Facile and rapid synthesis of some crown ethers under microwave irradiation

Article abstract of DOI:10.1080/10426500500271972

A series of crown ethers were synthesized from the reaction of 1,8-dichloro-3,6-dioxaoctane with the appropriate hydroxy compound under microwave irradiation in short times and high yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500500271972

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Phosphorus, Sulfur, and Silicon
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Facile and Rapid Synthesis
of Some Crown Ethers Under
Microwave Irradiation
Ahmad Ziafati a , Omolbanin Sabzevari a & Majid M.
Heravi a b
a Department of Chemistry , Ferdosi University of
Mashad , Mashad, Iran
b Azzahra University , Vanak, Tehran, Iran
Published online: 15 Aug 2006.
To cite this article: Ahmad Ziafati , Omolbanin Sabzevari & Majid M. Heravi (2006)
Facile and Rapid Synthesis of Some Crown Ethers Under Microwave Irradiation,
Phosphorus, Sulfur, and Silicon and the Related Elements, 181:4, 803-807, DOI:
10.1080/10426500500271972
To link to this article: http://dx.doi.org/10.1080/10426500500271972
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Phosphorus, Sulfur, and Silicon, 181:803–807, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500500271972
Facile and Rapid Synthesis of Some Crown Ethers
Under Microwave Irradiation
Ahmad Ziafati
Omolbanin Sabzevari
Department of Chemistry, Ferdosi University of Mashad, Mashad, Iran
Majid M. Heravi
Department of Chemistry, Ferdosi University of Mashad, Mashad, Iran,
and Azzahra University, Vanak, Tehran, Iran
A series of crown ethers were synthesized from the reaction of 1,8-dichloro-3,6-
dioxaoctane with the appropriate hydroxy compound under microwave irradiation
in short times and high yields.
Keywords Synthesis of crown ethers
Since the pioneering work of Pederson on the preparation and proper-
ties of macrocyclic polyethers (crown ethers),1 there have been waves
of interest concerning the synthesis of a wide variety of oxygen-, sulfur-
and nitrogen-containing crowns.2 The crown ethers have proved to be
enormously popular and extremely useful ligands (host) for a startling
range of metal ions and neutral or ionic organic species.3 Indeed, it
seems as if they bend into the majority of the elements of the periodic
table. The highly flexible crown ethers have proved to be capable of
adopting themselves to a wide variety of a coordination requirements
and media.4 Furthermore, immobilization of the crown ethers onto poly-
mers allows for the ease of handling recyclability and the adoption to
continuous processes for this important set of complexants.5
Crown ether derivatives can be useful as potential chiral selectors
in capillary electrophoresis for the chiral separation of amino acids.6
Crown ethers have been developed to increase the metal selectivity
and complex stability in analytical separation methods as well as in
Received February 22, 2005; accepted April 14, 2005.
We are grateful to Ferdowsi University and Mashad Research Council for partial
financial assistance.
Address correspondence to Majid M. Heravi, Azzahra University, Department of
Chemistry, School of Sciences, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
803

804
A. Ziafati et al.
biological membranes.7 Considerable attention also has been paied to
crown ether dyes containing a chromophore.8 The increasing interest
to rapidly provide highly pure large molecules is driving the develop-
ment of new technologies. Microwave-assisted organic chemistry is a
relatively new technology that has been shown to significantly improve
productivity in the rapid generation of complex molecules.9 Microwave
irradiation has been demonstrated not only to significantly accelerate
many organic reactions, but also to improve yields and selectivity.10
As a result of the work performed in our laboratories concerning the
synthesis of organic compounds under microwave irradiation,9 inter-
est has developed in the synthesis at variety of crown ethers by this
technique.11
While several syntheses for substituted derivatives of 12-crown-4
and 15-crown-512 have been reported, only a few syntheses of un-
substituted crown ethers have appeared in the literature.2d Cook and
colleagues2d prepared 12-crown-4 in 13% yields and 15-crown-5 in 14%
yields. Here we wish to report the facile and rapid modified Williamson
syntheses of 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7 in
good yields using easily prepared 1,8-dichloro-3,6-dioxaoctane 1 in the
presence of a base under microwave irradiation. Compound 1 was easily
prepared from the reaction of triethylene glycol with thionyl chloride
in benzene in the presence of piperidine.1a
Compound 1 was caused to react with an appropriate hydroxy com-
pound in the presence of potassium hydroxide under microwave irradi-
ation to afford the corresponding crown ether (Scheme 1).
Dibenzo-14-crown-4 was synthesized from the reaction of cathacol
with 1,3-dichloropropane in the same manner in the presence of sodium
hydroxide (Scheme 2).
In conclusion, we have developed a modified Williamson synthesis
for the rapid preparation of crown ethers under microwave irradiation
in good yields.
EXPERIMENTAL
IR spectra were obtained on a 4300 Shimdzu spectrometer. The 1HNMR
spectra were recorded on a Bruker Ac 100 unless otherwise stated using
TMS as a standard reference. Mass spectra were scanned on a Varian
CH-7 instrument at 70 ev.
SYNTHESIS OF CROWN ETHERS UNDER MICROWAVE
IRRADIATION: GENERAL PROCEDURE
Compound 1 (1 mmol) and an appropriate dihydroxy compound
(1 mmol) were mixed with potassium hydroxide (0.02 mol) and water

Synthesis of Crown Ethers
805
SCHEME 1
(1 mL). The mixture was placed in an unmodified microwave oven for
the indicated time. Progress of the reaction was monitored by TLC. After
completion of the reaction, the resulting thick, brown slurry was diluted
with dichloromethane (10 mL) and filtered. The filtrate was dried over
MgSO4 and evaporated to dryness to afford the corresponding crown
ether. The final product was purified by vacuum distillation.
SCHEME 2

806
A. Ziafati et al.
SELECTED DATA FOR 2
Irradiation time 6 min, yield 37%, b.p. 176 at 33 mmHg lit.1b 60–70
at 0.5 mmHg, IR (KBr disc) 2930, 1460, 1365, 1285, 1250, 1130, 1100,
920 cm−1, 1HNMR, δ(CDCl3), 3.65 (sharp s) MS, m/z, M+, 176.
SELECTED DATA FOR 3
Irradiation time, 8 min, yield 40%, b.p. 220–225 at 33 mmHg, IR (KBr
disc) 2870, 1440, 1350, 1285, 1255, 1185, 980 cm−1, 1HNMR, δ (CDCl3),
3.63 (sharp s) MS, m/z, M+, 220.
SELECTED DATA FOR 4
Irradiation time 8 min, yield 54%, b.p. 264 at 33 mmHg, lit.1c mp
36.5–38.0◦C, IR (KBr disc) 2870, 1450, 1350, 1120, 920 cm−1, 1HNMR,
δ(CDCl3), 3.65 (sharp s) MS, m/z, M+, 264.
SELECTED DATA FOR 5
Irradiation time 10 min, yield 68%, b.p. 308–310 at 33 mmHg, IR
1
(KBr disc) 2860, 1500, 1460, 1250, 920, 910 cm−1, HNMR, δ(CDCl3),
3.65 (sharp s), MS, m/z, M+, 308.
SYNTHESIS OF DIBENZO-14-CROWN-4.6
1,2-dihydroxybenzene (1.21 g, 0.011 mol), sodium hydroxide (0.8 g,
0.02 mol), and 1,3-dichloropropane (1.12, 0.01 mol) were mixed in
DMSO (1 mL). The mixture was placed in a household microwave oven
for 8 min. The crude product was taken up in conc. HCl (2 mL) and fil-
tered. The filtrate was extracted with CHCl3, dried, and evaporated to
afford a crude residue, which was crystallized from n-heptane to afford
the title compound. Yield 72%, m.p. 150, 150–152 lit.la IR (KBr disc)
3000, 1600, 1450, 1420, 1300, 900 cm.−1 1HNMR, δ(CDCl3) 2.25 (s, 4H,
CH2), 4.25 (t, 8H, CH2), M, m/z, M+, 300.
REFERENCES
[1] a) C. J. Pederson, J. Am. Chem. Soc., 89, 7017 (1967); b) Ibid, 92, 386 and 391 (1970).
[2] For reviews on Crown Ether Chemistry, see a) C. J. Pedersen and H. K. Frensdorff,
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R. M. Izatt, Chem. Rev., 74, 351 (1974); c) G. W. Gokel and D. J. Cram, J. Org. Chem.,
39, 2445 (1974); d) F. L. Cook, T. C. Caruso, M. P. Byrne, C. W. Bowers, D. H. Speck,
C. L. Liotta, Tetrahedron Lett., 46, 4029 (1974).

Synthesis of Crown Ethers
807
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