A R T I C L E S
Li et al.
affords the product in a yield of 3.15 g as an oil. 1H NMR (270 MHz,
CDCl3) δ 1.35 (m, 12H, 6 × CH2), 1.57 (m, 4H, 2 × CH2), 2.40 (m,
4H, CH2COO, CH2OH), 5.10 (s, 2H, CH2Ph), 7.40 (s, 5H, aromatic),
9.77 (s, 1H, COH); 13C NMR (63 MHz, CDCl3) δ 21.9, 24.8, 29.0,
29.1, 29.2, 34.2, 43.7, 65.9, 128.0, 128.4, 136.0, 173.5, 202.8; MS m/z
304 (M), 276 (M - CO).
by pH changes, and, (vi) most interestingly, for the establishment
of long-distance redox pairs in aqueous medium. Their advan-
tage with respect to assembled polymer capsules,8 which serve
similar purposes, is the rigidity of the membrane gaps, which
allows adjustment of the distance between components within
a few angstro¨ms.
Tetradec-2-enedioic Acid 14-Benzyl Ester (3b). Sodium hydride
(1.32 g, 32.90 mmol) was suspended in 100 mL of THF at 0 °C under
an argon atmosphere. tert-Butyl-P,P-dimethylphosphono acetate (7.38
g, 32.90 mmol) was added dropwise at this temperature. After the
evolution of H2 bubbles had ceased, a solution of (10 g, 32.90 mmol)
14-oxy-tetradec-12-enoic acid benzyl ester (2b) in 50 mL of THF was
added slowly. The resulting mixture was stirred for 24 h. The solvent
was removed under reduced pressure, and the residue was taken up
with water. After extraction with four portions of ether and subsequent
drying, a white solid was obtained which was recrystallized from hexane
2. Experimental Section
Synthesis. Toluene-4-sulfonic Acid 2-{2-[2-(2-Methoxyethoxy]-
ethoxy}ethyl Ester. Tri(ethylene glycol)monomethyl ether (2 g, 10
mmol) was suspended in dry pyridine (10 mL) at 0 °C under an argon
atmosphere. 4-Methylbenzenesulfonyl chloride (3.9 g, 20 mmol) was
added at room temperature. The resulting mixture was stirred for 24 h
at room temperature. The reaction mixture was poured into 20 mL of
water, the resulting suspension was extracted with CH2Cl2, and the
extract was dried with magnesium sulfate; evaporation followed by
flash chromatography (ethyl acetate) afforded white solids, 3.0 g (88%).
1H NMR (270 MHz, CDCl3) δ 2.4 (s, 3H), 3.24 (s,3H, CH3O), 3.79-
3.59 (m, 14 H), 3.56 (t, 2H, CH2O), 3.70 (t, 2H, CH2O), 7.34(d, 2H,
aromatic), 7.73 (d, 2H, aromatic).
1
to give 9.80 g of product. H NMR (270 MHz, CDCl3) δ 1.30 (m,
12H, 6 × CH2), 1.44 (s, 9H, (CH3)3C), 1.58 (m, 4H, 2 × CH2), 2.30
(m, 4H, 2 × CH2), 5.10 (s, 2H, CH2Ph), 5.73 (d, 1H, vinyl R-H), 6.87
(dt, 1H, vinyl â-H), 7.41 (s, 5H, aromat.); 13C NMR (63 MHz, CDCl3)
δ 24.8, 28.0, 28.1, 28.5, 28.7, 28.9, 29.0, 29.1, 29.3, 31.9, 34.2, 65.9,
79.8, 122.8, 128.0, 128.4, 136.0, 148.0, 166.7, 173.5; MS (FAB neg.,
Xe) m/z 682 (M), 653 (M - CO). Toluene solution (100 mL) containing
5 g of the above butyl ester (14.45 mmol) and 5 g of p-toluenesulfonic
acid was refluxed for 30 min and subsequently stirred at room
temperature overnight. After toluene was removed, 300 mL of 5%
aqueous potassium bicarbonate solution was added and stirred for 10
min. The white precipitate was filtered off, and the filtrate was acidified
to pH 3 with dilute HCl. The resulting suspension was extracted with
chloroform and dried with magnesium sulfate. After the removal of
solvent in vacuo, the resulting solid was recrystallized from chloroform/
1-{2-[2-(2-Azidoethoxy)ethoxy]ethoxy}-2-methoxyethane. Sodium
azide (1.1 g, 16.5 mmol) was added to a solution of toluene-4-sulfonic
acid 2-{2-[2-(2-methoxyethoxy]ethoxy}ethyl ester (3.0 g, 11 mmol)
in dry DMF (12 mL). The mixture was heated at 90 °C for 6 h and
then allowed to attain room temperature. The DMF was evaporated,
and the residue was purified by flash chromatography (ethyl acetate)
giving 2.26 g (94%) of compound as a light yellow oil. 1H NMR (270
MHz, CDCl3) δ 3.2 (t, 2H, CH2N3), 3.4 (t, 2H, CH2O), 3.24 (s, 3H,
CH3O), 3.56-3.62 (m, 12H, OCH2CH2O).
1-{2-[2-(2-Azidoethoxy)ethoxy]ethoxy}ethylamine (1). A solution
of 1-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}-2-methoxyethane (1.3 g, 5.58
mmol) in dry THF (30 mL) was cooled to 0 °C. Triphenyl phosphine
was added (1.8 g, 7.0 mmol), after which the mixture was allowed to
stand at room temperature for 24 h. Water (0.4 mL) was added, and
the reaction mixture was stirred for another 24 h to hydrolyze the
intermediate phosphorus adduct. The reaction mixture was diluted with
water and washed with toluene. Evaporation of the aqueous layer
yielded 1.1 g (97%) of compound as a pale yellow oil. 1H NMR (270
MHz, CDCl3) δ 1.5 (broad, 2H, NH2), 2.87 (broad, 2H, CH2NH2), 3.24
(s, 3H, CH3O), 3.6 (t, 2H, CH2O), 3.56-3.63 (m, 12H, OCH2CH2O);
13C NMR (63 MHz, CDCl3) δ 41.1, 58.3, 69.0, 69.5, 69.6, 69.8, 69.9,
70.29, 71.3.
1
hexane to give 3.95 g of white crystals. H NMR (270 MHz, CDCl3)
δ 1.33 (m, 12H, 6 × CH2), 1.48 (m, 2H, CH2), 1.61 (m, 2H, CH2),
2.20 (m, 2H, CH2), 2.38 (t, 2H, CH2COO), 5.10 (s, 2H, CH2Ph), 5.73
(d, 1H, vinyl R-H), 6.87 (dt, 1H, vinyl â-H), 7.41 (s, 5H, aromat.),
11.60 (m, 1H, COOH);13 C NMR (63 MHz, CDCl3) δ 24.8, 27.7, 28.5,
29.1, 29.2, 29.3, 29.4, 32.2, 34.2, 66.0, 120.4, 128.0, 128.4, 136.0, 152.2,
172.0, 173.6; MS (FAB, pos, Xe) m/z 347 (M), 329 (M - H2O).
13-(2-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}ethylcarbamoyl)-
tridec-12-enoic Acid Benzyl Ester (4b). Compounds 1 (0.595 g, 2.89
mmol) and 3b (1 g, 2.89 mmol) were dissolved in 200 mL of CH2Cl2.
After the solution was cooled to 0 °C for 15 min, DCC (1.48 g, 7.22
mmol) and DMAP (1 g, 9 mmol) were added. The reaction mixture
was then stirred at room temperature for 24 h further. The white
precipitate was filtered off, and the filtrate was washed successively
with 0.1 M HCl, 8% NaHCO3, and water and dried over MgSO4. The
solvent was removed in a vacuum, and the residue was purified by
silica column chromatography using CH2Cl2/MeOH (10:1) as eluent,
followed by crystallization from hexane/ethyl acetate. Yield: 1.3 g as
a white solid (84.9%). 1H NMR (270 MHz CDCl3) δ 1.24 (m, 12H, 6
× CH2), 1.49 (m, 4H, CH2), 1.63 (m, 2H, allyl-H), 2.37 (t, 2H, CH2-
COO), 3.45 (s, 3H, CH3-O), 3.56 (m, 2H, CH2NH), 3.56-3.7 (m,
14H, CH2O), 5.08 (s, 2H, CH2Ph), 5.73 (d, 1H, vinyl R-H), 6.30 (broad,
1H, NH), 6.87 (dt, 1H, vinyl â-H), 7.41 (s, 5H, aromat.); MS (FAB
neg., Xe) m/z 536 (M + H).+
12-Oxododecanoic Acid Benzyl Ester (2b). A solution of 12-
hydroxydodecanoate acid (10 g, 26.3 mmol) in 120 mL of DMF was
treated with potassium bicarbonate (5.10 g, 50.92 mmol) and benzyl
bromide (9.12 g, 53.24 mmol) and stirred at rt for 24 h. The solvent
was removed under reduced pressure. The resulting mixture was
partitioned between ethyl acetate and aqueous HCl. The organic phase
was separated, washed with water, and dried with MgSO4. Removal
of the solvent in a vacuum resulted in a solid, which was recrystallized
in methanol to afford white crystals in a yield of 8.50 g. 1H NMR (270
MHz, CDCl3) δ 1.36 (m, 14H, 7 × CH2), 1.57 (m, 4H, 2 × CH2), 2.38
(t, 2H, CH2COO), 3.63 (t, 2H, CH2OH), 5.11 (s, 2H, CH2Ph), 7.38 (s,
5H, aromatic); 13C NMR (63 MHz, CDCl3) δ 24.8, 25.6, 28.9, 29.0,
29.3, 29.4, 29.5, 32.6, 34.2, 62.7, 65.9, 128.0, 128.4, 136.0, 173.6; MS
m/z 306 (M), 278 (M - CO). Pyridinium chlorochromate (3.23 g, 15
mmol) was suspended in 100 mL of CH2Cl2, and the above benzyl
ester (3.50 g, 10 mmol) was rapidly added at room temperature. After
1.5 h, the oxidation was completed (monitored by TLC). The black
reaction mixture was diluted with 300 mL of anhydrous ether, the
solvent was decanted, and the black solid was washed twice with ether.
The product was isolated simply by filtration of the organic extracts
through Florisil, and evaporation of the solvent at reduced pressure
13-(2-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}ethylcarbamoyl)-
tridec-12-enoyl Chloride (5b). Benzyl ester 4b (1.2 g) was treated
with 25 mL of LiOH (1 M) suspension in 10 mL of THF, 5 mL of
(9) (a) Cao, G.; Rabenberg, L. K.; Nunn, C. N.; Mallouk, T. E. Chem. Mater.
1991, 3, 149. (b)Yang, H. C.; Aoki, K.; Hong, H.-G.; Sackett, D. D.; Arendt,
M. F.; Yau, S.-L.; Bell, C. M.; Mallouk, T. E. J. Am. Chem. Soc. 1993,
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(10) van Blaaderen, A.; Vrij, A. J. Coll. Interfacial Sci. 1993, 156, 1.
(11) For convex surfaces: Klyszcz, A. Ph.D. Thesis, FU: Berlin, 2001, p 99ff.
(12) for concave surfaces: Shin, Y.; Liu, J.; Wang, L.-Q.; Nie, Z.; Samuels,
W. D.; Fryxell, G. E.; Exarhos, G. J. Angew. Chem. 2000, 112, 2814.
(13) Pekharinen, L.; Linschitz, H. J. Am. Chem. Soc. 1960, 82, 2407.
(8) Dai, Z.; Dahne, L.; Donath, E.; Mo¨hwald, H. Langmuir 2002, 18, 4553.
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10694 J. AM. CHEM. SOC. VOL. 125, NO. 35, 2003