Calix[4]resorcinols functionalized with amino acid residues

Article abstract of DOI:10.1134/S1070363209070159

By the Mannich reaction in ternary systems calix[4]resorcinol-amino acid (amino acid ester, amino acid ester hydrochloride)-formaldehyde calix[4]resorcinols were obtained functionalized on the upper molecule rim by amino acid residues.

Full text of DOI:10.1134/S1070363209070159

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 7, pp. 1494–1498. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © N.I. Shatalova, E.L. Gavrilova, N.A. Sidorov, A.R. Burilovb, M.A. Pudovik, E.A. Krasil’nikova, A.I. Konovalov, 2009, published in
Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 7, pp. 1137–1141.
Calix[4]resorcinols Functionalized with Amino Acid Residues
N. I. Shatalovaa, E. L. Gavrilovaa, N. A. Sidorova, A. R. Burilovbb, M. A. Pudovikb,
E. A. Krasil’nikovaa, and A. I. Konovalovb
a Kazan State Technological University, ul. K. Marksa 68, Kazan, 420015 Tatarstan, Russia
e-mail: Gavrilova_elena_@mail.ru
b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received November 10, 2008
Abstract—By the Mannich reaction in ternary systems calix[4]resorcinol–amino acid (amino acid ester, amino
acid ester hydrochloride)–formaldehyde calix[4]resorcinols were obtained functionalized on the upper
molecule rim by amino acid residues.
DOI: 10.1134/S1070363209070159
Production of supramolecular materials is one of
the promising lines in solving of the nowadays
scientific problems, namely, the information
processing and storage, the producing of new
generation drugs, complexing agents, and metal
extractants [1–3]. Recently an active interest arose in
the chemistry of calixresorcinols and their
functionalized derivatives playing an important role in
the supramolecular systems production. One of the
most widespread methods for incorporating nitrogen-
containing fragments into the ortho-position relative to
hydroxy groups of the calixarene molecule is the
aminomethylation by the Mannich reaction. There are
some published reports devoted to aminomethylation
of calix[4]resorcinols, involving alkyl groups on the
upper molecule rim, using secondary amines [4–6].
Recently we described a preparation of aminoalkylated
calix[4]resorcinols having aryl fragments on the lower
molecule rim [7]. Calix[4]resorcinols containing amino
acid residues are undoubtedly interesting for the study
of their biological activity. There was an only report on
calix-resorcinols aminomethylation with amino acids
[4].
benzene mixture in the ratio 1:4:4 result in calix[4]-
resorcinols Vа–Vc in about 65% yield.
The calix[4]resorcinols aminoalkylation involving
primary amines is known from the literature to give
sometimes oxazine derivatives due to the participation
of the second hydrogen atom of the primary amine [9].
The reaction might stop on the stage of Mannich base
formation, when sterically hindered primary amines
were used [10]. Spectral data showed that the reaction
products obtained Vа–Vc had a zwitterions structure
characteristic of amino acids. Hence oxazine structure
formation was not observed. In the IR spectra of
aminomethylated calix[4]resorcinols Vа–Vc a strong
absorption band appears in the range 3000–2400 сm–1
belonging to the stretching vibrations of NH2+ group
[11]. The signal of methylene protons of CArCН2–N
fragment in the 1H NMR spectrum of Vа–Vc is
observed as a singlet at 3.75, 3.88 and 3.62 ppm
respectively in agreement with the literature data [4–6]
(Scheme 1).
Reaction of compound I with formaldehyde using
amino acid esters IIIа–IIIc (ratio 1:4:5) yields calixa-
renes having four oxazine fragments on the upper mole-
cule rim formed through participation of both protons
of the primary amino group in the condensation. In the
1Н NMR spectra of compounds VIа–VIc besides the
signal of CAr–CН2–N moiety methylene protons in the
range 3.9–4.0 ppm (multiplet) there is a resonance
signal at 4.8 ppm (multiplet) belonging to methylene
protons of the oxazine fragment О–CН2N (Scheme 2).
In this work calix[4]resorcinol I having tolyl groups
on the lower molecule rim was used as an investigation
object [8]. Amino acids glycine, D,L-alanine and D,L-
valine, their ethyl esters and hydrochlorides of the
latter were used as amines in the Mannich reaction.
Reactions of calix-resorcinol I, water solutions of
amino acids IIа–IIc, and formaldehyde in the ethanol-
1494

1495
CALIX[4]RESORCINOLS FUNCTIONALIZED WITH AMINO ACID RESIDUES
Scheme 1.
R1
+
NH2
HO
OH
HO
OH
HO
HO
OH
OH
HO
HO
OH
OH
+
NH2
R1
R
R
R
R
R
R
R
R
5 HCHO
+ 4 H3N+
R1
−4H2O
+
IIа−IIc
NH2
R1
HO
OH
HO
OH
I
+
H2N
R1
Vа−Vc
O
O
O
(b),
(c).
(а),
CH
C
CH
C
R = C6H4CH3; R1 =
CH2
C
O−
O−
O−
CH
CH3
H3C
CH3
Scheme 2.
R1
N
HO
OH
HO
O
O
OH
O
HO
OH
N
R1
R
R
R
R
R
R
R
10 CH2O
+ 4 R1NH2
−8H2O
R
N
R1
IIIа−IIIc
HO
OH
HO
O
OH
HO
OH
I
N
R1
VIа−VIc
O
O
O
C
(b),
OC2H5
(а),
(c).
R = C6H4CH3; R1 =
CH
C
CH2
C
CH
CH
OC2H5
OC2H5
CH3
H3C
CH3
Reactions of resorcinol I, amino acid ethyl esters
IIIа–IIIc, and formaldehyde in dioxane give rise to
aminoalkylated calix[4]resorcinols VIIа–VIIc contain-
ing a quaternary nitrogen atom (Scheme 3).
The signal of methylene protons of CAr–CН2–N
moiety in the spectra of compounds VIIа–VIIc is
observed as a singlet at 3.80, 3.86, 3.67 ppm
respectively. In the IR spectra there are broad
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009

1496
SHATALOVA et al.
Scheme 3.
R1
NH HCl
HO
OH
HO
OH
HCl
NH
HO
OH
OH
HO
HO
OH
OH
R1
R
R
R
R
R
R
R
R
5 CH2O
+ 4 R1NH2
HCl
−4H2O
NH
R1
HO
IVа−IVc
HCl
HO
OH
HO
OH
I
HCl
HN
R1
VIIа−VIIc
O
O
O
(b),
(а),
(c).
CH
C
CH2
R = C6H4CH3; R1 =
C
CH
CH
C
OC2H5
OC2H5
OC2H5
CH3
H3C
CH3
absorption band in the range 3100–3500 cm–1 originat-
ing from hydroxy and ammonium groups.
mixture (volume ratio 1:1) were added in succession
under stirring 0.106 g (0.0014 mol) of glycine IIа
dissolved in water and 0.053 g (0.00175 mol) of
formaldehyde (40% water solution). The reaction
mixture was refluxed for 20 h and cooled to room
temperature. The precipitate was separated, washed
with freshly distilled ethanol and dried under an oil
pump vacuum (3 h, 80–90°C, 0.4 mm Hg). Yield
0.256 g (62%), mp >308°C. 1Н NMR spectrum
[(CD3)2SO)], δ, ppm: 2.46 s (12H, CAr–CH3), 3.75 s
(16H, CH2–N), 5.7 s (4H, CH), 6.32 s (4H, m–
We performed the biological activity prediction for
compounds obtained Vа–Vc, VIа–VIc and VIIа–VIIc
using PASS program package. By these calculations,
calix[4]resorcinols functionalized with amino acid
residues may possess biological activity like sedative,
antiherpes, antiseborrhea, transaminase and phos-
phatase inhibitors.
EXPERIMENTAL
3
CHArC63H2), 6.7 d (8H, C6H4, JHH 7.6 Hz), 7.1 d (8H,
C6H4, JHH 7.6 Hz). IR spectrum, ν, cm–1: 1603
1
The Н NMR spectra were registered on a Bruker
+
(C=CAr), 3020 (NH2 ), 3418 (ОН). Found, %: C 69.11;
MSL-400 device (400.13 МHz) relative to signals of
residual protons of the deuterated solvent (CDCl3,
DMSO-d6). The IR spectra were recorded on a UR-20
spectrophotometer in the range 400–3600 сm–1 from
KBr pellets. The biological activity spectrum was
predicted using PASS C&T program package (http://
www.ibmh.msk.su/PASS/default.htm).
Н 5.88; N 4.97. C68Н64N4О16. Calculated, %: C 68.46;
Н 5.36; N 4.70.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(1-carboxylate-1-methyl)-ammoniomethyl-
2,8,14,20-tetra(4-methyl)phenylpentacyclo-
[19.3.1.13,7.19,13.115,19]octacoza-1(25),3,5,7(28),9,11,13-
(27),15,17,19(26),21,23-dodecaene (Vb) was prepared
similarly from 0.3 g (0.00035 mol) of calix[4]
resorcinol I in 30 ml of benzene-ethanol mixture
(volume ratio 1:1), 0.125 g (0.0014 mol) of D,L-
alanine IIb and 0.531 g (0.0177 mol) of formaldehyde
(40% water solution). Yield 0.28 g (63%), mp > 258°C.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(1-carboxylate)ammoniomethyl-2,8,14,20-tetra-
(4-methyl)phenylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacoza-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaene (Va). To a solution of 0.3 g (0.00035 mol)
of calix[4]resorcinol I in 30 ml of benzene–ethanol
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009

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CALIX[4]RESORCINOLS FUNCTIONALIZED WITH AMINO ACID RESIDUES
1Н NMR spectrum [(CD3)2SO)], δ, ppm: 1.3 d (12H,
CH3–CН, 3JHH 7.0 Hz); 2.4 s (12H, CAr–CH3), 3.5 br.m
(4H, –CH–N), 3.88 s (8H, CAr–CH2–N), 5.65 s (4H,
4,14,24,34-tetrahydroxy-2,12,22,32-tetra(4-methyl-
phenyl)-7,17,27,37-tetra[1-ethoxy-carbonyl(1-methyl)]-
ethyl-7,17,27,37-tetraazanocyclo[31.7.1.13,11.113,21.-
3
1
23,31.05,15.015,20.025,30]-tetratatraconta-1(41),3,5(10),11-
CH), 6.3 s (4H, m–CHAr C6H2), 6.6 d (8H, C6H4, JHH
7.6 Hz), 6.9 d (8H, C6H4, 3JHH 7.6 Hz). IR spectrum, ν,
(44),13,15(20),21(43),23,25(30),31(42),33,35(40)-do-
decaene (VIb) was prepared similarly from 0.3 g
(0.00035 mol) of calix[4]resorcinol I in 100 ml of
ethanol–methylene chloride mixture (volume ratio
1:1), 0.164 g (0.0014 mol) of D,L-alanine ethyl ester
IIb, and 0.106 g (0.00354 mol) of formaldehyde (40%
+
cm–1: 1621 (C=CAr), 3019 (NH2 ), 3393 (ОН). Found,
%: C 70.01; Н 6.10; N 5.17. C72Н72N4О16. Calculated,
%: C 69.23; Н 5.77; N 4.49.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(1-carboxylate-2-methyl)-propyl-ammoniome-
thyl-2,8,10,20-tetra(4-methyl)phenylpentacyclo-
[19.3.1.13,7.19,13.115,19]octacoza-1(25),3,5,7(28),9,11,13-
(27),15,17,19(26),21,23-dodecaene (Vc) was prepared
similarly from 0.3 g (0.00035 mol) of calix[4]
resorcinol I in 30 ml of benzene-ethanol mixture
(volume ratio 1:1), 0.1645 g (0.0014 mol) of D,L-
valine IIc 0.0525 g (0.00175 mol) of formaldehyde
(40% water solution). Yield 0.333 g (69%), mp >284°C.
1Н NMR spectrum [(CD3)2SO)], δ, mp: 0.83 d.d [24H,
1
water solution). Yield 0.323 g (64%), mp >320°C. Н
NMR spectrum (CDCl3), δ, ppm: 1.28 d (12Н,
3
3
CН3CН, JHH 7.0 Hz), 1.37 t (12Н, ОCН2CН3, JHH
6.85 Hz), 2.36 s (12Н, CArCН3), 3.3 br.m (4Н, CН–N),
3
3.78 m (8Н, CArCН2N), 4.12 q (8Н, ОCН2CН3, JHH
6.85 Hz), 5.0 m (8Н, ОCН2–N), 5.56 br.s (4Н, CH),
6.18 s (4Н, CНAr, C6Н2), 6.68 d (8Н, CНAr, C6Н4, 3JHH
3
7.6 Hz), 7.0 d (8Н, CНAr, C6Н4, JHH 7.6 Hz). IR
spectrum, ν, cm–1: 1610 (C=CAr), 1736 (C=О), 3485
(ОН). Found, %: C 72.24; Н 7.11; N 4.15.
C84Н92N4О16. Calculated, %: C71.39; Н 6.51; N 3.97.
3
CH(CH3)2, JHH 6.85 Hz], 2.38 s (12H, CAr–CH3), 3.3
br.m (4H, –CH–N), 3.62 s (8H, CAr–CH2–N), 5.7 s
(4H, CH), 6.2 s (4H, m–CHAr, C6H2), 6.6 d (8H, C6H4,
4,14,24,34-tetrahydroxy-2,12,22,32-tetra(4-methyl-
phenyl)-7,17,27,37-tetra[1-ethoxy-carbonyl(2-methyl)]-
propyl-7,17,27,37-tetraazanocyclo-[31.7.1.13,11.113,21.-
123,31.05,15.015,20.025,30]tetratetraconta-1(41),3,5(10),11-
(44),13,15(20),21(43),23,25(30),31(42),33,35(40)-do-
decaene (VIc) was prepared similarly from 0.3 g
(0.00035 mol) of calix[4]resorcinol I in 100 ml of
ethanol–methylene chloride mixture (volume ratio
1:1), 0.2 g (0.0014 mol) of D,L-valine ethyl ester IIc,
and 0.106 g (0.0035 mol) of formaldehyde (40% water
solution). Yield 0.28 g (51.8%), mp >320°C. 1Н NMR
spectrum (CDCl3), δ, ppm: 0.7 d.d [24Н, CН(CН3)2,
3
3JHH 7.6 Hz), 6.9 d (8H, C6H4, JHH 7.6 Hz). IR
+
spectrum, ν, cm–1: 1621 (C=CAr), 2967 (NH2 ), 3426
(ОН). Found, %: C 71.42; Н 7.27; N 4.51.
C80Н92N4О16. Calculated, %: C 70.59; Н 6.47; N 4.12.
4,14,24,34-Tetrahydroxy-2,12,22,32-tetra(4-methyl-
phenyl)-7,17,27,37-tetra(1-ethoxy-carbonyl)methyl-
7,17,27,37-tetraazanocyclo[31.7.1.13,11.113,21.123,31.05,15.-
015,20.025,30]-tetratetraconta-(41),3,5(10),11(44),13,15-
(20),21(43),23,25(30),31(42),33,35(40)-dodecaene
(VIа). To a solution of 0.3 g (0.00035 mol) of calix[4]-
resorcinol I in 100 ml of ethanol-methylene chloride
mixture (volume ratio 1:1) were added in succession
0.144 g (0.0014 mol) of glycine ethyl ester IIIа, and
0.106 g (0.00354 mol) of formaldehyde (40% water
solution) under stirring. The reaction mixture was kept
for 24 h at 20°C. The solvents were removed under a
water-jet pump vacuum and the residue was repre-
cipitated from chloroform with n-pentane. The product
isolated was dried under an oil pump vacuum (3 h, 80–
90°C, 0.4 mm Hg). Yield 0.322 g (67%), mp >300°C.
1Н NMR (CDCl3), δ, ppm: 1.12 t (12Н, О–CН2–CН3,
3JHH 6.85 Hz), 2.3 s (12Н, CArCН3), 3.1 s (8Н, CН2–
3
3JHH 6.85 Hz], 1.27 d (12Н, ОCН2CН3, JHH 6.85 Hz),
1.9 m [4Н, CН(CН3)2], 2.3 s (12Н, CArCН3), 3.1 br.m
(4Н, CН–N), 3.9 m (8Н, CArCН2N), 4.2 q (8Н,
3
ОCН2CН3, JHH 6.85 Hz), 4.8 m (8Н ОCН2–N), 5.6
br.s (4Н, CH), 6.2 s (4Н, m-CНAr, C6Н2), 6.67 d (8Н,
3
m-CНAr, C6Н4, JHH 7.6 Hz), 6.9 d (8Н, CНAr, C6Н4,
3JHH 7.6 Hz). IR spectrum, ν, cm–1: 1610 (C=CAr),
1733 (C=О), 3493 (ОН). Found, %: C 71.04; Н 7.58;
N 3.17. C92Н108 N4О16. Calculated, %: C 72.44; Н
7.08; N 3.7.
3
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra(1-ethoxycarbonyl)ammoniomethyl-2,8,14,20-
tetra(4-methyl)phenylpentacyclo[19.3.1.13,7.19,13.115,19]-
octacoza-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-
dodecaene (VIIа). To a solution of 0.3 g (0.00035 mol)
of calix[4]resorcinol I in 50 ml of dioxane were added
in succession under stirring 0.195 g (0.0014 mol) of
N), 3.9 m (8Н, CArCН2N), 4.2 q (8Н, ОCН2CН3, JHH
6.85 Hz), 4.8 m (8Н, ОCН2–N), 5.6 br.s (4Н, CH), 6.2
3
s (4Н, CНAr, C6Н2), 6.67 d (8Н, CНAr, C6Н4, JHH
7.6 Hz), 6.9 d (8Н, CНAr C6Н4, 3JHH 7.6 Hz). IR, ν, cm–1:
1610 (C=CAr), 1740 (C=О), 3502 (ОН). Found, %: C
71.17; Н 6.45; N 4.21. C80Н84N4О16. Calculated, %: C
70.80; Н 6.19; N 4.13.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009

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SHATALOVA et al.
1
hydrochloride IVa and 0.0525 g (0.00175 mol) of
paraformaldehyde. The mixture was acidified with
HCl to pH 1.0–2.0. The reaction mixture was refluxed
for 24 h. The solvent was removed under a water-jet
pump vacuum and residue was reprecipitated from
ethanol with diethyl ether. The product isolated was
dried under an oil pump vacuum (3 h, 80–90°C,
paraformaldehyde. Yield 1.09 g (60%), mp >90°C. Н
NMR spectrum [(CD3)2SO)], δ, ppm: 0.83 d.d [24H,
CH(CH3)2, 3JHH 6.85 Hz], 1.27 t (12Н, ОCН2CН3, 3JHH
6.85 Hz), 2.38 s (12H, CAr–CH3), 3.3 br.m (4H, –CH–N),
3
3.72 s (8H, CAr–CH2–N), 4.1 q (8Н, ОCН2CН3, JHH
6.85 Hz), 5.7 s (4H, CH), 6.2 s (4H, m-CHAr, C63H2),
3
6.6 d (8H, C6H4, JHH 7.6 Hz), 6.9 d (8H, C6H4, JHH
1
0.4 mm Hg). Yield 0.343 g (73%), mp >117°C. Н
7.6 Hz). IR spectrum, ν, cm–1: 1607 (C=CAr), 1737
(C=О), 2968 (NH2+), 3404 (ОН). Found, %: C 65.52; Н
7.28; N 4.01; Cl 9.15. C88Н108N4О16 ·4НCl. Calculated,
%: C 65.10; Н 6.91; N 3.45; Cl 8.76.
NMR spectrum [(CD3)2SO], δ, ppm: 1.27 t (12Н,
ОCН2CН3, 3JHH 6.85 Hz), 2.46 s (12H, CAr–CH3), 3.80
s (16H, CH2–N), 4.12 q (8Н ОCН2CН3, 3JHH 6.85 Hz),
5.7 s (4H, CH), 6.32 s (4H, m-CHAr, C6H2), 6.7 d (8H,
3
3
ACKNOWLEDGMENTS
C6H4, JHH 7.6 Hz), 7.1 d (8H, C6H4, JHH 7.6 Hz). IR
spectrum, ν, cm–1: 1599 (C=CAr), 1743 (C=О), 2984
(NH2+), 3406 (ОН). Found, %: C 63.02; Н 6.26; N
4.07; Cl 10.11. C76Н84N4О16·4НCl. Calculated, %: C
62.72; Н 6.05; N 3.85; Cl 9.77.
This work was financially supported by the Russian
Foundation for Basic Research (grants nos. 04-03-
32512, 07-03-0086306-03-32085).
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra[1-ethoxycarbonyl(1-methyl)]-ammoniomethyl-
2,8,14,20-tetra(4-methyl)phenylpentacyclo[19.3.1.13,7.-
REFERENCES
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1987, p. 95.
1
9,13.115,19]octacoza-1(25),3,5,7(28),9,11,13(27),15,17,-
19(26),21,23-dodecaene (VIIb) was prepared similarly
from 0.3 g (0.00035 mol) of calix[4]resorcinol I in
50 ml of dioxane, 0.21 g (0.0014 mol) of
hydrochloride IVb, and 0.106 g (0.00175 mol) of
paraformaldehyde. Yield 0.379 g (71%), mp >104°C.
1Н NMR spectrum [(CD3)2SO)], δ, ppm: 1.3 d (12H,
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3
3
CH3CН, JHH 7.0 Hz), 1.67 t (12Н, ОCН2CН3, JHH
6.85 Hz), 2.4 s (12H, CAr–CH3), 3.5 br.m (4H, –CH–N),
3
3.86 s (8H, CAr–CH2–N), 4.23 q (8Н, ОCН2CН3, JHH
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6.85 Hz), 5.65 s (4H, CH), 6.3 s (4H, m-CHAr, C63H2),
3
6.6 d (8H, C6H4, JHH 7.6 Hz), 6.9 d (8H, C6H4, JHH
7.6 Hz). IR spectrum (KBr), ν, cm–1: 1600 (C=CAr),
1740 (C=О), 3020 (NH2+), 3421 (ОН). Found, %: C
64.19; Н 6.52; N 4.03; Cl 10.09. C80Н92N4О16 ·4НCl.
Calculated, %: C 63.58; Н 6.36; N 3.71; Cl 9.40.
4,6,10,12,16,18,22,24-Octahydroxy-5,11,17,23-
tetra[1-ethoxycarbonyl(2-methyl)]-propylammonio-
methyl-2,8,14,20-tetra(4-methyl)phenylpentacyclo-
[19.3.1.13,7.19,13.115,19]-octacoza-1(25),3,5,7(28),9,11,13-
(27),15,17,19(26),21,23-dodecaene (VIIc) was prepared
similarly from 1 g (0.00118 mol) of calix[4]resorcinol
I in 50 ml of dioxane, 0.86 g (0.0047 mol) of
hydrochloride IVc, and 0.354 g (0.0118 mol) of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009