SOLVOLYSIS OF 3,5-Di-tert-BUTYL-4-HYDROXYBENZYL ACETATE
927
acetyl protons of benzyl acetate I at 2.19 ppm and
appearance of a signal at 4.19 ppm due to methylene
protons of benzylaniline IX.
A solution of 2.78 g of benzyl acetate I and 23.25 g
of aniline in 55 ml of methanol was allowed to stand
at room temperature for 1 day and then poured into
400 ml of water. The precipitate was filtered off,
washed with water, and dried in air. Recrystallization
from ethanol gave colorless crystals, mp 104 105 C,
yield 79%. 1H NMR spectrum (CDCl3), , ppm:
1.44 s (18H, CMe3), 4.19 s (2H, CH2N), 5.21 s (1H,
OH), 6.65 6.85 m (3H, Hb, Hd), 7.18 (2H, Ha), 7.21 t
(2H, Hc).
I + PhNH2
t-Bu
H c
H b
Ha
MeOH
H d + MeCO2H
CH2NH
HO
t-Bu
IX
REFERENCES
At a higher concentration of compound I, the reac-
tion with aniline, like methanolysis, slows down
because of decreasing concentration of methylene-
quinone III in the reaction mixture.
1. Bukharov, S.V., Nugumanova, G.N., and Mukmene-
va, N.A., Zh. Obshch. Khim., 1998, vol. 68, no. 10,
pp. 1678 1681.
2. Mukmeneva, N.A., Kadyrova, V.Kh., Bukharov, S.V.,
and Nugumanova, G.N., Zh. Obshch. Khim., 1996,
vol. 66, no. 10, pp. 1725 1727.
Thus, the reactions of benzyl acetate I with al-
cohols in the absence of acidic and basic catalysis
involve ionic dissociation of compound I with inter-
mediate formation of methylenequinone III which
then slowly takes up a molecule of the alcohol.
3. Liakumovich, A.G., Gurvich, Ya.A., Kumok, S.T., Sa-
muilov, Ya.D., and Bukharov, S.V., RU Patent
2036893, 1995, Byull. Isobret., 1995, no. 16.
The use of alcohols as solvents is an effective way
of generation of methylenequinone III from benzyl
acetate I, which allows one to avoid application of
stong bases in reactions of the latter with weak
nucleophiles.
4. Bukharov, S.V., Nugumanova, G.N., and Mukmene-
va, N.A., Zh. Obshch. Khim., 1999, vol. 69, no. 4,
p. 699.
5. Bukharov, S.V., Nugumanova, G.N., and Mukmene-
va, N.A., Zh. Obshch. Khim., 1998, vol. 68, no. 12,
pp. 1977 1981.
EXPERIMENTAL
6. Nugumanova, G.N., Cand. (Chem.) Dissertation, Kazan,
1
The H NMR spectra were obtained on a Varian
1999.
Gemini-200 spectrometer (200 MHz) using signals of
residual protons of deuterated solvents as internal
references. The electronic spectra were measured on a
Specord UV-Vis spectrophotometer. Solvents were
preliminarily dried over Zeolite NaX.
7. Nikiforov, G.A., Bannikov, G.F., Romero Mal’dona-
do, I.K.A., Malysheva, R.D., and Ershov, V.V., Izv.
Akad. Nauk SSSR, Ser. Khim., 1989, no. 12, pp. 2765
2770.
8. Volod’kin, A.A., Ershov, V.V., and Kudinova, L.I., Izv.
Akad. Nauk SSSR, Ser. Khim., 1978, no. 2, p. 512.
3,5-Di-tert-butyl-4-hydroxybenzylaniline (IX).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002