- The Ritter reaction of terpenes. Part 3. Investigation of carvone and related compounds
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The Ritter reaction of (R)-carvone (1), cis-carveol (2) and carvyl ethers 3 and 4 was investigated. For ketone 1 formation of 8-amido-6-p-menthen-2-ones (7-12) in moderate yields was observed. Alcohol 2 gave, depending on the reaction conditions, 2-amido-6,8(9)-p-menthadienes, 2-amido-4(8),6-p-menthadienes and/or 2,8-diamido-6-p-menthenes. Ethers 3 and 4 underwent cleavage to almost the same amides as it was observed for cis-carveol (2). Additionally, tertiary phenylcarveol (5) under similar conditions furnished 6-acetamido-2-phenyl-1,8(9)-p-menthadiene (28) as a result of dehydration, followed by migration of a double bond. The proposed mechanisms of the reactions are presented.
- Welniak
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- ACID-CATALYZED TRANSFORMATIONS OF THE DERIVATIVES OF TERPENES IN THE BICYCLO- AND BICYCLOHEPTANE SERIES
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Under the conditions of acid catalysis the formation of the p-methane derivatives is the main direction in the transformations of pinane derivatives with reaction centers at C2 and C3 (α-pinene epoxide, 2α-hydroxypinan-3-one, 2α-hydroxypinan-3-one oxime, isopinocampheol and 3-phenylpinocampheol).Here, in the Ritter reaction thermodynamic factors give rise to the preferential formation of isomers with an equatorial acylamino group.The ability to react with nitriles under the conditions of acid catalysis with the formation of the geminal amides is a common feature of terpenoid ketones of the bicycloheptane series.The transformations of the terpenoid bicyclic oximes under the influence of sulfuric acid in aliphatic nitriles lead to the formation of two types of azabicyclic products - bicyclic lactams and bicyclic N-acylamidines.
- Koval'skaya, S. S.,Kozlov, N. G.
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p. 1398 - 1407
(2007/10/03)
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- TRANSFORMATIONS OF 2α-HYDROXY-2,6,6-TRIMETHYLBICYCLO-HEPTAN-3-ONE UNDER CONDITIONS OF ACID CATALYSIS
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The transformation of 2α-hydroxy-2,6,6-trimethylbicycloheptan-3-one under the conditions of acid catalysis have been studied.It has been shown that this compound can be used for the synthesis of products of various structures: a bridged bicyclic lactone (1,8,8-trimethyl-2-oxabicyclooctan-3-one), an aromatic compound (carvacrol), and nitrogen-containing derivatives of p-menthane such as 8-acylamino-p-menth-6-en-2-ones.The structures of the compounds synthesized were shown by the results of 1H and 13C NMR spectroscopies.
- Koval'skaya, S. S.,Kozlov, N. G.,Novikova, M. G.,Shavyrin, S. V.
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