JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
solution was stirred for 3 h at reflux temperature. After cool-
ing to room temperature, the reaction mixture was filtered,
and the filtrate was evaporated to dryness. The residue was
purified by vacuum distillation to give 2-[2-(2-aminoethox-
y)ethoxy]ethanol as a colorless liquid.
Yield: 2.13 g (51.3%). Rf ¼ 0.23 (SiO2, AcOEt/MeOH ¼ 96/
4). 1H NMR (400 MHz, CDCl3): d 3.00 (s, 2H, Ph-CBCH),
3.60-3.76 (m, 16H, ꢁCH2-), 3.85 (dd, J ¼ 3.5, 5.9 Hz, 4H, Ph-
OACH2CH2AOA), 4.08 (dd,
J
¼
3.3, 5.7 Hz, 4H, Ph-
OACH2CH2AOA), 6.78 (d, J ¼ 8.8 Hz, 4H, phenyl), 6.90 (s,
2H, CONH), 7.34 (d, J ¼ 8.8 Hz, 4H, phenyl), 7.42 (d, J ¼ 7.3
Hz, 1H, isophthal), 7.88 (dd, J ¼ 2.0, 7.8 Hz, 2H, isophthal),
8.18 ppm (s, 1H, isophthal). 13C NMR (100 MHz, CDCl3): d
39.44 (CONHACH2A), 66.85 (Ph-OACH2A), 69.10, 69.25,
69.80, 70.28 (ACH2A), 75.48 (Ph-CBCH), 83.07 (PhCBCH),
113.89, 113.98 (phenyl), 124.95, 128.3, 129.48 (isophthal),
133.06 (phenyl), 134.27 (isopthal), 158.46 (phenyl), 166.12
(CO). Anal. Calcd. for C36H40N2O8: C, 68.77; H, 6.41; N, 4.46;
O, 20.36. Found: C, 68.74; H, 6.35; N, 4.32.
ꢂ
Yield: 16.84 g (40.1% overall). b.p.: 112 C/0.9 mmHg. Char-
acterization of this compound has been reported.36
N1,N3-Bis(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)isophthala-
mide (4)
DMT-MM (14.00g, 50.59 mmol) was added to a stirred solu-
tion of 2-[2-(2-aminoethoxy)ethoxy]ethanol (7.54 g, 50.54
mmol) and isophthalic acid (4.00 g, 24.08 mmol) in MeOH/
tetrahydrofuran (THF) (100 mL/100 mL). After stirring for 5
h at room temperature, the solvent was removed. The result-
ing residue was dissolved in acetone, and the insoluble mate-
rial was filtered off. The soluble part was evaporated to dry-
ness. The crude product was purified by column
chromatography on silica gel with AcOEt/MeOH (3/1, v/v)
to give 4 as pale yellow syrup.
N3,N5-Bis((S)-1-hydroxy-3-methylbutan-2-yl)pyridine-3,5-
dicarboxamide (5)
DMT-MM (8.05 g, 29.1 mmol) was added to a stirred solu-
tion of L-valinol (3.00 g, 29.1 mmol) and 3,5-pyridinedicar-
boxylic acid (2.43 g, 14.5 mmol) in THF/MeOH (50 mL/50
mL). After stirring for 8 h at room temperature, the insoluble
material in the reaction mixture was removed by filtration.
The filtrate was evaporated, and the resulting residue was
added acetone (50 mL). The insoluble material was removed
again, and the soluble part was evaporated to dryness. The
residue was purified by column chromatography on silica gel
with AcOEt/MeOH (95/5, v/v ! 85/15, v/v ! 75/25, v/v)
to give 5 as a white solid.
Yield: 7.53 g (73.0%). Rf ¼ 0.19 (SiO2, AcOEt/MeOH ¼ 3/1).
1H NMR (400 MHz, CDCl3): d 3.57 (m, 4H, CONHACH2A),
3.76–3.62 (m, 20H, ACH2A), 7.53 (t, J ¼ 11.3 Hz, 1H, iso-
phthal), 7.66 (s, 2H, CONH), 8.08 (dd, J ¼ 2.7, 11.7 Hz, 2H,
isophthal), 8.26 ppm (s, 1H, isophthal). 13C NMR (100 MHz,
CDCl3): d 40.30 (CONHACH2A), 50.84 (HOACH2A), 61.61,
70.29, 70.34, 72.78 (ACH2A), 125.04, 129.13, 131.18,
134.34 (isophthal), 167.37 ppm (CO). Anal. Calcd. for
(C20H32N2O8)3ꢀ(H2O): C, 55.29; H, 7.58; N, 6.45; O, 30.69.
Found: C, 55.35; H, 7.54; N, 6.65.
Yield: 3.29 g (67.1%). Rf ¼ 0.19 (SiO2, AcOEt/MeOH ¼ 95/
1
5). [a]D ¼ ꢁ33.9ꢂ (c 1.0, MeOH). H NMR (400 MHz, DMSO-
d6): d 0.88 [d, J ¼ 6.8 Hz, 6 H, ꢁCH (CH3)2], 0.89 [d, J ¼ 6.8
Hz, 6 H, ACH (CH3)2], 1.93 [sex, J ¼ 6.6 Hz, 2H, ACH(CH3)2],
3.53 (m, 4H, ACH2AOH), 3.84 (m, 2H, HOACH2ACHA), 4.64
(t, 2H, OH), 8.36 (d, 2H, CONH), 8.59 (t, J ¼ 1.9 Hz, 1H, py.),
9.10 ppm (d, J ¼ 2.5 Hz, 2H, py.). 13C NMR (100 MHz,
DMSO-d6): d 19.73, 19.99 [ACH(CH3)2], 28.56 [ACH(CH3)2],
65.96 (HOACH2ACHA), 61.20 (HOACH2ACHA), 130.16,
134.19, 150.31 (py.), 164.68 ppm (CO). Anal. Calcd. for
(C17H27N3O4)3ꢀ(H2O): C, 59.46; H, 8.12; N, 12.24; O, 20.19.
Found: C, 59.51; H, 8.06; N, 12.30.
N1,N3-Bis(2-(2-(2-(4-ethynylphenoxy)ethoxy)ethoxy)ethyl)-
isophthalamide (1)
An aqueous solution of NaOH (0.93 g, 22.6 mmol in 4.8 mL
of water) was added to a stirred solution of 4 (3.39 g, 7.91
mmol) in THF (8 mL). The stirred solution was slowly added
a solution of p-toluenesulfonyl chloride (3.06 g, 16.1 mmol)
in THF (10 mL) at 0–5 ꢂC over 1 h, and stirred for 2 h at
this temperature. The reaction mixture was poured into
water (120 mL), and partitioned with CH2Cl2 (250 mL). The
organic layer was washed with water (150 mL ꢃ 3), dried
over anhydrous Na2SO4, and evaporated to dryness to give
the corresponding ditosylate as pale yellow syrup with satis-
factory purity (4.87 g, 83.6%). The ditosylate (4.87 g, 6.61
mmol), 4-trimethylsilylethynylphenol (3.22 g, 19.6 mmol),
K2CO3 (4.58 g, 33.1 mmol), and tetra-n-butylammonium bro-
mide (0.11 g, 0.34 mmol) were suspended in dry THF (25
mL), and the mixture was stirred for 6 h at reflux tempera-
ture. After cooling to room temperature, methanol (10 mL)
was added to the stirred reaction mixture to deprotect the
trimethylsilyl group. After stirring for 1 h at room tempera-
ture, the reaction mixture was filtered, and the filtrate was
evaporated. The residue was dissolved in CH2Cl2 (100 mL),
then washed with water (100 mL ꢃ 3). The organic layer
was dried over anhydrous Na2SO4 and then evaporated to
dryness. The residue was purified by column chromatogra-
phy on silica gel with AcOEt/MeOH (96/4, v/v) to yield 1 as
pale yellow solid.
(2S,20S)-((Pyridine-3,5-dicarbonyl)bis(azanediyl))bis(3-
methylbutane-2,1-diyl)bis(3,3,3-triphenylpropanoate) (6)
5 (2.00 g, 5.93 mmol), 3,3,3-triphenylpropanoyl chloride
(4.18 g, 13.0 mmol), and N,N-dimethyl-4-aminopyridine
(0.036 g, 0.30 mmol) were dissolved in dry THF/triethyl-
amine (20 mL/5 mL), then the solution was refluxed for 14
h. After cooling to room temperature, the reaction mixture
was evaporated. The resulting residue was dissolved in
CH2Cl2 (50 mL), and washed with 2 mol Lꢁ1 citric acid aq.
(150 mL ꢃ 2), saturated NaHCO3 aq. (150 mL), and water
(150 mL). The organic layer was dried over anhydrous
MgSO4 and then evaporated to dryness. The residue was
immersed in n-hexane, washed with n-hexane, and dried in
vacuo to give 6 as a pale orange solid.
1
Yield: 4.63 g (86.2%). [a]D ¼ ꢁ22.9ꢂ (c 1.0, CHCl3). H NMR
(400MHz, CDCl3): d 0.88 (d, J ¼ 3.5 Hz, 6H, ACH(CH3)2),
0.89 (d, J ¼ 3.5 Hz, 6H, ꢁCH(CH3)2), 1.57 (sex, J ¼ 6.8 Hz,
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