Materials. Na[p-sulfonatocalix[5]arene].H2O (lb).

p-tert-Butylcalix[5]arene was synthesized according to the improved method of Gutschea resulting

in yields of ca. 5- 10%. Direct reaction of p-tertbutylcalix[5]arene (1.0 g, 1.23 mol) with H2SO4
(98%, 10 cm3) at 80-90 °C for 4 h, with periodic checking of the reaction mixture for solubility in
water, resulted in a dark solution in which most of the calixarene had dissolved. The mixture was
quenched in ice (10 g) and filtered. Addition of NaCl (0.25 g) to the filtrate resulted in the slow
deposition of the product as colorless prisms which were collected by filtration and dried in vacuo
at 100 °C for 72 h. Yield 1.05 g, 1.01 mol, 82%. Anal. Calcd for C35H25O20S5Na5*H2O C: 37.15;
H, 3.10; Na, 10.15. Found: C, 37.00; H, 3.15; Na, 10.05%. The physical and 1H-NMR spectral
properties of this material matched those reported previously.

Na.lp.sulfonatocalix[5]arene].8H2O. Following a procedure analogous to that given for lb, the

resulting quenched mother liquor was neutralized with Na2CO3 in place of NaCl to give the
heptaanionic salt as a white precipitate in yield comparable to that of lb. Slow evaporation of an
aqueous solution of this gave the inclusion complex 2 as large, colorless prisms which were
characterized by X-ray crystallography.

Na~lp-sulfonatocalix[5]arene].py-N-O.8.5H~(O3) . To a mixture of lb (0.150 g, 0.080 mmol) in

water (1.5 mL) were added Zn-(N03)2.H2O (0.048 g, 0.16 mmol) and pyridine N-oxide (0.059 g,
0.62 mmol), and the mixture was allowed to stand in air for ca. 14 d, resulting in the isolation of
the inclusion compound as thin, colorless plates in ca. 70% yield. Prismatic crystals consisting
solely of Zn-(N03)2.H20 (X-ray evidence) were also isolated.

Na~[La(H20)9][(p-sdfonatocalix[5]arene)]*py-N-1O*0 H20 (4), NaT-

[Gd(H~0)~(p-sulfonatocalix[5]arene)~]~2py-N-0(~334N,Ha ~[0E u-
(H~0)~]~[Eu(py-N-O)(H~O)5(p-sulfonatocalix[5]arene)~]~py-N-
0-17.5H20 (6), and Na~[Tb4(py-N-O)4(H~0)18(p-sulfonatocalix[5]-
arene)4]*52Hz0 (7). To a mixture of Na~[p-sulfonatocalix[5]arene]
(lb) (0.15 g, 0.080 mmol) in water (1.5 mL) were added pyridine
N-oxide (0.060 g, 0.63 mmol) and Ln(NO&.H20 (0.070 g, 0.15 mmol,
Ln = La, Gd, Eu, Tb), and the mixture was allowed to stand in air for
periods of up to several weeks, resulting in the deposition of the
crystalline inclusion compounds as large, colorless prisms as the sole
products, in yields ranging from ca. 40-60%. In the cases of 4 and 5
analytical data are corrected for the loss of 3 and 6 mol of water,
respectively, during transport. Such desolvation is consistent with the
observed poor stability of the crystals upon removal from the mother
liquor. Anal for 4 calcd for C40H62037La"a2S5: C, 32.15; H, 4.18;
N, 0.94; S, 10.73. Found: C, 32.2; H, 4.5; N, 1.3; S, 10.9%. Anal
for 5 calcd for C40H52035GQ5NNa4,5S5C:, 33.15; H, 3.62; N, 0.97; S,
11.06. Found: C, 33.3; H, 4.2; N, 1.0; S, 10.2%. Anal for 6 calcd for
C ~ ~ H I ~ , O ~ ~ . ~ E UC, ,N 2~9.N51~; HS,I 4O.0:5; N, 0.86; S, 9.84. Found:
C, 29.8; H, 4.3; N, 1.0; S, 10.0%. Anal for 7 calcd for C40H66040-
NNa2S5Tb: C, 30.68; H, 4.25; N, 0.89. Found: C, 30.65; H, 4.05; N,
0.80%.
Na~[Yb(py-N-O)(H~0)6(p-sulfonatocalix[5]arene)].l3H~(O8 ). To
a mixture of Na~[p-sulfonatocalix[5]arene(]l b)( 0.15 g, 0.080 mmol)
in water (1.5 mL) was added pyridine N-oxide (0.060 g, 0.63 mmol)
and YbClpH20 (0.070 g, 0.15 mmol), and the mixture allowed to stand
in air for three weeks, resulting in the deposition of the crystalline
inclusion compound as large, colorless prisms in ca. 40% yield.
Analytical data are corrected for the loss of 2 mol of water during
transport. Anal. Calcd for C40H65038NNa2S5Yb: C, 31.05; H, 4.23;
N, 0.91; S, 10.36. Found: C, 31.3; H, 4.0; N, 1.1; S , 11.5%.
From WO 1997049677 A1
Preparation of calix [4] arene-5, 11, 17, 23-tetrasulfonic acid
In a flask equipped with a reflux condenser and a magnetic stirrer, 5 grams (7.7 m moles) of tetra-p-tert-
butyl- calix[4]arene are carefully added, portion wise and under stirring, to 20 ml of concentrated sulfuric
acid (95 to 97%, Merck). The suspension which is formed is heated during 4 hours to about 80 °C. The real
duration of the reaction depends upon the result of a final water solubility test of a sample taken from the
mixture from time to time.
When there is no precipitate detectable with the naked eye any more, the mixture is allowed to cool, and
the precipitate is carefully filtered off on a fritted glass filter having the porosity of 3 or 4. The porosity of 3
is preferred since it requires a low suction force and a better flow of the viscous filtrate. The brown solid
recovered on the filter is washed twice with 2.5 ml of ice cold ethanol, the washings being collected in
another vessel. The residue which is now freed from excess sulfuric acid is treated until total solution with
several fractions of methanol, and the final volume of this solution is about 100 ml.
The solution is now treated with 1 gram of decoloring charcoal, filtered on celite, and added to 500 ml of
ethyl acetate under stirring. The precipitate which forms gradually acquires a structural form and is then
filtered, and the residue is dried under high vacuum at 30 to 40 °C, yielding 5 grams (6.7 m moles, 87 %)
of calix [4] arene-5, 11, - 17, 23-tetrasulfonic acid as a clear brown powder.
Analysis: iH-NMR: 5.08 (s, 4 Ar-CH2-Ar) ; 5.97 (s, 14H, (8 acidic H exchanged + 3 H20) ) ; 8.66 (s, 8H of Ar)
. 13C- NMR: 35.02 (Ar-CH2-Ar) ; 131.02 (C(H) of Ar) ; 132.53 (Ar- CH2-Ar) ;140.29 and 155.95 (C-OH and
C-S03H) . ES-MS, nega¬ tive mode: 743 (M-H) " ; 371 (M-2H)2" /2; 247 (M-3H)3~ /3; 185 (M-4H)4- I A ;
393(M-2H-2H + 2Na)2' /2 ; 382 (M-2H-H + Na)2~ /2; 254 (M-3H-H + Na)3~ /3.
Synthesis of calixarenes & calix[4]resorcinere

The synthesis of p-tert butylcalix[4]arene were carried out for the first time by our

group [26] using base-catalysed condensation of p-substituted phenol and

formaldehyde using microwave irradiation with an improvement of yield to 90-95%

(Scheme 1).

Microwave-Assisted of 5, 11, 17, 23-tetra-butyl-25, 26, 27, 28-tetrahydroxy

calix[4]arenes

For the microwave synthesis of p-tert butyl calix[4]arene, 10 g of p-tert-butylphenol was

mixed with NaOH (0.05 g, 1.2 mmol) dissolved 0.5 ml of water and 6.2 ml 37%

formaldehyde solution and was heated in a Discover BenchMate system-240 V(CEM

Corporation) microwave at 300 watt output power for 5 min to give a yellow solid. To this

was added 7 ml of diphenyl ether and 1 ml toluene and the mixture was heated at 300

watt output power for 15 min to obtain corresponding calix[4]arene. The purity was checked

by TLC and the results of mp, FT-IR, 1H NMR, 13C NMR and MS were compared with

standard sample.

Scheme 1: Microwave synthesis tert-butyl calix[4]arene

Synthesis of 25, 26, 27, 28-tetrahydroxycalix[4]arene

To a solution of p- tert-butyl calix[4]arene (5.0 g, 0.1 mol), phenol crystal (0.9 g, 0.01

mol), added anhy. AlCl3 (5.0 g, 0.1 mol) in 100 ml of toluene and stirred the solution

for 4 h. After the completion of the reaction, the reaction mixture was poured in to the

ice containing water. Taken the mixture in a separatory funnel containing 250 ml of
dichloromethane (DCM). Collected the organic layer and washed with 100 ml (2 N)

HCl. Evaporated the solvent under reduced pressure by flash evaporator, dissolved

the residue in 25 ml of diethyl ether and kept the solution at 0-50C overnight. Filtered

and dried.

Scheme 2: synthesis calix[4]arene

Synthesis of calix[4]resorcinarene

To a solution of resorcinol (11.01 g, 0.1 mol) and acetaldehyde (4.41 g, 0.1 mol) in 40 ml of water, was
carefully added in 10 ml of conc. HCl. The precipitate obtained were stirred at 75 0C for 4 h, cooled in ice
bath and filtered. The phenolic precipitate was washed and dried [25].

Scheme 3: synthesis of calix[4]resorcinarene

Preparation of 25,26,27,28-tetrabenzyloxy-5,11,17,23-tetra-tert-butyl-calix[4]arene, 3.

A mixture of p-tert.butylcalix[4]arene (0.65 g, 1.00 mmol), benzyl bromide (1.7 g, 9.94 mmol), NaOH (50%
in water, 1 mL) and tetrabutylammonium bromide (0.03 g) in toluene (25 mL) was vigorously stirred at 100
°C for 6 h. The reaction was cooled to room temperature, water was added, and the phases were separated.
The organic phase was washed with 1N HCl and water, then dried over MgSO4. The solvent was removed
and the residue triturated with methanol to give a solid, which was recrystallized twice from methanol,
yielding the pure final product (0.71 g, 70%), mp 232–234 °C. There was more product in the mother liquors
but it was discarded.
1H NMR: d 1.07 (27H, s, C(CH3)3), 2.85 (4H, d, J=12.6 Hz, Ar–CH2–Ar, equiv), 4.18 (4H, d, J=12.6 Hz,
Ar–CH2–Ar, ax), 4.86 (8H, s, OCH2), 7.24 (20H, m, Ar–H). 13C NMR (75 MHz, CDCl3) d 31.6, 33.9, 125.2,
127.8, 128.2, 129.9, 134.2, 138.7, 144.7, 153.1.