PAPER
Synthesis of Benzocrown Ethers
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evaporated. The residue was distilled under vacuum; yield: 140.7 g
(82%); colorless liquid; bp 210–212 °C/1.33 mbar.
1H NMR (500 MHz, CDCl3): = 2.98 (br s, 2 H), 3.66 (m, 4 H),
3.73 (m, 4 H), 3.88 (m, 4 H), 4.14 (m, 4 H), 6.89 (m, 4 H).
ture was vigorous stirred at reflux for 16 h. The organic layer was
separated and washed with H2O (3 200 mL), brine (100 mL), and
dried (MgSO4). The solvent was removed under vacuum, and the
residue was extracted with boiling hexane (3 150 mL). After cool-
ing, the pure products were isolated as colorless crystals (5a–c) or
oils (5d, 5e).
MS (EI+): m/z = 286 (M+).
Anal. Calcd for C14H22O6: C, 58.73; H, 7.74. Found: C, 58.82; H,
7.86
Procedure D: A solution of p-toluenesulfonyl chloride (50 mmol)
and the appropriate glycol 4a–d (50 mmol) in toluene (300 mL) was
added dropwise within 2.5 h to a vigorously stirred mixture of
Bu4NI (1.25 mmol), toluene (300 mL) and 50% aq NaOH (100 mL)
maintained at 70–75 °C. The mixture was stirred for a further 13 h
at this temperature. The organic layer was separated, filtered,
washed with H2O (3 200 mL), brine (100 mL), and dried
(MgSO4). The pure compounds 5a–d were obtained as describe
above.
2-[2-(2-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}phenoxy)-
ethoxy]-1-ethanol (4c)
A mixture of 6 (89.10 g, 450 mmol), triethylene glycol chlorohydrin
(84.30 g, 500 mmol) and K2CO3 (93.15 g, 675 mmol) in anhyd
DMF (600 mL) was stirred at 95–100 °C for 10 h under N2. After
cooling down to r.t., the mixture was filtered, and concentrated to
dryness under reduced pressure. The residue was poured into H2O
(400 mL), and extracted with CHCl3 (4 200 mL). The combined
organic phases were dried (Na2SO4), and the solvent was evaporat-
ed. The residue was distilled in vacuum to afford 4c; yield: 135.1 g
(91%); colorless liquid; bp 220–222 °C/0.23 mbar.
Analytical and spectral data (MS, 1H NMR) of benzocrown ethers
5a–d were in good agreement with the data reported.24,28
References
1H NMR (500 MHz, CDCl3): = 3.34 (br s, 2 H), 3.59 (m, 2 H),
3.69 (m, 4 H), 3.72 (m, 2 H), 3.76 (m, 4 H), 3.90 (m, 4 H), 4.17 (m,
4 H), 6.91 (m, 4 H).
(1) Pedersen, C. J. Angew. Chem. Int. Ed. 1988, 27, 1021.
(2) Vögtle, F.; Weber, E. In The Chemistry of Ethers, Crown
Ethers, Hydroxyl Groups and Their Sulphur Analogues;
Patai, S., Ed.; Wiley: Chichester, 1980, 59–156.
(3) Laidler, D. A.; Stoddart, J. F. In The Chemistry of Ethers,
Crown Ethers, Hydroxyl Groups and Their Sulphur
Analogues; Patai, S., Ed.; Wiley: Chichester, 1980, 1–58.
(4) Viout, P.; Lehn, J.-M. Macrocyclic Chemistry; VCH: New
York, 1993.
MS (EI+): m/z = 330 (M+).
Anal. Calcd for C16H26O7: C, 58.17; H, 7.93. Found: C, 57.92; H,
7.83
2-{2-[2-(2-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}phenoxy)-
ethoxy]ethoxy}-1-ethanol(4d)
(5) Vögtle, F. Supramolecular Chemistry; Wiley: New York,
1991.
(6) Lehn, J.-M. Supramolecular Chemistry; VCH: New York,
1995.
Following the method described for compound 4b, the title com-
pound was obtained from the catechol (1; 66.6 g, 600 mmol) and tri-
ethylene glycol chlorohydrin (222.0 g, 1.32 mol); yield: 165.5 g
(74%); colorless liquid; bp 220–225 °C/0.13 mbar.
(7) Fyfe, M. C. T.; Stoddart, J. F. Adv. Supramol. Chem. 1999,
5, 1.
(8) Cantrill, S. J.; Pease, A. R.; Stoddart, J. F. J. Chem. Soc.,
Dalton Trans. 2000, 3715.
(9) Amabilino, D. B.; Stoddart, J. F. Chem. Rev. 1995, 95, 2725.
(10) Gokel, G. W. Chem. Soc. Rev. 1992, 21, 39.
(11) Gibson, H. W. Macromol. Chem. Phys. 2000, 201, 815.
(12) Kakuchi, T.; Watanabe, T.; Matsunami, S.; Kamimura, H.
Polymer 1997, 38, 1233.
(13) Knops, P.; Sendhoff, N.; Mekelburger, H.-B.; Vögtle, F.
Top. Curr. Chem. 1992, 161, 3.
(14) Ostrowicki, A.; Koepp, E.; Vögtle, F. Top. Curr. Chem.
1992, 161, 39.
(15) Dehmlow, E. V.; Dehmlow, S. S. Phase Transfer Catalysis;
VCH: Weinheim, 1993.
(16) Bogatsky, A. V.; Lukyanenko, N. G.; Basok, S. S.;
Ostrovskaya, L. K. Synthesis 1984, 138.
1H NMR (500 MHz, CDCl3): = 2.82 (br s, 2 H), 3.59 (m, 4 H),
3.67 (m, 4 H), 3.70 (m, 4 H), 3.74 (m, 4 H), 3.87 (m, 4 H), 4.17 (m,
4 H), 6.90 (m, 4 H).
MS (EI+): m/z = 374 (M+).
Anal. Calcd for C18H30O8: C, 57.74; H, 8.08. Found: C, 57.82; H,
7.93
2-[2-(2-Hydroxyethoxy)ethoxy]phenol (6)
A mixture of catechol (1; 66.6 g, 600 mmol), diethylene glycol
chlorohydrin (104.5 g, 840 mmol), and K2CO3 (130.5 g, 950 mmol)
in anhyd DMF (700 mL) was stirred at 95–100 °C for 10 h. After
cooling, it was filtered and concentrated to dryness under reduced
pressure. The residue was poured into H2O (400 mL), and the aque-
ous layer was extracted with CHCl3 (4 200 mL). The combined
organic phases were dried (Na2SO4), and the solvent was evaporat-
ed. The residue was purified by distillation under vacuum to afford
6 (61.7 g, 52%); colorless liquid; bp 145–150 °C/1.33 mbar.
(17) Lukyanenko, N. G.; Basok, S. S.; Filonova, L. K. J. Chem.
Soc., Perkin Trans. 1 1988, 3141.
(18) Hodgkinson, L. C.; Sutherland, I. O. J. Chem. Soc., Perkin
Trans. 1 1979, 1908.
(19) Topal, G.; Demire, N.; Togrul, M.; Turgut, Y.; Hosgoren, H.
J. Heterocycl. Chem. 2001, 38, 281.
1H NMR (500 MHz, CDCl3): = 3.71 (m, 2 H), 3.78 (m, 2 H), 3.88
(m, 2 H),3.93 (m, 2 H), 4.06 (m, 2 H), 4.13 (m, 2 H), 4.32 (br s, 1
H), 4.80 (br s, 1 H), 6.92 (m, 4 H).
MS (EI+): m/z = 198 (M+).
(20) Weber, E. Chem. Ber. 1985, 118, 4439.
(21) Draye, M.; Favre-Reguillon, A.; Chomel, R.; Faure, R.;
Guy, A.; Foos, J.; Lemaire, M. Bull. Soc. Chim. Fr. 1996,
133, 183.
(22) Kyba, E. P.; Helheson, R. C.; Madan, K.; Gokel, G. W.;
Tarnowski, T. L.; Cram, D. G. J. Am. Chem. Soc. 1977, 99,
2564.
Anal. Calcd for C10H14O4: C, 60.59; H, 7.12. Found: C, 60.42; H,
6.96.
Benzocrown Ethers 5a–e; General Procedures
Procedures A–C: To a stirred solution of catechol (1; 50 mmol) or
glycol 2 (50 mmol) or the appropriate oligo(ethyleneglycol) (50
mmol) and Bu4NI in toluene (300 mL) was added 50% aq NaOH
(100 mL) at 50–60 °C. The mixture was stirred at this temperature
for further 30 min, whereupon a solution of corresponding ditosyl-
ate (50 mmol) in toluene (300 mL) was added. The resulting mix-
(23) Czech, B.; Czech, A.; Bartch, R. A. J. Heterocycl. Chem.
1984, 21, 341.
Synthesis 2002, No. 15, 2266–2270 ISSN 0039-7881 © Thieme Stuttgart · New York