Summary
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1.
An investigation was made of orientation in the addition of alcohols to methyl 3,4-epoxy-4-methylcyclohexanecarboxylate in presence of acid and alkaline catalysts.
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2.
In presence of alkoxides addition occurs only in the direction required by Markovnikov's rule with formation of the secondary monoether methyl 3-alkoxy-4-hydroxy-4-methylcyclohexanecarboxylate. In an alkaline medium addition at the epoxide ring is accompanied by transesterification with replacement of the methyl of the ester grouping by the hydrocarbon group of the alcohol. In the case of a secondary alcohol (isopropyl alcohol), transesterification does not occur.
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3.
In an acid medium the addition of alcohols to the epoxide goes in the direction contrary to that required by Markovnikov's rule with formation of the tertiary monoether methyl 4-alkoxy-3-hydroxy-4-methylcyclohexanecarboxylate. The addition of the alcohol is accompanied to a certain extent by the isomerization of methyl 3,4-epoxy-4-methylcyclohexanecarboxylate to methyl 4-methyl-3-oxocyclohexanecarboxylate. It was shown that water in presence of boron trifluoride etherate acts catalytically on the formation of the isomerization product.
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4.
The structure of the product of the isomerization of the epoxide was established.
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Literature cited
M. S. Malinovskii, Olefin Epoxides and Their Derivatives [in Russian] (Goskhimizdat, Moscow, 1961), p. 152.
A. A. Petrov, Zh. obshch. khimii,14, 1038 (1944);15, 690 (1945);16, 1206 (1946).
A. A. Petrov and E. N. Pritula, Zh. prikl. khimii,28, 556 (1955).
A. A. Petrov, B. V. Gantseva, and O. A. Kiseleva, Zh. obshch. khimii,23, 737 (1953).
A. A. Petrov, DAN SSSR,50, 249 (1945); Zh. obshch. khimii,16, 1625 (1946).
R. C. Kadesch, J. Am. Chem. Soc.,68, 41 (1946).
P. D. Bartlett and S. D. Ross, J. Am. Chem. Soc.,70, 926 (1948).
W. Reeve and J. Christoffel, J. Am. Chem. Soc.,72, 1480 (1950).
A. N. Pudovik and S. G. Denislamova, Zh. obshch. khimii,27, 2363 (1957).
Z. G. Isaeva and B. A. Arbuzov, Zh. obshch. khimii,10, 893 (1949).
Z. G. Isaeva and B. A. Arbuzov, Zh. obshch. khimii,19, 884 (1949).
B. A. Arbuzov and L. A. Mukhamedova, Izv. AN SSSR, Otd. khim. n.,1954, 442.
K. Alder and W. Vogt, Chem. Abstrs.,1950, 1067g.
M. Goryaev and I. Pliva, Methods of investigating Ester Oils [in Russian] (Izd. AN KazSSR, Alma-Ata, 1962), p. 192.
A. V. Topchiev, S. V. Zavgorodnii, and Ya. M. Paushkin, Boron Fluoride and its Compounds as Catalysts in Organic Chemistry [in Russian] (Izv. AN SSSR, Moscow, 1956), p. 50.
M. S. Malinovskii, Olefin Epoxides and Their Derivatives [in Russian] (GoskhimIzdat, Moscow, 1961), p. 395.
M. Goryaev and I. Pliva, Methods of investigating Ester Oils [in Russian] (Izd. AN KazSSR, Alma-Ata, 1962), p. 187.
M. Goryaev and I. Pliva, Methods of investigating Ester Oils [in Russian] (Izd. AN KazSSR, Alma-Ata, 1962), p. 171.
M. Goryaev and I. Pliva, Methods of investigating Ester Oils [in Russian] (Izd. AN KazSSR, Alma-Ata, 1962), p. 173.
B. A. Arbuzov, isomeric Transformations of Terpenes. Dissertation [in Russian] (Kazan', 1936), p. 209.
I. N. Nazarov, Yu. A. Titov, and A. I Kuznetsova, izv. AN SSSR, Otd. khim. n.,1959, 1412.
Henry E. J. Hennis, Organ. chem.,28, 10, 2570 (1963).
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Elemental analyses were carried out by T. S. Krivova. Infrared and Raman spectra were determined by R. R. Shagidullin, whom the authors thank.
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya No. 11, pp. 2042–2050, November, 1964
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Mukhamedova, L.A., Malyshko, T.M. Reactions of alcohols with methyl 3,4-epoxy-4-methylcyclohexanecarboxylate. Russ Chem Bull 13, 1937–1943 (1964). https://doi.org/10.1007/BF00844491
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DOI: https://doi.org/10.1007/BF00844491