Synthesis and supramolecular assemblies of tripodal 1,3,5- tris(phenoxymethyl)-2,4,6-triethylbenzene analogues

Article abstract of DOI:10.1002/cjoc.201180271

Tripodal 1,3,5-tris(phenoxymethyl)-2,4,6-triethylbenzene analogues have been synthesized and structurally characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and HRMS, and additionally, the single crystal structures of compounds bea

Full text of DOI:10.1002/cjoc.201180271

FULL PAPER
Synthesis and Supramolecular Assemblies of Tripodal
1,3,5-Tris(phenoxymethyl)-2,4,6-triethylbenzene Analogues
Ma, Minglianga(马明亮)
Jin, Haishana(金海善)
Kong, Lingweia(孔凌微)
Zhao, Xiaolib(赵小莉)
Li, Xiaoyana(李晓燕)
Wen, Ke*,a(文轲)
a Division of Supramolecular Chemistry and Medicinal Chemistry, Key Laboratory of Brain Functional Genomics,
MOE & STCSM, Shanghai Institute of Brain Functional Genomics,
East China Normal University, Shanghai 200062, China
b Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai 200062, China
Tripodal 1,3,5-tris(phenoxymethyl)-2,4,6-triethylbenzene analogues have been synthesized and structurally
characterized by IR, 1H NMR and 13C NMR spectroscopy and HRMS, and additionally, the single crystal structures
of compounds bearing ortho- (7), meta- (9) and para-hydroxymethyl (11) functions have been determined by X-ray
diffraction analysis. The structural study revealed that compounds 7, 9, and 11 do not adopt the expected
1,3,5-alternate conformation in the solid state. The packing diagrams of compounds 7, 9, and 11 revealed that six
hydrophilic hydroxymethyl groups from six individual molecules (7, 9 and 11) were arranged in close contact via
intermolecular hydrogen-bond interactions. For compounds 7 and 9, the six hydroxyl groups formed a distorted
hexagonal ring; however, formation of such a hexagonal ring was not clear in the case of compound 11. Compounds
9 and 11 were found to form hydrophobic cavities via intermolecular hydrogen-bond interactions in the solid state,
and the cavities were occupied by two ethyl groups from the two cavity-forming molecules.
Keywords 1,3,5-tris(phenoxymethyl)-2,4,6-triethylbenzene, conformation analysis, hydrogen bond, crystal structure
Introduction
not possess the expected up-down alternate arrangement,
only two functional arms of the scaffold lie on one side
of the central benzene ring, while the third functional
group together with the three ethyl groups locate on the
opposite side of the central benzene plane.14 1,3,5-Tris-
(phenoxymethyl)-2,4,6-triethylbenzene derivatives, have
not been structurally characterized previously, and the
conformation of these class of molecules remains un-
clear. Herein, we wish to report our results on the syn-
thesis, conformation analysis of several new 1,3,5-tris-
(phenoxymethyl)-2,4,6-triethylbenzene derivatives. Sin-
gle crystal structure studies revealed that compounds
with hydroxymethyl functions in ortho- (7), meta- (9),
and para- (11) positions of the 1,3,5-phenolic substitu-
ents do not adopt the expected up-down alternate con-
formation, but with their two functional arms residing
on one side of the central benzene plane, and the third
functional arm, together with the three ethyl groups,
residing on the opposite side of the central benzene ring.
The principle in designing supramolecular assem-
blies is to align functional groups of a respective mo-
lecular motif via specific interactions to achieve a tar-
geted structure.1 Molecules possess special topologies
are particular attractive in this prospective, such as
cyclodextron,2 calixarenes,3 and fused (aromatic) rings.4
Due to the steric gearing, the three functional substitu-
ents of 1,3,5-functinonalized triethylbenzene, prepared
from 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene,5 are
often disposed on the same side of the central phenyl
plane, while the three ethyl groups are positioned on the
opposite side of the central benzene ring, thus forming
an alternating up-down geometrical pattern. This struc-
tural motif provides an ideal molecular platform in
studying supramolecular systems,6 and it has been ex-
ploited by many researchers in achieving conforma-
tional control via its preorganized geometry. Examples
include the cr＋eation of a catechol-containing tripodal
ligand for Fe3 chelation as the mimic of the natural
ligand (enderobaction),7 scaffolds for assembling supra-
Results and discussion
＋
molecular structures via their coordination with Pd2 ,
2＋
2＋
2＋
Synthesis
Co , Cu , and Cd ,8-10 and molecular hosts for
cations,11 anions9b,12 and neutral13 guests. However, in
some case, the 1,3,5-functionalized triethylbenzenes do
The tripodal tris(phenoxymethyl)-2,4,6-triethylbenzene
species were synthesized by the reaction of 1,3,5-tris-
*
E-mail: kwen@brain.ecnu.edu.cn; Tel.: 0086-021-62237102; Fax: 0086-021-62601953
Received November 10, 2009; revised February 25, 2011; accepted March 27, 2011.
Project supported by the Shanghai Commission for Science and Technology (Nos. 06Pj14034, 06DZ19002), Ministry of Education (No. 106078).
Chin. J. Chem. 2011, 29, 1503— 1510
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1503

Ma et al.
FULL PAPER
(bromomethyl)-2,4,6-triethylbenzene 1 (obtained from
triethylbenzene according to literature procedure)5 with
appropriate phenols in DMF under basic condition, as
shown in Scheme 1. Compounds (2 and 3) with free
phenols on the phenolic substituents were synthesized by
employing large access of the corresponding di-phenols,
and compounds 2 and 3 were obtained in the yields of
44.7% and 74.3%, respectively (see experimental section).
Compounds 4, 5, 6, 8 and 10 were obtained with the
yields ranging from 60.2% to 84.6%. Compounds 7, 9,
and 11 bearing hydroxymethyl functions on the phenolic
substituents were obtained in high yields (＞88%) via
NaBH4 reduction of the corresponding aldehyde groups
of compounds 6, 8 and 10. Single crystals of 7, 9, and 11
suitable for X-ray diffraction studies were grown in
EtOAc and n-hexane. Two step reaction sequences were
employed in the synthesis of compound 13 (with each
phenolic substituent bearing two hydroxyl groups).
Compound 12 was first generated by the reaction of
compound 1 and 5-hydroxy-1,3-phenylene diacetate,15
followed by direct hydrolysis, compound 13 was ob-
tained in a combined yield of 31.7% (Scheme 2). At-
tempts to grow single crystals of compound 13 failed.
13
All compounds were characterized by IR, 1H NMR, C
NMR and HRMS. The 1H and 13C NMR spectra of these
molecules are in accord with the presence of high levels
of symmetry (see experimental section).
Solid state structure analysis
As shown in Figure 1, the crystal structure of com-
pound 7 reveals that it does not adopt the expected
1,3,5-alternate conformation in the solid state. Instead,
compound 7 adopts a highly unsymmetrical conformation
with two out of its three o-phenolic substituents residing
on one side of the central benzene ring, and the third
o-phenolic substituent, together with the three ethyl
groups, locating on the opposite side of the central ben-
zene plane. Thus, no molecular pocket is formed by the
Scheme 1 General synthesis of tripodal 1,3,5-tris(phenoxymethyl)-2,4,6-triethyl-benzene analogues
Scheme 2 Synthesis of compound 13
1504
www.cjc.wiley-vch.de
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1503— 1510

Supramolecular Assemblies of Tripodal 1,3,5-Tris(phenoxymethyl)-2,4,6-triethylbenzene Analogues
dOH… from 1.902 Å to 2.021 Å, and θ
angles
O—H…OH
OH
varied from 150.6° to 175.6°), resulting in the formation
of a distorted hexagonal ring. No solvent molecules
were found trapped in the crystal lattice.
As shown in Figure 3, compounds 9 and 11 adopt a
similar conformation to that of 7 with two out of the
three phenolic substituents (meta-hydroxymethyl sub-
stituted for 9 and para-hydroxymethyl substituted for 11)
residing on one side of the central benzene rings, and the
third phenolic substituent, together with the three ethyl
groups, residing on the opposite side of the benzene
plane. No intramolecular hydrogen-bond interactions
exist between the hydroxyl groups in both compounds 9
and 11, and no expected molecular cavities were formed
by the three phenolic substituents in the solid state. As
shown in Figure 4a, a cavity-like supramolecular struc-
ture was formed by two molecules of 9 via intermolecu-
lar hydrogen-bond interactions between two pairs of
hydroxymethyl groups (dO…O＝2.690 Å, dOH…OH＝1.888
Figure 1 Molecular structure of compound 7.
three o-phenolic substituents through intramolecular
hydrogen-bond interactions between the three hydroxy-
methyl groups (Figure 1). As shown in Figure 2a, two
molecules of 7 stacked together via intermolecular hy-
drogen-bond interactions between two pairs of hydroxyl
groups (dO…O＝2.788 Å, dOH…OH＝1.970 Å, θ
＝
O—H…OH
Å, θ
OH＝165.4°). The cavity is filled by two ethyl
O—H…
175.6°) and offset face-to-face π-π stack interactions
between the two central benzene rings (3.470 Å). The
three ethyl groups in each molecule (7) are directed
away from the center of the molecular stack. As shown
in Figure 2b, six hydroxymethyl groups from six indi-
vidual molecules are in close contacts via intermolecular
hydrogen bonds (dO…O ranged from 2.709 Å to 2.788 Å,
groups from the two cavity-forming molecules. The
third hydroxymethyl group in 9 is directed away from
the center of this cavity. For the two cavity-forming
molecules (9), the two central benzene rings are ar-
ranged in parallel, while two pairs of m-hydroxymethyl
substituted phenolic rings are arranged in a face-to-face
manner. Similar to compound 7, six hydroxyl groups
from six individual molecules (9) are in close contact
via the interaction of intermolecular hydrogen bonds
(dO… ranged from 2.690 Å to 2.738 Å, dOH… from
O
OH
1.888 Å to 1.923 Å, and θ
angles varied from
O—H…OH
165.4° to 172.8°), resulting in the formation of a dis-
torted hexagonal ring (Figure 4b). No solvent molecules
were found trapped in the crystal lattice.
Figure 2 Molecular stacks (a) and hydrophilic hexagonal ring
(b) formed by compound 7.
Figure 3 Molecular structures of 9 (a) and 11 (b).
Chin. J. Chem. 2011, 29, 1503— 1510
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1505

Ma et al.
FULL PAPER
zene derivatives bearing hydroxymethyl functions on
ortho- (7), meta- (9), and para- (11) positions of the
phenolic substituents revealed that they all do not adopt
the expected up-down alternating conformation in the
solid state, but a conformation with two out of the three
phenolic substituents residing on one side of the central
benzene ring and the third phenolic substituent, together
with the three ethyl groups, residing on the opposite side
of the central benzene plane. The packing diagrams re-
vealed the formation of supramolecular assemblies by
these compounds via intermolecular hydrogen-bond
interactions, as well as π-π stacking interaction (7).
Compounds 9 and 11 were found to form cavity-like
supramolecular structures in the solid state, and such
cavities, in the case of compound 11, could form a
one-dimensional supramolecular polymer via the link-
age of individual cavities by hydrogen bonds, and these
cavities were found filled by two ethyl groups from the
two cavity-forming molecules.
Experimental
General methods
DMF was dried before use, other solvents and re-
agents for synthesis were commercially available and
used as received. Chemical reactions were performed in
oven-dried glassware under an atmosphere of nitrogen.
Classic column chromatography was performed using
1
Merck 60 (70—230 mesh) silica gel. H and 13C NMR
Figure 4 Hydrophobic cage (a) and hydrophilic hexagonal ring
(b) formed by compound 9 in the solid state.
spectra were recorded at Bruker Avance 500 spec-
trometer in DMSO-d6 or CDCl3. Chemical shifts are
versus tetramethylsilane. Mass spectra were recorded on
a Bruker micrOTOF-Q spectrometer (LC/MS). Single
crystal X-ray diffraction data were collected on a Bruker
SMART APEX 2 X-ray diffractometer equipped with a
normal focus Mo-target X-ray tube (λ＝0.71073 Å).
Figure 5a shows the formation of a one-dimensional
supramolecular polymer by compound 11 in the solid
state via intermolecular hydrogen-bond interactions be-
tween hydroxyl groups (dO… O＝2.844 and 2.868 Å,
dOH…OH＝1.819 and 2.148 Å, θ
OH＝124.5° and
O—H…
146.4°). In the supramolecular polymer, two different
types of ring structures were formed and lined alter-
nately along the polymeric chain, and both rings are
filled by two ethyl groups from the two cavity-forming
molecules of 11. The packing diagram shows that six
hydroxymethyl functions from six individual molecules
of 11 are grouped together via intermolecular hydrogen
bond interactions (dO…O ranged from 2.669 Å to 2.868 Å,
General procedure for synthesis of compounds 2 and
3
Potassium carbonate (37.3 g, 270 mmol) and
diphenol (210.0 mmol) were dissolved in DMF (150 mL)
and the mixture was slowly heated to 50 ℃. A solution
of compound 1 (6.0 g, 14.0 mmol) in DMF (50 mL) was
then added dropwise in 1 h, and the reaction was
monitored by TLC until completion. The reaction
mixture was poured into ice water (400 mL) and
extracted by EtOAc (200 mL × 3). The combined
organic layer was washed with brine and dried over
MgSO4. The solvent was evaporated and the crude
products were purified by re-crystallization in PE/EA to
afford the pure products.
1,3,5-Tri[(4-hydroxyphenoxy)methyl]-2,4,6-triethyl-
benzene (2) White solid, yield 44.7%. m.p. 186.3—
187.4 ℃; 1H NMR (DMSO-d6) δ: 8.92 (s, 3H), 6.89 (d,
J＝9.0 Hz, 6H), 6.70 (d, J＝7.5 Hz, 6H), 4.94 (s, 6H),
2.70—2.75 (m, 6H), 1.13—1.18 (m, 9H); 13C NMR
(DMSO-d6) δ: 151.58, 151.45, 145.13, 131.07, 115.80,
115.34, 64.53, 22.37, 16.27; IR (KBr) ν: 3421, 3373,
dOH… from 1.997 Å to 2.000 Å, and θ
angles
O—H…OH
OH
varied from 158.4° to 179.1°), however, there is no clear
hexagonal ring formed as of those found for compounds
7 and 9 (Figure 5b). No solvent molecules were found
trapped in the crystal lattice.
Conclusions
Twelve tripodal 1,3,5-tris(phenoxymethyl)-2,4,6-
triethylbenzene derivatives have been synthesized and
1
structurally characterized. H and 13C NMR spectra of
these molecules are in accord with the presence of high
levels of symmetry. Single crystal X-ray diffraction
studies of 1,3,5-tris(phenoxymethyl)-2,4,6-triethylben-
1506
www.cjc.wiley-vch.de
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1503— 1510

Supramolecular Assemblies of Tripodal 1,3,5-Tris(phenoxymethyl)-2,4,6-triethylbenzene Analogues
Figure 5 Hydrophobic cages (a) and clustered six hydrophilic hydroxymethyls (b) formed by compound 11 in the solid state.
3031, 2964, 1705, 1632, 1605, 1571, 1508, 1455, 1371,
substituted phenol (49.6 mmol) were dissolved in DMF
(150 mL) and the mixture was slowly heated to 50 ℃.
A solution of compound 1 (6.0 g, 14.0 mmol) in DMF
(50 mL) was then added dropwise and the reaction was
monitored by TLC until completion. The reaction
mixture was poured into ice water (400 mL) and
extracted by EtOAc (200 mL × 3). The combined
organic layer was washed with brine and dried over
MgSO4. The solvent was evaporated under reduced
pressure to provide a white solid, and the crude products
were purified by recrystallization in petroleum ether/
ethyl acetate to afford the pure products.
1,3,5-Tri((4-tert-butylphenoxy)methyl)-2,4,6-trie-
thylbenzene (4) White solid, yield 67.7%. m.p. 207.2—
209.5 ℃; 1H NMR (CDCl3) δ: 7.35 (dd, J＝2.0, 9.0 Hz,
6H), 6.98 (dd, J＝2.0, 9.0 Hz, 6H), 5.06 (s, 6H), 2.81—
2.84 (m, 6H), 1.32 (s, 27H), 1.22—1.26 (m, 9H); 13C
NMR (CDCl3) δ: 156.68, 146.12, 143.54, 131.16,
126.27, 113.94, 63.97, 34.09, 31.53, 22.93, 16.51; IR
(KBr) ν: 3047, 2960, 2903, 2870, 2363, 1874, 1743,
－1
1295, 1219, 1103, 1048, 996, 828, 793, 761, 614 cm .
HRMS calcd for C33H36O6Na＋ [M＋Na＋] 551.2404,
found 551.2392.
1,3,5-Tri((4-(2-(4hydroxyphenyl)propan-2-yl)phen-
oxy)methyl)-2,4,6-triethylbenzene (3) White solid,
1
yield 74.3%. m.p. 90.1—90.4 ℃; H NMR (CDCl3) δ:
7.17 (d, J＝8.7 Hz, 6H), 7.13 (d, J＝8.6 Hz, 6H), 6.92 (d,
J＝8.7 Hz, 6H), 6.74 (d, J＝8.6 Hz, 6H), 5.04 (s, 6H),
4.66 (s, 3H), 2.80—2.84 (m, 6H), 1.65 (s, 18H), 1.21—
1.28 (m, 9H); 13C NMR (DMSO-d6) δ: 156.27, 154.98,
145.39, 143.17, 140.69, 130.84, 127.49, 127.31, 114.62,
113.69, 63.86, 41.06, 30.80, 22.40, 16.28; IR (KBr) ν:
3502, 3430, 3030, 2967, 2874, 2364, 1879, 1723, 1608,
1509, 1458, 1368, 1294, 1230, 1180, 1106, 1047, 1010,
＋
－1
831, 561 cm . HRMS calcd for C60H66O6Na [M＋
Na＋] 905.4752, found 905.4734.
General procedure for synthesis of 4, 5, 6, 8 and 10
Potassium carbonate (18.6 g, 134.4 mmol) and
Chin. J. Chem. 2011, 29, 1503— 1510
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1507

Ma et al.
FULL PAPER
1608, 1579, 1510, 1476, 1366, 1294, 1236, 1182, 1118,
reaction mixture was then heated at 50 ℃ for an
additional 30 min. After the completion of the reaction
(monitored by TLC), MeOH was removed under
reduced pressure. The residue was extracted by EtOAc
(200 mL×3) and the combined organic layer was
washed with water, dried over MgSO4. The organic
layer was filtered and concentrated under reduced
pressure. The crude products were purified by silica gel
chromatography eluted with PE ∶ EtOAc ＝ 9 ∶ 1
(Volune ratio) to afford the pure product 7 (9 or 11).
Single crystals of compound 7 (9 or 11) were obtained
by dissolving compound 7 (9 or 11, 10 mg) in EtOAc (3
mL), and n-hexane (5 mL) was then added slowly on
top of EtOAc solution to form a clear interface. The
setup was kept at room temperature in dark environment
in two weeks, and single crystals suitable for X-ray
analysis were grown.
－1
1048, 1014, 999, 863, 826, 770, 67＋7, 552 cm . HRMS
calcd for C45H60O3Na＋ [M＋Na ] 671.4434, found
671.4415.
1,3,5-Tri((3-formyl-4-hydroxyphenoxy)methyl)-
2,4,6-triethylbenzene (5) White solid, yield 60.2%.
1
m.p. 186.4—188.5 ℃; H NMR (CDCl3) δ: 11.54 (s,
3H), 9.76 (s, 3H), 7.48 (d, J＝10.0 Hz, 3H), 6.61—6.63
(m, 6H), 5.14 (s, 6H), 2.78—2.80 (m, 6H), 1.22—1.27
(m, 9H); 13C NMR (CDCl3) δ: 194.40, 165.79, 164.54,
146.76, 135.34, 130.21, 115.40, 108.85, 101.11, 64.61,
23.05, 16.34; IR (KBr) ν: 2964, 2837, 2361, 1644, 1576,
1502, 1368, 1330, 1291, 1224, 1184, 1166, 1117, 1042,
－1
990, 835, 80＋6, 745, 707, 641, 551 cm . HRMS calcd
for C36H37O9 [M＋H＋] 613.2432, found 613.2452.
1,3,5-Tri((2-formylphenoxy)methyl)-2,4,6-triethyl-
benzene (6) White solid, yield 68.2%. m.p. 178.7—
1
1,3,5-Tri((2-(hydroxymethyl)phenoxy)methyl)-
2,4,6-triethylbenzene (7) White solid, yield 90.1%.
m.p. 161.9—162.9 ℃; 1H NMR (DMSO-d6) δ: 7.41 (d,
J＝7.5 Hz, 3H), 7.26—7.30 (m, 6H), 6.98—7.00 (m,
3H), 5.10 (s, 6H), 4.43 (s, 6H), 2.75—2.80 (m, 6H),
1.16 (t, J＝7.5 Hz, 9H); 13C NMR (DMSO-d6) δ: 155.4,
145.9, 130.9, 130.5, 127.7, 126.9, 120.4, 111.1, 64.2,
57.9, 22.3, 16.3; IR (KBr) ν: 3294, 3066, 2965, 2873,
2286, 1685, 1599, 1490, 1454, 1371, 1287, 1227, 1112,
180.5 ℃; H NMR (CDCl3) δ: 10.42 (s, 3H), 7.88—
7.90 (m, 3H), 7.63—7.66 (m, 3H), 7.25 (d, J＝8.0 Hz,
3H), 7.09—7.12 (m, 3H), 5.23 (s, 6H), 2.85—2.89 (m,
6H), 1.23—1.26 (m, 9H); 13C NMR (CDCl3) δ: 189.50,
161.08, 146.82, 136.03, 130.26, 128.41, 125.09, 121.14,
112.37, 64.74, 23.04, 16.56; IR (KBr) ν: 3427, 2969,
2871, 2760, 2362, 1686, 1598, 1482, 1456, 1396, 1373,
1286, 1229, 1－191, 1162, 1101, 1044, 985, 855, 831, 759,
＋
1
653, 530 cm . HRMS calcd for C36H36O6Na [M＋
Na＋] 587.2404, found 587.2415.
－1
1043, 1001, 755, 7＋04, 680, 575 cm . HRMS calcd for
＋
C36H43O6 [M＋H ] 571.3054, found 571.3059.
1,3,5-Tri((3-formylphenoxy)methyl)-2,4,6-triethyl-
benzene (8) White solid, yield 84.6%. m.p. 161.7—
Crystallographic data for 7 [C72H84O12]; Mr＝
1141.39; triclinic; space group P 1 ; a＝12.9868(4) Å;
b＝13.3224(4) Å; c＝21.4200(6) Å; α＝74.4870(10)°;
1
162.9 ℃; H NMR (CDCl3) δ: 10.04 (s, 3H), 7.60 (s,
3H), 7.51—7.56 (m, 6H), 7.32 (t, J＝5.0 Hz, 3H), 5.20
(s, 6H), 2.88 (q, J＝5.0 Hz, 6H), 1.29 (t, J＝5.0 Hz, 9H);
13C NMR (CDCl3) δ: 192.05, 159.36, 146.42, 137.87,
130.67, 130.18, 124.10, 122.26, 112.08, 64.39, 22.99,
16.40; IR (KBr) ν: 3381, 2970, 2906, 2871, 2831, 2724,
2363, 1698, 1594, 1486, 1448, 1387, 1321, 1289, 1256,
1168, 1147, 1079, 1047, 1010, 985, 839, 7＋98, 680, 65＋0,
β＝76.2150(10)°; γ＝61.7020(10)°; V＝3116.96(16) Å3;
－3
ρ
calcd＝1.216 g•cm ; T＝296(2) K; 36912 independent
measured reflections; F2 refinement; R1＝0.0446; wR2＝
0.1076. These data were deposited in the Cambridge
Crystallographic data centre, CCDC 752636.
1,3,5-Tri((3-(hydroxymethyl)phenoxy)methyl)-
2,4,6-triethylbenzene (9) White solid, yield 89.9%.
m.p. 179.9—180.7 ℃; 1H NMR (DMSO-d6) δ: 7.29—
7.26 (m, 3H), 7.06 (s, 3H), 6.93—6.96 (m, 6H), 5.08 (s,
6H), 4.51 (s, 6H), 2.75 (q, J＝7.0 Hz, 6H), 1.19 (t, J＝
7.0 Hz, 9H); 13C NMR (DMSO-d6) δ: 158.65, 145.42,
144.45, 130.92, 129.26, 118.89, 112.77, 112.21, 63.93,
62.85, 22.46, 16.28; IR (KBr) ν: 3237, 2961, 2906, 2872,
1700, 1595, 1489, 1447, 1372, 1255, 1156, 1010, 986,
－1
574 cm . HRMS calcd for C36H36O6Na [M＋Na ]
587.2404, found 587.2393.
1,3,5-Tri((4-formylphenoxy)methyl)-2,4,6-triethyl-
benzene (10) White solid, yield 68.4%. m.p. 147.5—
150.2 ℃; 1H NMR (CDCl3) δ: 9.92 (s, 3H), 7.91 (d, J＝
8.6 Hz, 6H), 7.15 (d, J＝8.6 Hz, 6H), 5.20 (s, 6H), 2.81
—2.86 (m, 6H), 1.24—1.27 (m, 9H): 13C NMR (CDCl3)
δ: 190.68, 163.68, 146.65, 132.10, 130.47, 130.30,
114.82, 64.49, 23.06, 16.38; IR (KBr) ν: 3237, 3031,
2968, 2874, 2740, 2365, 1691, 1600, 1576, 1507, 1455,
1371, 1307, 1246,－1161, 1106, 1045, 987, 864, 830, 793,
－1
952, 922, 882, 779, 688, 574 cm . HRMS calcd for
＋
C36H43O6 [M＋H＋] 571.3054, found 571.3066.
Crystallographic data for 9 [C36H42O6]; Mr＝
570.70; Triclinic; space group P 1 ; a＝9.6330(2) Å;
b＝12.1626(2) Å; c＝14.1905(3) Å; α＝88.8440(10)°;
＋
1
766, 679, 573 cm . HRMS calcd for C36H37O6 [M＋
H＋] 565.2585, found 565.2606.
β＝78.7670(10)°; γ＝73.5960(10)°; V＝1563.29(5) Å3;
－3
General procedure for synthesis of compounds 7, 9
and 11
ρ
calcd＝1.212 g•cm ; T＝296(2) K; 18521 independent
measured reflections; F2 refinement; R1＝0.0482; wR2＝
0.1278. These data were deposited in the Cambridge
Crystallographic data centre, CCDC 752637.
NaBH4 (250.0 mg, 6.32 mmol, 96%) was added to
methanol in an ice bathed flask potion-wise to generate
a clear solution. Compound 6 (8 or 10) was then added
to the reacion mixture. The mixture was stirred at 5 ℃
for 30 min and warmed to room temperature. The
1,3,5-Tri((4-(hydroxymethyl)phenoxy)methyl)-
2,4,6-triethylbenzene (11) White solid, yield 88.5%.
m.p. 166.2—167.1 ℃; 1H NMR (CDCl3) δ: 7.28 (d, J＝
1508
www.cjc.wiley-vch.de
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1503— 1510

Supramolecular Assemblies of Tripodal 1,3,5-Tris(phenoxymethyl)-2,4,6-triethylbenzene Analogues
8.0 Hz, 6H), 6.97 (d, J＝8.5 Hz, 6H), 5.03 (s, 6H), 4.57
604.
(s, 6H), 2.75—2.80 (m, 6H), 1.73 (s, 3H), 1.16—1.19
3
(a) Gutsche, C. D. Calixarenes, Ed.: Stoddart, J. F., The
(m, 9H); 13C NMR (DMSO-d6) δ: 157.6, 145.3, 134.9,
130.9, 128.0, 114.0, 64.1, 62.6, 22.4, 16.2; IR (KBr) ν:
3239, 2963, 2929, 2873, 2363, 1611, 1584, 1511, 1455,
1372, 1301, 1－236, 1175, 1110, 1045, 999, 861, 835, 767,
Royal Society of Chemistry, Cambridge, 1989.
(b) Gutsche, C. D. Calixarenes Revisited, Ed.: Stoddart, J. F.,
The Royal Society of Chemistry, Cambridge, 1998.
(c) Calixarenes: A Versatile Class of Macrocyclic Compounds,
Eds.: Vicens, J.; Bömer, V., Kluwer, Dordrecht, 1991.
(d) Calixarenes 2001, Eds.: Asfari, Z.; Bömer, V.; Harrow-
field, J.; Vicens, J.; Saadioui, M., Kluwer, Dordrecht, 2001.
(a) Hedge, V.; Madhukar, P.; Madura, J. D.; Thummel, R. P.
J. Am. Chem. Soc. 1990, 112, 4549.
＋
1
679, 573 cm . HRMS calcd for C36H42O6Na [M＋
Na＋] 593.2874, found 593.2859.
Crystallographic data for 11 [C36H42O6]; Mr＝
570.70; monoclinic; space group C2/c; a＝36.0607(12)
Å; b＝9.5663(3) Å; c＝25.2886(8) Å; α＝90°; β＝
131.8380(10)°; γ＝90°; V＝6499.5(4) Å3; ρcalcd＝1.166
4
－3
(b) Hedge, V.; Hung, C.-Y.; Madhukar, P.; Cummingham,
R.; Höpfner, T.; Thummel, R. P. J. Am. Chem. Soc. 1993,
115, 872.
g•cm ; T＝296(2) K; 37189 independent measured
reflections; F2 refinement; R1＝0.0727; wR2＝0.1825.
These data were deposited in the Cambridge Crystallo-
graphic data centre, CCDC 752638.
(c) Bell, T. W.; Hou, Z.; Zimmerman, S. C.; Thiessen, P. A.
Angew. Chem., Int. Ed. 1995, 34, 2163.
The synthesis 1,3,5-tri((3,5-dihydroxyphenoxy)-
methyl)-2,4,6-triethylbenzene (13) To a mixture of
compound 1 (2.1 g, 4.8 mmol) and potassium carbonate
(4.0 g, 28.8 mmol) in DMF (200 mL), 5-hydroxy-1,3-
phenylene diacetate15 (3.3 g, 15.7 mmol) was added and
the reaction was monitored by TLC until completion.
The reaction mixture was poured into ice water (400 mL)
and acidified with 1 mol/L hydrochloride acid to pH of
5—6. The mixture was extracted by CH2Cl2 (300 mL×
3) and the combined organic layer was washed with
brine, dried over MgSO4. The crude product 12 obtained
after filtration and solvent removing was used directly in
next step. The residue 12 was dissolved in 1 mol/L po-
tassium hydroxide methanol solution (100 mL) and
stirred at room temperature overnight. MeOH was re-
moved under reduced pressure and the residue was
extracted by CH2Cl2 (300 mL×3). The combined or-
ganic layer was washed with brine and dried over
MgSO4. After filtration and solvent removing, the crude
product was purified by silica gel chromatography to
afford compound 13 (0.88 g, 31.7%) as a white solid.
(d) Bell, T. W.; Hext, N. M.; Khasanov, A. B. Pure Appl.
Chem. 1998, 70, 2371.
5
(a) Walsdorff, C.; Saak, W.; Pohl, S. J. Chem. Res. (M)
1996, 1601.
(b) Metzger, A.; Lynch, V. M.; Anslyn, E. V. Angew. Chem.,
Int. Ed. Engl. 1997, 36, 862.
6
7
Hennrich, G.; Anslyn, E. V. Chem. Eur. J. 2002, 8, 2218.
(a) Stack, T. D. P.; Hou, Z.; Raymond, K. N. J. Am. Chem.
Soc. 1993, 115, 6466.
(b) Hou, Z.; Stack, T. D. P.; Sunderland, C. J.; Raymond, K.
N. Inorg. Chim. Acta 1997, 263, 341.
(c) Hay, B. P.; Dixon, D. A.; Vargas, A.; Garza, J.; Ray-
mond, K. N. Inorg. Chem. 2001, 40, 3922.
8
9
Hartshorn, C. M.; Steel, P. J. Chem. Commun. 1997, 541.
(a) Ohi, H.; Tachi, Y.; Itoh, S. Inorg. Chem. 2004, 43, 4561.
(b) Amendola, V.; Boiocchi, M.; Colasson, B.; Fabbrizzi, L.;
Monzani, E.; Douton-Rodriguez, M. J.; Spadini, C. Inorg.
Chem. 2008, 47, 4808.
1
10 Al-Rasbi, N. K.; Tidmarsh, I. S.; Argent, S. P.; Adams, H.;
Harding, L. P.; Ward, M. D. J. Am. Chem. Soc. 2008, 130,
11641.
m.p. 191.3—193.3 ℃; H NMR (DMSO-d6) δ: 9.26 (s,
6H), 5.93 (s, 6H), 5.88 (s, 3H), 4.93 (s, 6H), 2.69—2.71
(m, 6H), 1.14—1.17 (m, 9H); 13C NMR (DMSO-d6) δ:
160.47, 159.09, 145.22, 130.89, 95.78, 93.18, 63.71,
22.32, 16.14; IR (KBr) ν: 3382, 2970, 2362, 1607, 1496,
11 (a) Chin, J.; Walsdorff, C.; Stanix, B.; Oh, J.; Chung, H. J.;
Park, S.-M.; Kim, K. Angew. Chem., Int. Ed. 1999, 38, 2756.
(b) Kim, S.-G.; Ahn, K. H. Chem. Eur. J. 2000, 6, 3399.
(c) Jon, S.-Y.; Kim, J.; Kim, M.; Park, S.-H.; Jeon, W. S.;
Heo, J.; Kim, K. Angew. Chem., Int. Ed. 2001, 40, 2116.
(d) Lélias-Vanderperre, A.; Chambron, J.-C.; Espinosa, E.;
Terrier, P.; Leize-Wagner, E. Org. Lett. 2007, 9, 2961.
12 (a) Niikura, K.; Metzger, A.; Anslyn, E. V. J. Am. Chem.
Soc. 1998, 120, 8533.
1372, 13－49, 1261, 1150, 1035, 1009, 950, 825, 781, 680,
＋
572 cm 1. HRMS calcd for C33H37O9 [M＋H＋ ]
577.2432, found 577.2415.
References
1
Lehn, J.-M. Supramolecular Chemistry: Concepts and Per-
spectives, VCH, Weinheim, 1995.
(b) Schmuck, C.; Schwegmann, M. J. Am. Chem. Soc. 2005,
127, 3373.
2
(a) Liu, Y.; Wang, H.; Liang, P.; Zhang, H.-Y. Angew.
Chem., Int. Ed. 2004, 43, 2690.
(c) Amendola, V.; Boiocchi, M.; Colasson, B.; Fabbrizzi, L.;
Douton, M.-J. R.; Ugozzoli, F. Angew. Chem., Int. Ed. 2006,
45, 6920.
(b) Andersson, T.; Westman, G.; Stenhagen, G.; Sundahl,
M.; Wennerström, O. Tetrahedron Lett. 1995, 36, 597.
(c) Yoshida, Z.-I.; Takekuma, H.; Takekuma, S.-I.; Matsubara,
Y. Angew. Chem., Int. Ed. Engl. 1994, 33, 1597.
(d) Turner, D. R.; Paterson, M. J.; Steed, J. W. Chem.
Commun. 2008, 1395.
(d) Anderson, T.; Nilsson, K.; Sundahl, M.; Westman, G.;
Wennerström, O. J. Chem. Soc., Chem. Commun. 1992,
13 (a) Francesconi, O.; Ienco, A.; Moneti, G.; Nativi, C.;
Chin. J. Chem. 2011, 29, 1503— 1510
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1509

Ma et al.
FULL PAPER
Roelens, S. Angew. Chem., Int. Ed. 2006, 45, 6693.
(b) Cacciarini, M.; Cordiano, E.; Nativi, C.; Roelens, S. J.
Org. Chem. 2007, 72, 3933.
14 Belcher, W. J.; Fabre, M.; Farhan, T.; Steed, J. W. Org.
Biomol. Chem. 2006, 4, 781.
15 Hamura, T.; Ibusuki, Y.; Uekusa, H.; Matsumoto, T.; Siegel,
J. S.; Baldridge, K. K.; Suzuki, K. J. Am. Chem. Soc. 2006,
128, 10032.
(c) Nativi, C.; Cacciarini, M.; Francesconi, O.; Moneti, G.;
Roelens, S. Org. Lett. 2007, 9, 4685.
(E0911102 Cheng, F.; Zheng, G.)
1510
www.cjc.wiley-vch.de
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1503— 1510