Novel lariat calix[4]-1,3-aza-crowns with two branched chains-the excellent phase transfer catalysts for nucleophilic substitution reaction

Article abstract of DOI:10.1139/V10-061

By reacting calix[4]-1,3-diethoxylaminoethyl derivative (2) with phenyl isothiocyanate, novel dendritic calix[4]-arene derivative (3) with two different branched chains was synthesized in a yield of 78%. By reacting compound 2 with 1,6-diisocyanatohexane or N,N'-bis(2-chloracetamide)ethylene in a ''1 + 1'' intermolecular addition mode, novel lariat calix[4]-1,3-aza-crowns (4 and 5, respectively) with two branched ethoxyl chains were prepared in reasonable yields. The composition, structures, and conformations of all new compounds were confirmed by elemental analyses, IR, ESI-MS, 1H NMR, and so forth. The liquid-liquid extraction experiments showed that all new hosts possessed good extraction abilities towards soft and hard metal cations. The liquid membrane transport experiments suggested that they had good transport abilities for K+ and Ag+. The experiments of phase transfer catalysis indicated that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimum yields of products in catalytic reaction were as high as approximately 100%.

Full text of DOI:10.1139/V10-061

622
Novel lariat calix[4]-1,3-aza-crowns with two
branched chains — The excellent phase transfer
catalysts for nucleophilic substitution reaction
Fafu Yang, Yanhua Wang, Hongyu Guo, Jianwei Xie, and Zhiqiang Liu
Abstract: By reacting calix[4]-1,3-diethoxylaminoethyl derivative (2) with phenyl isothiocyanate, novel dendritic calix[4]-
arene derivative (3) with two different branched chains was synthesized in a yield of 78%. By reacting compound 2 with
1,6-diisocyanatohexane or N,N’-bis(2-chloracetamide)ethylene in a ‘‘1 + 1’’ intermolecular addition mode, novel lariat
calix[4]-1,3-aza-crowns (4 and 5, respectively) with two branched ethoxyl chains were prepared in reasonable yields. The
composition, structures, and conformations of all new compounds were confirmed by elemental analyses, IR, ESI-MS,
1H NMR, and so forth. The liquid–liquid extraction experiments showed that all new hosts possessed good extraction abil-
ities towards soft and hard metal cations. The liquid membrane transport experiments suggested that they had good trans-
port abilities for K+ and Ag+. The experiments of phase transfer catalysis indicated that they possessed excellent catalytic
properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimum yields of prod-
ucts in catalytic reaction were as high as approximately 100%.
Key words: calix[4]crown, lariat, synthesis, liquid membrane transport, phase transfer catalysis.
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Resume : La reaction du derive 2 du calix[4]-1,3-diethoxylaminoethyle avec l’isothiocyanate d’ethyle a permis de realiser
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la synthese, avec un rendement de 78 %, du nouveau derive dendritique du calix[4]arene portant deux chaınes ramifiees
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differentes. La reaction du compose 2 avec le 1,6-diisocyanatohexane ou le N,N’-bis(2-chloroacetamide)ethylene dans un
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mode d’addition intermoleculaire « 1 + 1 », il est aussi possible de preparer avec des rendements raisonnables de nou-
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veaux ethers lariats, des calix[4]-1,3-azacouronnes (4 et 5) portant des chaınes ramifiees ethoxyles. La composition, les
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structures et les conformations de tous les nouveaux produits ont ete confirmees par analyse elementaire, spectrometrie de
masse avec ionisation par electronebulisation (SM-IEN), RMN du H et autres. Des experiences d’extraction liquide–
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liquide ont montre que toutes les nouvelles molecules hotes possedent de bonnes habilites pour l’extraction des cations me-
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talliques durs et mous. Des experiences de transport dans une membrane liquide suggere qu’elles possedent de bonnes ha-
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bilites pour le transport des ions K et Na . Les experiences en catalyse de transfert de phase indiquent qu’elles possedent
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d’excellentes proprietes catalytiques dans les reactions de substitution nucleophile aromatique et de substitution nucleo-
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phile benzylique. Les rendements optimaux de produits dans les reactions catalytiques vont jusqu’a environ 100 %.
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Mots-cles : calix[4]couronne, lariat, synthese, transport dans une membrane liquide, catalyse par transfert de phase.
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[Traduit par la Redaction]
In the field of crown ethers, it is well-known that the lar-
iat crown ethers with branched chains usually show out-
standing complexation abilities for guest due to the
coordinated recognition of crown ether chains and branched
chains. However, in the field of calixcrowns, although many
calixcrowns were reported, only Bitter and co-workers18,19
and Bond et al.20 reported several lariat calix[4]-aza-crowns
with one amino-branched chain. These lariat calix[4]-aza-
crowns exhibited excellent recognition properties due to the
favorable synergistic complexation18–19 but they were not
concerned with their phase catalytic properties. Thus, it is
interesting to study the syntheses and properties of novel lar-
iat calixcrowns with other functional groups and more
branched chains. In this paper, we report the syntheses of
Introduction
The importance of calixarenes in the family of host mac-
rocycles is now well-established.1–3 Since the first calix-
crown was reported in 1983,4 much research attention had
been paid to the synthesis of calixcrowns and the study of
their molecular and ion recognition to use them in the de-
sign of ion selective electrodes, liquid supported membranes
and catalyst, and so forth.5–7 All kinds of calixcrowns con-
taining only oxygen donor atoms were synthesized and ex-
hibited excellent recognition towards hard metal ions or
some soft metal ions, and calixcrowns containing heteroa-
toms such as aza and sulfur groups usually showed outstand-
ing complexation abilities for soft metal cations.8–17
Received 31 January 2010. Accepted 21 April 2010. Published on the NRC Research Press Web site at canjchem.nrc.ca on 6 June 2010.
F. Yang.1 College of Chemistry and Materials, Fujian Normal University, Fuzhou 350007, P.R. China; Fujian Key Laboratory of
Polymer Materials, Fuzhou 350007, P.R. China.
Y. Wang, H. Guo, J. Xie, and Z. Liu. College of Chemistry and Materials, Fujian Normal University, Fuzhou 350007, P.R. China.
1Corresponding author (e-mail: yangfafu@fjnu.edu.cn).
Can. J. Chem. 88: 622–627 (2010)
doi:10.1139/V10-061
Published by NRC Research Press

Yang et al.
623
Scheme 1. Synthetic routes for compounds 2, 3, 4, and 5.
two novel lariat calix[4]-1,3-aza-crowns with two branched
ethoxyl chains and a novel dendritic calix[4]arene derivative
with two different branched chains. Also, their interesting
properties of metal ion extraction, liquid membrane trans-
port, and phase transfer catalysis were studied.
this condensation reaction, no catalyst, such as KI, was added
to avoid the reaction of N,N’-bis(2-chloracetamide)ethylene
with the phenolic hydroxyl groups of compound 2. Moreover,
to test the reaction activity of phenolic hydroxyl groups of
compound 2 in this reaction, compound 1 was refluxed with
N,N’-bis(2-chloracetamide)ethylene with the same reaction
conditions, but no materials took part in the reaction in 72 h
(if KI was added, materials took part in reaction). This result
certainly suggested that it was not the phenolic hydroxyl
groups but the amino groups of compound 2 taking part in
the condensation reaction as showed in Scheme 1. To the
best of our knowledge, compound 3 was the novel dendritic
calix[4]arene derivative with two different branched chains,
and compounds 4 and 5 were the first examples of lariat
calix[4]-1,3-aza-crowns with two branched ethoxyl chains.
All new compounds were tested by elemental analyses,
Results and discussion
Syntheses and characterization of products
The synthetic routes are shown in Scheme 1. 1,3-Broethoxyl-
calix[4]arene (1) was prepared according to the published
procedures.21 By refluxing compound 1 with excess ethanol-
amine (molar ratio = 1:10) in K2CO3/MeCN for 48 h, the
calix[4]-1,3-diethoxylaminoethyl derivative (2) was obtained
in a yield of 73% after recrystallization in CH3OH/H2O. By
further reacting compound 2 with phenyl isothiocyanate
under room temperature, novel dendritic calix[4]arene deriva-
tive (3) with two different branched chains was obtained in a
yield of 78% after recrystallization in CHCl3/petroleum ether
(60*90 8C). On the other hand, by refluxing compound 2
with 1,6-diisocyanatohexane in high diluted CHCl3 solution
over night, novel lariat calix[4]-1,3-aza-crown (4) with two
branched ethoxyl chains was prepared with a yield of 62%
in a ‘‘1 + 1’’ addition mode after recrystallization in CHCl3/
petroleum ether (60*90 8C). Also, by refluxing compound 2
with N,N’-bis(2-chloracetamide)ethylene in K2CO3/MeCN for
72 h, novel lariat calix[4]-1,3-aza-crown (5) with two
branched ethoxyl chains was obtained in a yield of 42% in a
‘‘1 + 1’’ condensation mode after column chromatography. In
1
IR, ESI-MS, and H NMR spectra. The ESI-MS spectra of
compounds 2, 3, 4, and 5 clearly showed molecular ion
peaks (M+, MH+, or MNa+) at 824.0, 1116.0, 990.3, and
1
985.8, respectively. In the H NMR spectra, all of the com-
pounds showed two singlets (1:1) for the tert-butyl groups
and one pair of doublets (1:1) for the methylene bridges of
1
the calix[4]arene skeleton. Comparing with the similar H
NMR spectra of the other calix[4]arene 1,3-bisubstituted or
1,3-bridged derivatives in cone conformation,8–11 all these
1H NMR spectra data of the new compounds 2–5 were in
accordance with the assigned structures and indicated that
the calix[4]arene units adopted cone conformation as shown
in Scheme1.
Published by NRC Research Press

624
Can. J. Chem. Vol. 88, 2010
Liquid–liquid extraction for metal cations
Fig. 1. Percentage extraction (%) of 2, 3, 4, and 5 towards picrate
salts.
The complexation abilities of compounds 2, 3, 4, and 5
towards a series of metal cations were studied by two-phase
extraction experiments (H2O/CHCl3) of metal cation picrate
salts. The results were summarized in Fig. 1. Compounds 2,
3, 4, and 5 exhibited good extraction abilities for both soft
and hard metal cations. These results were in accordance
with the ‘‘soft and hard acids and bases’’ concept, i.e.,
amino groups and hydroxyl groups were favorable for bind-
ing soft and hard metal cations, respectively. It is worthy to
note that the extraction percentage of compound 2 for Zn2+
and Hg2+ were as high as 100%. On the other hand, hosts 4
and 5 showed lower extraction percentages but higher
extraction selectivities than that of hosts 2 and 3. For exam-
ple, the extraction selectivity of host 4 for Hg2+/Ag+ was
6.75 (extraction percentage of Hg2+/extraction percentage of
Ag+ = 50.6/7.5). These extraction results might suggest that
the crown structures of compounds 4 and 5 were more fa-
vorable for producing the complexation selectivity than that
of the open-chain structures of compounds 2 and 3.
complexing abilities and then higher speeds of liquid mem-
brane transport than that of 2 and 3.
Liquid membrane transport for K+, Zn2+, and Ag+
To investigate the potential application of new hosts 2, 3,
4, and 5, they were studied by liquid membrane transport
experiments. Based on the extraction experiments, the K+,
Zn2+, and Ag+ were chosen as representative usual metal
cations of hard and soft cations, and representative extrac-
tion abilities with variational extraction percentages (from
10% to 100%) in extraction experiments. The fluorinion
was chosen as the anion of these metal salts because F–
plays an important role in the nucleophilic substitution reac-
tion of preparing fluorine compounds. The transport results
were summarized in Table 1. It could be seen that the salt
concentration in the receiving phase increased with prolong-
ing the running times. It was interesting that hosts 2, 3, 4,
and 5 possessed transport abilities for cations in the similar
order of K+ & Ag+ > Zn2+. For example, in compound 5,
the salts concentrations in the receiving phase of K+ and
Ag+ in 20 h were 8.9 Â 10–3 mol/L and 7.8 Â 10–3 mol/L,
respectively. However, the salt concentration of Zn2+ was as
low as 4.3 Â 10–3 mol/L under the same transport condi-
tions. On the other hand, hosts 4 and 5 showed far higher
transport amounts than that of hosts 2 and 3 in the running
times over 20 h. For example, the concentrations of K+ in
the receiving phase using hosts 4 and 5 as carriers in 20 h
were 6.8 Â 10–3 mol/L and 8.9 Â 10–3 mol/L, respectively.
However, the concentrations of K+ in jthe receiving phase
using hosts 2 and 3 were as low as 1.8 Â 10–3 mol/L and
1.7 Â 10–3 mol/L, respectively, under the same transport
conditions. These results of liquid membrane transport were
utterly different from the results of two phase extraction ex-
periments. It was known that the liquid membrane transport
ability relied on the balance of the complexation ability of
the host for guest and the decomplexing ability of the com-
plexes.22,23 These results of liquid membrane transport might
suggest that complex 2M+(and 2M2+, 3M+, 3M2+) possessed
stronger stabilities and lower decomplexing abilities in com-
parison with the corresponding complexes with hosts 4 and
5. Thus, although the two phase extraction abilities of hosts
4 and 5 were lower than that of hosts 2 and 3, the lower
stabilities of the complexes with 4 and 5 led to higher de-
The phase transfer catalysis of the nucleophilic
substitution reaction
Based on the experiment results of liquid membrane
transport, the phase transfer catalytic properties of aromatic
nucleophilic substitution reactions were studied. Aromatic
fluorine compounds have important applications in insectici-
dal and refined chemicals.24 The replacement of aromatic Cl
by F in nucleophilic substitution reactions was chosen as a
reaction system to evaluate the phase transfer catalytic abil-
ities of new hosts 2, 3, 4, and 5. The experiment results are
shown in Table 2. It can be seen that the yield of the prod-
uct was as low as 8.5% when the reaction was performed
without a catalyst (Table 2, entry 1). As catalysts were
added, the yields greatly increased. Under the same reaction
conditions, hosts 4 and 5 showed higher catalytic activity
than that of hosts 2 and 3 (Table 2, entries 2–5). These re-
sults were in accordance with the results of the liquid mem-
brane transport experiment. Using AgF instead of KF, hosts
4 and 5 still keep the high catalytic activity, although the
yields of the product decreased a little (Table 2, entries 6–7).
On the other hand, the yields of the products were over 90%
when the reaction time was prolonged to 24 h and 36 h
(Table 2, entries 8–11). Also, p-nitrochlorobenzene, having
an electron withdrawing group (1,2-dichloro-4-nitrobenzene
or 2,4-dinitrochlorobenzene), offered higher yields (Table 2,
entries 12–13), which were attributed to the favorable influ-
ence of the electron withdrawing group for an aromatic nucle-
ophilic substitution reaction. The yields were as high as 100%
when using 2,4-dinitrochlorobenzene as material.
Also, the replacement of aliphatic Cl by a nitrile group in
a benzyl nucleophilic reaction was studied by using new
hosts 2, 3, 4, and 5 as phase transfer catalysts. The experi-
ment results are shown in Table 3, which are similar to the
results in Table 2. The yields of products were greatly in-
creased from 6.4% to approximately 90% when catalysts
were added. Although hosts 4 and 5 showed higher catalytic
activities than that of hosts 2 and 3, the differences in yields
were not remarkable. The yields were as high as almost
Published by NRC Research Press

Yang et al.
625
Table 1. Salts concentrations (in the receiving phase) change with running times for different carriers in cation transport.
K+(10–3 mol/L) Zn2+(10–3 mol/L) Ag+(10–3 mol/L)
Carriersa
2 h
0.5
0.4
2.3
3.0
5 h
1.1
0.8
4.5
5.6
10 h
1.5
1.4
5.8
7.2
20 h
1.8
1.7
6.3
8.9
2 h
0.2
0.5
1.4
0.8
5 h
0.6
1.0
3.1
1.8
10 h
0.9
1.4
4.5
3.2
20 h
1.1
1.6
5.5
4.3
2 h
0.4
0.4
2.0
2.6
5 h
1.0
0.9
4.1
4.9
10 h
1.6
1.5
5.3
6.6
20 h
1.9
1.7
6.5
7.8
2
3
4
5
Note: The source aqueous solution: 0.05 mol/L of each salt.
aMembrane: 5.0 Â 10–4 mol/L carrier in CHCl3. For a blank experiment, no transport rate was detected in the absence of carriers during more than
12 h of continuous running.
Table 2. Catalytic investigation of compounds 2, 3, 4, and 5 in
aromatic nucleophilic reactions.
Table 3. Catalytic investigation of compounds 2, 3, 4,
and 5 in benzyl nucleophilic substitution.
Entry
1
2
3
4
5
6
7
8
R
H
H
H
H
H
H
H
H
H
H
H
Cl
NO2
M+
K+
K+
K+
K+
K+
Ag+
Ag+
K+
K+
K+
K+
K+
K+
Catalyst
None
Run time (h) Yield (%)
Entry
1
2
3
4
5
6
7
8
9
10
11
R
H
H
H
H
H
H
H
CH3
CH3
CH3
CH3
Catalyst
None
Run time (h) Yield (%)
12
12
12
12
12
12
12
24
24
36
36
24
24
8.5
12
12
12
12
12
24
24
12
12
24
24
6.4
2
3
4
5
4
5
4
5
4
5
5
5
72.5
79.3
88.2
90.5
86.4
88.6
94.3
96.7
97.8
98.2
98.8
99.2
2
3
4
5
4
5
4
5
4
5
84.2
88.5
93.6
97.4
98.6
98.9
92.1
88.4
98.5
98.2
9
10
11
12
13
Note: Reaction conditions: benzyl chloride or p-methylbenzyl
chloride (5 mmol), potassium cyanide (10 mmol), catalyst
(3.0 mol%), DMSO as solvent (12 mL), reaction temperature
(40 8C).
Note: Reaction conditions: p-nitrochlorobenzene or its derivatives
(5 mmol), potassium fluoride or silver fluoride (10 mmol), catalyst
(3.0 mol%), DMSO as solvent (12 mL), reaction temperature (40 8C).
sis exhibited that they possessed excellent catalytic proper-
ties of aromatic nucleophilic substitution reaction and
benzyl nucleophilic substitution. The yields of products in
catalytic reaction were as high as approximately 100%.
100% when the reaction time was prolonged to 24 h. All
these catalytic results in Table 2 and Table 3 indicate that
novel lariat calix[4]-1,3-aza-crowns (4 and 5) are excellent
phase transfer catalysts for nucleophilic substitution reactions.
Experimental section
Conclusion
Instruments
Novel dendritic calix[4]arene derivative (3) with two dif-
ferent branched chains was prepared by reacting calix[4]-
1,3-diethoxylaminoethyl derivative (2) with phenyl isothio-
cyanate. Novel lariat calix[4]-1,3-aza-crowns (4 and 5) with
two branched ethoxyl chains were prepared by reacting
compound 2 with 1,6-diisocyanatohexane or N,N’-bis(2-
chloracetamide)ethylene in a ‘‘1 + 1’’ intermolecular addi-
tion mode. The composition, structures, and conformations
of all new compounds were confirmed by elemental analy-
1
Melting points are uncorrected. H NMR spectra were re-
corded in CDCl3 on a Bruker-ARX 500 instrument, using
TMS as a reference. ESI-MS spectra were obtained from a
DECAX-30000 LCQ Deca XP mass spectrometer in MeCN,
setting the ESI capillary at 3.5 kV and the cone voltage at
40 V. Elemental analyses were performed at a Vario EL III
elemental analyzer. The UV–vis measurements were per-
formed on a Varian UV–vis spectrometer. The gas chroma-
tography was performed on a Varian 450-GC/240-MS
instrument. Atomic absorption was measured on a WFX-II
spectrograph. All solvents were purified by standard proce-
dures. 1,3-Broethoxyl-calix[4]arene (1) was prepared accord-
ing to the published procedures.21 The picrate salts were
prepared according to literature.25,26
1
ses, IR, ESI-MS, H NMR, and so forth. The liquid–liquid
extraction experiment showed that all new hosts possessed
good complexation abilities towards soft metal cations and
hard metal cations. The liquid membrane transport experi-
ments suggested that they had good transport abilities for
both K+ and Ag+. The experiments of phase transfer cataly-
Published by NRC Research Press

626
Can. J. Chem. Vol. 88, 2010
Fig. 2. Liquid membrane cell: (1) source phase, (2) receiving
phase, (3) membrane phase, and (4) magnetic stirring bar.
reduced pressure. The residue was treated with 10 mL petro-
leum ether (60 8C*90 8C) and a white precipitate separated
out. The precipitate was filtered and recrystallized by
CHCl3/petroleum ether (60*90 8C). Compound 4 was ob-
tained as a white powder in a yield of 62%; mp 232–
1
234 8C. IR (KBr, cm–1) n: 1703 (C=O). H NMR (CDCl3,
500 MHz) d: 0.90 (s, 18H, C(CH3)3), 1.31 (s, 18H,
C(CH3)3), 1.42 (bs, 4H, CH2), 1.86 (bs, 4H, CH2),
3.16*3.30 (m, 8H, NCH2 and OCH2), 3.32 (d, 4H, J =
12.5 Hz, ArCH2Ar), 3.49*4.11 (m, 12H, NH2 and OCH2),
4.18 (d, 4H, J = 12.5 Hz, ArCH2Ar), 4.90, 6.34, 6.54 (s,
each, 2H, each, OH and NH), 6.66 (s, 4H, ArH), 7.08 (s,
4H, ArH). ESI-MS m/z (%): 990.3 (M+, 100). Anal. calcd.
for C60H86N4O8: C 72.69, H 8.74, N 5.65; found: C 72.58,
H 8.82, N 5.55.
Syntheses of calix[4]-1,3-diethoxylaminoethyl derivative (2)
Under N2 atmosphere, a mixture of compound 1 (0.430 g,
0.5 mmol), ethanolamine (0.30 mL, 5 mmol), and K2CO3
(0.280 g, 2 mmol) was stirred in refluxing dry acetonitrile
(30 mL) for 48 h. Thin layer chromatography (TLC) detec-
tion showed the disappearance of compound 1. After distill-
ing off the solvent under reduced pressure, the residue was
treated with 30 mL HCl (10%) and a white precipitate sepa-
rated out. The precipitate was filtered and recrystallized by
MeOH/H2O. Compound 2 was obtained as a white powder
in a yield of 73%; mp 204–206 8C. IR (KBr, cm–1) n: 3421
Synthesis of novel lariat calix[4]-1,3-aza-crown (5)
Under N2 atmosphere, a mixture of compound 2 (0.205 g,
0.25 mmol), N,N’-bis(2-chloracetamide)ethylene (0.064 g,
0.3 mmol), and K2CO3 (0.280 g, 2 mmol) was stirred in re-
fluxing dry acetonitrile (30 mL) for 72 h. The TLC detec-
tion indicated the disappearance of compound 2. After
distilling off the solvent under reduced pressure, the residue
was purified by column chromatography (50 cm  3 cm,
SiO2 100–200 mesh, acetone/CH2Cl2 (3:2, v/v) as eluant,
500 mL). Compound 5 was then obtained as a white powder
in a yield of 42%; mp 241–244 8C. IR (KBr, cm–1) n: 1653
(C=O). 1H NMR (CDCl3, 500 MHz) d: 0.89 (s, 18H,
C(CH3)3), 1.30 (s, 18H, C(CH3)3), 3.26*3.36 (m, 12H,
ArCH2Ar, NCH2, and OCH2), 3.65*4.06 (m, 8H, NH2 and
OCH2), 4.12 (d, 4H, J = 12.5 Hz, ArCH2Ar), 4.14*4.33 (m,
8H, OCH2CO and NCH2), 6.61 (s, 4H, ArH), 7.08 (s, 4H,
ArH), 6.82, 7.01, 8.52 (s, each, 2H, each, OH and NH).
ESI-MS m/z (%): 985.8 (MNa+, 100). Anal. calcd. for
C58H82N4O8: C 72.31, H 8.58, N 5.81; found: C 72.21, H
8.66, N 5.70.
1
(OH and NH). H NMR (CDCl3, 500 MHz) d: 0.97 (s, 18H,
C(CH3)3), 1.23 (s, 18H, C(CH3)3), 3.28 (bs, 8H, ArCH2Ar
and OCH2), 3.49*3.53 (bs, 8H, NH2 and OCH2),
3.88*3.92 (bs, 4H, NCH2), 4.16 (s, 4H, OH and NH), 4.24
(d, 4H, J = 13.5 Hz, ArCH2Ar), 6.85 (s, 4H, ArH), 7.01 (s,
4H, ArH), 7.24 (s, 2H, ArOH). ESI-MS m/z (%): 824.0
(MH+, 100). Anal. calcd. for C52H74N2O6: C 75.87, H 9.06,
N 3.40; found: C 75.77, H 9.15, N 3.29.
Synthesis of novel dendritic calix[4]arene derivative (3)
A mixture of compound 2 (0.205 g, 0.25 mmol) and phe-
nyl isothiocyanate (0.3 mL, 2 mmol) was stirred in 10 mL
CHCl3 for 4 h under room temperature. TLC detection indi-
cated the disappearance of compound 2. The solvent was re-
moved under reduced pressure at room temperature. The
residue was treated with 10 mL petroleum ether
(60*90 8C) and a white precipitate separated out. The pre-
cipitate was filtered and recrystallized by CHCl3/petroleum
ether (60*90 8C). Compound 3 was obtained as a white
powder in a yield of 78%; mp 213–216 8C. IR (KBr, cm–1)
Procedures for two phase extraction experiments of
metallic picrates
According to the reported method,25 3 mL of chloroform
solution containing calixarene derivatives (2.0 Â 10–5 mol/L)
and 3 mL of aqueous solution containing metallic picrate
(2.0 Â 10–5 mol/L) were placed in a flask (Caution: metallic
picrates are hazardous materials; avoid fire, extrusion, high
temperature, and so forth). The pH of 6.9*7.1 of these
aqueous solutions suggests that little hydrolysis happened.
The mixture was shaken for 5 min and stored for 2 h at
room temperature. The extraction ability was not affected
by further shaking, indicating that the equilibrium had been
attained within 2 h. The aqueous phase was separated and
subjected to the analysis by UV absorption spectrometry in
near 357 nm. The extracting percentage (E%) was deter-
mined by the decrease of the picrate concentration in the
aqueous phase, E% = {([Pic]blank – [Pic]water)/[Pic]blank} Â
100, where [Pic]blank denoted the picrate concentrations in
the aqueous phase after extraction with pure chloroform,
and [Pic]water denoted the picrate concentrations in the aque-
ous phase after extraction with chloroform solution contain-
ing calixarene derivatives as extractants. The average of the
twice-independent experiments was carried out. Control ex-
1
n: 1239 (C=S). H NMR (500 MHz, CDCl3) d: 0.95 (s, 18H,
C(CH3)3), 1.21 (s, 18H, C(CH3)3), 3.22 (t, 4H, OCH2), 3.38
(d, 4H, J = 14.5 Hz, ArCH2Ar), 3.57 (t, 4H, OCH2), 3.82 (t,
4H, NCH2), 3.96*4.01 (m, 4H, NCH2), 4.28 (d, 4H, J =
14.5 Hz, ArCH2Ar), 6.79 (s, 2H, ArH), 6.96 (d, 4H, J =
7.5 Hz, ArH), 7.15 (s, 4H, ArH), 7.32 (m, 8H, ArH), 7.18,
7.40, 9.48 (s, each, 2H, each, OH and NH). MS m/z (%):
1116.0 (MNa+, 100). Anal. calcd. for C66H84N4S2O6: C
72.50, H 7.74, N 5.12; found: C 72.33, H 7.83, N 5.01.
Synthesis of novel lariat calix[4]-1,3-aza-crown (4)
A mixture of compound 2 (0.205 g, 0.25 mmol) and 1,6-
diisocyanatohexane (0.048 mL, 0.3 mmol) was refluxed in
100 mL CHCl3 for 12 h. TLC detection indicated the disap-
pearance of compound 2. The solvent was removed under
Published by NRC Research Press

Yang et al.
627
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absence of the calixarene derivatives.
Procedures for metal ion transport experiments
According to the reported method,27 liquid membrane
transport experiments were conducted using the bulk liquid
membrane apparatus presented in Fig. 2. The membrane
phase was the CHCl3 solution of new host with a concentra-
tion of 5.0 Â 10–4 mol/L. The membrane phase (25.0 mL)
was added to the bottom of the vessel and stirred magneti-
cally at 200 rpm. An aqueous salt solution (15 mL) with a
concentration of 0.05 mol/L (source phase, fluorides) and
15 mL of doubly distilled deionized water (receiving phase)
were poured on top of the organic phase. The two water
phases were separated by a cylindrical glass cell holding a
glass tube. The interface between the membrane phase and
the source phase (or the receiving phase) was 7.5 cm2. The
measurements were performed at a constant temperature of
25 8C. The concentration of salt in the receiving phase was
determined by atomic absorption spectrography. The pH
value of the source phase and receiving phase changed in
the scope of 6.9*7.2, which indicated that little hydrolysis
happened in the metal ion transport experiments. Blank ex-
periment showed that no transport was detected in the ab-
sence of host during more than 12 h of continuous running.
Each experiment was repeated three times. The cation con-
centration in the receiving phase was reported as the mean
of the determination and the relative standard deviation
from the mean was less than 5%.
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The procedures of phase transfer catalysis of a
nucleophilic substitution reaction
A typical nucleophilic substitution reaction was conducted
by mixing reactant (5 mmol) and corresponding inorganic
salt (10 mmol) in 12 mL of DMSO. The catalyst (3.0 mol%)
was added and the reaction was stirred (800 rpm) for a stipu-
lated time period (Table 2 and Table 3) at 40 8C. The yields
of product were analyzed by gas chromatography (Varian
450-GC/240-MS).
´
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Acknowledgements
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Financial support from the National Natural Science
Foundation of China (No. 20402002), the Fujian Natural
Science Foundation of China (No. 2009J01019), and the
Program for New Century Excellent Talents in the Univer-
sity of Fujian Province are greatly acknowledged.
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Published by NRC Research Press