Reaction of catechol with α-aminoacetals. Synthesis of new polyphenols

Full text of DOI:10.1134/S1070363213060339

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 6, pp. 1172–1174. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.S. Gazizov, N.I. Kharitonov, A.R. Burilov, M.A. Pudovik, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 6,
pp. 1042–1044.
LETTERS
TO THE EDITOR
Reaction of Catechol with α-Aminoacetals.
Synthesis of New Polyphenols
A. S. Gazizov, N. I. Kharitonov, A. R. Burilov, and M. A. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, ul. Akademika Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: agazizov@iopc.ru
Received February 18, 2013
DOI: 10.1134/S1070363213060339
The basic method for the synthesis of calix[4]
resorcinarenes is a condensation of resorcinol and their
derivatives with aliphatic and aromatic aldehydes [1–
3]. Recently it was shown that the condensation of
resorcinol and 2-methylresorcinol with dimethylacetal
of α-methylaminoacetic aldehyde in aqueous solutions
of hydrogen halides results in hydrohalides of
substituted diarylethylmethylamines as the products of
the interaction of two molecules of resorcinol with one
molecule of aminoacetal [4–7]. At the same time, in
dioxane in the presence of trifluoromethanesulfonic
acid these reactions lead to the formation of the
corresponding calixarenes [8].
To determine the effect of the nature of the used
phenol on the reaction result we carried out the
reactions of α-aminoacetic aldehyde derivatives Ia–Ic
with pyrocatechol. The reactions afford the
corresponding polyphenols IIa–IIc comprising two
catechol moieties with yields of 60–90%.
HO
OH
R2
OH
H2O / EtOH / HBr
− 2R3OH
HO
OH
NCH2CH(OR3)2
2
+
R1
H
R1
OH
Br−
N+
R2
Iа−Ic
IIа−IIc
R1 = R2 = H, R3 = Me (а); R1 = H, R2 = R3 = Me (b); R1 = R2 = Me, R3 = Et (c).
The reaction of acetal derivative Ib with alkyl
halides in ethanol results in acetals IIIa–IIIc contain-
ing an onium moiety in the molecule. The reaction of
pyrocatechol acetals in an aqueous alcohol medium in
the presence of hydrobromic acid leads to the
formation of polyphenols IVa–IVc. Due to the
presence of the quaternary ammonium moiety the
latter are of interest as antibiotics, antivirals and anti-
fungicidal agents.
0.50 g of catechol in 4 ml of ethanol was added 1 ml of
concentrated hydrobromic acid. The reaction mixture
was refluxed for 5 h. After the removal of the solvent
the residue was washed with ether (3 × 50 ml) and
dried in a vacuum (10 h, 15 mm Hg). Yield 0.77 g
(98%), mp 172°C. IR spectrum, ν, cm–1: 1607 (Ar),
2723 (NH+), 3320 (OH). 1H NMR spectrum (CD3OD),
δ, ppm (J, Hz): 3.47 d (2Н, СН2, J 8.24), 4.05 t (1Н,
СН, J 8.20), 6.69 d. d (2Н, СНAr, J 8.13, 2.10), 6.74 d
(2Н, СНAr, J 2.10), 6.78 d (2Н, СНAr, J 8.13). Found,
%: C 49.01; H 4.81; Br 23.63; N 4.11. C14H16BrNO4.
Calculated, %: C 49.14; H 4.71; Br 23.35; N 4.09.
The structure and composition of the products
obtained were confirmed by spectroscopic methods
and elemental analysis.
2,2-Bis(3,4-dihydroxyphenyl)-N-methylethyl-
amine hydrobromide (IIb) was prepared similarly
2,2-Bis(3,4-dihydroxyphenyl)ethylamine hydro-
bromide (IIa). To a solution of 0.24 g of acetal Ia and
1172

REACTION OF CATECHOL WITH α-AMINOACETALS
1173
Me
Me
Me
Br−
EtOH
R1 Br
R1 +NCH2CH(OEt)2
+
NCH2CH(OEt)2
Me
IIIа−IIIc
Ic
HO
HO
OH
OH
OH
H2O / EtOH / HBr
2
IIIа−IIIc
+
Me
R1
− 2EtOH
+
N
OH
Br−
Me
IVа−IVc
R1 = Me (а), n-Bu (b), n-C10H21 (c).
from 1.35 g of acetal Ib, 2.50 g of pyrocatechol, and 3
ml of concentrated hydrobromic acid. Yield 2.80 g
(89%), mp 160°C. IR spectrum, ν, cm–1: 1610 (Ar),
N-(2,2-Diethoxy)ethyl-N,N-dimethyl-N-butyl-
ammonium bromide (IIIb). To a solution of 2.65 g of
acetal Ic in 5 ml of ethanol was added 2.25 g of n-butyl
bromide. The reaction mixture was refluxed for 2 h.
After removal of the solvent, the waxy residue was
washed with diethyl ether and dried in a vacuum (2 h,
1
2730 (NH+), 3180 (OH). H NMR spectrum (D2O), δ,
ppm (J, Hz): 2.62 s (3Н, СН3N), 3.44 d (2Н, СН2,
J 8.25), 4.01 t (1Н, СН, J 8.20), 6.63 d. d (2Н, СНAr,
J 8.16, 1.92), 6.77 d (2Н, СНAr, J 1.92), 6.77 d (2Н,
СНAr, J 8.16). Found, %: C 50.03; H 5.22; Br 22.51; N
3.83. C15H18BrNO4. Calculated, %: C 50.58; H 5.09;
Br 22.43; N 3.93.
1
0.01 mm Hg). Yield 4.01 g (82%). H NMR spectrum
(СD3OD), δ, ppm (J, Hz): 1.03 t (3Н, СН3, J 7.40),
1.25 t (6Н, CH3, J 7.05), 1.38–1.48 m (2Н, СН2),
1.76–1.86 m (2Н, СН2), 3.23 s (6Н, CH3N), 3.46–
3.50 m (2Н, CH2N), 3.53 d (2Н, СН2N, J 4.95), 3.71 q
(2Н, СН2O, J 7.05), 3.78 q (2Н, СН2O, J 7.05), 5.07 t
(1Н, СН, J 4.92). Found, %: C 44.40; H 8.98; Br
29.55; N 5.17. C10H24BrNO2. Calculated, %: C 44.45;
H 8.95; Br 29.57; N 5.18.
2,2-Bis(3,4-dihydroxyphenyl)-N,N-dimethylethyl-
amine hydrobromide (IIc) was prepared similarly
from 0.73 g of acetal Ic, 1.0 g of catechol, and 1 ml of
concentrated hydrobromic acid. Yield 0.99 g (59%),
mp 154°C. IR spectrum, ν, cm–1: 1610 (Ar), 2730
1
(NH+), 3180 (OH). H NMR spectrum (D2O), δ, ppm
N-(2,2-Diethoxy)ethyl-N,N-dimethyl-N-decyl-
ammonium bromide (IIIc) was prepared analogously
from 1.0 g of acetal derivative Ic and 1.37 g of 1-
(J, Hz): 2.59 s (6Н, СН3N), 3.31 d (2Н, СН2, J 8.49),
3.89 t (1Н, СН, J 8.44), 6.49 d. d (2Н, СНAr, J 8.25,
2.14), 6.66 d (2Н, СНAr, J 8.25), 6.67 d (2Н, СНAr,
J 2.14). Found, %: C 51.65; H 5.53; Br 21.65; N 3.52.
C16H20BrNO4. Calculated, %: C 51.90; H 5.44; Br
21.58; N 3.78.
1
bromodecane as a waxy gum. Yield 2.30 g (97%). H
(СD3OD), δ, ppm (J, Hz): 0.89 t (3Н, СН3СН2, J
6.94), 1.23 t (6Н, СН3CH2O, J 7.02), 1.32 m (12Н,
(СН2)6), 1.40 m (2Н, СН2СН2СН2N), 1.81–1.83 m
(2Н, СН2СН2N), 3.33 s (6Н, СН3N), 3.45–3.49 m (2Н,
СН2СН2N), 3.51 d (2Н, СНСН2N, J 4.84), 3.68–3.81
m (4Н, СН2O), 5.06 t (1Н, СН, J 4.92). Found, %: С
56.41; Н 10.40; Br 20.97; N 3.59. C18H40BrNO2.
Calculated, %: С 56.54; Н 10.47; Br 20.94; N 3.66.
N-(2,2-Diethoxy)ethyl-N,N,N-trimethylammonium
bromide (IIIa). To a cooled (–20°C) solution of 1.77 g
of acetal Ic in 3 ml of ethanol was added 1.15 g of
cooled (–20°C) methyl bromide. The reaction mixture
was kept at room temperature for 12 h. After removal
of the solvent, the waxy residue was dried in a vacuum
N-2,2-Bis(3,4-dihydroxyphenyl)ethyl-N,N,N-tri-
methylammonium bromide (IVa). To a mixture of
2.0 g of acetal IIIa, 1.72 g of pyrocatechol, and 10 ml
of ethanol was added 2 ml of concentrated
hydrobromic acid. The reaction mixture was refluxed
for 5 h, and the solvent was removed. The residue was
washed with diethyl ether and dried in a vacuum (10 h,
15 mm Hg). Yield 2.58 g (86%), mp 145°C. IR
1
(2 h, 0.01 mm Hg). Yield 2.60 g (89%). H NMR
spectrum (СD3OD), δ, ppm (J, Hz): 1.25 t (6Н, CH3
J 7.06), 3.27 s (9Н, СН3N), 3.55 d (2Н, СН2, J 4.67),
3.69 q (2Н, СН2O, J 7.06), 3.79 q (2Н, СН2O, J 7.06),
5.06 t (1Н, СН, J 5.03). Found, %: C 36.83; H 7.97; Br
35.01; N 6.16. C7H18BrNO2. Calculated, %: C 36.85;
H 7.95; Br 35.03; N 6.14.
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1174
GAZIZOV et al.
1
spectrum, ν, cm–1: 1605 (Ar), 3300 (OH). H NMR
spectrum (D2O), δ, ppm (J, Hz): 2.79 s (9Н, СН3N),
3.74 d (2Н, СН2, J 6.82), 4.13 t (1Н, СН, J 6.62), 6.66
d. d (2Н, СНAr, J 8.24, 2.14), 6.77 d (2Н, СНAr, J
8.24), 6.82 d (2Н, СНAr, J 2.14). Found, %: C 53.04; H
5.83; Br 20.70; N 3.58. C17H22BrNO4. Calculated, %:
C 53.14; H 5.77; Br 20.79; N 3.65.
residual protons of the deuterated solvent (CD3OD).
The IR spectra were registered on an UR-20 spec-
trometer in the range of 400–3600 cm–1 in a slurry in
mineral oil or in thin layer. All solvents were purified
before use [9].
ACKNOWLEDGMENTS
N-2,2-Bis(3,4-dihydroxyphenyl)ethyl-N,N-di-
methyl-N-butylammonium bromide (IVb) was
prepared analogously from 0.98 g of acetal IIIb, 0.72 g
of catechol, and 1 ml of concentrated hydrobromic
acid. Yield 0.80 g (57%), mp 132°C. IR spectrum, ν,
cm–1: 1609 (Ar), 3325 (OH). 1H NMR spectrum (D2O),
δ, ppm (J, Hz): 0.69 t (3Н, СН3, J 7.33), 0.88–0.98 m
(2Н, СН2), 1.28–1.38 m (2Н, СН2), 2.77 s (6Н,
СН3N), 2.86–2.94 m (2Н, СН2), 3.71 d (2Н, СН2,
J 6.42), 4.11 t (1Н, СН, J 6.30), 6.69 d. d (2Н, СНAr,
J 8.20, 1.94), 6.79 d (2Н, СНAr, J 8.20), 6.86 d (2Н,
СНAr, J 1.94). Found, %: C 56.30; H 6.72; Br 18.55; N
3.18. C20H28BrNO4. Calculated, %: C 56.34; H 6.62;
Br 18.74; N 3.29.
This work was financially supported by the Russian
Foundation for Basic Research (project 11-03-00416-a).
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1
cm–1: 1601 (Ar), 3305 (OH). H NMR spectrum
(СD3OD), δ, ppm (J, Hz): 0.91 t (3Н, СН3СН2,
J 6.93), 1.08–1.18 m (2Н, СН3СН2), 1.23–1.38 m
[12Н, (СН2)6], 1.59–1.69 m (2Н, СН2СН2N), 3.05 s
(6Н, СН3N), 3.20–3.27 m (2Н, СН2СН2N), 4.00 d
(2Н, СНСН2N, J 6.50), 4.32 t (1Н, СН, J 6.30), 6.77 d
(2Н, СНAr, J 8.09), 6.81 d. d (2Н, СНAr, J 8.09, 2.02),
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Br 15.53; N 2.68. C26H40BrNO4. Calculated, %: C
61.17; H 7.90; Br 15.65; N 2.74.
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1
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The H NMR spectra were recorded on an Avance
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600 instrument operating at 600.13 MHz relative to the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 6 2013