1010
B. A. Burkett, T. H. Chan
PAPER
1H NMR (400 MHz, CDCl3): d = 3.36–3.63 (m, 20 H), 3.96 (d, J =
6 Hz, 2 H), 5.11 (dd, J = 10, 1 Hz, 1 H), 5.21 (dd, J = 17, 1 Hz, 1
H), 5.85 (ddt, J = 17 Hz, 10, 6, 1 H).
13C NMR (100 MHz, CDCl3): d = 69.3, 70.42, 70.47, 72.1, 117.0,
134.6.
Acknowledgment
This work was supported by the Areas of Excellence Scheme esta-
blished under the University Grants Committee of the Hong Kong
Special Administrative Region, China (Project No. AoE/P-10/01).
We thank the Hong Kong Polytechnic University for financial sup-
port. We are grateful to Professor C. W. Tsang for helpful discuss-
ions. T. H. C. acknowledges the support of McGill University for
the granting of leave.
IR: 2878 (s), 1647 (w-m), 1458 (m), 1346 (m), 1290 (w), 1241 (w),
1100 (s), 925 (m) cm–1.
ES–MS: m/z [MNa+] calcd for C26H50O11Na: 561.3251; found:
561.3237.
References
Undecaethylene Glycol Bis(allyl ether) (7, x = 11)
The title compound was isolated as a colorless oil (289 mg, 80%)
following purification by flash column chromatography; Rf < 0.1
(EtOAc).
1H NMR (400 MHz, CDCl3): d = 3.30–3.66 (m, 22 H), 3.96 (d, J =
6 Hz, 2 H), 5.11 (dd, J = 10, 1 Hz, 1 H), 5.21 (d, J = 17, 1 Hz, 1 H),
5.84(ddt, J = 17, 10, 6 Hz, 1 H).
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13C NMR (100 MHz, CDCl3): d = 69.3, 70.50, 70.69, 72.1, 117.0,
134.7.
(5) Hashizaki, K.; Taguchi, H.; Itoh, C.; Sakai, H.; Abe, M.;
Saito, Y.; Ogawa, N. Chem. Pharm. Bull. 2003, 51, 815.
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3204. (b) Anellie, P. L.; Montanari, F.; Quici, S. J. Org.
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Bartsch, R. A. Tetrahedron 1985, 41, 5439.
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4, 163.
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Ambudkar, S. V. Tetrahedron Lett. 2001, 42, 3819.
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IR: 2863 (m), 1642 (w), 1457 (w), 1351 (w), 1251 (w), 1095 (s), 953
(w) cm–1.
ES–MS: m/z calcd for [MNa+] C28H54O12Na: 605.3513; found:
605.3507.
Dodecaethylene Glycol Bis(allyl ether) (x = 12)
The title compound was isolated as a colorless oil (307 mg, 79%)
following purification by flash column chromatography; Rf < 0.1
(EtOAc).
1H NMR (400 MHz, CDCl3): d = 3.23–3.66 (m, 24 H), 4.02 (d, J =
6 Hz, 2 H), 5.18 (dd, J = 10, 1 Hz, 1 H), 5.28 (d, J = 17, 1 Hz, 1 H),
5.85 (ddt, J = 17, 10, 6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 69.7, 70.50, 70.66, 72.12, 117.0,
134.6.
IR: 2875 (m), 1640 (w), 1458 (w), 1346 (m), 1290 (w), 1248 (m),
1100 (s), 939 (m) cm–1.
ES–MS: m/z [MNa+] calcd for C30H58O13Na: 649.3775; found:
649.3727.
Deprotection of Oligo(ethylene glycol) Bis(ally ethers); General
Procedure
To a stirred solution of the appropriate oligo(ethylene glycol) bis(al-
lyl ether) 7 (1 equiv) in MeOH–water (24:1, 5 mL/mmol) was added
p-toluenesulfonic acid (0.05 equiv), and 10% Pd/C [equal mass to
that of protected oligo(ethylene glycol)]. The resulting reaction
mixture was refluxed under an atmosphere of nitrogen and moni-
tored by 1H NMR spectroscopy for the disappearance of 7 (2–24 h).
Upon complete consumption of starting material, the reaction was
filtered through a cotton plug and the filtrate was concentrated in
vacuo to afford the elongated oligo(ethylene glycols) in high purity
as colorless oils in 82–95% yield as indicated in Table 3. All the oli-
go(ethylene glycols) are known compounds.6,10
Synthesis 2004, No. 7, 1007–1010 © Thieme Stuttgart · New York