SUPPORTING INFORMATION
POST-FUNCTIONALIZATION
THROUGH
THE
OF
COMBINATION
POLYOXANORBORNENE
OF
BROMINATION
AND
BACKBONE
NITROXIDE
RADICAL COUPLING REACTIONS
Lale Nur Atici, Erhan Demirel, Umit Tunca, Gurkan Hizal and Hakan Durmaz*
Department of Chemistry, Istanbul Technical University, Maslak, 34469, Istanbul, Turkey
*Correspondence to H. Durmaz (E mail: durmazh@itu.edu.tr)
EXPERIMENTAL
Materials
All reagents were supplied from Aldrich and used as received without further purification.
Solvents unless specified here were purified by conventional procedures. Dichloromethane
(CH2Cl2) was used after distillation over P2O5. Tetrahydrofuran (THF) was dried and distilled
over benzophenone-metallic sodium. N,N-dimethylformamide (DMF) was dried and distilled
under vacuum over CaH2. Methanol and hexane were in technical grade and distilled prior to
use.
Synthesis of PONB-acrylatevia NRC Reaction
PONB-Br (0.4 g, 0.042 mmol, Mn,theo = 9600, 1 equiv.) was dissolved in DMF (10 mL),
TEMPO-acrylate (0.95 g, 4.2 mmol, 100 equiv.), PMDETA (0.44 mL, 2.1 mmol, 50 equiv.),
CuBr (0.3 g, 2.1 mmol, 50 equiv.) and Cu (0) (0.67 g, 10.5 mmol, 250 equiv.) were added in a
25 mL of Schlenk tube. The reaction mixture was degassed by three FPT cycles, left in
vacuum and stirred at room temperature overnight. The solution was diluted with THF and
filtered through a column filled with neutral alumina to remove copper complex and finally
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precipitated in hexane/diethyl ether.After decantation, the product was dissolved in CH2Cl2
and extracted with water, dried over Na2SO4, filtered and evaporated to dryness. Finally, the
crude product was dissolved in THF and precipitated in hexane-diethyl ether. After
decantation, the obtained polymer was dried overnight in a vacuum oven at 40 °C. (Yield =
0.15 g, 51 % ) Mn,GPC = 3800; Mw/Mn = 1.39 (RI detector relative to PS standards). 1H NMR
(CDCl3, δ) 6.5-6.2 (br, C=OCH=CH2), 6.08 (bs, CH=CH), 6.0-5.7 (br, C=OCH=CH2), 4.47
(bs, OCHof oxanorbornene and CHO-TEMPO), 3.48 (bs, N-CH2), 3.32 (bs, CH-CH, bridgehead protons), 1.9-0.4 (m, CH3 and CH2 of butyl and TEMPO).
Synthesis of PONB-thiophenol via (thiol-ene) Michael Addition Reaction
PONB-acrylate (0.1 g, 0.014 mmol, Mn,theo = 7000, 1 equiv.) was dissolved in 5 mL of THF.
To the reaction mixture were added thiophenol (0.15 mL, 1.4 mmol, 100 equiv.) and Et3N
(0.021 mL, 0.15 mmol, 10 equiv.) in that order under nitrogen. The reaction mixture was
stirred for 2 h at room temperature. After that time, THF was removed and the crude product
was dissolved in CH2Cl2 and extracted with water, dried over Na2SO4, filtered and evaporated
to dryness. Finally, the crude product was dissolved in THF and precipitated in hexane-diethyl
ether.After decantation, the obtained polymer was dried overnight in a vacuum oven at 40 °C.
(Yield = 0.1 g, 91 % ) Mn,GPC = 4250; Mw/Mn = 1.30 (RI detector relative to PS standards).1H
NMR (CDCl3, δ) 7.5-7.2 (m, ArH), 6.08 (bs, CH=CH), 4.47 (br,OCHof oxanorbornene and
CHO-TEMPO), 3.48 (bs, N-CH2), 3.32 (bs, CH-CH, bridge-head protons), 3.1-27 (br, ArSCH2CH2C=O), 2.1-0.4 (m, CH3 and CH2 of butyl and TEMPO).
Synthesis of PONB-PEG via NRC reaction
PONB-Br (0.2 g, 0.021 mmol, Mn,theo = 9600, 1 equiv.) was dissolved in DMF (10 mL),
TEMPO-PEG (1.66 g, 2.1 mmol, 100 equiv.), PMDETA (0.21 mL, 1.05 mmol, 50 equiv.),
CuBr (0.14 g, 1.05 mmol, 50 equiv.) and Cu (0) (0.32 g, 5.25 mmol, 250 equiv.) were added
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in a 25 mL of Schlenk tube. The reaction mixture was degassed by three FPT cycles, left in
vacuum and stirred at room temperature overnight. The solution was diluted with THF and
filtered through a column filled with neutral alumina to remove copper complex and finally
precipitated in diethyl ether. After decantation, the product was dissolved in CH2Cl2 and
extracted with water, dried over Na2SO4, filtered and evaporated to dryness. Finally, the
crude product was dissolved in THF and precipitated in diethyl ether. After decantation, the
obtained polymer was dried overnight in a vacuum oven at 40 °C. (Yield = 0.05 g, 33 % )
Mn,GPC = 6700; Mw/Mn = 1.25 (RI detector relative to PS standards). 1H NMR (CDCl3, δ) 6.08
(bs, CH=CH), 4.47 (br, OCH of oxanorbornene and CHO-TEMPO), 4.25 (bs, PEGCH2OC=O), 3.65 (OCH2CH2 of PEG backbone), 3.48 (bs, N-CH2), 3.32 (bs, CH-CH, bridgehead protons), 2.62 (br, C=OCH2CH2C=O), 2.1-0.4 (m, CH3 and CH2 of butyl and TEMPO).
Conversion of PONB-Br to PONB under NRC condition without utilizing functionalTEMPO
PONB-Br (0.2 g, 0.021 mmol, Mn,theo = 9600, 1 equiv.) was dissolved in DMF (10 mL),
PMDETA (0.22 mL, 1.05 mmol, 50 equiv.), CuBr (0.15 g, 1.05 mmol, 50 equiv.) and Cu (0)
(0.34 g, 5.25 mmol, 250 equiv.) were added in a 25 mL of Schlenk tube. The reaction mixture
was degassed by three FPT cycles, left in vacuum and stirred at room temperature overnight.
The solution was diluted with THF and filtered through a column filled with neutral alumina
to remove copper complex and finally precipitated in hexane/diethyl ether. After decantation,
the product was dissolved in CH2Cl2 and extracted with water, dried over Na2SO4, filtered and
evaporated to dryness. Finally, the crude product was dissolved in THF and precipitated in
hexane-diethyl ether.
After decantation, the obtained polymer was dried overnight in a
vacuum oven at 40 °C. (Yield = 0.07 g, 58 % ) Mn,GPC = 4750; Mw/Mn = 1.33 (RI detector
relative to PS standards). 1H NMR (CDCl3, δ) 6.08 (bs, CH=CH), 4.47 (bs, OCH of
3
oxanorbornene), 3.48 (bs, N-CH2), 3.32 (bs, CH-CH, bridge-head protons), 1.55 (bs, CH2 of
butyl), 1.30 (bs, CH2 of butyl), 0.93 (bs, CH3 of butyl).
Synthesis of PBONB-TEMPO via NRC reaction (1st NRC)
PBONB-Br (0.70 g, 0.073 mmol, Mn,theo = 9600, 1 equiv.) was dissolved in DMF (15 mL),
TEMPO (1.14 g, 7.30 mmol, 100 equiv.), PMDETA (0.76 mL, 3.65 mmol, 50 equiv.), CuBr
(0.52 g, 3.65 mmol, 50 equiv.) and Cu (0) (1.15 g, 18.2 mmol, 250 equiv.) were added in a 25
mL of Schlenk tube. The reaction mixture was degassed by three FPT cycles, left in vacuum
and stirred at room temperature overnight. The solution was diluted with THF and filtered
through a column filled with neutral alumina to remove copper complex and finally
precipitated in hexane/diethyl ether.After decantation, the product was dissolved in CH2Cl2
and extracted with water, dried over Na2SO4, filtered and evaporated to dryness. Finally, the
crude product was dissolved in THF and precipitated in hexane-diethyl ether. After
decantation, the obtained polymer was dried overnight in a vacuum oven at 40 °C. (Yield =
0.25 g, 57 % ) Mn,GPC = 4850; Mw/Mn = 1.26 (RI detector relative to PS standards).1H NMR
(CDCl3, δ) 6.08 (bs, CH=CH), 4.47 (bs, OCHof oxanorbornene and CHO-TEMPO), 3.48 (bs,
N-CH2), 3.32 (bs, CH-CH, bridge-head protons), 1.9-0.4 (m, CH3 and CH2 of butyl and
TEMPO).
Bromination of PONB-TEMPO (PONB-TEMPO-Br) (2nd bromination)
PONB-TEMPO (0.20 g, 0.033 mmol, Mn,theo = 6000, 1 equiv.) was dissolved in 80 mL of
CHCl3. The reaction mixture was then cooled to 0 oC. Bromine (0.085 mL, 1.67 mmol, 50
equiv.) in 10 mL of CHCl3 was added dropwise within 30 min. to this solution under nitrogen.
The reaction mixture was stirred for 15 min. at 0 oC then for 4h at room tempeature. The
solvent was evaporated under reduced pressure. The remaining residue was diluted with THF,
and precipitated in hexane/diethyl ether. This procedure (THF/ hexane-diethyl ether) was
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repeated two times. The polymer was filtered and dried for 24 h in a vacuum oven at 40 oC.
(Yield: 0.27 g, 84 %) Mn,theo = 9600; Mn,GPC = 6650; Mw/Mn = 1.20 (RI detector relative to PS
standards). 1H NMR (CDCl3, δ) 4.73 (br, OCHof oxanorbornene and CH-Br),3.77 (bs, NCH2), 3.54 (bs, CH-CH, bridge-head protons), 1.58 (bs, CH2 of butyl), 1.33 (bs, CH2 of
butyl), 0.94 (bs, CH3 of butyl).
Synthesis of PONB-TEMPO-acrylatevia NRC Reaction (2nd NRC)
PONB-TEMPO-Br (0.2 g, 0.021 mmol, Mn,theo = 9600, 1 equiv.) was dissolved in DMF (10
mL), TEMPO-acrylate (0.47 g, 2.10 mmol, 100 equiv.), PMDETA (0.22 mL, 1.05 mmol, 50
equiv.), CuBr (0.15 g, 1.05 mmol, 50 equiv.) and Cu (0) (0.67 g, 10.5 mmol, 250 equiv.) were
added in a 25 mL of Schlenk tube. The reaction mixture was degassed by three FPT cycles,
left in vacuum and stirred at room temperature overnight. The solution was diluted with THF
and filtered through a column filled with neutral alumina to remove copper complex and
finally precipitated in hexane/diethyl ether.After decantation, the product was dissolved in
CH2Cl2 and extracted with water, dried over Na2SO4, filtered and evaporated to dryness.
Finally, the crude product was dissolved in THF and precipitated in hexane-diethyl ether.
After decantation, the obtained polymer was dried overnight in a vacuum oven at 40 °C.
(Yield = 0.06 g, 43 % ) Mn,GPC = 5000; Mw/Mn = 1.26 (RI detector relative to PS standards).1H
NMR (CDCl3, δ) 6.5-6.2 (br, C=OCH=CH2), 6.08 (bs, CH=CH), 6.0-5.7 (br, C=OCH=CH2),
4.47 (bs, OCHof oxanorbornene and CHO-TEMPO), 3.48 (bs, N-CH2), 3.32 (bs, CH-CH,
bridge-head protons), 1.9-0.4 (m, CH3 and CH2 of butyl and TEMPO).
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Figure S1. 1H (500 MHz) (top) and
CDCl3.
13
C NMR (125 MHz) (bottom) spectra of PONB in
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Figure S2. 1H NMR spectra of PONB-acrylate (top) and PONB-thiphenol (bottom) in
CDCl3 (500 MHz).
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Figure S3. 1H NMR spectra of PONB-Br (a) PONB-TEMPO (b) PONB-TEMPO-Br (c)
and PONB-TEMPO-acrylate (d) in CDCl3 (500 MHz).
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