5354
Z. B. Huang, S. H. Chang / Tetrahedron Letters 46 (2005) 5351–5355
4
. Experimental
The mixture stirred at 50 ꢁC for 30 h. The solvent was
evaporated and was subjected to flash chromatography
on silica gel (EtAc) affording a yellow oil 106 mg, iso-
Elemental analyses (C, H and N) were performed using
1
13
1
a Vario EL Elementar. The H and C NMR spectra
were obtained on a Varian Mercury 300 NMR spec-
trometer in CDCl . The chemical shifts were expressed
lated yield 61%. H NMR (300 MHz, CDCl , ppm) d
3
0.82–0.87 (t, 6H), 1.24–1.27 (q, 4H), 2.46–2.51 (t,
12H), 2.73–2.77 (t, 24H), 2.85–2.90 (t, 12H), 3.48–3.74
3
1
3
in ppm (d scale) using tetramethylsilane as an internal
standard. GC–MS data were obtained from a Shimadzu
GC–Mass Spectrometer GCMSD-QP5050. FAB MS
data were obtained from a Jeol JMS 700 mass spectro-
meter. FT-IR spectra were recorded on a Mattson
Instrument Genesis II spectrometer. The absorption
spectrum was recorded on a Hewlett Packard UV–vis
spectrophotometer UV-8453.
(m, 92H), C NMR (75 MHz, CDCl , ppm) d 173.18,
3
70.90, 70.87, 70.75, 70.69, 70.66, 70.62, 70.31, 70.11,
69.86, 65.98, 54.47, 51.95, 51.62, 42.81, 32.40, 23.10,
ꢀ
1
7.48; IR (NaCl, cm ): 2921.6, 2895.3, 1730.8, 1575.4,
1454.9, 1355.7, 1252.5, 1191.6, 1114.5, 1061.6, 985.3,
939.1, 851.4; MS(FAB): m/z 1732.5 [M+H] , calcd for
+
C H N O : M, 1731.0. Anal. Calcd for C H150-
82
8
2
150
6
32
N O : C, 56.86; H, 8.73; N, 4.85. Found: C, 57.09; H,
6
32
8
.72; N, 4.77.
All the crown ethers and reagents were purchased from
the Aldrich Company and used as received. The solvents
were of analytical grade, purchased from DC Chemical
Co. Ltd of Korea, and used without further purification.
4
.4. Penta-crown ether 2
Compound 4 86 mg (0.1 mmol) and 1-aza 18-crown-6
32 mg (0.5 mmol) were dissolved in methanol (5 mL).
Operating similarly to that of 1 afforded a yellow oil
1
4
.1. TMPTA 3
1
1
22 mg, isolated yield 64%. H NMR (300 MHz,
Trimethylolpropane 13.42 g (0.1 mol) was dissolved in
benzene (50 mL). Pyridine (3 mL) was added and the mix-
ture stirred for 30 min. In an ice bath acryloyl chloride
CDCl , ppm) d 0.82–0.87 (t, 6H), 1.25–1.27 (q, 4H),
3
2
1
.46–2.51 (t, 12H), 2.74–2.78 (t, 24H), 2.85–2.90 (t,
2H), 3.44–3.77 (m, 108H), C NMR (75 MHz, CDCl3,
1
3
2
9.90 g (0.33 mol) was dropped into the flask over 3 h,
then the reaction mixture was stirred below 50 ꢁC. After
0 h the solution was washed with aqueous K CO
ppm) d 173.23, 70.95, 70.92, 70.88, 70.76, 70.71, 70.67,
0.61, 70.30, 70.09, 69.84, 65.76, 54.29, 51.96, 51.65,
42.72, 32.37, 23.14, 7.49; IR (NaCl, cm ): 2905.7,
7
ꢀ1
3
2
3
(
2 N, 20 mL), water (20 mL · 3), some active carbon
2
1
1
879.3, 1727.1, 1577.5, 1456.9, 1352.8, 1249.7, 1190.2,
110.8, 1060.2, 982.3, 948.7, 835.0; MS(FAB): m/z
added and dried over magnesium sulfate for 12 h. After
filteration, the solvent was evaporated and filtered again
through a pad of silica to give a colourless oil 24.1 g, iso-
+
908.6 [M+H] , calcd for C H N O , M, 1907.1.
9
0
166
6
36
Anal. Calcd for C H N O : C, 56.65; H, 8.77; N,
166
9
0
6
36
1
lated yield 81%. H NMR (300 MHz, CDCl , ppm) d
3
4.40. Found: C, 56.28; H, 8.71; N, 4.29.
0
.88–0.96 (t, 3H), 1.53–1.61 (q, 2H), 4.18 (s, 6H), 5.83–
.88 (d, 3H), 6.07–6.17 (d–d, 3H), 6.38–6.44 (d, 3H);
5
1
3
C NMR (75 MHz, CDCl , ppm) d 165.87, 131.33,
3
Acknowledgement
1
28.27, 64.10, 40.88, 23.19, 7.41; MS(GC): m/z 296
M] , calcd for C H O : M, 296.1. Anal. Calcd for
+
[
C H O : C, 60.80; H, 6.80. Found: C, 60.68; H, 6.81.
1
5
20
6
This paper was partly supported by the Daegu Univer-
sity 2004 Research Fund.
1
5
20
6
4
.2. Compound 4
Diaza 18-crown-6 262 mg (1 mmol) and TMPTA
.778 g (6 mmol) were dissolved in methanol (15 mL).
References and notes
1
1
2
3
. Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 7017.
. Lehn, J. M. Pure Appl. Chem. 1980, 52, 2441.
. Carroy, A.; Lehn, J. M. J. Chem. Soc., Chem. Commun.
1986, 1232.
The mixture was stirred at 50 ꢁC for 30 h. The solvent
was evaporated and subjected to flash chromatography
on silica gel (CHCl /EtAc) to afford a colourless oil
3
1
51 mg, isolated yield 76%. H NMR(300 MHz, CDCl ,
6
3
4
. Chambron, J. C.; Sauvage, J. P. Tetrahedron Lett. 1986,
7, 865.
ppm) d 0.81–0.91 (t, 6H), 1.26–1.53 (q, 4H), 2.45–2.50 (t,
2
4
H), 2.53–2.67 (t, 8H), 2.71–2.83 (t, 4H), 3.28–3.62 (m,
6H), 4.00–4.13 (m, 6H), 5.80–5.84 (d, 4H), 6.02–6.14
5
6
. Beer, P. D. J. Chem. Soc., Chem. Commun. 1986, 1678.
. Pedersen, C. J.; Frensdorff, H. K. Angew. Chem., Int. Ed.
Engl. 1972, 11, 16.
1
1
d–d, 4H), 6.33–6.40 (d, 4H); C NMR (75 MHz,
3
(
CDCl , ppm) d 173.22, 165.78, 131.30, 128.08, 70.93,
7. Dietrich, B. J. Chem. Educ. 1985, 62, 954.
8. An, H.; Bradshaw, J. S.; Izatt, R. M.; Yan, Z. Chem. Rev.
3
7
4
0.91, 70.67, 70.65, 70.60, 69.78, 64.10, 54.39, 51.56,
0.80, 32.52, 23.67, 7.52; MS(FAB): m/z 855.2
1
994, 94, 939.
9. Christensen, J. J.; Hill, J. O.; Izatt, R. M. Science 1971,
74, 459.
+
[M+H] , calcd for C H N O : M, 854.4. Anal. Calcd
for C H N O : C, 59.00; H, 7.78; N, 3.28. Found: C,
4
2
66
2
16
1
4
2
66
2
16
1
1
0. Marcotte, N.; Rodrigues, F.; Lavabre, D.; Fery-Forgues,
S. New J. Chem. 2004, 28, 295.
1. Kikukawa, K.; He, G.; Abe, A.; Goto, T.; Arata, R.;
Ikeda, T.; Wada, F.; Matsuda, T. J. Chem. Soc., Perkin
Trans. 2 1987, 135.
5
9.29; H, 7.72; N, 3.19.
4
.3. Penta-crown ether 1
Compound 4 86 mg (0.1 mmol) and 1-aza 15-crown-5
10 mg (0.5 mmol) was dissolved in methanol (5 mL).
12. Wada, F.; Arata, R.; Goto, T.; Kikukawa, K.; Matsuda,
T. Bull. Chem. Soc. Jpn. 1980, 53, 2061.
1