Reaction of α-aminoacetals with 2-methylresorcinol

Full text of DOI:10.1134/S1070363209090199

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 9, pp. 1929–1930. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.S. Gazizov, A.R. Burilov, M.S. Khakimov, N.I. Kharitonova, M.A. Pudovik, A.I. Konovalov, 2009, published in Zhurnal Obshchei
Khimii, 2009, Vol. 79, No. 9, pp. 1573–1574.
LETTERS
TO THE EDITOR
Reaction of α-Aminoacetals with 2-Methylresorcinol
A. S. Gazizov, A. R. Burilov, M. S. Khakimov, N. I. Kharitonova,
M. A. Pudovik, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: pudovik@iopc.knc.ru
Received July 30, 2008
DOI: 10.1134/S1070363209090199
The main method of synthesis of calix[4-resor-
cinols is the condensation of resorcinol and its
derivatives with aliphatic or aromatic aldehydes [1–3].
We have recently extended synthetic opportunities of
this method by involvement into the reaction with
resorcinol of phosphorylated acetals to obtain calix[4]
resorcinols with phosphorylalkyl substituents at the
lower rim of the molecule [4]. A special attention
should be paid to their aminoalkyl analogs that can
serve as primary compounds (due to involvement of
amino groups) in the syntheses of new cavitands,
container compounds, and nanotubes. For the synthesis
of the calixarenes of this type we studied reaction of
aminoacetaldehyde diethylacetal (Ia) and dimethyl-
aminoacetaldehyde diethylacetal (Ib) with 2-methyl-
resorcinol. We found that synthetic result of this reac-
tion depends considerably on the reaction conditions.
The process carried out in dioxane in the presence of
trifluoromethanesulfonic acid leads to formation of
calix[4]resorcinols IIIa and IIIb as the final products.
Me
Me
OH
HO
OH
HO
dioxane/CF3SO3H
+ 4 R2NCH2CH(OEt)2
4
−8 EtOH
H
C
4
I
IIа, IIb
CH2
CF3SO3H R2N
IIIа, IIIb
II, III: R = H (а), Me (b).
In water–alcohol medium containing some
hydrochloric acid the same reaction affords diaryl-
methane derivatives IVa, IVb.
Structure of the synthesized compounds is
confirmed by spectral methods, their composition, by
the data of elemental analysis.
Me
Me
CH3
OH
HO
OH
HO
O
H
OH
H2O/EtOH/HCl
2
+ R2NCH2CH(OEt)2
H
−2 EtOH
C
H2C
+
Cl−
NHR2
IVа, IVb
IV: R = H (а), Me (b).
1929

1930
GAZIZOV et al.
6.29; Cl 10.95; N 4.12. C16H20ClNO4. Calculated, %:
C 58.99; H 6.19; Cl 10.88; N 4.30.
2,8,14,20-Tetra(aminomethyl)pentacyclo[19.3.1.-
13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,1,13-(27),15,17,-
19(26),21,23-dodecaen-4,6,10,12,16,18,22,24-octol
tetratriflate (IIIa). A solution of 2.29 g of methyl-
resorcinol I, 1.94 g of acetal IIa, and 2.90 g of tri-
fluoromethanesulfonic acid in 22 ml of anhydrous
dioxane was heated for 5 h at 80°С. The solvent was
removed and the residue was precipitated from ethanol
into diethyl ether. 5.21 g (89.5 %) of compound IIIa
1-Amino-2,2-bis(2,4-dihydroxy-3-methylphenyl)-
N,N-dimethylethane hydrochloride (IVb) is prepared
similarly to compound IVa from 1.54 g of methyl-
resorcinol I, 1.0 g of acetal IIb, 2.5 ml of concentrated
solution of hydrochloric acid, 6 ml of water, and 6 ml
of ethanol. 2.2 g (98.5 %) of compound IVb is
obtained, mp 148ºС. 1Н NMR spectrum (D2O), δ, ppm
(J, Hz): 2.03 s (6Н, СН3), 2.81 s (6Н, СН3N), 3.58 d
1
was obtained, mp above 250°C. Н NMR spectrum
(D2O), δ, ppm (J, Hz): 2.11 s (12Н, СН3), 3.78 d (8Н,
3
3
(2Н, СН2, JНН 7.70), 4.97 t (1Н, СН, JНН 7.70), 6.46
3
3
СН2, JНН 8.07), 4.85 t (4Н, СН, JНН 7.88), 6.93 s
(4Н, СНarom). IR spectrum, ν, cm–1: 1603 (arom.),
3110–3490 (ОН). Found, %: C 37.98; H 3.95; N 4.10;
S 9.72. C40H48F12N4O20S4. Calculated, %: C 38.10; H
3.84; N 4.44; S 10.17.
3
d, (2Н, ortho-СНarom, JНН 8.80), 6.83 d(2Н, meta-
СНarom, 3JНН 8.80). IR spectrum, ν, cm–1: 1600 (arom.),
3100–3500 (ОН). Found, %: C 60.89; H 6.95; Cl
10.53; N 3.55. C18H24ClNO4. Calculated, %: C 61.10;
H 6.84; Cl 10.02; N 3.96.
The 1Н NMR spectra were registered on an Avance
600 instrument at the operating frequency 600.13 МHz,
the signals of residual protons of deuterated solvent
(D2O) serving as internal refernce. The IR spectra of
the studied compounds were registered on an UR-20
spectrometer in the frequency range 400–3600 cm–1
from a paste with mineral oil or from thin layers.
2,8,14,20-Tetra-(N,N-dimethylaminomethyl)penta-
cyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,-
1,13(27),15,17,19(26),21,23-dodecaen-4,6,10,12,16,-
18,22,24-octol tetratriflate (IIIb) was prepared
similarly from 0.77 g of 2-methylresorcinol I, 1.0 g of
acetal IIb, 0.97 g of trifluoromethanesulfonic acid in
8 ml of anhydrous dioxane. Yield 2.05 g (89 %), mp
1
above 250°C. The Н NMR spectrum (D2O), δ, ppm
(J, Hz): 2.11 s (12Н, СН3), 3.06 s (24Н, СН3N), 4.20 d
ACKNOWLEDGMENTS
3
3
(8Н, СН2, JНН 8.43), 5.12 t (4Н, СН, JНН 8.43), 7.17
s (4Н, СНarom). IR spectrum, ν, cm–1: 1604 (arom.),
3100–3500 (ОН). Found,` %: C 41.53; H 4.89; N 3.99;
S 9.01. C48H64F12N4O20S4. Calculated, %: C 41.98; H
4.70; N 4.08; S 9.34.
This work was financially supported by the Russian
Foundation for Basic Research (grant no. 08-03-
00512).
REFERENCES
1-Amino-2,2-bis(2,4-dihydroxy-3-methylphenyl)-
ethane hydrochloride (IVa). A mixturte of 1.0 g of
methylresorcinol I, 0.42 g of acetal IIa, 1.5 ml of
concentrated solution of hydrochloric acid, 4 ml of
distilled water, and 4 ml of ethanol was heated for 12 h
at 90°С. The solvent was removed and the residue was
reprecipitated from ethanol into diethyl ether. 0.53 g
(40.4 %) of compound IVa was obtained, mp 125ºС.
1Н NMR spectrum (D2O), δ, ppm (J, Hz): 1.92 s (6Н,
1. Gutsche, C.D., Calyxarenes, Cambridge: Royal Society
of Chemistry, 1989, p. 132.
2. Vicens, J. and Bohmer, V., Calyxarenes, a Versatile
Class of Macrocyclic Compounds, Dodrecht: Kluwer
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no. 10, p. 2168.
3
СН3), 3.42 d (2Н, СН2, JНН 8.07), 4.74 t (1Н, СН,
3JНН 8.07), 6.34 d (2Н, ortho-СНarom, 3JНН 8.68), 6.68 d
3
(2Н, meta-СНarom, JНН 8.68). IR spectrum, ν, cm–1:
1605 (arom.), 3100–3500 (ОН). Found, %: C 58.43; H
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