutral imide occurs with the simultaneous creation of a carboxylic acid nearby. In one synthetic event, an amine acts as the template and is converted into a structure that is the complement of an amine in size, shape and functionality. In this manner the triacid 15 shows high selectivity toward the parent triamine in binding experiments. Complementarity in binding is self-evident. Cyclodextrins for example, provide a hydrophobic inner surface complementary to structures such as benzenes, adamantanes and ferrocenes having appropriate shapes and sizes 12) (cf. 1). Complementary functionality has been harder to arrange in macrocycles the lone pairs of the oxygens of crown ethers and the 7t-surfaces of the cyclo-phanes are relatively inert13). Catalytically useful functionality such as carboxylic acids and their derivatives are available for the first time within these new molecular clefts. 

Kollner et al. (29) prepared a Josiphos derivative containing an amine functionality that was reacted with benzene-1,3,5-tricarboxylic acid trichloride (11) and adamantane-l,3,5,7-tetracarboxylic acid tetrachloride (12). The second generation of these two types of dendrimers (13 and 14) were synthesized convergently through esterification of benzene-1,3,5-tricarboxylic acid trichloride and adamantane-1,3,5,7-tetracarboxylic acid with a phenol bearing the Josiphos derivative in the 1,3 positions. The rhodium complexes of the dendrimers were used as chiral dendritic catalysts in the asymmetric hydrogenation of dimethyl itaconate in methanol (1 mol% catalyst, 1 bar H2 partial pressure). The enantioselectivities were only... 

RuCl(dmso)(tpa)](PF ) and RuCl(dmso)(BPG) (tpa=tris(2-pyridylmethyl) amine, BPG=A,iV-bis(2-pyridylmethyl)glycmate) no preparation was given. The X-ray crystal structure of the (tpa) complex showed sulfur co-ordination from (dmso). As [RuCl(dmso)(tpa)](PFg) and RuCl(dmso)(BPG)/MCPBA/CHCl3 they catalysed hydroxylation of adamantane [951]. 

Chemical Class Adamantane derivative tricyclic amine... 

Amino-adamantan 9,0 g (0,05 mol) 1 -Formylamino-adamantan wird in 150 ml konz. Salzsaure 5 h unter Ruckflufi gekocht. Nadi dem Abkuhlen macht man alkalisch und extrahiert das Amin mit Ether. Der Extrakt wird mil festem Natriumhydroxid getrocknet und der Ether abdestilliert Ausbeute 7,3 g (97%) Schmp. (nach Sublimation) 180-192 . 

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