Pre-organized oligomodified resorcinarene ligands. Preparation, structure, and complex formation

Article abstract of DOI:10.1134/S1070363214040240

Interaction of various conformations of resorcinarenes with carbamoyl chloride, thiocarbamoyl chloride, and trifluoromethanesulfonic acid anhydride has resulted in a series of derivatives with certain pre-organization of the macrocyclic scaffold and the immobilized electron-donating groups. Complex formation of the selected prepared compounds towards Pd(II) derivatives has been studied.

Full text of DOI:10.1134/S1070363214040240

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 4, pp. 745–752. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © O.S. Serkova, A.V. Burikhina, L.K. Vasyanina, O.S. Kuprina, V.I. Maslennikova, E.E. Nifantiev, 2014, published in Zhurnal
Obshchei Khimii, 2014, Vol. 84, No. 4, pp. 670–678.
Pre-Organized Oligomodified Resorcinarene Ligands.
Preparation, Structure, and Complex Formation
O. S. Serkova, A. V. Burikhina, L. K. Vasyanina, O. S. Kuprina,
V. I. Maslennikova, and E. E. Nifantiev
Moscow Pedagogical State University, Nesvizhski per. 3, Moscow, 119021 Russia
e-mail: him-vim@mail.ru
Received June 20, 2013
Abstract―Interaction of various conformations of resorcinarenes with carbamoyl chloride, thiocarbamoyl
chloride, and trifluoromethanesulfonic acid anhydride has resulted in a series of derivatives with certain pre-
organization of the macrocyclic scaffold and the immobilized electron-donating groups. Complex formation of
the selected prepared compounds towards Pd(II) derivatives has been studied.
Keywords: calix[4]resorcinarenes, conformation, carbamoylation, metalated cycle
DOI: 10.1134/S1070363214040240
Calix[4]resorcinarenes I containing four pairs of
hydroxy groups per molecule are easily modified and
are convenient precursors of receptors and coordina-
tion systems. Their conformation state depends on the
nature of substituents in methylene bridges; hence, pre-
organization of macrocyclic scaffold of the molecule
can be achieved to form certain orientation of the
functional groups, an important part of designing
special purpose complexes [1–10].
The parent macrocycles were rctt-tetranaphthyl-
resorcinarene Ia existing in the chair conformation and
rccc-tetraalkylresorcinarenes Ib–If with preferential
crown conformation. The following functionalized
reagents were used: N,N-dimethylcarbamoyl chloride
IIa, N,N-dimethylthiocarbamoyl chloride IIb, and tri-
fluoromethanesulfonic acid anhydride IIc (Scheme 1).
Reactions of resorcinarenes I with IIa and IIb were
performed in acetone at 50–55°С in the presence of
Cs2CO3 (Scheme 2).
In this work we addressed the possibility to
functionalize resorcinarenes I in order to construct pre-
organized ligands with defined orientation of electron-
donor groups capable of chelate complex formation.
The complete acylation of hydroxy groups occurred
under the above conditions. Carbamoylation of Ia–If
Scheme 1.
OH
HO
HO
OH
OH
HO
OH
HO
OH
HO
HO
R
R
R
R
OH
HO
R
R
OH
R
R
OH
HO
Ib_If
Ia
R = α-naphthyl (a), CH3 (b), CH2CH2C6H5 (c), Pr (d), C6H13 (e), C9H19 (f).
745

746
SERKOVA et al.
Scheme 2.
OX
XO
OX
R
XO
OX
OX
XO
OX
OX
XO
XO
R
R
R
R
IIa, IIc
IIa_IIc
Ia_If
XO
R
OX
XO
R
R
XO
OX
IIIb_IIIf, IVa_IVc, Vb, Vc
IIIa, Va
Va: X = SO2CF3; II: ClC(O)N(CH3)2 (a), ClC(S)N(CH3)2 (b), (SO2CF3)2O (c); III: X = C(O)N(CH3)2; R = α-naphthyl (a),
CH3 (b), CH2CH2Ph (c), C3H7 (d), C6H13 (e), C9H19 (f); IV: X = C(S)N(CH3)2, CH3 (a), CH2CH2Ph (b), C3H7 (c); V: X =
SO2CF3 (a), CH3 (b), C3H7 (c).
1
was complete within 8 h; complete thiocarbamoylation
of calixarenes Ib–Id took 48 h. Yields of О-(di-
methyloctacarbamoyl)- and О-(dimethyloctathiocarba-
moyl)resorcinarenes III and IV were 52–86% (Table 1).
absence of Н NMR signals of hydroxy group protons
1
and the ratio of integral intensities of the Н NMR
signals of aminomethyl protons and those of
resorcinarene scaffold confirmed the formation of
perfunctionalized derivatives. In the 13С NMR spectra
the signals of carbon atoms of aminomethyl groups
and of carbonyl (III) or thiocarbonyl (IV) groups were
Elemental analysis data and mass spectra features
of resorcinarenes III and IV (Table 1) along with the
Table 1. Yields, melting points, elemental analysis data, and mass spectra features of octafunctionalized resorcinarenes III–V
Found, %
Calculated, %
H N
Comp. Yield,
mp,
°С
Formula
m/z
no.
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IVа
IVb
IVc
Vа
%
83
72
82
84
71
66
86
86
52
60
C
H
N
C
260–262 70.77
301–303 60.38
203–210а 68.41
310–314а 62.55
257–260а 69.24
270–274а 71.28
266–268а 50.68
196–198 62.51
182–184а 57.00
268–270 44.35
268–270 34.77
281–283 33.44
5.65
7.15
С92Н88N8O16
С56Н72N8O16
C84H96N8O16
С64Н88N8O16
С64Н92N4O12
С76Н116N4O12
70.75 5.68 7.17
6.47 10.00
60.42 6.52 10.07 1174 [M+ + Na+ + K+]
68.40 6.57 7.60
6.55
7.16
8.40
9.11
5.46
6.02
6.52
2.04
1.08
2.37
7.62
9.08
5.07
4.40
8.38
6.63
8.25
62.73 7.24 9.14 1434.5 [M+]
69.29 8.36 5.05 1584 [M+ + Na+]
71.44 9.15 4.38
C56H72N8O8S8·СHCl3 50.30 5.41 8.23 1241.4 [M+]
C84H96N8O8S8
С64Н88N8O8S8
C76H40F24O24S8
C40H24F24O24S8
C48H40F24O24S8
62.97 6.04 6.99 1601.9 [M+]
56.77 6.55 8.28
44.54 1.98
35.01 1.51
33.65 2.35
2066 [M+ + Н2O]
1409 [M+ – CF3SO2]
Vb
Vc
65
61
a Melting with decomposition.
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PRE-ORGANIZED OLIGOMODIFIED RESORCINARENE LIGANDS
747
Scheme 3.
R
R
R
R
R
R
R
R
R
R
R
R
boat (A)
crown
boat (B)
observed. The IR spectra contained intense band at
around 1660 cm–1 typical of C=О stretching vibrations
(III) or around 1120 cm–1 (C=S stretching vibrations)
(IV).
were isolated in 60–65% yields. Elemental analysis
and mass spectrometry data of compounds Va–Vc
coincided with the theoretical predictions (Table 1). In
the1 Н NMR spectra the hydroxy protons signals were
absent thus confirming their complete substitution.
Introduction of eight functional groups into rctt-
resorcinarene Ia containing distant benzene rings did
not influence the macrocyclic scaffold conformation.
Compound IIIa, similarly to Ia, existed in the chair
conformation (C2h symmetry) as evidenced by
duplication of signals of protons and carbon atoms of
19F NMR spectra of compounds Va and Vb
contained pairs of singlet signals of fluorine atoms of
triflate fragments of vertically and horizontally
oriented benzene rings of resorcinarene scaffold. The
1
downfield part of Н and 13С NMR spectra of octa-
1
benzene rings and of carbamate groups in Н and 13С
triflates Va and Vb (reflecting the molecules
conformation) corresponded to С2 symmetry of the
macrocyclic scaffolds. In 19F and 1Н NMR spectra of
tetrapropylcalixarene Vc the signals of the corres-
ponding nuclei were degenerate, typical of crown con-
formation of resorcinarenes С4v symmetry). Com-
parison of NMR spectra of Va–Vc and of IIIa, IIIb,
IIId confirmed their structural similarity.
NMR spectra as well as by upfield shift (δ 5.24 ppm)
of the benzene ring protons (Н3h) in 1Н NMR spectrum
[11].
1
At the same time, Н and 13С spectra of octa-
carbamate IIIb and octathiocarbamates IVa and IVc
indicated the conformational changes of the
resorcinarene scaffold. Regardless of the solvent used,
their spectra contained signals of protons and carbon
atoms oriented vertically and horizontally, typical of
resorcinarenes in conformation of hindered boat (C2v
symmetry) [12]. The pointed structural changes
resulted from slowing down of the boat (A)–crown-
boat (B) interconversion due to immobilization of
eight bulky functional groups at spatially close
benzene rings of the macrocycle [13, 14] (Scheme 3).
The prepared perfunctionalized resorcinarenes III–
V were octadental ligands capable of chelate formation
with transition metals, due to spatially close electron-
donor substituents of benzene rings of macrocyclic
scaffold. Depending on the ligand conformation, the
metal ion could coordinate at functional groups of one
of the benzene rings [chair (IIIa), hindered boat (IIIb,
IVa, and IVc)], at two adjacent benzene rings [crown
(IIIc–IIIf and IVb)], or at distal vertically oriented
benzene rings [boat (IIIb, IVa, IVc, and Va–Vc)] of
the macrocyclic scaffold.
Spatial orientation of octafunctionalized resorci-
narenes IIIc–IIIf and IVb depended on the solvent
1
used, as seen from the Н and 13С NMR spectra (see
Using the ligands (IIIa–IIIc, IVa, and IVb)
existing in different conformational states and Pd(II)
derivatives we prepared a series of complexes with
metal to ligand ratio of 4 : 1 (VIa, VIb, and VIIa–
VIIc) or 2 : 1 (VIII) (Scheme 4). Conditions of the
complex formation were slightly different depending
on the reagents used. In particular, complex formation
of compounds III and IV with Pd[C6H5CN]2Cl2
occurred at room temperature within 6 h (III) or 24 h
(IV). In the case of compounds IV interaction with
PdCl2 the reaction mixture was refluxed during 20
min, and then stirred during 24 h at room temperature;
Fig. 1). In chloroform, due to the repulsion of the
carbamate groups and slowed interconversion the boat
conformation was preferential (see Fig. 1a). In di-
methylsulfoxide a strong liophilic interaction of the
alkyl substituents R [15, 16] favored the crown
conformation (С4v symmetry) (see Fig. 1b), as
evidenced by degeneracy of protons and carbon atoms
signal in the NMR spectra.
О-Octatriflatoresorcinarenes Va–Vc were obtained
via interaction of compounds Ia–Ic, respectively, with
IIc in pyridine at 20–25°С (Scheme 2). The products
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

748
SERKOVA et al.
(a)
H3v H5v
H5h
H3h
(b)
δ, ppm
Fig. 1. 1Н NMR spectra of О-(dimethyloctacarbamoyl)(tetrahexyl)resorcinarene IIIe in CDCl3 (a) and in DMSO-d6 (b).
in the case of compounds III the reaction was
complete within 46 h at 35–40°С or within 8 h at 75°С.
The interaction of Pd(II) derivatives with rccc-
octacarbamoylresorcinarene IIIc with C4v symmetry
(preferential crown conformation with spatially close
carbamoyl groups located at the adjacent aromatic
rings) could lead to the formation of metalated
cavitand VIII containing two diagonally located 12-
membered metalated cycles. Other carbamate groups
became distant and lost the ability of chelate
formation.
Complexes VI–VIII were yellow powders melting
with decomposition (Table 2), insoluble in the majority
of organic solvents. Their yields were 62–94%. From
elemental analysis data complexes VI and VII
contained four cyclopalladated fragments, whereas two
such fragments were found in VIII.
Taking into account the ligands pre-organization,
we suggest that the cyclopalladation of resorcinarenes
with C2 symmetry [chair (IIIa) and hindered boat
(IIIb, IVa, and IVb) conformations with spatially
isolated functional groups of the adjacent aromatic
rings] occurred via coordination of Pd with functional
groups of the same benzene ring. That led to the
formation of complexes VI and VII with four 10-
membered metalated cycles, two of which located in
the macrocycle plane, and two others located per-
pendicular to it to the same side (VIb, VIIa, and VIIb)
or to different sides (VIa) of the plane (Scheme 4).
To conclude, the prepared octafunctionalized
resorcinarenes III–V were pre-organized oligodental
ligands capable of formation of complexes with
defined orientation of metalated fragments. Therefore,
they can serve as basis for constructing various
supramolecular systems.
EXPERIMENTAL
1Н and 13С NMR spectra (TMS as internal
reference), 31Р NMR spectra (85% Н3РО4 as external
reference) were recorded using a Jeol ECX-400
spectrometer [400 (1Н) and 100.5 (13C) MHz] at 25°С.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

PRE-ORGANIZED OLIGOMODIFIED RESORCINARENE LIGANDS
Table 2. Yields, melting points, and elemental analysis data of complexes VI–VIII
Found, %
749
Calculated, %
H N
Yield,
%
Mp,
Comp. no.
Formula
°С
C
H
N
C
VIa
82а, 80b
88а, 94b
62а, 62b
90а, 88b
88а, 83b
205–207c
240–242
291–295c
290–293c
285–289c
48.55
3.76
4.92
C92H88Cl8N8O16Pd4
C56H72Cl8N8O16Pd4
C56H72Cl8N8O8Pd4S8
C84H96Cl8N8O8Pd4S8
C84H96Cl4N8O16Pd2
48.46
36.90
42.13
45.08
46.22
3.91
3.98
4.55
4.62
4.41
4.94
6.15
7.02
4.67
5.13
VIb
36.85
42.14
44.63
46.26
3.90
4.52
4.15
4.41
6.11
6.58
4.68
5.11
VIIa
VIIb
VIII
a Method a. b Method b. c Melting with decomposition.
Scheme 4.
Cl2
Pd
O
O
NMe2
Me2N
O
O
NMe2
O
Me2N
O
O
O
O
R
R
R
PdCl2
PdCl2
IIIa
Cl2Pd
R
O
O
O
Me2N
NMe2
O
O
NMe2
Me2N
O
O
Pd
Cl2
VIa
IIIb, IIIc, IVа, IVb
PdCl2
PdCl2
Cl2
Pd
Cl2
O
Pd
NMe2
O
Y
O
NMe2
O
O
Y
O
Me2N
Cl2
Pd
Me2N
NMe2
NMe2
O
Y
Y
O
O
O
O
NMe2
NMe2
Me2N
O
NMe2
Y
O
Me2N
Y
O
Me2N
O
O
O
PdCl2
O
O
O
O
Cl2Pd
O
PdCl2
R
R
Y
Me2N
NMe2
O
Y
R
O
R
R
R
NMe2
Me2N
R
R
VIb, VIIa, VIIb
VIII
VI, Y = O, R = α-naphthyl (а), CH3 (b); VII, Y = S, R = Me (a), CH2CH2Ph (b); VIII, R = CH2CH2Ph.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

750
SERKOVA et al.
Mass spectra (MALDI–TOF) were recorded using the
Bruker Ultra-flex TOF/TOF spectrometer (Bruker
Daltonics GmbH), using 1,8,9-trihydroxyantracene as
matrix. IR spectra (4000–500 cm–1, mull in nujol) were
7.37 s (2Н, Н3v). 13С NMR spectrum (CDCl3), δС, ppm:
20.31 (СН3), 32.26 (С1); 35.99, 36.48, 36.83 (NCH3);
115.87 (C5h), 116.90 (C5v), 125.26 (С3h), 125.68 (С3v),
131.97 (C2v); 135.68 (C2h), 146.22 (С4h), 148.22 (С4v),
153.89 (C=O), 154.43 (C=O).
registered using
a
NICOLETTE 380 Thermo
spectrometer in reflection mode. Elemental analysis
was carried out with a Thermo Flash EA112 СНN-
analyzer.
О-Octa(dimethylcarbamoyl)[tetra(2-phenyl-
ethyl)]calix[4]resorcinarene (IIIc). 1Н NMR
spectrum (DMSO-d6), δ, ppm: 2.23
m
(8Н,
Calix[4]resorcinarenes Ia–If were obtained as
described in [16, 17].
СН2СН2PH), 2.55 br.t (8Н, СН2СН2PH), 2.78 s (24H,
3
NCH3) 2.85 s (24H, NCH3), 4.33 t (4Н, H1, JНН 7.3
Hz), 7.04 m (10H, H3, o-PH), 7.16 m (14H, Н5, p,m-
PH). 13С NMR spectrum (DMSO-d6), δС, ppm: 33.92
(СН2СН2PH), 35.47 (СН2СН2PH), 35.88 (NCH3),
36.03 (С1), 36.19 (NCH3), 116.41 (C5), 125.66 (C2),
126.08 (С3), 128.10 (PH), 128.14 (PH), 141.39 (С4),
153.35 (C=O).
Carbamoylation of resorcinarenes I. N,N-Di-
methylcarbamoyl chloride (2.4 mmol) was added to
suspension of the corresponding compound
I
(0.2 mmol) and cesium carbonate (2.42 mmol) in
10 mL of acetone. The reaction mixture was refluxed
during 8 h at stirring. Then acetone was distilled off,
and 10 mL of 5% aqueous sulfuric acid solution was
added to the residue. The formed precipitate was
filtered off, washed with water (60 mL) and hexane
(20 mL), and dried during 5 h at 80–90°C (1 mmHg).
In the cases of Ie and If, the reaction product was
extracted with chloroform (3 × 5 mL) after addition of
sulfuric acid. Organic layers were combined,
chloroform was distilled off, and the residue was dried
during 6 h at 75–80°С (1 mmHg).
О-Octa(dimethylcarbamoyl)(tetrapropyl)calix[4]-
1
resorcinarene (IIId). Н NMR spectrum (DMSO-d6),
3
δ, ppm: 0.83 t (12Н, СН2СН2СН3, JHH 7.3 Hz), 1.14
3
m (8Н, СН2СН2СН3, JHH 7.4 Hz), 2.03 m (8Н,
СН2СН2СН3); 2.46 s (24H, NCH3), 2.64 s (24H,
3
NCH3), 4.16 t (4Н, JHH 7.4 Hz), 6.10 s (4H, H3), 7.19
s (4Н, H5). 13С NMR spectrum (DMSO-d6), δ, ppm:
14.39 s (СН3), 20.90 s (CH2), 21.19 s (CH2), 33.09 s
(С1); 36.10 s, 36.75 s, 38.77 s; 40.01 s (NCH3); 102.92
s (C5), 123.78 s (С3), 125.48 s (C2), 152.11 s (С4),
154.02 s (C=O).
О-Octa(dimethylcarbamoyl)(tetranaphth-1-yl)-
calix[4]resorcinarene (IIIa). IR spectrum (nujol), ν,
1
cm–1: 1714.3 (С=О). Н NMR spectrum (CDCl3), δ,
О-Octa(dimethylcarbamoyl)(tetrahexyl)calix[4]-
ppm: 2.24 s, 2.35 s, 2.68 s, 2.92 s (12H each, NCH3);
1
resorcinarene (IIIe). Н NMR spectrum (CDCl3), δ,
5.25 s (2Н, H3h), 6.20 s (2H, H3v) 6.21 s (4Н, H1), 6.50
3
ppm: 0.83 t [12H, CH2(CH2)4CH3, JНН 6.4 Hz], 1.22
3
d (4Н, H2-Naphth, JHH 6.8 Hz), 6.93 d.d (4Н, H7-
m [32Н, CH2(CH2)4CH3], 1.75 m [8Н, CH2(CH2)4CH3];
3
3
Naphth, JHH 6.8, JHH 8.0 Hz), 6.95 d.d (4Н, H3-
2.62 s, 2.80 s, 3.00 s, 3.08 s (12H each, NCH3); 4.26 t
3
3
Naphth, JHH 7.3, JHH 6.8 Hz), 7.03 d.d (4Н, H6-
Naphth, 3JHH 7.1, 3JHH 6.8 Hz), 7.14 s (2Н, Н5h), 7.17 s
(2Н, Н5v), 7.39 d (4Н, H4-Naphth, 3JHH 8.0 Hz), 7.41 d
3
(4H, Н1, JНН 6.8 Hz), 6.06 s (2Н, Н3h), 6.69 s (2Н,
Н5h), 7.19 s (2Н, Н5v), 7.32 s (2Н, Н3v). 1Н NMR spec-
trum (DMSO-d6), δ, ppm: 0.84 t [12H, CH2(CH2)4CH3,
3JНН 6.8 Hz], 1.25 m [32Н, CH2(CH2)4CH3], 2.08 m
[8Н, CH2(CH2)4CH3], 2.89 s (24H, NCH3), 2.91 s
(4Н, H5-Naphth, JHH 7.8 Hz), 7.44 d (4Н, H8-Naphth,
3
3JHH 8.2 Hz). 13С NMR spectrum (CDCl3, 25°C), δС,
ppm: 34.72 (С1), 35.25 (NCH3), 36.13 (NCH3), 36.14
(NCH3), 36.21 (NCH3), 116.70 (C5h), 117.50 (C5v);
124.10, 124.42, 124.53, 124.79, 126.23, 126.34,
127.82, 128.01 s (CNaphtH); 128.57 (C2v); 128.55 (C2h);
130.62 (С3h), 130.84 (С3v), 147.74 (С4h); 148.50 (С4v),
152.82 (C=O), 153.77 (C=O).
3
(24H, NCH3), 4.16 t (4H, Н1, JНН 7.55 Hz), 6.00 s
(4Н, Н3), 7.12 s (4Н, Н5). 13С NMR spectrum (CDCl3),
δC, ppm: 14.11 (СН3), 22.80 (CH2), 23.05 (CH2), 28.20
(CH2), 29.71 (CH2), 31.84 (CH2), 33.09 (С1); 36.47,
36.60, 36.74, 36.78 (NCH3); 115.88 (C5), 117.08 (C5),
125.94 (С3), 126.03 (C3), 130.03 (C2), 134.62 (C2),
146.04 (С4), 148.75 (С4), 153.93 (C=O), 154.28
(C=O). 13С NMR spectrum (DMSO-d6), δC, ppm:
13.76 (СН3), 22.04 (CH2), 27.60 (CH2), 28.85 (CH2),
31.17 (CH2), 31.51 (CH2), 35.49 (С1), 36.28 (NCH3),
38.18 (NCH3), 102.57 (C5), 123.08 (С3), 125.66 (C2),
151.65 (С4), 153.48 (C=O).
О-Octa(dimethylcarbamoyl)(tetramethyl)calix-
[4]resorcinarene (IIIb). IR spectrum (nujol), ν, cm–1:
1
1720.6 (С=О). Н NMR spectrum (CDCl3), δ, ppm:
3
1.46 d (12H, CH3, JHH 6.9 Hz); 2.61 s, 2.82 s, 3.01,
3.09 s (12H each, NCH3); 4.40 q (4H, Н1, 3JHH 6.8 Hz),
6.01 s (2Н, Н3h), 6.77 s (2Н, Н5h), 7.16 s (2Н, Н5v),
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PRE-ORGANIZED OLIGOMODIFIED RESORCINARENE LIGANDS
751
О-Octa(dimethylcarbamoyl)(tetranonyl)calix[4]-
(C4h), 151.77 (С4v), 186.29 (C=S), 186.67 (C=S). 13С
NMR spectrum (DMSO-d6), δС, ppm: 34.48 (СН2),
36.27 (СН2), 36.97 (С1), 38.77 (NCH3), 43.34 (NCH3),
119.41 (C5), 126.08 (PH), 127.00 (С3), 128.61 (PH),
128.81 (PH), 141.87 (C2); 148.63 (C4), 186.26 (C=S).
1
resorcinarene (IIIf). Н NMR spectrum (DMSO-d6),
δ, ppm: 0.84 t [12Н, CH2(CH2)7CH3, 3JHH 6.9 Hz], 1.22
m [56Н, CH2(CH2)7CH3], 2.00 m [8Н, CH2(CH2)7CH3],
3
2.88 br.s (48Н, NCH3), 4.17 t (2Н, Н1, JHH 7.4 Hz),
3
4.22 t (2Н, Н1, JHH 7.6 Hz), 6.15 s (4Н, Н3), 7.12 s
О-Octa(dimethylthiocarbamoyl)(tetrapropyl)-
calix[4]resorcinarene (IVc). 1Н NMR spectrum
(DMSO-d6), δ, ppm: 0.80 br.s (12Н, СН2СН2СН3),
1.20 br.s (8Н, СН2СН2СН3), 1.83 br.s (8Н,
СН2СН2СН3), 2.46 s (24H, NCH3), 2.89 s (24H,
NCH3), 4.19 br.t (4Н, H1), 6.27 br.s (2H, H3h), 6.56
br.s (2H, H5v), 6.84 br.s (2H, H5h), 7.42 br.s (2Н, H3v).
13С NMR spectrum (DMSO-d6), δС, ppm: 14.03 (СН3),
20.77 (CH2СН3), 20.93 (СНCH2), 32.20 (С1); 38.61,
39.86, 40.28, 40.49 (NCH3); 118.26 (C5), 126.49 (С3),
132.10 (С2), 153.79 (С4), 185.90 (C=S), 186.16 (C=S).
(4Н, Н5). 13С NMR spectrum (DMSO-d6), δС, ppm:
14.40 (СН3), 22.90 (СН2), 21.18 (CH2), 33.09 (С1),
36.10 (NCH3), 36.75 (NCH3), 102.92 (C5), 123.72
(С2), 125.48 (С3), 152.11 (С4), 154.28 (C=O).
Thiocarbamoylation of resorcinarenes I. N,N-
Dimethylthiocarbamoyl chloride (9.6 mmol) was
added to suspension of the corresponding compound I
(0.8 mmol) and cesium carbonate (9.6 mmol) in 10 mL
of acetone. The reaction mixture was refluxed during
48 h at stirring. Then acetone was distilled off, and
10 mL of 5% sulfuric acid was added to the residue.
The precipitate was filtered off, washed with water
(60 mL) and hexane (20 mL), and dried during 5 h at
80–90°C (1 mmHg).
Triflate derivatives of resorcinarenes I. Tri-
fluoromethylsulfonic acid anhydride (2.8 mmol) was
added dropwise to a solution of 0.3 mmol of the
corresponding compound I in 3 mL of pyridine at
cooling to 0°С. The reaction mixture was maintained
during 24 h at room temperature, and then 20 mL of
water was added. The formed precipitate was filtered
off, washed with 5% hydrochloric acid (20 mL) and
with water till neutral reaction, and with hexane
(20 mL). The precipitate was dried at 80–90°С
(1 mmHg).
О-Octa(dimethylthiocarbamoyl)(tetramethyl)-
calix[4]resorcinarene (IVa). IR spectrum (nujol), ν,
1
cm–1: 1173.4 (C=S), 1135.6 (C=S). Н NMR spectrum
(CDCl3, 25°C), δ, ppm: 1.56 d (12Н, СН3,3JHH 6.9 Hz);
2.95 s, 3.23 s, 3.35 s, 3.44 s (12H each, NCH3); 4.35 q
3
(4H, Н1, JHH 7.3 Hz), 6.47 s (2Н, Н3h), 6.89 s (2Н,
Н5v), 7.25 s (2Н, Н5h), 7.47 s (2Н, Н3v). 13С NMR
spectrum (CDCl3), δС, ppm: 21.45 (СН3), 32.17 (С1);
38.42, 39.36, 42.98, 43.52 (NCH3); 119.43 (C5h, C5v),
126.18 (С3h), 126.79 (С3v), 132.63 (C2v), 136.50 (C2h),
148.61 (С4h); 150.55 (С4v), 186.30 (C=S), 187.09
(C=S).
О-Octa(trifluoromethylsulfonyl)(tetranaphth-1-
yl)calix[4]resorcinarene (Va). 1Н NMR spectrum
(CDCl3), δ, ppm: 5.80 s (2H, H3h), 6.29 d (4H, H2-
3
Napht, JHH 6.9 Hz), 6.35 s (2H, H3v), 6.59 s (4H, Н1),
3
3
6.98 d.d (8H, H3-Napht, H7-Napht, JHH 7.3, JHH
7.7 Hz), 7.21 d (4H, H8-Napht, JHH 8.3 Hz), 7.25 d.d
3
О-Octa(dimethylthiocarbamoyl)[tetra(2-phenyl-
ethyl)]calix[4]resorcinarene (IVb). IR spectrum
(nujol), ν, cm–1: 1170.6 (C=S), 1128.8 (C=S). 1Н NMR
spectrum (CDCl3), δ, ppm: 2.31 m (8Н, СН2СН2Ph,
(4H, H6-Napht, 3JHH 7.4, 3JHH 6.8 Hz), 7.61 d (4H, H4-
Napht, JHH 8.3Hz), 7.63 s (2H, H5h), 7.65 d (4H, H5-
3
Napht, JHH 8.2 Hz), 7.88 s (2H, H5v). 13С NMR
3
spectrum (acetone-d6), δС, ppm: 38.74 (С1), 102.57
3
3
3JНН 6.9, JНН 7.3 Hz), 2.57 m (4Н, СН2СН2Ph, JНН
(C5), 122.55 q (CF, JСF 308.6 Hz), 124.08 (CNaphtH),
3
3
7.8 Hz), 2.75 m (4Н, СН2СН2Ph, JНН 6.4 Hz); 2.92 s,
3.05 s, 3.18 s, 3.31 s (12Н, NCH3); 4.24 t (4Н, H1, 3JHH
6.4 Hz), 6.61 s (2Н, Н3h), 6.65 s (2Н, Н5v), 6.80 s (2Н,
124.25 (CNaphtH), 124.41 (CNaphtH), 124.47 (CNaphtH),
124.63 (СNaphtH), 125.13 (CNaphtH), 126.01 (CNaphtH),
128.20 (C2h), 128.37 (C2v), 131.67 (С3, CNaphtH),
133.50 (С3, CNaphtH), 141.25 (CNaphtH), 152.70 (С4h),
153.64 (С4v). 19F NMR spectrum (acetone-d6), δF, ppm:
–74.49, –75.35.
Н5h), 7.06–7.15 m (20Н, PH) 7.59 s (2Н, H3v). Н
1
NMR spectrum (DMSO-d6), δС, ppm: 2.46 m (8Н,
СН2СН2PH), 2.95 m (8Н, СН2СН2PH), 3.21 s (24Н,
3
NCH3), 3.30 s (24Н, NCH3), 4.25 t (4Н, H1, JHH
6.4 Hz), 7.00 m (10Н, Ph, Н3h), 7.11 s (16Н, Ph, Н5v).
13С NMR spectrum (CDCl3, δС, ppm: 34.19
(СН2СН2PH), 36.27 (СН2СН2PH), 36.54 (С1); 38.61,
39.36, 42.92, 43.42 s (NCH3); 119.47 (C5h), 120.63
(C5v), 125.61 (PH), 127.32 (С3h), 128.68 (PH), 129.10
(PH), 129.82 (C3v), 135.22 (C2v), 141.59 (C2h); 148.63
О-Octa(trifluoromethylsulfonyl)(tetramethyl)-
calix[4]resorcinarene (Vb). 1Н NMR spectrum
3
(acetone-d6), δ, ppm: 1.79 d (12H, СH3, JHH 6.9 Hz),
3
4.79 q (4H, СH, JHH 6.9 Hz), 6.77 s (2H, H3h), 7.14 s
(2H, H5v), 7.47 s (2H, H5h), 7.66 s (2H, H3v). 13С NMR
spectrum (acetone-d6), δС, ppm: 19.24 (СН3), 32.39
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014

752
SERKOVA et al.
3
(С1), 114.52 (C5), 118.50 q (CF, JСF 319.2 Hz),
129.33 (C2), 129.59 (С3), 145.66 (C4). 19F NMR
spectrum (acetone-d6), δF, ppm: –73.71, –74.17.
Complex VIIb was prepared similarly via inter-
action of 0.046 mmol of IVb and 0.18 mmol of the
corresponding palladium salt (methods a and b).
О-Octa(trifluoromethylsulfonyl)(tetrapropyl)-
Complex VIII was prepared similarly to VIa via
interaction of 0.003 mmol of IIIc with 0.012 mmol of
the corresponding palladium salt (methods a and b).
calix[4]resorcinarene (Vc). 1Н NMR spectrum
3
(acetone-d6), δ, ppm: 0.99 t (12Н, СН2СН2СН3, JНН
6.9 Hz), 1.41 m (8Н, СН2СН2СН3), 2.02 m (8Н,
ACKNOWLEDGMENTS
3
СН2СН2СН3), 4.57 t (4Н, СН, JHH 7.4 Hz), 8.04 s
(4H, H5), 8.89 s (4Н, H3). 13С NMR spectrum
(acetone-d6), δС, ppm: 13.27 (СН3), 20.84 (СН2), 35.75
This work was financially supported by the Russian
Foundation for Basic Research (project no. 12-03-00213a).
3
(СН2), 37.38 (С1), 114.57 (C5), 118.39 q (CF, JСF
REFERENCES
320.2 Hz), 129.86 (C2), 135.16 (С3), 146.07 (C4). 19F
NMR spectrum (acetone-d6): δF –74.08 ppm
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 4 2014