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(CBCH), 71.79 (Cc), 64.80 (CH2OCH2CBCH), 56.61
(CH2OCH2CBCH), 52.59 (Cb). HRMS: (ESI, m/z): [M 1 H]1
calcd for C15H17O2, 229.1150; found, 229.1043.
2H), 5.61 (s, CH2N, 4H), 5.11 (s, COOCH2, 4H), 3.83 (s, Hb,
2H), 2.02 (bs, Hc, 2H).
Synthesis of 13
The general procedure for CuAAC polyaddition was applied
to dialkyne 2 (151 mg, 0.59 mmol), diazide 8 (177 mg, 0.59
mmol), CuP(OEt)3I (28 mg, 0.03 mmol), and DIPEA (76 mg,
0.59 mmol) to obtain 13 as a light brown solid (240 mg,
73.1%).
Synthesis of 4,40-Di(2-azidoethoxy)benzophenone (10)
Potassium carbonate (9.70 g, 70.2 mmol), 1,2-dibromoethane
(61.0 mL, 708 mmol), and 18-crown-6 (6 mg, 0.02 mmol)
were added to a solution of 4,40-dihydroxybenzophenone (5.00
g, 23.3 mmol) in acetone (125 mL). The reaction mixture was
refluxed under argon for 96 h, filtered, and evaporated to dry-
ness. The residue was extracted with dichloromethane (3 3
100 mL). The combined organic phases were dried over
MgSO4, filtered, and concentrated under vacuum. The obtained
solid (9.72 g, 98.0%) was used in the azidation step without
any further purification. 4,40-Di(2-bromoethoxy)benzophenone
(9.72 g, 22.8 mmol) and sodium azide (8.90 g, 137 mmol)
were added to a round-bottom flask containing 80 mL of
dimethylformamide. The mixture was stirred in the dark for
20 h at 60 ꢀC. The solvents were evaporated under reduced
pressure and the residue was extracted with ethyl acetate (3
3 100 mL). The organic layer was dried over MgSO4, filtered,
and concentrated under reduced pressure. The residue was
purified by column chromatography on silica gel, with a 1:1
mixture of petroleum ether and ethyl acetate eluting 10 as a
white solid (6.04 g, 75.1%) after evaporation of the eluents.
1H NMR (250 MHz, DMSO-d6, d): 8.96 (s, C@CH, 2H), 8.49 (s,
H4, 2H), 8.12 (bs, H1, H2, 4H), 7.78 (bs, H3, 2H), 6.90 (s, Ha,
2H), 5.26 (s, COOCH2C, 4H), 3.88 (s, Hb, 2H), 2.06 (bs, Hc,
2H).
Synthesis of 14
The general procedure for CuAAC polyaddition was applied
to dialkyne 2 (151 mg, 0.59 mmol), diazide 9 (177 mg, 0.59
mmol), CuP(OEt)3I (28 mg, 0.03 mmol), and DIPEA (76 mg,
0.59 mmol) to obtain 14 as a brown solid (323 mg, 98.4%).
1H NMR (250 MHz, DMSO-d6, d): 8.91 (s, C@CH, 2H), 8.14
(d, J 5 7.5 Hz, H1, H2, 8H), 6.93 (s, Ha, 2H), 5.26 (s, COOCH2,
4H), 3.89 (s, Hb, 2H), 2.06 (bs, Hc, 2H).
Synthesis of 15
The general procedure for CuAAC polyaddition was applied
to dialkyne 2 (151 mg, 0.59 mmol), diazide 10 (208 mg,
0.59 mmol), CuP(OEt)3I (28 mg, 0.03 mmol), and DIPEA (76
mg, 0.59 mmol) to obtain 15 as a brown solid (320 mg,
89.1%).
1H NMR (400 MHz, DMSO-d6, d): 7.71 (d, J 5 8.8 Hz, H3, 4H),
7.01 (d, J 5 8.8 Hz, H2, 4H), 4.27 (t, J 5 4.8 Hz, CH2CH2N3,
4H), 3.69 (t, J 5 4.8 Hz, CH2CH2N3, 4H); 13C NMR (100 MHz,
DMSO-d6, d): 193.10 (C5), 161.22 (C4), 131.84 (C3), 130.30
(C1), 114.22 (C2), 67.06 (CH2CH2N3), 49.41 (CH2CH2N3).
HRMS: (ESI, m/z): [M 1 H]1 calcd for C17H17O3N6, 353.1283;
found, 353.1357.
1H NMR (250 MHz, DMSO-d6, d): 8.23 (s, C@CH, 2H), 7.61
(d, J 5 8.5 Hz, H3, 4H), 7.01 (d, J 5 8.5 Hz, H2, 4H), 6.88 (s,
Ha, 2H), 5.13 (s, COOCH2, 4H), 4.81 (s, CH2CH2N, 4H), 4.49
(s, CH2CH2N, 4H), 3.83 (s, Hb, 2H), 2.08 (bs, Hc, 2H).
General Procedure for the Synthesis of NBD-Containing
Polytriazoles by CuAAC Polyaddition in DMSO
Synthesis of 11
Synthesis of 16
The general procedure for CuAAC polyaddition was applied
to dialkyne 5 (256 mg, 1.12 mmol), diazide 6 (210 mg, 1.12
mmol), CuP(OEt)3I (52 mg, 0.056 mmol), and DIPEA (145
mg, 1.12 mmol) to obtain 16 as a brown solid (280 mg,
60.0%).
Diazide 6 (156 mg, 0.59 mmol) was added to a solution of
dialkyne 2 (251 mg, 0.98 mmol), CuP(OEt)3I (46 mg, 0.05
mmol), and DIPEA (127 mg, 0.98 mmol) in 6 mL of DMSO.
After stirring at 60 ꢀC for 24 h, the crude product was pre-
cipitated twice in methanol, centrifuged, and dried under
1H NMR (250 MHz, DMSO-d6, d): 8.10 (s, C@CH, 2H), 7.28 (s,
H1, 4H), 6.71 (s, Ha, 2H), 5.54 (s, CH2N, 4H), 4.33 (s,
CH2OCH2CN, 4H), 4.05 (dd, J1 5 12 Hz, J2 5 39 Hz,
CH2OCH2CN, 4H), 3.42 (s, Hb, 2H), 1.77 (bs, Hc, 2H).
ꢀ
vacuum at 60 C for 8 h resulting in pure polytriazole 11 as
a light brown powder (405 mg, 60.0%).
1H NMR (250 MHz, DMSO-d6, d): 8.17 (s, C@CH, 2H), 7.28 (s,
H1, 4H), 6.89 (s, Ha, 2H), 5.56 (s, CH2N, 4H), 5.09 (s, COOCH2,
4H), 3.83 (s, Hb, 2H), 2.02 (bs, Hc, 2H).
Synthesis of 17
The general procedure for CuAAC polyaddition was applied
to dialkyne 5 (150 mg, 0.66 mmol), diazide 7 (174 mg, 0.66
mmol), CuP(OEt)3I (28 mg, 0.03 mmol), and DIPEA (85 mg,
0.66 mmol) to obtain 17 as a brown solid (260 mg, 80.2%).
Synthesis of 12
The general procedure for CuAAC polyaddition was applied
to dialkyne 2 (151 mg, 0.59 mmol), CuP(OEt)3I (28 mg, 0.03
mmol), DIPEA (76 mg, 0.59 mmol), and diazide 7 (156 mg,
0.59 mmol) to obtain 12 as a light yellow powder (290 mg,
66.6%).
1H NMR (250 MHz, DMSO-d6, d): 8.14 (s, C@CH, 2H), 7.58
(bs, H2, 4H), 7.35 (bs, H1, 4H), 6.73 (s, Ha, 2H), 5.59
(s, CH2N, 4H), 4.36 (s, CH2OCH2CN, 4H), 4.08 (dd, J1 5 12
Hz, J2 5 39 Hz, CH2OCH2CN, 4H), 3.43 (s, Hb, 2H), 1.77 (bs,
Hc, 2H).
1H NMR (250 MHz, DMSO-d6, d): 8.21 (s, C@CH, 2H), 7.57
(d, J 5 8.0 Hz, H2, 4H), 7.36 (d, J 5 8 Hz, H1, 4H), 6.89 (s, Ha,
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