Cyclic adamantanone ketals have pleasant odors and are of interest in the cosmetic field as fragrances. They are usually prepared by condensation of adamantanone-2 with 1,2-ethanediol and 1,2-propanediol in the presence of catalytic amounts of strong Bronsted or Lewis acids. These reactions are often carried out using Dean-Stark trap and azeotropic removal of water to prevent hydrolysis of the product. Sometimes the reactions require high temperatures, long reaction times, or are difficult to perform. We first developed a CuBr2-catalyzed method for ketalization of adamantanone-2 with 1,2-ethanediol and 1,2-propanediol. The reaction takes place in 1-2 hours at a temperature of 40-100 oC, giving the corresponding cyclic ketals in high yields. 4-Мethylspiro[1,3-dioxolane-2,2'-tricyclo[3.3.1.13,7]decane] has a persistent fruit-apple/honey smell and can be used to flavor shampoos, gels, soaps. Spiro[1,3-dioxolane-2,2'-tricyclo[3.3.1.13,7]decane] has a faint note of sage and thyme, as well as a persistent note of freshness, and can be used to flavor toothpaste and mouthwash.
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CuBr2-Catalyzed adamantanone-2 ketalization in the synthesis of practically important cyclic ketals.
Published:
14 November 2021
by MDPI
in The 25th International Electronic Conference on Synthetic Organic Chemistry
session General Organic Synthesis
https://doi.org/10.3390/ecsoc-25-11698
(registering DOI)
Abstract:
Keywords: Adamantanone-2; 1,2-ethanediol; 1,2-propanediol;cyclization; catalysis; copper catalysts; fragrances