Supporting Information
Synthesis of thermally stable aromatic poly(spiroothocarbonate)s having cardo or bent structures
Masaki Moritsugu,1 Ryota Seto,1 Kozo Matsumoto,1,2 Takeshi Endo1*
1
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka Prefecture
820-8555, Japan
2
Department of Biological & Environmental Chemistry, Kinki University, 11-6 Kayanomori, Iizuka,
Fukuoka Prefecture 820-8555, Japan
*Correspondence to: T. Endo (E-mail: tendo@moleng.fuk.kindai.ac.jp)
Contents
I. Experimental Section
II. Synthesis of Raw Materials
III. SEC Curves of Polymers
IV. Results of Thermal Analysis
V. Original Spectra (1H NMR, 13C NMR, and IR spectra of all compounds)
VI. References and Notes
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I. Experimental Section
1. Materials
Chlorobenzene was purchased from Wako Pure Chemical Industries (Osaka, Japan) and dried over CaCl 2
and distilled over P2O5 before use.
6,6’,7,7’-Tetrahydroxy-4,4,4’,4’-tetramethyl-2,2’-spirobichroman
(BCSPC), 5,5’,6,6’-tetrahydroxy-3,3,3’,3’-tetramethyl-1,1’-spirobiindane (BCSPI), sesamol, CH2Br2, and
catechol were purchased from Tokyo Chemical Industry Co., Ltd. (Tokyo, Japan) and used as received.
Frémy’s salt (potassium nitrosodisulfonate, NO(SO3K)2), NaOH, KH2PO4, NaCl, methanol, ethyl acetate,
toluene, Na2S2O4, hydrochloric acid, Cs2CO3, dimethylformamide (DMF), hexane, PCl5, PCl3,
1,4-dioxane, sulfuric acid, and methyl isobutyl ketone were purchased from Wako Pure Chemical
Industries (Osaka, Japan) and used as received.
(Tokyo, Japan) and used as received.
MgSO 4 was purchased from Kanto Chemical Co., Inc.
9-Fluorenone and 3-mercaptopropionic acid were purchased from
Sigma-Aldrich Co., LLC. (St. Louis, Missouri, USA) and used as received.
2. Characterization
1
H and 13C NMR spectra were recorded on a JEOL JNM-ECS 400 spectrometer at a resonance frequency
of 400 and 100 MHz for 1H and 13C, and JEOL JMN-AL 300 spectrometer at a resonance frequency of
300 and 75 MHz for 1H and 13C with tetramethylsilane (TMS) as an internal standard.
13
The solid-state
C CP/MAS NMR spectra were recorded on a JEOL ECX-400 spectrometer at a resonance frequency of
100 MHz for
units (δ).
13
C with adamantane as external standard.
NMR chemical shifts were reported in delta
Infrared (IR) spectra were recorded on a Thermo Scientific Nicolet iS10 spectrometer
equipped with a Smart iTR Sampling Accessory.
a JASCO V-570 UV-vis spectrometer.
Ultraviolet-visible (UV-vis) spectra were recorded on
Number-average and weight-average molecular weights (Mn, Mw)
and polydispersity indices (Mw/Mn) of the polymers were estimated by size exclusion chromatography
(SEC) using tetrahydrofuran (THF) as the eluent at a flow rate of 0.6 mL/min at 40 ºC, performed on a
Tosoh TSKgel SuperHM-H styrogel columns (3.0 mm  × 15 cm, 3 and 5 m bead sizes), UV-vis
detector (254 nm).
The molecular weight calibration curve was obtained with polystyrene standards.
Thermogravimetric analysis (TGA) was performed on a Seiko Instrument Inc. TG-DTA 6200 with an
aluminum pan under a 200 mL/min N2 flow at a heating rate of 10 ºC/min.
Differential scanning
calorimetry (DSC) was carried out with a Seiko Instrument Inc. DSC-6200 using an aluminum pan under
a 50 mL/min N2 flow at a heating rate of 10 ºC/min.
Scientific SMP3.
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Melting points (mp) were measured with a Stuart
3. Experimental Procedure
3.1. Benzo[d][1,3]dioxole-5,6-dione (S1)1
To 1 L three neck flask, KH2PO4 (10.9 g, 80.0 mmol) and water (800 mL) were added. The mixture was
cooled to 5 ºC, Frémy’s salt (17.1 g, 63.7 mmol) was added to the mixture.
Sesamol (3.00 g, 21.7
mmol) solved in methanol (60 mL) was added to the mixture, and stirred at 5 ºC.
amount of NaCl was added to the mixture to saturate.
mL portions of ethyl acetate.
After 1 h, a large
The aqueous mixture was extracted with ten 100
The solution was dried over MgSO4 and evaporated in vacuum.
The
crude mixture was recrystallized with 100 mL of toluene to give S1 (1.40 g, 9.22 mmol) as a yellow
powder in 43 % yield.
S1: mp 203.5–204.3 ºC (ref1 194–195 ºC); 1H NMR (400 MHz, 293 K, CDCl3, δ): 6.12 (s, 2 H, Ph–H),
6.03 (s, 2 H, –OCH2O–) ppm;
C NMR (100 MHz, 293 K, CDCl3, δ): 177.5 (C=O), 161.0 (O–C=C),
13
104.3 (–C=CH–C–), 101.6 (–OCH2O–), 101.4 (–OCH2O–) ppm.
3.2. Benzo[d][1,3]dioxole-5,6-diol (S2)1
To 1 L round bottom flask, S1 (1.37 g, 9.00 mmol) and ethyl acetate (300 mL) were added. To the
solution, Na2S2O4 (6.00 g, 34.5 mmol) solved in water (100 mL) was added and stirred at room
temperature.
After 5 min, the yellow color changed to a colorless solution.
The organic layer was
washed with hydrochloric acid (1N), extracted with ethyl acetate, washed with water, dried over MgSO 4,
and evaporated to give S2 (1.33 g, 8.66 mmol) as a light pink powder in 96% yield.
S2: 1H NMR (400 MHz, 293 K, DMSO-d6, δ): 8.46 (s, 2 H, –OH), 6.40 (s, 2 H, Ph–H), 5.79 (s, 2 H,
–OCH2O–) ppm.
3.3. Benzo[1,2-d:4,5-d’]bis([1,3]dioxole) (S3)2
To 30 mL round bottom flask, Cs2CO3 (3.20 g, 9.82 mmol, 1.2 eq. to S2) and distilled DMF (10 mL) were
added. The solution was degassed through three freeze-pump-thaw cycles, the atmosphere was replaced
with dried Ar.
S2 (1.26 g, 8.18 mmol) was added to the mixture, and stirred at room temperature.
CH2Br2 (0.86 mL, 12.3 mmol) was added to the mixture, and stirred at room temperature for 30 min.
The mixture was stirred at 90 ºC for 20 h.
After cooling, ether (100 mL) was added to the mixture, and
the mixture was filtered to remove solid salts.
The filtrate was washed with water and brine, dried over
MgSO4, and evaporated to dryness under reduced pressure.
The crude mixture was purified by silica gel
column chromatography (eluent: EtOAc:hexane = 1:10) to give S3 (579 mg, 3.48 mmol) as white solids
in 43% yield.
S3: mp 142.5–143.2 ºC (ref2 139–140 ºC); 1H NMR (400 MHz, 293 K, CDCl3, δ): 6.49 (s, 2 H, Ph–H),
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5.88 (s, 4 H, –OCH2O–) ppm; 13C NMR (100 MHz, 293 K, CDCl3, δ): 141.3 (Ph–O), 101.3 (–OCH2O–),
93.2 (Ph) ppm; IR (ATR): νmax = 2890 (w, C–H), 1456 (m, C=C), 1142 (s, C–O) cm–1.
3.4. 2,2,6,6-tetrachlorobenzo[1,2-d:4,5-d’]bis[1,3]dioxole (4ClBD)2
To 25 mL two neck flask, S3 (1.00 g, 6.02 mmol), PCl5 (5.01 g, 24.1 mmol), and PCl3 (22 mL) were
added. The mixture was refluxed for 4h and evaporated to dryness under reduced pressure.
The crude
mixture was purified by sublimation at 70 ºC, to give 4ClBD (1.41 g, 4.64 mmol) as white solids in 77%
yield.
4ClBD: mp 98.8–100.0 ºC; 1H NMR (400 MHz, 293 K, CDCl3, δ): 6.90 (s, 2 H, Ph–H) ppm; 13C NMR
(100 MHz, 293 K, CDCl3, δ): 140.1 (Ph–O), 129.6 (spiro), 94.7 (Ph) ppm.
3.5. 4,4’-(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol) (BCFL)3
To 100 mL three neck flask, 9-fluorenone (3.60 g, 20.0 mmol), catechol (8.80 g, 80.0 mmol),
3-mercaptopropionic acid (0.07 mL), and 1,4-dioxane (6.00 mL) were added.
80 ºC.
The mixture was stirred at
Concentrated sulfuric acid (0.50 mL) was added dropwise to the mixture.
The mixture was
stirred at 80 ºC for 24 h, color of solution was changed from yellow to red-purple and solid was deposited.
After cooling, methyl isobutyl ketone (200 mL) was added to mixture to solve deposited solid.
The
water solved desired compound was extracted with water and evaporated to dryness under reduced
pressure.
The crude mixture was purified by recrystallization with water (100 mL) and methanol (50
mL) to give BCFL (4.84 g, 12.6 mmol) as a white solid in 63 % yield.
BCFL: mp 220 ºC (decomposed); 1H NMR (400 MHz, 293 K, DMSO-d6, δ): 8.75 (br, 2 H, –OH), 7.86
(dd, J = 7.8, 1.3 Hz, 2 H, Ph–H), 7.35 (ddd, J = 7.8, 7.8, 1.3 Hz, 2 H, Ph–H), 7.34 (dd, J = 7.8, 1.3 Hz, 2
H, Ph–H), 7.29 (ddd, J = 7.8, 7.8, 1.3 Hz, 2 H, Ph–H), 6.55 (d, J = 8.3 Hz, 2 H, Ph–H), 6.54 (d, J = 2.2
Hz, 2 H, Ph–H), 6.33 (dd, J = 8.3, 2.2 Hz, 2 H, Ph–H) ppm; 13C NMR (100 MHz, 293 K, DMSO-d6, δ):
151.7 (fluorene), 144.7 (Ph), 144.0 (Ph), 139.4 (fluorene), 136.7 (Ph), 127.5 (fluorene), 127.2 (fluorene),
126.0 (fluorene), 120.3 (fluorene), 118.6 (Ph), 115.6 (Ph), 115.1 (Ph), 63.8 (fluorene) ppm; IR (ATR):
νmax = 3256 (br, O–H), 1603 (w, C=C), 1513 (m, C=C), 1444 (m, C=C), 1278 (s, C–O), 741 (s, C–H)
cm–1.
3.6. Benzo[d][1,3]dioxole (S4)4
To 300 mL three neck flask, (Bu)4N+Cl– (560 mg, 2.00 mmol) and CH 2Br2 (10.5 mL, 150 mmol) were
added and the atmosphere was replaced with dried Ar.
The mixture was stirred at 110 ºC.
Water
solution (30 mL) of NaOH (6.20 g, 150 mmol) and catechol (8.25 g, 75.0 mmol) was added dropwise to
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the mixture for 90 min.
The mixture was stirred for 2 h at 110 ºC.
After cooling, the mixture was
extracted with toluene, dried over MgSO4 and evaporated in vacuum.
The crude mixture was purified
by silica gel column chromatography (eluent: EtOAc:hexane = 1:10) to give S4 (4.42 g, 36.2 mmol) as
clear oil in 48% yield.
S4: bp 172.0 ºC; Rf value 0.4 (eluent: hexane); 1H NMR (400 MHz, 293 K, CDCl3, δ): 6.81 (m, 4 H,
Ph–H), 5.91 (s, 2 H, –OCH2O–) ppm; 13C NMR (75 MHz, 293 K, CDCl3, ): 147.5 (Ph–O), 121.7 (Ph),
108.7 (Ph), 100.7 (–OCH2O–) ppm.
3.7. 2,2-Dichloro-1,3-benzodioxole (2ClBD)2
To 200 mL round bottom flask, PCl5 (50.3 g, 487 mmol) and S4 (12.5 mL, 122 mmol) were added.
mixture was stirred at 90 ºC for 5 h and evaporated to dryness under reduced pressure.
The
The residue was
distilled under reduced pressure to afford 2ClBD (19.8 g, 104 mmol) as yellow oil in 85% yield.
2ClBD: bp 98.0 ºC (28 mmHg); 1H NMR (300 MHz, 293 K, CDCl3, δ): 7.07 (m, 4 H, Ph–H) ppm; 13C
NMR (75 MHz, 293 K, CDCl3, ): 144.4 (Ph–O), 128.6 (spiro), 124.0 (Ph), 110.0 (Ph) ppm.
3.8. Poly(SOC-FL)
To 200 mL two neck flask, BCFL (674 mg, 1.76 mmol), 4ClBD (536 mg, 1.76 mmol), and
chlorobenzene (35 mL, 0.05 mol/L) were added.
under N2 gas flow.
The mixture was heated to 130 ºC and stirred for 12 h
After cooling, the reaction mixture was poured into a large amount of methanol (300
mL), and the resulting precipitate was collected by filtration to give 874 mg of poly(SOC-FL) as a white
powder in 92% yield.
3.9. Poly(SOC-SPI)
To 200 mL two neck flask, BCSPI (681 mg, 2.00 mmol), 4ClBD (608 mg, 2.00 mmol), and
chlorobenzene (40 mL, 0.05 mol/L) were added.
under N2 gas flow.
The mixture was heated to 130 ºC and stirred for 12 h
After cooling, the reaction mixture was poured into a large amount of methanol (300
mL), and the resulting precipitate was collected by filtration to give 980 mg of poly(SOC-SPI) as a white
powder in 98% yield.
3.10. Poly(SOC-SPC)
To 200 mL two neck flask, BCSPC (745 mg, 2.00 mmol), 4ClBD (608 mg, 2.00 mmol), and
chlorobenzene (40 mL, 0.05 mol/L) were added.
under N2 gas flow.
The mixture was heated to 130 ºC and stirred for 12 h
After cooling, the reaction mixture was poured into a large amount of methanol (300
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mL), and the resulting precipitate was collected by filtration to give 1.04 g of poly(SOC-SPC) as a white
powder in 98% yield.
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II. Synthesis of Raw Materials
1. Synthesis of 2,2,6,6-tetrachlorobenzo[1,2-d:4,5-d’]bis[1,3]dioxole (4ClBD)
2,2,6,6-Tetrachlorobenzo[1,2-d:4,5-d’]bis[1,3]dioxole (4ClBD) was prepared from sesamol according to
the reported procedures1,2 in four steps (Scheme S1).
Scheme S1.
Synthesis of 4ClBD from sesamol.
2. Synthesis of 4,4’-(9H-fluorene-9,9-diyl)bis(benzene-1,2-diol) (BCFL)
4,4’-(9H-Fluorene-9,9-diyl)bis(benzene-1,2-diol) (BCFL) was prepared from catechol and 9-fluorenone
according to the reported procedure3 in one step (Scheme S2).
Scheme S2.
Synthesis of BCFL from catechol and 9-fluorenone.
3. Synthesis of 2,2-Dichloro-1,3-benzodioxole (2ClBD)
2,2-Dichloro-1,3-benzodioxole (2ClBD) was prepared form catechol according to the reported
procedure2,4 in two steps (Scheme S3).
Scheme S3.
Synthesis of 2ClBD from catechol.
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III. SEC Curves of Polymers
Figure S01.
SEC curves of poly(SOC)s.
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IV. Results of Thermal Analysis
Figure S02.
Figure S03.
TGA and DSC curves of poly(SOC-FL).
TGA and DSC curves of poly(SOC-SPC).
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Figure S04.
TGA and DSC curves of poly(SOC-SPI).
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V. Original Spectra (1H NMR, 13C NMR, and IR spectra of all compounds)
(a)
(b)
Figure S05.
(a) 1H NMR spectrum of S1 (400 MHz, 293 K, CDCl3).
(100 MHz, 293 K, CDCl3).
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(b)
13
C NMR spectrum of S1
(a)
Figure S06.
(a) 1H NMR spectrum of S2 (400 MHz, 293 K, DMSO-d6).
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(a)
(b)
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(c)
Figure S07.
(a) 1H NMR spectrum of S3 (400 MHz, 293 K, CDCl3).
(100 MHz, 293 K, CDCl3).
(c) IR spectrum of S3 (ATR, 293 K).
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(b)
13
C NMR spectrum of S3
(a)
(b)
Figure S08.
(a) 1H NMR spectrum of 4ClBD (400 MHz, 293 K, CDCl3).
4ClBD (100 MHz, 293 K, CDCl3).
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(b) 13C NMR spectrum of
(a)
(b)
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(c)
Figure S09.
(a) 1H NMR spectrum of BCFL (400 MHz, 293 K, DMSO-d6).
BCFL (100 MHz, 293 K, DMSO-d6).
(b) 13C NMR spectrum of
(c) IR spectrum of BCFL (ATR, 293 K).
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(a)
(b)
Figure S10.
(a) 1H NMR spectrum of S4 (400 MHz, 293 K, CDCl3).
MHz, 293 K, CDCl3).
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(b) 13C NMR spectrum of S4 (75
(a)
(b)
Figure S11.
(a) 1H NMR spectrum of 2ClBD (300 MHz, 293 K, CDCl3).
2ClBD (75 MHz, 293 K, CDCl3).
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(b)
13
C NMR spectrum of
(a)
(b)
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(c)
Figure S12.
(a) 1H NMR spectrum of SOC-FL (400 MHz, 293 K, THF-d8).
SOC-FL (100 MHz, 293 K, THF-d8).
(b) 13C NMR spectrum of
(c) IR spectrum of SOC-FL (ATR, 293 K).
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(a)
(b)
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(c)
Figure S13.
(a) 1H NMR spectrum of SOC-SPC (400 MHz, 293 K, THF-d8).
of SOC-SPC (100 MHz, 293 K, THF-d8).
(b) 13C NMR spectrum
(c) IR spectrum of SOC-SPC (ATR, 293 K).
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(a)
(b)
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(c)
Figure S14.
(a) 1H NMR spectrum of SOC-SPI (400 MHz, 293 K, THF-d8).
of SOC-SPI (100 MHz, 293 K, THF-d8).
(b) 13C NMR spectrum
(c) IR spectrum of SOC-SPI (ATR, 293 K).
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(a)
(b)
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(c)
Figure S15.
(a) 1H NMR spectrum of poly(SOC-FL) (400 MHz, 293 K, THF-d8).
(b)
13
C NMR
spectrum of poly(SOC-FL) (100 MHz, 293 K, THF-d8). (c) IR spectrum of poly(SOC-FL) (ATR, 293
K).
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(a)
(b)
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(c)
Figure S16.
(a) 1H NMR spectrum of poly(SOC-SPC) (400 MHz, 293 K, THF-d8).
spectrum of poly(SOC-SPC) (100 MHz, 293 K, THF-d8).
293 K).
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(b)
13
C NMR
(c) IR spectrum of poly(SOC-SPC) (ATR,
(a)
(b)
Figure S17.
(a) 13C CP/MAS NMR spectrum of poly(SOC-SPI) (100 MHz, 293 K). (b) IR spectrum
of poly(SOC-SPI) (ATR, 293 K).
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VI. References and Notes
1.
H. H. Hussain, G. Babic, T. Durst, J. S. Wright, M. Flueraru, A. Chichirau, L. L. Chepelev, J.
Org. Chem. 2003, 68, 7023–7032.
2.
T. Endo, T. Takata, S. Komatsu, Japan Patent JPA-H5-125180.
3.
H. Murase, S. Kawasaki, K. Ogata, M. Yamada, Y. Suda, Japan Patent JPA-2005-104935.
4.
Y. Araki, M. Umeno, Japan Patent JPA-H3-275683.
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