ABOUT SELECTIVE METHODS OF SYNTHESIS
1161
benzyl)-4-methylphenol V, 4 g of NaOH and 30 ml of
methanol, and the mixture was treated at the autoclave
rotation at the temperature 220°C for 4 h. After
cooling the content was extracted with ether, the
extract was washed with water and evaporated. 3 g of
dark liquid was obtained that contained by the GLC
data 48% of 2,2-methylene-bis-(6-tert-butyl-4-methyl-
phenol), 20% of 6-tert-butyl-4-methylphenol and 22%
of 6-tert-butyl-2,4-dimethylphenol. By the method of
chromato-mass spectrometry in the reaction mixture
was also identified 1.5% of parent ether V and 0.5% of
2-tert-butyl-4-methylanisol.
(10%) and one ethanol molecule was obtained, mp
262°C . The 1H NMR spectrum [in (CD3)2SO], δ, ppm:
8.34 s (4H, Ar–OH), 6,70 s (4H, Ar–H), 6.58 s (4H,
Ar–H), 4.28s (1H, OH), 3.74 s (4H, –CH2–), 3.59 s
(4H,CH2), 3.40 q (2H,CH3CH2OH), 1.36 s (36H,
C4H9-t), 1,08 t (3H, CH3CH2OH). At short time
heating of a sample of this complex at the temperature
100°C calixarene V was obtained, mp 278–282°C.
Found: m/z 648.42201. C44H56O4 . Calculated: m/z
1
648.41783. Melting pouint and H NMR spectrum of
the sample V coincided completely with the published
data [20].
Synthesis of calix[4]arene V. To a rotating steel
autoclave 0.25 l capacity was loaded 20 g of 2-tert-
butylphenol, 150 ml of methanol, 20 g of NaOH, and
3 g of ZnO, and the mixture was heated at rotation at
the temperature 250°C for 15 h. After cooling, the
reaction mixture was neutralized with hydrochloric
acid and extracted with methyl-tert-butyl ether.
Solvent was evaporated and 18 g of labile oil was
obtained from which was distilled off in a vacuum a
fraction 6 g, bp 110–125°C (10 mm Hg) containing
mainly 6-tert-butyl-2,4-dimethylphenol, and bottom
residue remained.
REFERENCES
1. Ershov, V.V., Nikiforov, G.A., and Volod’kin, A.A.,
Prostranstvenno-zatrudnennye
Hindered Phenols), Moscow: Khimiya, 1972.
2. Vol’f, M.B., Khimicheskaya stabilizatsiya motornykh
and reaktivnykh topliv (Chemical Stabilization of
Engine and Rocket Fuel), Moscow: Khimiya, 1970,
p. 116.
fenoly
(Sterically
3. Khimicheskie dobavki
k
polimeram. Spravochnik
(Chemical Additives for Polymers. Handbook), Mas-
lova, I.P., Ed., Moscow: Khimiya, 1981.
4. Soldatenkov, A.T., Kolyadina, I.M., and Shendrik, I.V.,
Osnovy organicheskoi khimii lekarstvennykh sredstv
(Basicity of Organic Chemistry of Medicine Remedies),
Moscow: Mir, 2003, p. 107.
5. Khomchenko, T.M., Salomatina, O.V., Kurbakova, S.Yu.,
Il’ina, I.V., Volcho, K.P., Komarova, N.I., Korchagi-
na, D.V., Salakhutdinov, N.F., and Tolstikov, G.A., Zh.
Org. Khim., 2006, vol. 42, no. 11, p. 1666.
The bottom residue composition was determined by
the method of liquid chromatography on an Agilent
1100 device with a mass-selective detector. Below are
listed the components with the following data for each
one: retention time in column (min), content in the
mixture (%) and molecular mass. 6-tert-Butyl-4-(4'-
hydroxybenzyl)-2-methylphenol, 1.75(5), 256; 2,4'-
methylene-bis(2-tert-butylphenol), 2.45(5), 312; 2-(5'-
tert-butyl-3'-methyl-4'-hydroxybenzyl)-6-tert-butyl-
phenol, 2.72(6), 326; 4,4'-methylene-bis(2-tert-butyl-
phenol), 3.49(4), 312; 4-(5'-tert-butyl-3'-methyl-4'-
hydroxybenzyl)-6-tert-butylphenol, 3.97(10) , 326;
compound VI, 4.55(10), 340; 2-(6'-tert-butyl-4'-
hydroxybenzyl)-4-(3''-tert-butyl-5''-methyl-2''-hydroxy-
benzyl)-6-tert-butylphenol, 5.29(8) 488; 2,4-бис-(5'-
tert-butyl-3'-methyl-4'-hydroxybenzyl)-6-tert-butyl-
phenol, 6.13'(5), 502; a compound with the structure of
calixarene IV but containing only three tert-butyl
groups, 7.45(10), 592; calixarene IV, 8.47(18), 648; a
compound isomeric to the calixarene IV, 8.77(4) 648;
compounds 3% each with the molecular masses 650,
664, 768 and 812.
6. Hart, H. and Haglind, E.A., J. Org. Chem., 1950, vol. 15,
p. 396.
7. Japan Paent 19880804, 1988; C. A., 1989, vol. 110,
no. 23529.
8. Japan Patent 09241198, 1997; C. A., 1997, vol. 127,
no. 262523.
9. Gorbunov, B.N., Gurvich, Ya.A., and Maslova, I.P.,
Khimiya and tekhnologiya stabilizatorov polimernykh
materialov (Chemistry and Technology of Stabilizers
for Polymer Materials), Moscow: Khimiya, 1981, p. 197.
10. Petrik, A.I., Valiullina, G.A., Afimovich, T.S., and
Kudrin, V.S., Invetntor’s Sertificate no. 1116586, 1982,
Byul. Izobret., 1984, no. 36.
11. Valiullina, T.A., Kishkan’,.L.N., Khlebnikov, B.M.,
Krysin, A.P., Titova, T.F., and Egorova, T.G., RF Patent
2027694, 1993, Byul. Izobret., 1995, no. 3.
The bottom residue 12 g was dissolved at boiling in
40 ml of ethanol and white precipitate dropped upon
cooling was filtered off. Complex of 5,11,17,23-tetra-
tert-butyl-4,12,16,24-tetrahydroxycalix[4]arene IV, 2 g
12. Krysin, A.P., Pokrovskii, L.M, and Shakirov, M.M., Zh.
Org. Khim., 2000, vol. 36, no. 1, p.79.
13. Richmond, G.Kh. and Nemeryuk, M.P., Invetntor’s
Certificate no. 196887, 1967; Byul. Izobret., 1967, no. 12.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009