formal aryne/carbon monoxide copolymerization to form
TRANSCRIPT
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Supporting Information For:
Formal Aryne/Carbon Monoxide Copolymerization to
Form Aromatic Polyketones/Polyketals
Shingo Ito,*,† Wenhan Wang,† Katsuyuki Nishimura,‡ and Kyoko Nozaki*,†
† Department of Chemistry and Biotechnology, Graduate School of Engineering The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
‡ Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki, Aichi 444-8585, Japan
Experimental Section
General: All manipulations were carried out using glove boxes and standard Schlenk techniques under
argon purified by passing through a hot column packed with BASF catalyst R3-11. All polymerizations
were carried out using a 50-mL autoclave.
Instrumentation: Nuclear magnetic resonance (NMR) spectra in solution were recorded on JEOL
JNM-ECP500 (1H: 500 MHz, 13C: 126 MHz with digital resolution of 0.239, 0.960 Hz, respectively) or
JEOL JNM-ECS400 (1H: 400 MHz, 13C: 101 MHz with digital resolution of 0.0913, 0.767 Hz,
respectively) NMR spectrometers. Solid-state NMR spectra were recorded on a Bruker Avance 600
spectrometer at 1H resonant frequency of 600 MHz, equipped with a 2.5mm O.D. 1H-13C-15N triple
resonance MAS probe. Temperatures were controlled to 293 K using VT controller. MAS frequency
was actively controlled to 20 kHz using Bruker MAS controller. Typical rf fields of 1H and 13C pulses
were 100 and 93 kHz, respectively. 1H heteronuclear dipolar decoupling was achieved by TPPM[1] at
rf fields of 100 kHz. Repetition time was 2 seconds. The number of scans was 20000. Non- and Proton
attached 13C signals were differentiated from the comparison of the spectra from CPMAS[2,3] and 1H
homonuclear dipolar decoupled cross polarization scheme LGCPMAS[4,5,6] (data not shown) at
contact time of 3 ms and 40 µs, respectively. Infrared (IR) spectra were recorded on a Shimadzu FTIR-
8400 spectrometer equipped with an attenuated total reflection (ATR) system. Size-exclusion
chromatography (SEC) analyses were carried out on GL Science GPC apparatus or a Viscotek
TDAmax using two columns (Shodex KF-804L) with tetrahydrofuran (THF) as an eluent. Molecular
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weights were calibrated against standard polystyrene samples. Mass spectra (MS) are taken with a
MALDI (matrix-assisted laser desorption/ionization) method on a Bruker Autoflex III mass
spectrometer. Differential scanning calorimetry (DSC) measurements of polymers were performed on a
Seiko DSC 7020 analyzer at a heating and cooling rate of 10 °C/min. Thermogravimetric (TG)
analyses were performed on a Seiko EXSTAR 6000 TG/DTA 6200 analyzer at a heating rate of
10 °C/min. X-ray diffraction (XRD) analyses were performed on a Rigaku MiniFlex II instrument.
Elemental analysis was performed by the Microanalytical Laboratory, Department of Chemistry,
Graduate School of Science, The University of Tokyo.
Materials: Anhydrous dichloromethane was purchased from Kanto Chemical Co. Inc (Kanto) and
purified by the method of Pangborn et al.[7] Carbon Monoxide was purchased from Takachiho
Chemical Industrial Co. and used as received. The following compounds were purchased from
commercial suppliers and used as received: 1,4-dihydro-1,4-epoxynaphthalene (1a) (Wako Pure
Chemical Industries, Ltd. (Wako)), silver hexafluoroantimonate (Tokyo Chemical Industry, Co., Ltd.
(TCI)), 1,2-bis(diphenylphophino)ethane (Kanto), 1,3-bis(diphenylphophino)propane (Kanto), 1,4-
bis(diphenylphophino)butane (Kanto), 2,2'-bipyridine (TCI), 1,10-phenanthroline (Sigma-Aldrich
Corporation), hydrogen chloride in 1,4-dioxane (Sigma-Aldrich), 1,2-dichloroethane (TCI), and dry
methanol (Wako). The following compounds were prepared according to literature procedures:
PdMeCl(cod) [ 8 ], Pd2(dba)3⋅CHCl3 [9 ], 2-{di(2-methoxyphenyl)phosphonio}benzene-sulfonate (4)
[10], palladium complex 5 [11], 6,7-difluoro-1,4-dihydro-1,4-epoxynaphthalene (1b) [12], and 1,4-
dihydro-6,7-dioctyl-1,4-epoxynaphthalene (1c) [13].
Preparation of 1,4-Dihydro-6,7-dioctyloxy-1,4-epoxynaphthalene (1d)
BuLi (1.6 M solution in hexane, 13.4 mL, 21.4 mmol) was slowly added at −50°C to a solution of 1,2-
dibromo-4,5-dioctyloxybenzene (10.4 g, 21.2 mmol) in anhydrous THF (200 mL) and furan (45 mL)
under argon atmosphere, and the solution was stirred for 2.5 h at –50 °C. After adding distillated water
(30 mL) at −50 °C, the mixture was warmed to room temperature. The reaction mixture was extracted
with diethyl ether, dried over Na2SO4, filtrated, and evaporated. Purification by flash chromatography
(20% ethyl acetate in hexanes) gave a white solid (5.04 g, 59.4%); Rf = 0.42 on silica gel (20% ethyl
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acetate in hexane); mp 66.8 ºC; IR (neat, cm−1) ν 2954, 2920, 2850, 1600 (C=C), 1461, 1292, 1207,
1076, 833, 702, 644. 1H NMR (400 MHz, CDCl3) δ 7.00 (t, J = 1.0 Hz, 2H, H(2) and H(3)), 6.92 (s, 2H,
H(5) and H(8)), 5.63 (t, J = 1.0 Hz, 2H, H(1) and H(4)), 3.92 (m, 4H, OCH2), 1.74–1.69 (m, 4H, CH2),
1.47–1.36 (m, 4H, CH2), 1.36–1.20 (m, 16H, CH2), 0.86 (t, J = 6.9 Hz, 6H, CH3); 13C NMR (101 MHz,
CDCl3) δ 146.2 (2C, C(6) and C(7)), 143.3 (2C, C(2) and C(3)), 141.9 (2C, C(9) and C(10)), 109.9 (2C,
C(5) and C(8)), 82.6 (2C, C(1) and C(4)), 70.3 (2C, OCH2), 31.9 (2C, CH2), 29.6 (2C, CH2), 29.5 (2C,
CH2), 29.4 (2C, CH2), 26.1 (2C, CH2), 22.8 (2C, CH2), 14.2 (2C, CH3); ESI–MS (m/z): [M+H]+ calcd
for C26H41O3, 401.30; found 401.28. C26H40O3: calcd. C 77.95, H 10.06; found C 77.78, H 10.28.
Copolymerization of [2.2.1]Oxabicyclic Alkenes 1 with Carbon Monoxide (Table 2): To a mixture
of palladium complex 5 (20.4 mg, 0.030 mmol) and silver hexafluoroantimonate (10.2 mg, 0.030
mmol) was added dichloromethane (9.0 mL) at room temperature. After stirring for 10 min at room
temperature, the resulting suspension was filtrated through a membrane filter (pore size: 0.25 µm) and
added to a solution of monomer 1 (3.0 mmol) in dichloromethane (9.0 mL) in a 50-mL stainless
autoclave. After charged with carbon monoxide (5.0 MPa), the resulting mixture was stirred for 24 h at
70 °C (100 °C only for entry 5). After cooling to room temperature, the mixture was added to methanol
(ca. 100 mL). The polymer was isolated by filtration, washed with methanol, and dried under vacuum
at 70 °C. The obtained copolymers 2 were analyzed by 1H and 13C NMR, SEC, DSC, TG analyses
without further purification.
Dehydration of Polymer 2: To a suspension of polymer 2 (600 mg) in 1,1,2,2-tetrachloroethane (3.0
mL) was added hydrogen chloride in 1,4-dioxane (4.0 M, 1.5 mL, 6.0 mmol) at room temperature. The
mixture was stirred for 24 h at 110 °C (for entry 1), 48 h at 80 °C (for entries 3 and 4), and 24 h at
80 °C (for entry 5). After cooling to room temperature, the suspension was evaporated and the residue
was washed with methanol using an ultrasound bath. The obtained polymers 3 were analyzed by 1H
and 13C NMR, SEC, DSC, and TG analyses.
Control Experiment: Polymerization of 1a in the Absence of Carbon Monoxide: To a mixture of
palladium complex 5 (6.9 mg, 0.010 mmol) and silver hexafluoroantimonate (3.4 mg, 0.010 mmol) was
added dichloromethane (3.0 mL) at room temperature. After stirring for 10 min at room temperature,
the resulting suspension was filtrated through a membrane filter (pore size 0.25 µm) and added to a
solution of monomer 1a (1.0 mmol) in dichloromethane (3.0 mL) in a 10-mL Schlenk tube. The
resulting mixture was stirred for 24 h at 70 °C. After cooling to room temperature, the mixture was
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analyzed by 1H NMR and GC analyses with internal standards. 1H NMR yields: 1a: 69%, 1-naphthol
(6a): 13%. GC analysis indicated no formation of oligo-1a, including dimer and trimer.
Elemental Analysis: Elemental analyses were performed for polymers 2c, 3c, 2d, and 3d obtained in
Table 2:
2c: calcd. C 81.77, H 10.17; found C 79.41, H 10.21.
3c: calcd. C 85.66, H 10.12; found C 84.04, H 10.70.
2d: calcd. C 75.66, H 9.41; found C 73.59, H 9.36.
3d: calcd. C 78.98, H 9.33; found C 78.04, H 9.95.
Although these values are outside the acceptable ranges, they are provided to illustrate the best values
obtained to date.
References
(1) Bennett, A. E.; Rienstra, C. M.; Auger, M.; Lakshmi, K. V.; Griffin, R. G. J. Chem. Phys. 1995, 103, 6951–6958.
(2) Hartmann, S. R.; Hahn, E. L. Phys. Rev. 1962, 128, 2042–2053. (3) Stejskal, E. O.; Shaefer, J.; Waugh, J. S. J. Magn. Reson. 1977, 28, 105–112. (4) Lee, M.; Goldburg, W. I. Phys. Rev. 1965, 140, A1261–A1271. (5) Hester, R. K.; Ackerman, J. L.; Cross, V. R.; Waugh, J. S. Phys. Rev. Lett. 1975, 34, 993–995. (6) van Rossum, B.-J.; de Groot, C. P.; Ladizhansky, V.; Vega, S.; de Groot, H. J. M. J. Am. Chem. Soc.
2000, 122, 3465–3472. (7) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics
1996, 15, 1518–1520. (8) Rülke, R. E.; Ernsting, J. M.; Spek, A. L.; Elsevier, C. J.; van Leeuwen, P. W. N. M.; Vrieze, K.
Inorg. Chem. 1993, 32, 5769–5778. (9) Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J. J.; Ibers, J. A. J. Organomet. Chem. 1974. 253–266. (10) Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. Chem. Commun. 2002, 964–965. (11) Kochi, T.; Yoshimura, K.; Nozaki, K. Dalton Trnas. 2006, 25–27. (12) Caster, K. C.; Keck, C. G.; Walls, R. D. J. Org. Chem. 2001, 66, 2932–2936. (13) Ito, S.; Takahashi, K.; Nozaki, K. 2014, 136, 7547–7550.
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Polymer 2a (entry 1 in Table 2)
500100015002000250030003500ν / cm–1
Figure S1. IR spectrum of polymer 2a.
Figure S2. 13C-CPMAS solid-state NMR spectrum of polymer 2a.
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Figure S3. DSC chart of polymer 2a.
Figure S4. TG chart of polymer 2a.
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Polymer 3a (entry 1 in Table 2)
500100015002000250030003500ν / cm–1
Figure S5. IR spectrum of polymer 3a.
Figure S6. 13C-CPMAS solid-state NMR spectrum of polymer 3a.
O
n
O
na
aaromatic, a
a
S8
Figure S7. DSC chart of polymer 3a.
Figure S8. TG chart of polymer 3a.
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Polymer 2b (entry 2 in Table 2)
Figure S9. SEC chart of polymer 2b.
500100015002000250030003500ν / cm–1
Figure S10. IR spectrum of polymer 2b (KBr).
S10
Figure S11. 1H NMR spectrum of polymer 2b (500 MHz, CD2Cl2).
Figure S12. 13C NMR spectrum of polymer 2b (101 MHz, CD2Cl2).
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Figure S13. DSC chart of polymer 2b.
Figure S14. TG chart of polymer 2b.
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Polymer 2c (entry 3 in Table 2)
Figure S15. SEC chart of polymer 2c.
500100015002000250030003500�
/ cm–1
Figure S16. IR spectrum of polymer 2c.
S13
Figure S17. 1H NMR spectrum of polymer 2c (500 MHz, CDCl3).
Figure S18. 13C NMR spectrum of polymer 2c (101 MHz, CDCl3).
solvent
ArCH2
C8H17
e cb
O
O
C8H17 C8H17
nO
C8H17 C8H17
O
n
e
b c b c
e
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2000 3000 4000 5000 6000 7000 8000m/z
Figure S19. MALDI-TOF-MS spectrum of polymer 2c.
O
O
C8H17 C8H17
nO
C8H17 C8H17
O
n
mass of repeating unit: 396.3
396 interval
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Figure S20. DSC chart of polymer 2c.
Figure S21. TG chart of polymer 2c.
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Polymer 3c (entry 3 in Table 2)
Figure S22. SEC chart of polymer 3c.
Figure S23. IR spectrum of polymer 3c.
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Figure S24. 1H NMR spectrum of polymer 3c (500 MHz, CDCl3).
Figure S25. 13C NMR spectrum of polymer 3c (101 MHz, CDCl3).
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1000 2000 3000 4000 5000 6000m/z
Figure S26. MALDI-TOF-MS spectrum of polymer 3c.
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Figure S27. DSC chart of polymer 3c.
Figure S28. TG chart of polymer 3c.
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Polymer 2d (entry 4 in Table 2)
Figure S29. SEC chart of polymer 2d.
500100015002000250030003500�
/ cm–1
Figure S30. IR spectrum of polymer 2d.
O
O
C8H17O OC8H17
nO
C8H17O OC8H17
O
n2922
2854
1470
1086
980835
667
1305
1214
17141591
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Figure S31. 1H NMR spectrum of polymer 2d (500 MHz, CDCl3).
Figure S32. 13C NMR spectrum of polymer 2d (101 MHz, CDCl3).
O
O
C8H17O OC8H17
nO
C8H17O OC8H17
O
na
a
de
f
b c b cd
ef
solvent OCH2C7H15
a
de
f
cb
OCH2C7H15
a
solvent
OCH2
OCH2C7H15
H2O TMS
e c b
O
O
C8H17O OC8H17
nO
C8H17O OC8H17
O
n
e
b c b c
e
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Figure S33. DSC chart of polymer 2d.
Figure S34. TG chart of polymer 2d.
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Polymer 3d (entry 4 in Table 2)
Figure S35. SEC chart of polymer 3d.
Figure S36. IR spectrum of polymer 3d.
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Figure S37. 1H NMR spectrum of polymer 3d (500 MHz, CDCl3).
Figure S38. 13C NMR spectrum of polymer 3d (101 MHz, CDCl3).
O
C8H17O OC8H17
n
C8H17O OC8H17
O
n
solvent OCH2C7H15
OCH2C7H15
otheraromaticsignals
f'
f' f'e' e'
e'
S25
Figure S39. DSC chart of polymer 3d.
Figure S40. TG chart of polymer 3d.
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Polymer 2e (entry 5 in Table 2)
Figure S41. IR spectrum of polymer 2e.
Figure S42. 13C-CPMAS solid-state NMR spectrum of polymer 2e.
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Figure S43. DSC chart of polymer 2e.
Figure S44. TG chart of polymer 2e.
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2000 3000 4000 5000 6000 7000 8000m/z
Figure S45. MALDI-TOF-MS spectrum of polymer 2e.
O
n
O
n
222 interval
mass of repeating unit: 222.1
O O
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Polymer 3e (entry 4 in Table 2)
Figure S46. IR spectrum of polymer 3e.
Figure S47. 13C-CPMAS solid-state NMR spectrum of polymer 3e.
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Figure S48. DSC chart of polymer 3e.
Figure S49. TG chart of polymer 3e.
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1000 2000 3000 4000m/z
Figure S50. MALDI-TOF-MS spectrum of polymer 3e.