Supplementary Information
Polymerization of 4,6-Diaminoisophthalic Acid-Type Monomers
Bearing Anthranilic Acid Ester and Isatoic Anhydride Moieties
Akihiro Yokoyama,1 Makoto Karasawa,2 Ryohei Kiyota,2 Masahisa Taniguchi,2 Yuta Hirano,2
Yoshihiro Ohta,2 and Tsutomu Yokozawa2
1
Department of Materials and Life Science, Faculty of Science and Technology, Seikei University,
Musashino, Tokyo, Japan
2
Department of Material and Life Chemistry, Kanagawa University, Yokohama, Japan
Correspondence: Professor A Yokoyama, Department of Materials and Life Science, Faculty of
Science and Technology, Seikei University, 3-3-1 Kichijoji-kitamachi, Musashino, Tokyo 180-8633,
Japan
E-mail: ayokoyama@st.seikei.ac.jp
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Monomer Synthesis
Synthesis of 6
To a solution of 5 (2.10 g, 8.20 mmol) in methanol (80 mL) was added 5% Pd-C (352 mg), and
mixture was stirred at room temperature for 4 h under a H2 atmosphere, and filtered with Celite.
Concentration of the filtrate gave 6 as a brown solid (1.49 g, 93%). Mp > 300 C. 1H NMR (500
MHz, DMSO-d6)  11.98 (br s, 2H), 8.30 (s, 1H), 6.89 (br s, 4H), 5.85 (s, 1H). 13C NMR (126 MHz,
DMSO-d6)  169.0, 154.9, 138.0, 100.7, 97.2. IR (KBr) 3504, 3381, 1632, 1562, 1508, 1439, 1219,
1132, 818, 771, 692 cm−1.
Synthesis of 7
The compound 6 (501 mg, 2.55 mmol) was dissolved in dry 1,4-dioxane (8 mL), and triphosgene
(503 mg, 1.69 mmol) was added. The mixture was stirred at 90 C for 8 h, cooled to 5 C, and
poured in water. The precipitates were collected by filtration with suction, and dried under reduced
pressure. The target molecule 7 was obtained as a pale red solid (523 mg, 82%). Mp > 300 C. 1H
NMR (500 MHz, DMSO-d6)  12.10 (br s, 2H), 8.31 (s, 1H), 6.80 (s, 1H). 13C NMR (126 MHz,
DMSO-d6)  158.4, 146.8, 146.7, 132.0, 106.6, 99.4. IR (KBr) 3449, 3046, 2913, 1784, 1544, 1499,
1374, 1196, 989, 872, 752 cm−1.
Synthesis of 8
A mixture of 7 (300 mg, 1.21 mmol) and distilled triethylamine (0.37 mL, 2.7 mmol) in dry
methanol (8 mL) was stirred at room temperature for 4 h. Then, water was added, and the
precipitates were collected by filtration with suction and dried under reduced pressure. The target
molecule 8 was obtained as a colorless solid (230 mg, 86%). Mp 209.6–212.0 C. 1H NMR (500
MHz, DMSO-d6)  8.32 (s, 1H), 6.91 (br s, 4H), 5.90 (s, 1H), 3.73 (s, 6H). 13C NMR (150 MHz,
DMSO-d6)  167.0, 154.6, 136.9, 100.2, 97.2, 51.0. IR (KBr) 3437, 3324, 2955, 1686, 1636, 1319,
1117, 850 cm−1.
Synthesis of 1
To a stirred mixture of 8 (49.9 mg, 0.223 mmol) and octanal (0.09 mL, 0.6 mmol) in 1,2dichloroethane (2 mL) at 0 C was added sodium triacetoxyborohydride (156 mg, 0.736 mmol), and
the mixture was stirred at room temperature for 8 h. Then, water was added, and the mixture was
extracted with CH2Cl2. The organic layer was washed with saturated aqueous solution of NaHCO3
and water, dried over anhydrous MgSO4, and concentrated. Purification with silica gel column
chromatography (hexane/AcOEt = 2/1) afforded 1 as a colorless solid (83 mg, 83%). Mp 71.7–73.0
C. 1H NMR (600 MHz, CDCl3)  8.55 (s, 1H), 8.09 (t, J = 4.8 Hz, 2H), 5.57 (s, 1H), 3.81 (s, 6H),
3.17 (dt, J = 7.2 and 4.8 Hz, 4H), 1.70 (quint, J = 7.3 Hz, 4H), 1.44 (quint, J = 7.3 Hz, 4H), 1.38–
1.23 (m, 16H), 0.88 (t, J = 7.0 Hz, 6H). 13C NMR (150 MHz, CDCl3)  168.6, 154.7, 138.0, 99.6,
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88.6, 51.1, 42.8, 31.8, 29.4, 29.2, 28.9, 27.2, 22.6, 14.1. IR (KBr) 3437, 3323, 2954, 2924, 2853,
1686, 1594, 1544, 1440, 1321, 1239, 850, 779 cm−1.
Synthesis of 4
A mixture of 1 (308 mg, 0.687 mmol) and triphosgene (67 mg, 0.23 mmol) in dry 1,4-dioxane (10
mL) was stirred at 90 C for 1 h, cooled to 5 C, and poured into water. The mixture was extracted
with CH2Cl2, and the organic layer was washed with saturated aqueous solution of NaHCO3, dried
over anhydrous MgSO4, and concentrated. The crude product was purified with silica gel column
chromatography (CH2Cl2), and 4 was obtained as a pale yellow solid (232 mg, 72%). Mp 62.0–63.6
C. 1H NMR (600 MHz, CDCl3)  8.70 (s, 1H), 8.63 (t, J = 4.8 Hz, 1H), 6.08 (s, 1H), 4.00 (t, J =
7.7 Hz, 2H), 3.88 (s, 3H), 3.25 (dt, J = 5.2 and 6.8 Hz, 2H), 1.79–1.72 (m, 4H), 1.48–1.41 (m, 4H),
1.40–1.24 (m, 16H), 0.90–0.87 (m, 6H). 13C NMR (150 MHz, CDCl3)  167.6, 157.8, 155.9, 148.3,
145.4, 137.0, 107.5, 98.5, 92.9, 52.0, 44.9, 43.1, 31.8, 31.7, 29.3, 29.23, 29.15, 28.6, 27.1, 26.73,
26.68, 22.62, 22.60, 14.1. IR (KBr) 3379, 3310, 2925, 2852, 1719, 1695, 1614, 1214, 829, 750 cm−1.
Synthesis of 2
A mixture of 1 (1.43 g, 3.19 mmol) and triphosgene (671 mg, 2.26 mmol) in dry 1,4-dioxane (15
mL) was stirred at 90 C for 22 h, cooled to 5 C, and poured into water. The mixture was extracted
with CH2Cl2, and the organic layer was washed with saturated aqueous solution of NaHCO3, dried
over anhydrous MgSO4, and concentrated. The target compound 2 was obtained as a pale yellow
solid (1.48 g, 98%). Mp 208.7–209.2 C. 1H NMR (600 MHz, CDCl3)  8.94 (s, 1H), 6.67 (s, 1H),
4.10 (t, J = 7.9 Hz, 4H), 1.78 (quint, J = 7.7 Hz, 4H), 1.46 (quint, J = 7.4 Hz, 4H), 1.42–1.24 (m,
16H), 0.89 (t, J = 7.0 Hz, 6H). 13C NMR (150 MHz, CDCl3)  156.0, 147.2, 146.9, 136.2, 107.6,
97.9, 45.9, 31.7, 29.3, 29.2, 26.84, 26.79, 22.6, 14.0. IR (KBr) 2918, 2852, 1799, 1779, 1739, 1373,
1038, 747, 675 cm−1.
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