1228
A. Mathieu et al. / Tetrahedron Letters 43 (2002) 1225–1229
6. The crystal structure of 6 is described in: Pe`pe, G.; Astier,
ArCH2
(d, 2Hax, J=13.2 Hz, ArCH2
OCH2CH2O), 3.19 (d, 2Heq, J=13.2 Hz, ArCH2
(d, 1Heq, J=13.0 Hz, ArCH2Ar), 3.10 (d, 1Heq, J=13.0
Hz, ArCH2Ar). Anal. calcd for C42H48O9·1/2CH2Cl2: C,
69.05; H, 6.68. Found C, 69.05; H, 6.95. FAB MS
m/z=697.1 (MH+). Yield: 13%. Compound
was
6
Ar), 4.54 (d, 1Hax, J=13.0 Hz, ArCH2
Ar), 4.37–3.72 (m, 28H,
Ar), 3.12
6 Ar), 4.37
J. P.; Estienne, J.; Bressot, C.; Asfari, Z.; Vicens, J. Acta
Crystallogr. 1995, C51, 726.
6
6
6
6
7. General: All reagents and solvents were commercial and
used without further purification. DMF is analytical
grade from Prolabo. Calix[4]arene was prepared accord-
ing to the literature.12 The melting points were taken on
Bu¨chi apparatus in a capillary sealed under nitrogen.
Chromatography, SiO2 columns with Kieselgel Merck
(art. 11567). 1H NMR in CDCl3 or in D2O, Brucker
SY200 (l in ppm, J in Hz), FAB(+), VG-Analytical ZAB
HF. Elemental analyses performed at the Service de
Microanalyse of the Institut de chimie de Strasbourg.
Compound 23 was prepared as described elsewhere.
8. Preparation of 4, 6 and 8. Calix[4]arene (8.49 g, 20.00
mmol), NaH (2.40 g, 100.00 mmol), appropriated ethyl-
ene glycol ditosylate (24.00 mmol) and dimethylfor-
mamide (1800 ml) were heated at 50°C under N2. After 3
days, the same quantities of NaH and ethylene glycol
ditosylate were added. 3 days later, methanol and water
were added and solvents were evaporated to dryness and
the residue was dissolved in dichloromethane. The solu-
tion was acidified with conc. aq. HCl. The organic layer
was dried over Na2SO4, filtered and evaporated to dry-
ness. Compound 4 was precipitated with ethanol and 6
and 8 were purified by column chromatography. Com-
pound 4 was obtained pure as a white solid by precipita-
6
6
7
obtained pure as a yellow oil by chromatography (SiO2,
1
80/20 dichloromethane/acetone as eluent). H NMR (200
MHz, CDCl3): 6.66–6.57 (m, 12H, ArH
position), 4.61 (d, 1Hax, J=13.1 Hz, ArCH2
1Hax, J=13.5 Hz, ArCH2Ar), 4.39 (d, 2Hax, J=13.5 Hz,
ArCH2Ar), 4.20–3.87 (m, 16H, OCH2CH2O), 3.74–3.66
(m, 20H,OCH2CH2O), 3.20–3.10 (m, 4Heq, ArCH2Ar).
6
in meta and para
6
Ar), 4.60 (d,
6
6
6
6
6
6
6
Anal. calcd for C46H56O11: C, 70.39; H, 7.19. Found C,
70.23; H, 7.21. FAB MS m/z=785.5 (MH+). Yield: 14%.
9. Preparation of 9–13. Calixarenes 4–8 (2.00 mmol),
HSO3Cl (9.32 g, 8.00 mmol) in 30 ml of dichloromethane
were stirred at room temperature under N2 for 3 h. Ice
was added and the aqueous layer was washed three times
with dichloromethane. The organic layer was dried over
Na2SO4, filtered and evaporated to dryness to afford the
corresponding 9–13. 9: 1H NMR (200 MHz, CDCl3): 7.51
(s, 8H, ArH
ArCH2Ar), 4.58–3.68 (m, 26H, ArCH2
OCH2CH2O), 3.54 (d, 2Heq, J=13.8 Hz, ArCH2
(d, 2Heq, J=13.5 Hz, ArCH2Ar). Yield: quantitative. 10:
1H NMR (200 MHz, CDCl3): 7.53–7.47 (m, 8H, ArH
in
meta position), 5.31 (d, 1Hax, J=13.4 Hz, ArCH2Ar),
5.30 (d, 1Hax, J=13.7 Hz, ArCH2Ar), 4.60–3.66 (m, 28H,
OCH2CH2O), 4.53 (d, 2Hax, J=13.4 Hz, ArCH2Ar), 3.50
(d, 2Heq, J=13.4 Hz, ArCH2Ar), 3.39 (d, 1Heq, J=13.7
Hz, ArCH2Ar), 3.37 (d, 1Heq, J=13.4 Hz, ArCH2Ar).
Yield: quantitative. 11: 1H NMR (200 MHz, CDCl3):
7.49 (s, 8H, ArH in meta position), 4.92 (d, 2Hax, J=13.6
Hz, ArCH2Ar), 4.52 (d, 2Hax, J=13.7 Hz, ArCH2Ar),
4.45–3.87 (m, 32H, OCH2CH2O), 3.47 (d, 2Heq, J=13.7
Hz, ArCH2Ar), 3.39 (d, 2Heq, J=13.6 Hz, ArCH2Ar).
Yield: quantitative. 12: 1H NMR (200 MHz, CDCl3):
7.49 (s, 8H, ArH in meta position), 4.97 (d, 1Hax, J=13.4
Hz, ArCH2Ar), 4.90 (d, 1Hax, J=14.0 Hz, ArCH2Ar),
4.66 (d, 2Hax, J=13.4 Hz, ArCH2Ar), 4.45–3.36 (m, 40H,
OCH2CH2O and ArCH2
Ar). Yield: quantitative. 13: 1H
NMR (200 MHz, CDCl3): 7.49 (s, 8H, ArH in meta
position), 4.91 (d, 2Hax, J=13.9 Hz, ArCH2Ar), 4.84 (d,
2Hax, J=13.4 Hz, ArCH2Ar), 4.46–3.33 (m, 44H,
OCH2CH2O and ArCH2Ar). Yield: quantitative.
6
in meta position), 5.24 (d, 2Hax, J=13.5 Hz,
Ar and
Ar), 3.38
6
6
6
6
6
6
1
tion with ethanol. Mp 158–160°C. H NMR (200 MHz,
6
CDCl3): 6.76–6.55 (m, 12H, ArH
tion), 4.98 (d, 2Hax, J=13.0 Hz, ArCH2
(m, 6H, ArCH2Ar and ArOCHHCH2O), 4.26–4.15 (m,
4H, ArOCHHCH2O), 3.96–3.67 (m, 16H, OCH2CH2O),
3.22 (d, 2Heq, J=13.4 Hz, ArCH2Ar), 3.11 (d, 2Heq,
J=13.0 Hz, ArCH2Ar). Anal. calcd for
6
in meta and para posi-
6
6
Ar), 4.39–4.31
6
6
6
6
6
6
6
6
6
6
6
6
6
6
C40H44O8·C2H6O: C, 72.17; H, 7.22. Found C, 72.22; H,
7.24. FAB MS m/z=653.3 (MH+). Yield: 17%. Com-
pound 6 was obtained pure as a white solid by chro-
matography (SiO2, 95/5 dichloromethane/acetone as
6
6
6
6
6
6
6
1
eluent). Same H NMR as a sample of 6 obtained previ-
ously.5 Mp 82–84°C. Mp lit. 206–207°C.5 Yield: 13%.
Compound 8 was obtained pure as a yellow oil by
chromatography (SiO2, 95/5 dichloromethane/acetone as
6
6
6
6
1
eluent). H NMR (200 MHz, CDCl3): 6.67–6.53 (m, 12H,
6
6
6
ArH
Hz, ArCH
4.22–3.63 (m, 40H, OCH
Hz, ArCH2Ar). Anal. calcd for C48H60O12: C, 69.85; H,
6
in meta and para position), 4.58 (d, 2Hax, J=13.2
2Ar), 4.39 (d, 2Hax, J=13.2 Hz, ArCH2Ar),
2CH2O), 3.15 (d, 4Heq, J=13.2
6
6
6
6
6
6
6
6
6
6
6
7.24. Found C, 69.55; H, 7.30. FAB MS m/z=829.5
(MH+). Yield: 20%. Preparation of 5 and 7. 1,2-Calix[4]-
monocrown (ꢀ7.00 mmol), NaH (0.84 g, 35.00 mmol),
appropriate ethylene glycol ditosylate (7.70 mmol) and
dimethylformamide (1000 ml) were heated at 50°C under
N2. After 3 days, the same quantities of NaH and ethyl-
ene glycol ditosylate were added. 3 days later, methanol
and water were added and solvents were evaporated to
10. Preparation of 14–18. Calixarenes 9–13 (1.80 mmol), pyr-
idine (10 ml) and water (2.5 ml) were stirred at room
temperature for 2 h. Solvents were evaporated to dryness.
The residue was dissolved in a minimum amount of water
and treated with a solution of 10% NaOH in water.
Precipitation with acetone afforded 14 as a white solid.
Mp >260°C. 1H NMR (200 MHz, D2O): 7.15 (s, 8H,
ArH
ArCH
4.10 (m, 8H, ArOCH
OCH2CH2O), 3.34 (d, 2Heq, J=13.2 Hz, ArCH2
(d, 2Heq, J=12.9 Hz, ArCH2Ar). Anal. calcd for
6
in meta position), 4.81 (d, 2Hax, J=12.9 Hz,
2Ar), 4.72 (d, 2Hax, J=13.2 Hz, ArCH2Ar), 4.38–
2CH2O), 3.82–3.56 (m, 16H,
Ar), 3.19
dryness
and
the
residue
was
dissolved
in
6
6
dichloromethane. The solution was acidified with conc.
aqueous HCl. The organic layer was dried over Na2SO4,
filtered and evaporated to dryness. Compound 5 was
obtained pure as a white solid by chromatography (SiO2,
95/5 dichloromethane/acetone as eluent). Mp 210–212°C.
6
6
6
6
6
C40H40Na4O20S4·3H2O: C, 43.09; H, 4.16. Found C,
43.09; H, 4.17. ES MS m/z=1037.1 (M−Na+). Yield:
1H NMR (200 MHz, CDCl3): 6.70–6.54 (m, 12H, ArH
meta and para position), 4.99 (d, 1Hax, J=13.0 Hz,
6
in
quantitative. 15 as a white solid. Mp >260°C. H NMR
1
(200 MHz, D2O): 7.16–7.14 (m, 8H, ArH6 in meta posi-