The determining factor of the reaction of 2,6-di-tert-butylphenol with alkaline metal hydroxides is temperature, depending on which two types of potassium or sodium 2,6-di-tert-butyl phenoxides are formed with different catalytic activity in alkylation of 2,6-di-tert-butylphenol with methyl acrylate. More active forms of 2,6-But2C6H3OK or 2,6-But2C6H3ONa are synthesized at temperatures higher than 433 K representing predominantly monomers of 2,6-di-tert-butylphenoxides which produce dimers when cooling. The data of NMR 1Н, electronic, and IR spectra for the corresponding forms of 2,6-But2C6H3OK and 2,6-But2C6H3ONa isolated in the individual state showed a cyclohexadienone structure. In DMSO or DMF media the dimeric forms of 2,6-di-tert-butylphenoxides react with methyl acrylate to form methyl 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate with 64–92 % yield.
[1] US Pat. 3277148, Chem. Abstrs, 1966, 65, 18535.
[2] US Pat. 3526668, Chem. Abstrs, 1970, 73, 98589.
[3] Jpn Pat. 161350, Chem. Abstrs, 1982, 96, 162344.
[4] US Pat. 5264612, Chem. Abstrs, 1993, 120, 191356.
[5] US Pat. 5177247, Chem. Abstrs, 1993, 116, 6249.
[6] Stillson G.: J. Am. Chem. Soc., 1946, 68, 722.
[7] Volod`kin A. and Zaikov G.: Russ. Chem. Bull., Int. Ed., 2002, 51, 2189.
[8] Volod`kin A. and Zaikov G.: Mendeleev Chem. J., 2000, 44, 81.
[9] Volod`kin A., Paramonov V., Egidis F. and Popov L.: Khim. Promyshlennost., 1988, 12, 7.
[10] Volod`kin A.: Russ. Chem. Bull., 1994, 43, 769.
[11] Volod`kin A., Zaitsev A., Rubailo V. et al.: Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 1829.
[12] Titova T., Krysin A., Bulgakov V. and Mamatyuk V.: Zh. Org. Khim,, 1984, 20, 1899.
[13] Bulgakov V., Gorodetskaya N., Nikiforov G. and Ershov V.: Izv. Akad. Nauk SSSR, Ser. Khim., 1983, 71.
[14] Shobatake K. and Nakamoto K.: J. Inorg. Chem. Acta, 1970, 4, 485.
[15] Muller E., Ziemek P. and Rieker A.: Tetrahedron Lett., 1964, 4, 207.
[16] Bekhli E., Novikov D. and Entelis S.: Vysokomolek. Soedin. A, 1967, 9, 2754.
[17] Malysheva N., Prokof``ev A., Bubnov N. et al.: Izv. Akad. Nauk SSSR, Ser. Khim., 1977, 1522.
[18] PaQuette L. and Farley W.: J. Org. Chem., 1967, 32, 2718