Method for the high-yield production of giant P-(R)calixarenes

Abstract

Giant p-(R)calixarenes, a process for the preparation of giant p-(R)calixarenes with high yields, and their use as the constitution of a material or in the context of the reinforcement of the material.

Claims

1. Mixture of calixarenes of the following formula (IV): ##STR00015## in which n is an integer comprised from 21 to at most 220, and in which R is selected from the group consisting of: a benzyloxy group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, a linear or branched C.sub.1-C.sub.20 alkyloxy group, a linear or branched PEG-1 to 10, the OH end group of which is alkylated with a linear or branched C.sub.1-C.sub.20 alkyl, a benzyl thioether group SCH.sub.2-Ph optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, a linear or branched C.sub.1-C.sub.20 alkyl thioether group, of formula S(C.sub.1-C.sub.20-alkyl), an NR.sub.aR.sub.b group, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, and a dibenzylamine group of formula N(benzyl).sub.2, in which the two benzyl groups are, independently of one another, optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl.

2. A material comprising a mixture of giant p-(R)calixarenes the size of which is greater than 20, R being selected from the group consisting of: a benzyloxy group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, a linear or branched C.sub.1-C.sub.20 alkyloxy group, a linear or branched PEG-1 to 10, the OH end group of which is alkylated with a linear or branched C.sub.1-C.sub.20 alkyl, a benzyl thioether group SCH.sub.2-Ph optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, a linear or branched C.sub.1-C.sub.20 alkyl thioether group, of formula S(C.sub.1-C.sub.20-alkyl), an NR.sub.aR.sub.b group, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, and a dibenzylamine group of formula N(benzyl).sub.2, in which the two benzyl groups are, independently of one another, optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, as the constitution of said material or in the context of reinforcement of materials.

3. A material comprising a mixture of calixarenes according to claim 1, as the constitution of as material or in the context of reinforcement of materials.

4. The mixture of calixarenes according to claim 1, wherein R is selected from the group consisting of: a benzyloxy group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, and a linear or branched C.sub.1-C.sub.20 alkyloxy group, a linear or branched PEG-1 to 10, the OH end group of which is alkylated with a linear or branched C.sub.1-C.sub.20 alkyl.

5. The mixture of calixarenes according to claim 4, wherein R is selected from the group consisting of: a benzyloxy group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.br PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.5-C.sub.20 alkyl, and a linear or branched C.sub.5-C.sub.20 alkyloxy group, a linear or branched PEG-1 to 10, the OH end group of which is alkylated with a linear or branched C.sub.5-C.sub.20 alkyl.

6. The mixture of calixarenes according to claim 1, wherein R is an octyloxy group, using GPC a peak molar mass corresponding to 35 phenolic units.

7. The mixture of calixarenes according to claim 1, wherein R is a benzyloxy group and average size determined by the centred Gaussian measure varies from 21 to approximately 212.

8. The material according to claim 2, wherein in which said mixture further comprises a p-(R)calix[7]arene and/or a p-(R)calix[8]arene.

9. The material according to claim 3, wherein said mixture further comprises a p-(R)calix[7]arene and/or a p-(R)calix[8]arene.

10. The material according to claim 1 wherein R is selected from the group consisting of: a benzyloxy group optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.br PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, a linear or branched C.sub.5-C.sub.20 alkyloxy group, a linear or branched PEG-1 to 10, the OH end group of which is alkylated with a linear or branched C.sub.5-C.sub.20 alkyl, an NR.sub.aR.sub.b group, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl, and a dibenzylamine group of formula N(benzyl).sub.2, in which the two benzyl groups are, independently of one another, optionally substituted in the ortho and/or para and/or meta position with one or more substituents selected from a halogen, SR and OR, R representing a linear or branched C.sub.1-C.sub.20 alkyl chain, a C.sub.3 to C.sub.20 cycloalkyl group, NR.sub.aR.sub.b, PR.sub.aR.sub.b, P(O)R.sub.aR.sub.b, P(O)OR.sub.aOR.sub.b, R.sub.a and R.sub.b representing, independently of one another, a linear or branched C.sub.1-C.sub.20 alkyl.

Description

DESCRIPTION OF FIGURES

(1) FIG. 1 shows the calibration curve obtained with the pure samples of p-(benzyloxy)calix[4-16]arenes using diffusional NMR synthesized according to Example 5. It makes it possible to validate the molar mass of the pure p-(benzyloxy)calix[4-16]arenes determined by size exclusion chromatography. X-axis: ln(M) where M represents the molecular weight of the p-(benzyloxy)calix[4-16]arenes.

(2) Y-axis: ln(D) where D represents the self diffusion coefficient of the molecules which depends among other things on their hydrodynamic volume determined by diffusional NMR PGSE (Pulse Gradient Spin Echo) diffusion NMR.

(3) This curve makes it possible to link the self diffusion coefficient to the average molar mass of a mixture of calixarenes.

(4) FIG. 2 shows the size exclusion chromatography of the pure reference samples of p-(benzyloxy)calix[6]arene, p-(benzyloxy)calix[7]arene, p-(benzyloxy)calix[8]arene, p-(benzyloxy)calix[10]arene, p-(benzyloxy)calix[12]arene and p-(benzyloxy)calix[16]arene,

(5) This technique makes it possible to separate the molecules depending on their hydrodynamic volume and to estimate the molar mass of pure or mixed samples starting from a range of pure standards. The molar masses representative of a pure calixarene or of a mixture of calixarenes are expressed by peak molar masses (Mp) and average molar masses, giving information respectively on the majority population and on the average of the populations.

(6) On the x-axis: Elution volume: Ve(ml)

(7) On the y-axis: RI SIGNAL, corresponding to the refractive index of samples or standards in solution leaving the chromatography column.

(8) FIG. 3 shows the use of the giant calixarenes as reinforcement of materials by the insertion of polymers into the cavity thereof, which allows better distribution of stress inside, as well as slowing the propagation of cracks (fracture initiation).

(9) FIG. 4 shows an NMR analysis of the microcrystalline solid obtained at the end of the recrystallization presented in Example 1a).

(10) FIG. 5a shows an NMR analysis of the solid obtained after the reflux process without stirring presented in Example 1b).

(11) FIG. 5b shows an NMR analysis of the solid obtained after the recrystallization presented in Example 1b).

(12) FIG. 6 shows an NMR analysis of the microcrystalline solid obtained at the end of the recrystallization presented in Example 1 d)A.

(13) FIG. 7 shows a measurement of the molar mass using gel permeation chromatography (GPC) of the microcrystalline solid obtained at the end of the recrystallization presented in Example 1d)A.

(14) FIG. 8 shows an NMR analysis of the microcrystalline precipitate obtained at the end of the recrystallization presented in Example 1d)B.

(15) FIG. 9 shows a measurement of the molar mass using GPC of the microcrystalline precipitate obtained at the end of the recrystallization presented in Example 1 d)B.

(16) FIG. 10a shows an NMR analysis of the solid mainly constituted by the dimer, obtained as reaction intermediate in Example 1d)C.

(17) FIG. 10b shows an NMR analysis of the solid obtained after reflux, in Example 1d)C.

(18) FIG. 10c shows a .sup.1H NMR analysis of calix[80]arene described in Example 1d)C-2.

(19) FIG. 11 shows an NMR analysis of the microcrystalline solid obtained at the end of the recrystallization presented in Example 1e)A.

(20) FIG. 12 shows a measurement of the molar mass using GPC of the microcrystalline solid obtained at the end of the recrystallization presented in Example 1e)A.

(21) FIG. 13 shows an NMR analysis of the solid obtained at the end of the recrystallization presented in Example 1e)B.

(22) FIG. 14 shows a measurement of the molar mass using GPC of the solid obtained at the end of the recrystallization presented in Example 1e)B.

(23) FIG. 15 shows an NMR analysis of the white solid obtained at the end of the reaction presented in Example 1 g).

(24) FIG. 16 shows an NMR analysis of the white solid obtained at the end of the reaction presented in Example 2a).

(25) FIG. 17 shows an NMR analysis of the solid obtained, before the addition of toluene, in Example 4 (FIG. 17.1) as well as the reference NMR spectrum of p-(tBu)calix[8]arene (FIG. 17.2).

(26) FIG. 18 shows an NMR analysis of the solid obtained after reflux and neutralization, in Example 4.

(27) FIG. 19 shows an NMR analysis of the clear orange-coloured solution obtained in Example 5.

(28) FIG. 20 shows a diagram of the purification of a mixture of large calixarenes obtained in Example 5, after a stage of crystallization from the acetone-DMSO mixture (10% by volume of DMSO). The abbreviations PX and FX correspond respectively to the precipitate of the fraction X and the filtrate of the fraction X. The fractions in bold correspond to isolated pure calixarenes.

(29) Each letter in italics corresponds to a purification stage, carried out in chronological order under the following conditions:

(30) A: the crude product containing the mixture of calixarenes is stirred in ethyl acetate then filtered in order to obtain the fractions P0 and F0.

(31) B: the precipitate P0 is heated under reflux for 1 h under argon and with stirring in 450 mL of chlorobenzene then filtered in order to obtain the fractions P1 and F1.

(32) C: the precipitate P1 is placed under vigorous stirring in 40 mL of THF overnight, filtered and copiously rinsed with THF in order to obtain the fractions P8 (640 mg, Mp corresponds to 20 units) and F8.

(33) D: F1 is heated under reflux under argon and with stirring in 75 mL of chlorobenzene then cooled down and stirred for 1 h at ambient temperature. The solution is placed overnight at 20 C. and filtered in order to obtain the fractions P2 and F2.

(34) E: P2 is placed under stirring in 20 mL of dichloromethane at ambient temperature overnight in order to obtain the fractions F3 and P3 (40 mg, mixture of calixarenes the Mps of which correspond to 22, 11 and 8 units).

(35) F: F3 is dissolved in 40 mL of toluene under reflux then cooled down to ambient temperature. After stirring for 4 h at ambient temperature, the suspension is filtered in order to obtain F5 (428 mg, a mixture of calixarenes the Mps of which correspond to 11 and 17 units) and P5 (15 mg).
G: F2 is dissolved hot in toluene and deposited on a silica column. The calixarene mixture is firstly eluted with dichloromethane in order to obtain the fractions F2a and F2b, then with tetrahydrofuran in order to obtain the fraction Fc.
H: 15 mL of DCM is added to the fraction F2a and a white precipitate immediately appears. After leaving to rest for 1 h without stirring, the suspension is filtered in order to obtain P4 (40 mg, pure calix[16]arene) and F4.
I: F4 is heated briefly under reflux of toluene (20 mL) until totally dissolved then placed at ambient temperature for 24 h without stirring. A suspension is obtained which is filtered in order to obtain the fractions F6 and P6 (30 mg, mixture of large calixarenes).
J: F6 is dissolved in toluene then deposited on a silica column. Chromatography is carried out with an eluent gradient 70/30 to 100/0 of dichloromethane/toluene. The following are isolated, in order of elution: calix[7]arene (30 mg), calix[9]arene and a mixture of calix[10+12]arenes (fraction F6c).
K: F6c is heated briefly under reflux of toluene (6 mL) until totally dissolved then placed at ambient temperature for 48 h without stirring. A suspension is obtained that is diluted in 20 mL of toluene. The suspension is filtered in order to obtain P7 (44 mg, pure calix[10]arene) and F7.
L: F2b is dissolved in 10 mL of toluene. A white precipitate rapidly appears and the suspension is stored for 5 days without stirring. 25 mL of toluene is added and, after 2 weeks without stirring, the suspension is filtered in order to obtain P9 (88 mg, pure calix[10]arene) and F9.
M: F7 and F9 are collected, dispersed in 150 mL of acetone then heated for 1 h under reflux of the solvent. The suspension is filtered in order to obtain P10 (688 mg, pure calix[12]arene) and F5 (75 mg, mixture of calix[10]arene and other large calixarenes).
N: F2c is placed under stirring in acetone at ambient temperature for 24 h then filtered in order to obtain a precipitate. This precipitate is subjected to three cycles of washings/filtrations in acetone. P11 (512 mg) and, after assembly of the filtrates, F11 (1.43 g) are obtained.
O: P11 is placed under stirring in 25 mL of dichloromethane at ambient temperature over a weekend. P12 (50 mg, mixture of calixarenes the Mp of which corresponds to 21 units) and F12 (547 mg, two populations the Mps of which correspond to 19 and 30 units) are obtained.
P: F8 and P13 are assembled and placed with stirring in acetone for 24 h in order to obtain P14 (790 mg, two populations the Mps of which correspond to 19 and 12 units) and F14 (92 mg, two populations the Mps of which correspond to 17 and 11 units).
Q: F11 is mixed with 50 mL of acetonitrile. After heating for 15 min under reflux of the solvent, a type of viscous black oil is deposited on the walls of the flask and the supernatant is separated immediately. This operation is repeated and P15 (696.5 mg, mixture of calixarenes the Mp of which corresponds to 34 units) and, after assembly of the filtrates, F15 (425.6 mg) are obtained.
R: F15 is placed under stirring in 50 mL of acetonitrile at ambient temperature for 24 h. F16 (30 mg, pure calix[13]arene) and P16 (401 mg, two populations the Mps of which correspond to 18 and 12 units) are obtained.

(36) FIG. 21 shows the set of size exclusion chromatographies carried out on the mixtures of large calixarenes originating from the purification diagram shown in FIG. 3. Each chromatogram includes the reference calix[16]arene.

(37) FIG. 22 shows the Maldi-Tof mass spectra of the pure samples of p-(benzyloxy)calix[9]arene, p-(benzyloxy)calix[10]arene, p-(benzyloxy)calix[12]arene and p-(benzyloxy)calix[16]arene. This technique makes it possible to accurately determine the molar mass of a compound in order to arrive at its chemical composition.

(38) FIG. 23 shows the NMR spectra of the pure samples of p-(benzyloxy)calix[9]arene, p-(benzyloxy)calix[10]arene, p-(benzyloxy)calix[12]arene, p-(benzyloxy)calix[13]arene and p-(benzyloxy)calix[16]arene.

(39) FIG. 24 shows the GPC chromatogram of the macroinitiator obtained from calix[50]arene (Example C).

(40) FIG. 25 shows the GPC chromatogram of the star polymers obtained from calix[50]arene, said polymers differing by the duration of the ATRP process.

(41) FIG. 26 shows the characterization of the structures of the star polymers, by expressing log Rh where Rh corresponds to the hydrodynamic radius of the polymer studied, as a function of log Mw where Mw is the molar mass of polymer.

(42) FIG. 27 shows a .sup.1H NMR analysis of the solid obtained in Example 1d)D.

(43) FIG. 28 shows a MALDI mass spectrometry analysis of the giant calixarenes obtained using 0.4 equivalents of LiOH with respect to the phenol (Example 1d)D). The values indicated correspond to the number of phenolic units. The calixarenes appear mainly potassium-cationized (sodium cationization observed in the minority). The peaks at M-91 correspond to debenzylation reactions of the calixarenes induced by the laser beam (during the analysis).

(44) FIG. 29a shows a .sup.1H NMR analysis of the purified mixture of giant calixarenes obtained using 0.4 equivalents of CsOH (Example 1d)E).

(45) FIG. 29b shows a .sup.13C NMR (63 MHz) analysis of the purified mixture of giant calixarenes obtained using 0.4 equivalents of CsOH (Example 1d)E).

EXAMPLES

A) Synthesis of Giant Calixarenes

Example 1: Preparation of Giant p-(benzyloxy)calixarenes

(46) a) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water. Solid Precursor in the Form of an Isolated Brittle Resin.

(47) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(48) The resulting suspension is heated at 140 C. under the protection of argon.

(49) A solution of 12 g of KOH (0.214 mol; 0.41 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(50) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(51) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(52) The hard and brittle solid resin obtained is washed with a mixture of 750 ml of methanol, acidified with 50 ml of 37% HCl in an aqueous solution. The precursor is dispersed under vigorous mechanical stirring.

(53) The resulting suspension is filtered.

(54) An NMR analysis shows that this precursor isolated in this way appears to be 50% constituted by giant calixarenes. The main impurity is the dimer, plus a small percentage of linear oligomers.

(55) This precursor is dissolved in 1 liter of an acetone/DMSO mixture (90:10 by volume) and is placed in a refrigerator to crystallize (1 C./4 days). 20 g of a microcrystalline solid is recovered, the NMR analysis of which is shown in FIG. 4. This solid comprises approximately 80% of giant calixarenes.

(56) Measurement of the molar mass using GPC: 4600 g/mol, number of repeat units=22.

(57) Measurement of the hydrodynamic radius of the calixarenes formed using dynamic light scattering (DLS): 4 nm.

(58) b) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux

(59) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(60) The resulting suspension is heated at 140 C. under the protection of argon.

(61) A solution of 12 g of KOH (0.214 mol; 0.41 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(62) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(63) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(64) This solid resin then has 300 ml of octane added to it and the system is placed under reflux without stirring for 3 h30. NMR analysis of the solid obtained is shown in FIG. 5a.

(65) This solid appears to be 60% constituted by giant calixarenes.

(66) This solid is dissolved in 2 liters of an acetone/DMSO mixture (90:10 by volume) and is placed in a refrigerator to crystallize (1 C./4 days). 32 g of giant calixarenes is recovered. The NMR (DMSO)-d6 of this the product is shown in FIG. 5b. Yield: 30%

(67) Measurement of the hydrodynamic radius of the calixarenes formed by DLS scattering: 4.5 nm. Estimation of number of repeat units is n=30.

(68) c) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in a Silicone Oil (140 C.).

(69) A sample of 10 g of solid precursor (not neutralized) obtained in Example 1b (KOH 0.4 equivalent) is immersed in 100 ml of silicone oil in a 250 ml Schlenk flask, and heated at 140 C. for 8 h. A proton NMR analysis shows that the resulting solid is 68% constituted by giant calixarenes.

(70) c-2) by Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in an Oven (140 C.).

(71) A sample of 10 g of solid precursor (not neutralized) obtained in Example 1.d)C (KOH 1 equivalent) is placed in a Schlenk tube and degassed under primary vacuum for 3 h, in order to remove the volatile residues (water, residual formaldehyde).

(72) This product is then placed in an oven at 140 C. for 22 h. A proton NMR analysis shows that the resulting solid is 60% constituted by giant calixarenes.

(73) d) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux with Stirring.

Example A: KOH (0.4 Equivalent with Respect to the Phenol)

(74) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(75) The resulting suspension is heated at 140 C. under the protection of argon.

(76) A solution of 12 g of KOH (0.214 mol; 0.41 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(77) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(78) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(79) Then 600 ml of xylene is added to this solid, and the resulting suspension is taken to reflux under vigorous mechanical stirring, so as to thoroughly redisperse the solid precursor during this period of time.

(80) After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring, filtration of the suspension obtained makes it possible to recover 40 g of p-(benzyloxy)calix[8]arene.

(81) The filtrate is evaporated to dryness. The solid obtained is dissolved in 1 liter of an acetone/DMSO mixture (90:10 by volume) and crystallized in a refrigerator (1 C./4 days). 17 g of a microcrystalline solid is recovered, the NMR analysis of which (DMSO-d6) is shown in FIG. 6.

(82) This solid appears to be 95% constituted by giant calixarenes.

(83) The measurement of the molar mass using GPC is shown in FIG. 7: M=6000 g/mol, number of phenolic units (n)=28.

(84) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=4.5 nm.

Example B: Ba(OH)2 (0.4 Equivalent with Respect to the Phenol)

(85) A) A solution of 60 g of Ba(OH).sub.2.8H.sub.2O (0.19 mol; 0.4 equivalent) in 135 ml of aqueous formaldehyde at 30% is prepared in a 250 ml Erlenmeyer flask, under vigorous magnetic stirring. A white suspension is obtained, hereafter called solution A.

(86) B) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol). Solution A is added thereto. Then heating of the resulting suspension is started (140 C.), under the protection of argon.

(87) At a measured temperature of 50 C. 40 ml of ethanol is then added, while continuing heating. The white suspension then instantaneously transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(88) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the bright yellow clear solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(89) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h of flushing of argon.

(90) Then 300 ml of xylene is added to this solid, and the resulting suspension is taken to reflux under stirring for 8 h.

(91) After returning to ambient temperature, the suspension is filtered, then the precipitate is neutralized by being placed in suspension in a mixture of 500 ml of methanol/50 ml of 37% HCl, under vigorous stirring.

(92) After filtration, a brown solid is recovered, which is dissolved in 1 liter of an acetone/DMSO mixture (90:10 by volume). This solution is immediately filtered in order to isolate p-(benzyloxy)calix[8]arene.

(93) After storage in a refrigerator (1 C.) for 4 days, 63 g of a microcrystalline precipitate is recovered, the NMR analysis of which (DMSO-d6) is shown in FIG. 8.

(94) The solid obtained in this way appears to be 90% constituted by giant calixarenes.

(95) The measurement of the molar mass using GPC is shown in FIG. 9: the peak molar mass (centred Gaussian)=10400, i.e. n=50.

(96) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=7 nm.

Example C: KOH (1 Equivalent with Respect to the Phenol)

(97) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(98) The resulting suspension is heated at 140 C. under the protection of argon.

(99) A solution of 28 g of KOH (0.519 mol; 1 equivalent) in 20 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(100) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(101) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(102) NMR analysis (DMSO-d6) of this solid obtained in this way is shown in FIG. 10a.

(103) This solid appears to be constituted mainly by the dimer, accompanied by a lower proportion of linear oligomers.

(104) Then 400 ml of xylene is added to this solid, and the resulting suspension is taken to reflux under stirring for 3 h.

(105) After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring, filtration of the suspension obtained makes it possible to recover 15 g of p-(benzyloxy)calix[8]arene.

(106) The filtrate is evaporated to dryness. The solid obtained is dissolved in 1 liter of an acetone/DMSO mixture (90:10 by volume) and crystallized in a refrigerator (1 C./4 days). A microcrystalline solid is recovered.

(107) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=6 nm, for a number of phenolic units estimated at 50 (centred Gaussian using GPC).

(108) NMR analysis of this solid is shown in FIG. 10b.

Example C-2: KOH (1 Equivalent with Respect to the Phenol), Production of Calix[80]Arenes

(109) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 104 g of 4-(benzyloxy)phenol (0.52 mol), 28 g of KOH (0.5 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(110) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(111) After returning to ambient temperature, 400 ml of xylene is then added. The suspension obtained in this way is then taken to reflux under stirring. Monitoring the reaction then shows an evolution of the composition towards the formation of giant calixarenes.

(112) At the end of 4 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as one liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered. After drying, a white solid obtained in this way is dissolved in a mixture of 100 ml of DMSO and 1000 ml of acetone, then filtered. The white solid obtained in this way is dried in air, then placed in suspension in 300 ml of THF. The filtrate recovered after filtration is evaporated to dryness, then washed with 50 ml of acetone. After removal of the supernatant, 2 g of giant calixarenes is obtained (size estimated using GPC (centred Gaussian):80 phenolic units).

(113) The .sup.1H NMR analysis of this product is shown in FIG. 10c.

Example D: LiOH (0.4 Equivalent with Respect to the Phenol)

(114) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 100 g of 4-(benzyloxy)phenol (0.5 mol), 8.4 g of LiOH.H.sub.2O (0.2 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After refluxing for 20 minutes, a bright yellow clear solution is obtained.

(115) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(116) .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by the phenolic dimer (FIG. 27).

(117) After returning to ambient temperature, 400 ml of xylene is then added. The suspension obtained in this way is then taken to reflux under vigorous stirring. Monitoring the reaction shows an evolution of the composition towards the formation of giant calixarenes.

(118) At the end of 2 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as one liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. An NMR analysis shows that the reaction medium contains 40% of giant calixarenes.

(119) An analysis by MALDI mass spectrometry confirms the presence of these calixarenes (FIG. 28).

Example E: CsOH (0.4 Equivalent with Respect to the Phenol)

(120) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 104 g of 4-(benzyloxy)phenol (0.52 mol), 36 ml of a solution of CsOH at 50% (0.208 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(121) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(122) After returning to ambient temperature, 200 ml of xylene is then added. The suspension obtained in this way is then taken to reflux under stirring. Monitoring the reaction then shows an evolution of the composition towards the formation of giant calixarenes.

(123) At the end of 2 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as 500 ml of tetrahydrofuran, under vigorous mechanical stirring. The resulting suspension is evaporated to dryness. The resulting solid is washed with 2 liters of methanol, then filtered. After drying, the white solid obtained in this way is recrystallized from a mixture of 100 ml of DMSO and 1000 ml of acetone.

(124) After filtration, the filtrate is left in a refrigerator (1 C.) for 3 days.

(125) After filtration of the solid which has spontaneously precipitated, 30 g of giant calixarenes is obtained (size estimated using GPC: 20 phenolic units). Yield: 28%.

(126) An NMR analysis of this product is shown in FIG. 29a.

(127) A .sup.13C analysis of this same product is shown in FIG. 29b.

(128) e) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux without Stirring.

Example A: RbOH (0.4 Equivalent with Respect to the Phenol)

(129) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(130) The resulting suspension is heated at 140 C. under the protection of argon.

(131) 25.2 ml of a solution of RbOH at 50% by weight in water (0.4 equivalent) is rapidly injected at 90 C. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(132) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(133) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(134) 170 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux without stirring for 2 h.

(135) The reaction medium is then neutralized by the addition of a mixture of 500 ml of methanol and 70 ml of 37% HCl in water under vigorous stirring.

(136) After filtration of the solid and drying under vacuum, the solid is dissolved in 2 liters of an acetone/DMSO mixture (90:10 by volume).

(137) Filtration of the suspension obtained makes it possible to recover 10 g of p-(benzyloxy)calix[8]arene.

(138) The filtrate is then placed in a refrigerator (1 C./4 days).

(139) 25 g of a microcrystalline solid is recovered, the NMR analysis of which is shown in FIG. 11. This solid appears to be 90% constituted by giant calixarenes.

(140) Measurement of the molar mass of this solid using GPC is shown in FIG. 12: M=6000 g/mol, number of phenolic units (n)=29 (centred Gaussian).

(141) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=4.6 nm.

Example B: KOH (0.4 Equivalent with Respect to the Phenol)

(142) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(143) The resulting suspension is heated at 140 C. under the protection of argon.

(144) 12 g of KOH in 10 ml of water (0.4 equivalent) is rapidly injected at 90 C. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(145) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(146) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(147) 170 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux without stirring for 2 h.

(148) The reaction medium is then neutralized by the addition of a mixture of 500 ml of methanol and 70 ml of 37% HCl in water under vigorous stirring.

(149) After filtration and drying under vacuum, the solid is dissolved in 2 liters of an acetone/DMSO mixture (90:10 by volume).

(150) Filtration of the suspension obtained makes it possible to recover 10 g of p-(benzyloxy)calix[8]arene.

(151) The filtrate is then placed in a refrigerator (1 C./4 days).

(152) 35 g of a microcrystalline solid is recovered, the NMR analysis of which (DMSO-d6) shows that it appears to be 90% constituted by giant p-(benzyloxy) calixarenes.

(153) Recrystallization of this solid from dichlorobenzene makes it possible to recover 10 g of a brown solid of improved purity, the NMR analysis of which (DMSO-d6) is shown in FIG. 13.

(154) This solid appears to be more than 95% constituted by giant calixarenes.

(155) Measurement of the molar mass using GPC is shown in FIG. 14: M=12700 g/mol, number of phenolic units (n)=60 (centred Gaussian).

(156) Measurements of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=8 nm.

Example C: KOH (0.13 Equivalent with Respect to the Phenol)

(157) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 104 g of 4-(benzyloxy)phenol (0.519 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(158) The resulting suspension is heated at 140 C. under the protection of argon.

(159) A solution of 3.7 g of KOH (0.066 mol; 0.13 equivalent) in 5 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(160) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(161) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 3 h.

(162) 200 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux without stirring for 2 h.

(163) After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring, filtration of the suspension obtained makes it possible to recover 15 g of p-(benzyloxy)calix[8]arene.

(164) The filtrate is evaporated to dryness. The solid obtained is dissolved in 1 liter of an acetone/DMSO mixture (90:10 by volume) and crystallized in a refrigerator (1 C./4 days). 50 g of a microcrystalline solid is recovered, 90% constituted by giant calixarenes.

(165) DLS: average diameter measured=4.7 nm, which corresponds to a number of phenolic units estimated at 35.

(166) f) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(167) A 250 ml three-necked flask equipped with a mechanical stirrer is loaded with 22.6 g (double space) (0.113 mol) of 4-(benzyloxy)phenol, 30 ml of 37% formaldehyde in an aqueous solution and 2.53 g (0.045 mol, 0.4 equivalent with respect to the phenol) of KOH in pellets.

(168) The bright yellow clear solution obtained in this way is placed under reflux with mechanical stirring and under argon. At the end of approximately 1 h, the formation of a precipitate within the aqueous phase is observed.

(169) 40 ml of octane is then added, and the solution is taken to reflux. At the end of 1 h, the reaction medium solidifies. The heating and the stirring are stopped.

(170) The solid obtained in this way is washed with a mixture of 200 ml of methanol and 10 ml of 37% HCl, under vigorous stirring.

(171) After filtration, a white solid is recovered quantitatively, the NMR analysis of which shows that it is 60% constituted by giant calixarenes.

(172) g) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(173) A 250 ml three-necked flask equipped with a mechanical stirrer is loaded with 22.6 g (0.113 mol) of 4-(benzyloxy)phenol, 30 ml of 37% formaldehyde in an aqueous solution and 2.53 g (0.045 mol, 0.4 equivalent with respect to the phenol) of KOH in pellets.

(174) The bright yellow clear solution obtained in this way is placed under reflux with mechanical stirring and under argon. At the end of approximately 1 h, the formation of a precipitate within the aqueous phase is observed.

(175) 40 ml of xylene is then added, and the solution is taken to reflux. At the end of 2 h, the reaction medium solidifies. The heating and the stirring are stopped.

(176) The solid obtained in this way is washed with a mixture of 200 ml of methanol and of 10 ml of HCl at 37%, under vigorous stirring.

(177) After filtration, a white solid is recovered quantitatively, the NMR analysis of which is shown in FIG. 15.

(178) This solid appears to be 80% constituted by giant calixarenes.

(179) Measurement of the molar mass using GPC: M=4600 g/mol, number of phenolic units (n)=22.

(180) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=3.2 nm.

(181) h) By Heat Treatment of the Dimer of Benzyloxyphenol, Isolated, in Octane Under Reflux.

(182) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 100 g of 4-(benzyloxy)phenol (0.5 mol), 8.4 g of LiOH.H.sub.2O (0.2 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(183) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(184) A .sup.1H NMR analysis of this solid shows that it is almost exclusively constituted by the phenolic dimer (FIG. 27).

(185) The reaction medium is then neutralized with an HCl/methanol mixture, under vigorous stirring.

(186) After filtration and washing with water, a white solid is recovered quantitatively.

(187) All of the solid thus recovered is placed in a 1 L two-necked flask. A solution of KOH (11 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of octane is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 8 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 60%.

(188) i) By Heat Treatment of the Dimer of Benzyloxyphenol, Isolated, in Xylene or Toluene Under Reflux.

(189) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 100 g of 4-(benzyloxy)phenol (0.5 mol), 8.4 g of LiOH.H.sub.2O (0.2 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(190) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(191) A .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by phenolic dimer (FIG. 27).

(192) The reaction medium is then neutralized with a HCl/methanol mixture, under vigorous stirring.

(193) After filtration and washing with water, a white solid is recovered quantitatively.

(194) All of the solid thus recovered is placed in a 1-liter two-necked flask. A solution of KOH (11 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of xylene is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 4 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 40%.

(195) j) By Reaction of Benzyloxyphenol with a Base and Formaldehyde in Water, and an Organic Solvent (without Removal of Water)

(196) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 100 g of 4-(benzyloxy)phenol (0.5 mol), 13 g of KOH (0.214 mol), 100 ml of a 37% formaldehyde solution (1.34 mol) and 800 ml of xylene. The yellow emulsion thus obtained is taken to reflux for 5 h.

(197) NMR analysis shows that the reaction medium contains 60% giant calixarenes.

Example 2: Preparation of p-(Octyloxy)Calixarenes

(198) a) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water. Solid Precursor in the Form of an Isolated Brittle Resin.

(199) In a 250 ml two-necked flask, a suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) is prepared under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained.

(200) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(201) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of two hours.

(202) A bright yellow solid is obtained quantitatively.

(203) NMR analysis (CDCl.sub.3/DMSO) shows that this crude product appears to be 85% constituted by giant calixarenes.

(204) The hard and brittle yellow solid obtained previously is dispersed under vigorous stirring in a solution of 10 ml of 37% HCl in 200 ml of methanol.

(205) After filtration, a white solid is recovered quantitatively, the NMR analysis of which (CDCl.sub.3/DMSO) is shown in FIG. 16.

(206) This solid appears to be 95% constituted by giant calixarenes.

(207) Measurement of the molar mass by gel permeation chromatography (GPC):

(208) M=7700 g/mol, number of phenolic units (n)=35; average molar mass corresponding to 57 phenolic units.

(209) Measurement of the hydrodynamic radius of the calixarenes formed using DLS: D (diameter)=4.2 nm.

(210) b) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(211) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained.

(212) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(213) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of two hours.

(214) A bright yellow solid is obtained quantitatively.

(215) This solid then has 100 ml of octane added to it, and is taken to reflux for 8 h. After neutralization with a HCl/methanol mixture, a pale yellow solid is obtained quantitatively. A GPC analysis shows an increase in the size of the macrocycles obtained with respect to the preceding case (40 phenolic units, centred Gaussian).

(216) c) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(217) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained.

(218) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(219) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of two hours.

(220) A bright yellow solid is obtained quantitatively.

(221) This solid then has 100 ml of xylene added to it, and is taken to reflux for 4 h. An NMR analysis shows a decrease in the proportion of giant calixarenes (60%). A GPC study shows that the size of the macrocycles obtained is 40 phenolic units (centred Gaussian).

(222) d) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(223) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained. At the end of another 1 h of reflux, a clear brown precipitate appears in the reaction medium. After the addition of 50 ml of octane, the fluid and homogeneous suspension obtained in this way is placed under reflux for 2 h, at the end of which period of time a voluminous precipitate appears.

(224) After neutralization with a solution of HCl in methanol and filtration, a pale yellow solid is obtained.

(225) An NMR analysis shows a decrease in the proportion of giant calixarenes (60%). A GPC study shows that the size of the macrocycles obtained is 40 phenolic units (centred Gaussian).

(226) e) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(227) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained. At the end of another 1 h of reflux, a clear brown precipitate appears in the reaction medium. After the addition of 50 ml of xylene, the fluid and homogeneous suspension obtained in this way is placed under reflux for 2 h, at the end of which period of time a voluminous precipitate appears. An NMR analysis shows a decrease in the proportion of giant calixarenes (50%). A GPC study shows that the size of the macrocycles obtained is 45 phenolic units (centred Gaussian).

(228) f) By Heat Treatment of the Dimer of Octyloxyphenol, Isolated, in Octane Under Reflux.

(229) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 1.93 g of LiOH.H.sub.2O (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained.

(230) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(231) At the end of approximately 20 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of one hour.

(232) A bright yellow solid is obtained quantitatively, essentially constituted by the dimer of octyloxyphenol.

(233) This solid is neutralized under vigorous stirring with HCl in methanol, then filtered. 2.60 g of KOH (0.046 mol, 0.41 equivalent) in solution in 50 ml of methanol is then added under argon, with mechanical stirring. At the end of 4 hours, the methanol is evaporated off using a vane pump.

(234) 100 ml of octane is then added and the reaction medium is put back under reflux for 4 h.

(235) An NMR analysis of the yellow solid obtained shows that it is constituted by an 80% proportion of giant calixarenes. A GPC study shows that the size of the macrocycles obtained is 35 phenolic units (centred Gaussian).

(236) g) By Heat Treatment of the Dimer of Octyloxyphenol, Isolated, in Xylene or Toluene Under Reflux.

(237) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 1.93 g of LiOH.H.sub.2O (0.046 mol, 0.41 equivalent) is prepared in a 250 ml two-necked flask, under the protection of argon. At the end of 1 h of reflux, a bright yellow clear solution is obtained.

(238) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(239) At the end of approximately 20 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of one hour.

(240) A bright yellow solid is obtained quantitatively, essentially constituted by the dimer of octyloxyphenol.

(241) This solid is neutralized under vigorous stirring by HCl in methanol, then filtered.

(242) 2.60 g of KOH (0.046 mol, 0.41 equivalent) in solution in 50 ml of methanol is then added under argon, with mechanical stirring. At the end of 4 hours, the methanol is evaporated off using a vane pump.

(243) 100 ml of xylene is then added and the reaction medium is put back under reflux for 4 h.

(244) An NMR analysis of the yellow solid obtained shows that it is constituted by an 80% proportion of giant calixarenes. A GPC study shows that the size of the macrocycles obtained is 33 phenolic units (centred Gaussian).

(245) h) By Reaction of Octyloxyphenol with a Base and Formaldehyde in Water and an Organic Solvent (without Removal of the Water)

(246) A suspension of 25 g of 4-(octyloxy)phenol (0.113 mol), 30 ml of formaldehyde at 37% and 2.60 g of KOH (0.046 mol, 0.41 equivalent) and 200 ml of xylene is prepared in a 250 ml two-necked flask, under the protection of argon.

(247) The yellow emulsion obtained in this way is taken to reflux for 5 h.

(248) An NMR analysis shows that the reaction medium contains 80% of giant calixarenes.

Example 2.1: Preparation of p-(methoxy)calixarenes

(249) a) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and then Removal of the Water. Solid Precursor in the Form of an Isolated Brittle Resin.

(250) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(251) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour. A .sup.1H NMR analysis of this solid shows that it is 40% constituted by giant calixarenes.

(252) b) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(253) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(254) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(255) After returning to ambient temperature, 400 ml of octane is then added. The heterogeneous reaction medium obtained in this way is then taken to reflux without stirring. Monitoring the reaction then shows an evolution of the composition towards the formation of giant calixarenes.

(256) At the end of 6 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as one liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. 60 g of a powdery solid is recovered. Yield: 92%. A GPC analysis shows that this solid is constituted by giant calixarenes (size estimated using GPC: 50 phenolic units).

(257) c) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(258) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(259) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(260) After returning to ambient temperature, 400 ml of xylene is then added. The suspension obtained in this way is then taken to reflux without stirring for 4 h. The reaction medium is neutralized with 50 ml of 37% hydrochloric acid in solution in 1 liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. 60 g of a brown solid is recovered. Yield: 92%. A .sup.1H NMR analysis of this solid shows that it is 60% constituted by giant calixarenes.

(261) d) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(262) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained. Reflux is continued for 2 h, at the end of which period of time a yellow precipitate appears. 400 ml of octane is then added, and reflux is continued with stirring for 1 h, at the end of which period of time the reaction medium solidifies. The reaction medium is neutralized with 50 ml of 37% hydrochloric acid in solution in 1 liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. 60 g of a brown solid is recovered. Yield: 92%. A .sup.1H NMR analysis of this solid shows that it is 80% constituted by giant calixarenes.

(263) e) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(264) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained. Reflux is continued for 2 h, at the end of which period of time a yellow precipitate appears. 400 ml of xylene is then added, and reflux is continued with stirring for 1 h, at the end of which period of time the reaction medium solidifies. The reaction medium is neutralized with 50 ml of 37% hydrochloric acid in solution in 1 liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. 60 g of a brown solid is recovered. Yield: 92%. A .sup.1H NMR analysis of this solid shows that it is 80% constituted by giant calixarenes.

(265) f) By Heat Treatment of the Dimer of 4-(methoxy)phenol, Isolated, in Octane Under Reflux.

(266) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 10.08 g of LiOH.H.sub.2O (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(267) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(268) A .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by the phenolic dimer.

(269) The reaction medium is then neutralized with an HCl/methanol mixture, under vigorous stirring.

(270) After filtration and washing with water, a white solid is recovered quantitatively.

(271) All of the solid thus recovered is placed in a 1-liter two-necked flask. A solution of KOH (13.2 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of octane is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 4 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 80%.

(272) g) By Heat Treatment of the Dimer of 4-(methoxy)phenol, Isolated, in Xylene or Toluene Under Reflux.

(273) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 10.08 g of LiOH.H.sub.2O (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(274) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(275) A .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by the phenolic dimer.

(276) The reaction medium is then neutralized with a HCl/methanol mixture, under vigorous stirring.

(277) After filtration and washing with water, a white solid is recovered quantitatively.

(278) All of the solid thus recovered is placed in a 1-liter two-necked flask. A solution of KOH (13.2 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of xylene is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 4 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 50%.

(279) h) By Reaction of 4-(Methoxy)Phenol with a Base and Formaldehyde in Water and an Organic Solvent (without Removal of the Water).

(280) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 65 g of 4-(methoxy)phenol (0.523 mol), 12 g of KOH (0.214 mol), 100 ml of a 37% formaldehyde solution (1.34 mol) and 800 ml of xylene. The yellow emulsion obtained in this way is taken to reflux for 5 h.

(281) An NMR analysis shows that the reaction medium contains 70% of giant calixarenes.

Example 2.2: Preparation of p-(methyl)calixarenes

(282) a) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and Removal. Solid Precursor in the Form of a Brittle Resin, Isolated.

(283) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a solution of 55 g of p-cresol (0.5 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a clear pale yellow solution is obtained.

(284) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. (double space) The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a pale yellow colour. A proton NMR analysis shows that this solid is 30% constituted by giant calixarenes

(285) b) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(286) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a solution of 55 g of p-cresol (0.5 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a clear pale yellow solution is obtained.

(287) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a pale yellow colour.

(288) After returning to ambient temperature, 400 ml of octane is then added. The heterogeneous reaction medium obtained in this way is then taken to reflux without stirring. Monitoring the reaction then shows an evolution of the composition towards the formation of giant calixarenes.

(289) At the end of 6 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as one liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. 40 g of a powdery solid is recovered. Yield: 72%.

(290) c) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and Removal of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, is not Isolated, in Xylene or Toluene Under Reflux.

(291) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a solution of 55 g of p-cresol (0.51 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a clear pale yellow solution is obtained.

(292) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a pale yellow colour.

(293) After returning to ambient temperature, 400 ml of xylene is then added. The reaction medium is then taken to reflux under stirring.

(294) At the end of 6 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as one liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, and the precipitate obtained in this way is dried in air. An analysis of the reaction medium by proton NMR shows that it is 30% constituted by giant calixarenes.

(295) d) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Octane Under Reflux.

(296) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 55 g of p-cresol (0.5 mol) (0.51 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained. Reflux is continued for 2 h, at the end of which period of time a yellow precipitate appears. 400 ml of octane is then added, and reflux is continued with stirring for 1 h, at the end of which period of time the reaction medium solidifies. The reaction medium is neutralized with 50 ml of 37% hydrochloric acid in solution in 1 liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, the precipitate is washed with water, and dried in air. A .sup.1H NMR analysis of this solid shows that it is 80% constituted by giant calixarenes.

(297) e) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and Retention of the Water then Heat Treatment of the Solid Precursor in the Form of a Brittle Resin, not Isolated, in Xylene or Toluene Under Reflux.

(298) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 55 g of p-cresol (0.5 mol), 12 g of KOH (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained. Reflux is continued for 2 h, at the end of which period of time a yellow precipitate appears. 400 ml of xylene is then added, and reflux is continued with stirring for 1 h, at the end of which period of time the reaction medium solidifies. The reaction medium is neutralized with 50 ml of 37% hydrochloric acid in solution in 1 liter of methanol, under vigorous mechanical stirring. The resulting suspension is filtered, the precipitate is washed with water, and dried in air. An analysis by .sup.1H NMR of this solid shows that it is 80% constituted by giant calixarenes.

(299) f) By Heat Treatment of the Dimer of 4-(methyl)phenol, Isolated, in Octane Under Reflux.

(300) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 55 g of 4-(methyl)phenol (0.5 mol), 10.08 g of LiOH.H.sub.2O (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(301) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(302) A .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by the phenolic dimer.

(303) The reaction medium is then neutralized with a HCl/methanol mixture, under vigorous stirring.

(304) After filtration and washing with water, a white solid is recovered quantitatively.

(305) All of the solid thus recovered is placed in a 1-liter two-necked flask. A solution of KOH (12 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of octane is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 4 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 50%.

(306) g) By Heat Treatment of the Dimer of 4-(methyl)phenol, Isolated, in Xylene or Toluene Under Reflux.

(307) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 55 g of 4-(methyl)phenol (0.5 mol), 10.08 g of LiOH.H.sub.2O (0.214 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(308) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(309) A .sup.1H NMR analysis of this solid shows that it is constituted almost exclusively by the phenolic dimer.

(310) The reaction medium is then neutralized with a HCl/methanol mixture, under vigorous stirring. After filtration and washing with water, a white solid is recovered quantitatively.

(311) All of the solid thus recovered is placed in a 1-liter two-necked flask. A solution of KOH (12 g) in 150 ml of methanol is added with mechanical stirring, under argon. At the end of 8 h, the methanol is evaporated off using a vane pump. 400 ml of xylene is then added to the yellow solid obtained in this way. After fixing a water trap of the Dean-Stark type onto one of the ground glass necks, the medium is taken to reflux for 4 h. NMR monitoring of the reaction shows the evolution of the composition of the reaction medium towards the formation of giant calixarenes. Final proportion: 50%.

(312) h) By Reaction of 4-(methyl)phenol with a Base and Formaldehyde in Water and an Organic Solvent (without Removal of Water).

(313) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 55 g of p-cresol (0.5 mol), 12 g of KOH (0.214 mol), 100 ml of a 37% formaldehyde solution (1.34 mol) and 800 ml of xylene. The yellow emulsion obtained in this way is taken to reflux for 5 h.

(314) An NMR analysis shows that the reaction medium contains 70% of giant calixarenes.

Example 2.3: Preparation of p-(ethyl)calixarenes

(315) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 61.04 g of 4-(ethyl)phenol (0.5 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(316) The resulting suspension is heated at 140 C. under the protection of argon.

(317) A solution of 12 g of KOH (0.214 mol; 0.43 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(318) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(319) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(320) 600 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux under vigorous mechanical stirring, so as to thoroughly redisperse the solid precursor during this period of time.

(321) After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring and filtration, a white solid is recovered 60% constituted by giant calixarenes (.sup.1H NMR analysis).

Example 2.4: Preparation of p-(benzyl)calixarenes

(322) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 92.12 g of 4-(benzyl)phenol (0.5 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(323) The resulting suspension is heated at 140 C. under the protection of argon.

(324) A solution of 12 g of KOH (0.214 mol; 0.43 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(325) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(326) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(327) 600 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux under vigorous mechanical stirring, so as to thoroughly redisperse the solid precursor during this time. After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring and filtration, a white solid is recovered 65% constituted by giant calixarenes (.sup.1H NMR analysis).

Example 2.5: Preparation of p-(dibenzylamino)calixarenes

(328) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 150.66 g of 4-(dibenzylamino)phenol (0.5 mol) and 135 ml of formaldehyde in an aqueous solution at 30%.

(329) The resulting suspension is heated at 140 C. under the protection of argon.

(330) A solution of 12 g of KOH (0.214 mol; 0.43 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(331) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(332) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(333) 600 ml of xylene is then added to this solid, and the resulting suspension is taken to reflux under vigorous mechanical stirring, so as to thoroughly redisperse the solid precursor during this time. After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring and filtration, a white solid is recovered 55% constituted by giant calixarenes (.sup.1H NMR analysis).

Example 2.5: Preparation of p-(methyl)calixarenes in the Presence of CsOH (0.4 Equivalent)

(334) A 2-liter three-necked flask equipped with a mechanical stirrer and Dean-Stark-type water trap is loaded with a suspension of 54.03 g (0.52 mol) of 4-(methyl)phenol (p-cresol), 36 ml of a solution of CsOH at 50% (0.208 mol) and 100 ml of a 37% formaldehyde solution (1.34 mol). After 20 minutes of reflux, a bright yellow clear solution is obtained.

(335) While still maintaining reflux, a strong stream of argon is then established inside the flask, with the aim of removing the water. The initially very fluid reaction medium becomes more and more viscous, until it completely solidifies into a brittle solid with a yellow colour.

(336) After returning to ambient temperature, 200 ml of xylene is then added. The suspension obtained in this way is then taken to reflux under stirring. Monitoring the reaction then shows an evolution of the composition towards the formation of giant calixarenes.

(337) At the end of 2 h of reflux, 50 ml of 37% hydrochloric acid is added, as well as 500 ml of tetrahydrofuran, under vigorous mechanical stirring. The resulting suspension is evaporated to dryness. A .sup.1H NMR analysis shows that this solid is 50% constituted by giant calixarenes.

B) Examples of the Functionalization of Giant Calixarenes

(338) Pegylation (PEG2) of the Low Crown of a Giant Calixarene (KOH 0.4 Equivalent without Stirring, Number of Phenolic Units at Peak=60)

(339) 1 g of giant calixarenes and 5 mL of 2-(2-ethoxyethoxy)ethyl bromide are introduced into a 25 mL three-necked flask under argon. Heating is carried out at 60 C. and a suspension of 377.4 mg of sodium hydride (60% in paraffin, 9.43 mmol, 2 equivalent by phenol) in 5 mL of DMF is introduced slowly under vigorous stirring. After a night at 60 C., the reaction medium is cooled down to ambient temperature and 50 mL of methanol is added, followed by filtering and rinsing the solid with water then with methanol. The solid is placed under stirring in 50 mL of acetonitrile for 2 h then filtered and dried under vacuum. 1.41 g (=91%) of an orange-coloured solid is obtained which is solubilized hot in DMSO. 1H NMR (DMSO-d.sub.6, 50 C., , ppm): 7.22 (s, 5H, aromatics); 6.54 (s, 2H, hydroquinones); 4.83 (s, 2H, benzyl methylenes); 4.05 (s, 2H, PEG); 3.85 (s, 2H, bridging methylenes); 3.69 (s, 2H, PEG); 3.54 (s, 2H, PEG); 3.44 (s, 2H, PEG); 3.36 (m, 2H, PEG), 1.01 (s, 3H, PEG).

(340) Acetylation of the Low Crown of a Giant Calixarene (Number of Phenolic Units at Peak=60)

(341) 0.6 g of calixarene, 1.6 mL of ethyl bromoacetate, 3.91 g of potassium carbonate (2.61 mmol, 80 equivalent by phenol), 100 mg of tetrabutylammonium sulphate (0.29 mmol) and 5 mL of acetonitrile are introduced into a 10 mL three-necked flask. Heating is carried out at 75 C. overnight and 50 mL of methanol is added. Filtering is carried out followed by rinsing with water then with methanol. The solid obtained is dried under vacuum (787 mg, =91%). 1H NMR (DMSO-d.sub.6, , ppm): 7.22 (s, 5H, aromatics); 6.52 (s, 2H, hydroquinones); 4.80 (s, 2H, benzyl methylene); 4.29 (s, 2H, methylene in the alpha position of the carbonyl); 4.05 (m, 2H, methylene function ethyl); 3.96 (s, 2H, bridging methylene); 1.11 (s, 3H, methyl).

Example C)

Use of Giant Calixarenes for the Synthesis of Nanomaterials: Star Polymers

(342) The procedure used is in two stages. During the first stage, the phenolic groups of calixarene are acylated with bromopropionyl bromide. These groups constitute polymerization initiators, used during a second stage for the growth of polystyrene chains.

(343) Synthesis of the initiator for calix[50]arene.

(344) ##STR00013##

(345) The giant calixarene (500 mg, 0.0002 mol) is introduced into a Schlenk tube. 5 mL of DMF and 1.5 mL of Et.sub.3N are then added under argon. The system is immersed in an ice bath. Then 300 L of bromopropionyl bromide is introduced. The solution is stirred for 1 h. Precipitation is carried out from 50 mL of MeOH, followed by filtering under vacuum. The initiator is solubilized in a few milliliters of THF. Then a second precipitation is carried out with 50 mL of MeOH, followed by filtering under vacuum. The product is dried in a desiccator.

(346) yield=60%.

(347) .sup.1H NMR (350 MHz, CDCl.sub.3) .sub.ppm: 7.1-7.6 (m, 60H, OCH.sub.2Ar), 6.8-6.4 (m, 24H, Ar), 5.1-4.7 (m, 24H, OCH.sub.2Ar), 4-3.5 (m, 24H, Ar(phenol)-CH.sub.2), 3-1.5 (m, 24H, CH.sub.3CH(COR)Br), 2-1.5 (m, 36H, CH.sub.3CH(COR)Br).

(348) This macroinitiator is also characterized by size exclusion chromatography (FIG. 24).

(349) Synthesis of Star Polymer by Atom Transfer Radical Polymerization (ATRP)

(350) ##STR00014##

(351) CuBr (25 mg, 0.00017 mol), bipyridine (80 mg, 0.00052 mol), the previously synthesized initiator (60 mg, 0.00017 mol) and 2 mL of styrene are introduced into a Schlenk tube under argon. The reaction medium is degassed using 3 freeze-thaw cycles. The Schlenk tube is immersed in an oil bath heated at 100 C. for a given time. The mixture is solubilized in THF. The mixture is filtered on a column of basic Al.sub.2O.sub.3. The polymer is precipitated from MeOH (with a

(352) $\mathrm{ratio}=\frac{\mathrm{THF}}{\mathrm{MeOH}}-10),$
then filtered under vacuum and rinsed with MeOH. The product is dried in a desiccator.

(353) Yield=50%.

(354) .sup.1H NMR (360 MHz, CDCl.sub.3) .sub.ppm: 7.1-7.6 (m, 5H, OCH.sub.2Ar), 7.2-6.9 (m, 5H, Ar.sub.styrene).sub., 7.2-6.9 (m, 1H, CH.sub.2CH(Ar)CH.sub.2), 6.8-6.4 (m, 2H, Ar), 2.1-1.6 (m, 2H, CHCH.sub.2CH), 2.1-1.6 (m, 1H, HO.sub.2CCH(CH.sub.3)CH.sub.2), 1.6-1.3 (m, 3H, CH.sub.3CH).

(355) The star polymers obtained, which differ by the duration of the ATRP, are also characterized by size exclusion chromatography (FIG. 25).

(356) Study of the Structure of the Polymers in Solution.

(357) In order to study the behaviour of said star polymers in solution, a scaling law can be used:
Rh=KM.sup.
where Rh corresponds to the hydrodynamic radius, M corresponds to the molar mass; K and are coefficients. The terms K and are constants which vary with the polymer.
log Rh=log K+ log M

(358) The term provides information on the behaviour of polymer in solution:

(359) If tends towards 1 then the polymer behaves as a linear polymer.

(360) If tends towards 0.5 then the polymer behaves as a random coil.

(361) If tends towards 0 then polymer behaves as a hard sphere.

(362) The curve of the hydrodynamic radius (measured by light scattering) as a function of the molar mass (obtained by measuring the molar mass of the polystyrene branches (after detaching the central calixarene core by saponification) therefore make it possible to provide information on the structure of these nanoobjects in solution (FIG. 26).

(363) In the case of said star polymers originating from calix[50]arene, the alpha exponent tends to 0 (hard sphere-type behaviour in solution). The giant calixarenes therefore exhibit specific hard sphere-type hydrodynamic behaviour, and therefore form well-defined nanoobjects in solution (THF), which are potentially useful for encapsulation and vectorization.

Example 3: Comparative Examples: Production of Small p-(benzyloxy)calixarenes with CsOH<0.5 Eq and Xylene

Example A: Production of a Compound Consisting of p-(benzyloxy)calix[6]arene or of p-(benzyloxy)calix[7]arene in the Form of Caesium Salt or Neutralized or of a Mixture Comprising p-(benzyloxy)calix[6]arene and p-(benzyloxy)calix[7]arene with Caesium Hydroxide

Example A.1: Concentration of Caesium Hydroxide of 0.15 Equivalent

(364) A suspension of 50.6 g of p-(benzyloxy)phenol (0.254 mol), 20 g (0.667 mol) of paraformaldehyde (melting point: 135 C.) in 700 ml of xylene is placed under argon in a 2-liter three-necked flask equipped with a mechanical stirrer and a Dean-Stark type water trap.

(365) The suspension heated with stirring. When the temperature reaches 90 C., 7.4 ml (0.0425 mol) of a solution of CsOH at 50% (by weight) in water is added rapidly using a syringe (and under flushing with argon).

(366) The suspension is left under reflux for 6 h, during which period of time the formation of a voluminous white precipitate is observed.

(367) This precipitate is filtered, washed with xylene, then with pentane. M=35 g, yield of p-(benzyloxy)calix[7]arene (in the form of caesium monosalt): 58%

(368) The spectroscopic characteristics of this precipitate correspond to that of a monoanion of p-(benzyloxy)calix[7]arene.

(369) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.60-7.20 (multiplet, aromatics); 6.72 (fine singlet, hydroquinone); 4.93 (fine singlet, benzyl protons); 3.71 (fine singlet, intracyclic methylenes). Mass spectrometry (MALDI, DHB matrix): m/z=1617.41 (M+Cs).sup.+.

(370) A sample of 1 g of this precipitate is placed in suspension in 5 ml of dichloromethane, then neutralized with a concentrated aqueous solution of HCl, under vigorous stirring for 24 h.

(371) The organic phase is recovered, then evaporated to dryness in a rotary evaporator.

(372) 0.91 g of a white solid is recovered, the spectroscopic characteristics of which are perfectly consistent with neutral p-(benzyloxy)calix[7]arene.

(373) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.62 (fine singlet, hydroquinone); 4.84 (fine singlet, benzyl protons); 3.74 (fine singlet, intracyclic methylenes).

(374) Mass spectrometry (MALDI, DHB matrix): m/z=1507.65 (M+Na).sup.+.

(375) The loss of mass observed (90 mg) is completely consistent with that expected for neutralization of a caesium monosalt: p-(benzyloxy)calix[7]arene.sup..Cs.sup.+.fwdarw.p-(benzyloxy)calix[7]arene.

Example A.2: Concentration of Caesium Hydroxide of 0.3 Equivalent

(376) A suspension of 50.6 g of p-(benzyloxy)phenol (0.254 mol), 20 g (0.667 mol) of paraformaldehyde (melting point: 135 C.) in 700 ml of xylene is placed under argon in a 2-liter three-necked flask equipped with a mechanical stirrer and a Dean-Stark type water trap. The suspension is heated with stirring. When the temperature reaches 90 C., 14.8 ml (0.085 mol) of a solution of CsOH at 50% (by weight) in water is added rapidly using a syringe (and under flushing with argon).

(377) The suspension is left under reflux for 5 h 30. Then a perfectly clear bright orange solution is obtained.

(378) 100 ml of a solution of 37% HCl in water is then added, and the formation of a precipitate is observed. The suspension is left under vigorous stirring for two days, then evaporated to dryness in a rotavapor.

(379) After washing with 500 ml of water (removal of the salts and excess HCl), the solid is dissolved hot (130 C.) in 200 ml of DMSO. Then a clear solution black is obtained, to which 2 l of acetone is added hot.

(380) After returning to ambient temperature, this clear solution is left for a week, during which a crystalline precipitate of p-(benzyloxy)calix[6]arene (18 g) is deposited on the walls of flask.

(381) The filtrate is evaporated in a rotary evaporator, then with a heat gun until a black solid is obtained. This solid is washed with acetone, which leads to the recovery of a second batch of p-(benzyloxy)calix[6]arene (10 g). Total: 28 g, yield 51%.

(382) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.62 (fine singlet, hydroquinones); 4.79 (fine singlet, benzyl protons); 3.72 (fine singlet, intracyclic methylenes).

(383) Mass spectrometry (MALDI, DHB matrix): m/z=1295.49 (M+Na).sup.+.

(384) Production of a Compound Consisting of p-(benzyloxy)calix[6]arene or p-(benzyloxy)calix[7]arene in Neutralized Form or p-(benzyloxy)calix[8]arene or a Mixture Comprising p-(benzyloxy)calix[6]arene, p-(benzyloxy)calix[7]arene and p-(benzyloxy)calix[8]arene with Sodium or Potassium Hydroxide.

Example B.1: Concentration of Sodium or Potassium Hydroxide of 0.15 Equivalent

(385) A suspension of 34.5 g of p-(benzyloxy)phenol (0.173 mol), 20 g (0.667 mol) of paraformaldehyde (melting point: 135 C.) in 450 ml of xylene is placed under argon in a 1-liter three-necked flask equipped with a mechanical stirrer and a Dean-Stark type water trap. The suspension is heated with stirring. When temperature reaches 95 C., a solution of 1.43 g (0.03 mol) of KOH in 6 ml of Millipore water is added rapidly using a syringe (and under flushing with argon). The immediate appearance of a yellow coloration is observed.

(386) The reaction medium is taken to reflux for 3 h 30, during which period of time the formation of a copious white precipitate and a bright orange solution is observed.

(387) After returning to ambient temperature, the precipitate is recovered by filtration, washed with 100 ml of xylene and 300 ml of pentane.

(388) Analysis of this precipitate indicates that it is constituted by pure p-(benzyloxy)calix[7]arene. M=20 g, yield 54%.

(389) Characterizations:

(390) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.62 (fine singlet, hydroquinone); 4.84 (fine singlet, benzyl protons); 3.74 (fine singlet, intracyclic methylenes). Mass spectrometry (MALDI, DHB matrix): m/z=1524.62 (M+K).sup.+.

Example B.2: Concentration of Sodium or Potassium Hydroxide of 0.3 Equivalent

(391) A suspension of 51.5 g of p-(benzyloxy)phenol (0.258 mol), 20 g (0.667 mol) of paraformaldehyde (melting point: 135 C.) in 700 ml of xylene is placed under argon in a 2-liter three-necked flask equipped with a mechanical stirrer and a Dean-Stark type water trap.

(392) The suspension is heated with stirring. When the temperature reaches 90 C., 3.056 g of NaOH (0.0764 mol) in 10 ml of water is added rapidly using a syringe (and under flushing with argon).

(393) The suspension is left under reflux for 4 h30, a period at the end of which the reaction medium solidifies.

(394) After returning to ambient temperature, the reaction medium is neutralized with 500 ml of a 2M HCl solution, under very vigorous stirring.

(395) The resulting emulsion is evaporated to dryness and washed with 500 ml of water (removal of the sodium salts).

(396) The resulting orange solid is washed with 500 ml of THF and the resulting white precipitate is filtered, which leads to the recovery of 20 g of pure p-(benzyloxy)calix[8]arene. Yield: 36.6%.

(397) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.58 (fine singlet, hydroquinones); 4.80 (fine singlet, benzyl protons); 3.77 (fine singlet, intracyclic methylenes).

(398) Mass spectrometry (MALDI, DHB matrix): m/z=1719.62 (M+Na).sup.+.

(399) The corresponding filtrate is evaporated to dryness, and dissolves hot in 45 ml of DMSO, which leads to formation of a black homogeneous solution. 1 liter of toluene is added thereto, and the dark orange clear solution is placed in the freezer (23 C.) for 1 week, which leads to the formation of a microcrystalline precipitate. This precipitate is filtered, and its analysis by .sup.1H NMR shows that it is pure p-(benzyloxy)calix[6]arene; m=6.3 g, 11%.

(400) .sup.1H NMR (DMSO-d.sub.6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.62 (fine singlet, hydroquinone); 4.79 (fine singlet, benzyl protons); 3.72 (fine singlet, intracyclic methylenes).

(401) Mass spectrometry (MALDI, DHB matrix): m/z=1295.49 (M+Na).

(402) The corresponding DMSO/toluene filtrate is evaporated until an orange-coloured liquid is obtained. After the addition of 1 liter of methanol and filtration, 28.5 g of pure p-(benzyloxy)calix[7]arene is recovered. Yield: 52%.

(403) .sup.1H NMR (DMSO-d6): (chemical shifts, ppm) 7.30 (broad multiplet, aromatics); 6.62 (fine singlet, hydroquinones); 4.84 (fine singlet, benzyl protons); 3.74 (fine singlet, intracyclic methylenes).

(404) Mass spectrometry (MALDI, DHB matrix): m/z=1524.62 (M+K).sup.+.

Example 4: Comparative Example: Reaction of p-(t-butyl)phenol with a Base at <0.5 Eq in Water without Organic Solvent

(405) A 2-liter three-necked flask equipped with a mechanical stirrer, a Dean-Stark trap and a condenser as well as heating using an oil bath, is loaded with 100 g of 4-(tBu)phenol (0.666 mol) and 135 ml of 37% formaldehyde in an aqueous solution.

(406) The resulting suspension is heated at 140 C. under the protection of argon.

(407) A solution of 15 g of KOH (0.266 mol; 0.4 equivalent) in 10 ml of water is rapidly injected at 90 C., while continuing heating. The white suspension transforms into a bright yellow clear solution. This solution is maintained under reflux for 1 h.

(408) One of the ground glass necks of the flask is then equipped with a swan-neck connected to a bubbler, and the solution is then subjected to vigorous flushing with argon (20 bubbles/s), the argon inlet being via the top of the condenser.

(409) At the end of approximately 40 min of flushing, the initially clear and fluid solution becomes more and more viscous, and finally solidifies at the end of 1 h.

(410) NMR analysis of this solid (DMSO-d6) is shown in FIG. 17.1.

(411) This solid seems essentially constituted by p-(tBu)calix[8]arene, by comparison with the reference sample of this compound in DMSO-d6 (FIG. 17.2).

(412) 400 ml of toluene is then added to this solid, and the resulting suspension is taken to reflux without stirring for 2 h.

(413) After neutralization with a mixture of 500 ml of THF/50 ml of 37% HCl under vigorous stirring, NMR analysis of this solid (CDCl.sub.3, FIG. 18) shows that the product obtained comprises a significant proportion of p-(tBu)calix[4,6,8]arenes (comparison with authentic samples), as well as a high proportion of polymers (broad signals).

(414) The characteristic evolution of the spectroscopic signature of the bridging methylenes of the large-sized calixarenes (9 to 16 repeat units) in CDCl.sub.3 is not observed (C. D. Gutsche et al., JACS 1999).

(415) Moreover, the presence of intense signals at 5 ppm indicates a high proportion of linear oligomers.

Example 5: Comparative Example: Preparation of a Mixture of p-benzyloxycalix[9-20]arenes with CsOH or RbOH (0.6 Eq)

(416) A suspension of 50 g (0.25 mol) of 4-(benzyloxy)phenol and 18 g (0.6 mol) of paraformaldehyde in 700 ml of xylene is prepared under argon in a 2-liter two-necked flask equipped with a Dean-Stark trap and a condenser.

(417) The suspension is heated under argon and vigorous magnetic stirring, and at 90 C. 26 ml of a solution of CsOH at 50% in water is added rapidly.

(418) The reaction medium is taken to reflux for 6 h, during which period of time a clear orange-coloured solution is obtained.

(419) An NMR analysis (DMSO-d6, FIG. 19) of this solution shows that it comprises approximately 60% of large calixarenes (identifiable by characteristic signals at 6.52 ppm).

(420) This solution is neutralized by the addition of 200 ml of THF containing 20 ml of 37% HCl under vigorous stirring.

(421) The resulting suspension is evaporated, and washed with 200 ml of acetonitrile (removal of the small calixarenes).

(422) The resulting solid is dissolved in 1 liter of an acetone/DMSO mixture (90/10 by volume), filtered (removal of calix[8]arene) and left in a refrigerator (1 C.) for 4 days.

(423) 15 g of a microcrystalline solid is recovered.

(424) This solid is constituted by a mixture of large calixarenes.

(425) Its different constituents can be separated by a succession of recrystallizations/chromatographies using different solvents. The corresponding purification diagram is given in FIG. 20.