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19 The polymer supported aldehyde was
characterized by 500 MHz 1H NMR analysis in
CDCl3:δ = 8.19 (s,
1 H), 8.12 (d, J = 8.3
Hz, 2 H), 7.71 (d, J = 8.3
Hz, 2 H), 4.53 (t, J = 4.7 Hz,
2 H, -PEGOCH2CH
2CO),
3.70-3.90 (m, PEG) ppm. The polymer supported imine 2c (R = p-FC6H4) was characterized
by 500 MHz 1H NMR analysis in CDCl3: δ = 8.51
(s, 1 H), 8.15 (d, J = 8.1
Hz, 2 H), 7.96 (d, J = 8.1 Hz,
2 H), 7.26 (m, 2 H), 7.11 (m, 2 H), 4.51 (t, J = 4.7
Hz, 2 H, -PEGOCH2CH
2CO),
3.50-3.78 (m, PEG) ppm.
20
Typical Procedure
for the Synthesis of 1,2,4-Oxadiazolines: N-Chlorosuccinimide
(NCS, 2 mmol) was stirred in a flask containing dry CH2Cl2 (5
mL). The oxime (2 mmol) was added at 25 °C in
one portion.The polymer-supported acrylate (0.25 mmol) was added
in one portion after the chlorination was over. Usually after ca
30 min, Et3N (0.14 mL in 2 mL of CH2Cl2)
was added drop by drop over ca 2 h. The reaction mixture was stirred
overnight at r.t. To this was added a five fold excess of dry benzene
and the resulting triethylamine hydrochloride was removed by filtration.
The solution was concentrated and Et2O was added to afford
the polymer-supported 1,2,4-oxadiazolines 3.
The resin 3 is then cleaved with CH3ONa/CH3OH
at r.t. to give the desired 1,2,4-oxadiazolines 4.
Compound 3a:
1H
NMR (500 MHz, CDCl3): δ = 8.13
(d, J = 8.0
Hz, 2 H), 7.67 (d, J = 8.0
Hz, 2 H), 7.53 (d, J = 8.5
Hz, 2 H), 7.18 (d, J = 8.4
Hz, 2 H), 6.80-7.10 (m, 5 H), 6.54 (s, 1 H), 4.25 (t, J = 4.7 Hz,
2 H, -PEGOCH2CH
2CO),
3.80 (s, 3 H), 3.50-3.78 (m, PEG) ppm. Compound 4a: 1H NMR (500 MHz, CDCl3): δ = 8.11
(d, J = 8.0
Hz, 2 H), 7.67 (d, J = 8.0
Hz, 2 H), 7.53 (d, J = 8.5
Hz, 2 H), 7.18 (d, J = 8.4
Hz, 2 H), 6.80-7.10 (m, 5 H), 6.54 (s, 1 H), 4.11 (s, 3
H), 3.88 (s, 3 H) ppm. GC/MS: m/z = 388
(M+).