Adamantane-1 -carboxylic acid synthesis

Conversion of the methyl ester of 1-adamantane carboxylic acid to 1-ada-mantyl dimethylcarbinol (66) by reaction with CH3Mgl followed by dehydration and subsequent hydrogenation provides a convenient route to 1-iso-propyladamantane (66a) 164> 20°). Simmons-Smith cyclopropanation of 1-isopropenyladamantane (67) followed by hydrogenolysis of the cyclopropane ring gives 1-r-butyladamantane (68) 204>. An alternative synthesis... 

Functional group manipulations are equally successful for the preparation of a wide variety of 2-substituted adamantanes. Starting with the methyl ester of 2-adamantane carboxylic acid S7> 2061, 2-t-butyladamantane (71) may be prepared in a manner anlogous to that described above for the synthesis of the bridgehead isomer (Scheme 17) 2M These reactions illustrate the... 

Synthesis of compound 68 by oxidative decarboxylation of adamantane carboxylic acid is described in [25], Initially, for the synthesis of 2-(l-adamantyl)benzimidazole (68), adamantan radical was obtained in sulphuric acid diluted by silver nitrate in the presence of ammonia persulfate. Then, the synthesized radical was inserted directly into the heterocycle. After N-methylation, 2-(l-adamantyl)benzimidazole (68) was transferred in l-methyl-2-(l-adamantyl)-benzimidazole (79). The experiments carried out on chicken embryo revealed high antiviral activity of both obtained compounds [25] ... 

Calixarenes, which are macrocyclic compounds, are one of the best building blocks to design molecular hosts in supramolecular chemistry [158]. Synthesis of calix[4]arenes, which have been adamantylated, has been reported [105, 109]. In calix[4]arenes, adamantane or its ester/carboxylic acid derivatives were introduced as substituents (Fig. 29). The purpose of this synthesis was to learn how to employ the flexible chemistry of adamantane in order to construct different kinds of molecular hosts. The X-ray structure analysis of p-(l-adamantyl)thiacalix[4]arene [109] demonstrated that it contained four CHCI3 molecules, one of which was located inside the host molecule cavity, and the host molecule assumed the cone-like conformational shape (Fig. 30). 

Figure 29 (a) Synthesis route of the molecule (b) (i) S8, NaOH, tetraethyleneglycol dimethyl ether, heat, (28%). (b) Adamantane upper rim derivative based on the thiacalix[4]arene platform. (c,d) The carboxylic acid and ester derivative of adamantane can also be used as substituents. Taken from Ref. [109] with permission. 

Adamantane-2-earboxyUe acU. In a new, convenient synthesis of adamantane-2-carboxylic acid (4), adamantanone (1) is treated with dimethyloxosulfonium methylide to give 2-mcthyIeneadaman(ane epoxide (2). This is rearranged by treatment with boron trifluoride etheratc to the aldehyde (3, unstable). Oxidation with Jones reagent gives (4) in an overall yield of about 70% from (1). 

Nucleoside synthesis Adamantane-1-carboxylic acid chloride. Bis-(p-nitrophenyl)hydrogen phosphate. /3,)3, 8-Tribromoethyl chloroformate. 

Glycidic esters. Wynberg et all state that the simplest synthesis of adaman-tane-2-carboxylic acid (4) involves conversion of adamantanone (1) into the glycidic ester (2), pyrolysis to adamantane-2-carboxaldehyde (3), and finally chromic acid oxidation. The overall yield is 71 %. 

Ethyl tricyclodecanecarboxylate CAS 2094-73-7 EINECS/ELINCS 218-253-2 Synonyms 1-Adamantanecarboxylic acid ethyl ester Ethyl adamantane-1-carboxylate Ethyl tricycio [3.3.1.1 ] decane-1-carboxylate Tricycio [3.3.1.1(3,7)-] decane-1-carboxylic acid, ethyl ester Empiricai Ci H2o02 Properties M.w. 208.30 Uses Fragrance in cosmetics Manuf./Distrib. Lancaster Synthesis... 

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