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M. Pretze et al. · Synthesis and Radiofluorination of Iodophenyl Esters
1.33 – 1.38 (m, 2 H, H-β), 1.41 – 1.48 (m, 2 H, H-δ), 2.24 (t, 2-Iodophenyl 4-fluorobutanoate (9a)
3J = 7.5 Hz, 2 H, H-α), 2.64 (t,3J = 7.0 Hz, 2 H, H-ε), 6.41
AgF (112 mg, 0.88 mmol) was added to a solution of 7b
(91 mg, 0.22 mmol) in dry acetonitrile (2 mL) under an ar-
gon atmosphere, and the mixture was stirred at r. t. overnight
in the dark. After the removal of the solvent the residue was
purified via bulb tube distillation◦to yield 9a as a pale-yellow
liquid (60 mg, 89 %). B. p. 100 C C/5 × 10−3 mbar. Rf =
0.63 (petroleum ether/EtOAc 8 : 1). – 1H NMR (400 MHz,
C6D6): δ = 1.69 – 1.78 (m, 2 H, H-β), 2.29 (t, 3J = 7.3 Hz,
(dt, 3J3,4 = 7.5 Hz, 4J4,6 = 1.6 Hz, 1 H, 4-H), 6.85 (t, 3J4,5
=
7.8 Hz, 1 H, 5-H), 6.92 (d, 3J5,6 = 7.8 Hz, 1 H, 6-H), 7.50 (d,
3J3,4 = 7.8 Hz, 1 H, 3-H). – 13C NMR (101 MHz, C6D6): δ =
6.0 (C-ε), 23.6 (C-β), 29.8 (C-γ), 33.1 (C-δ), 33.9 (C-α),
90.9 (C-2), 123.2 (C-6), 127.3 (C-4), 129.2 (C-5), 139.4
(C-3), 151.7 (C-1), 170.2 (C=O). – MS ((+)-ESI): m/z (%) =
467 (10) [M+Na]+. – C12H14I2O2 (444.05): calcd. C 32.46,
H 3.18; found C 35.88, H 3.63.
3
2 H, H-α), 4.08 (dt, JH,F = 46.9 Hz, 3J = 5.7 Hz, 2 H,
3
4
H-γ), 6.40 (dt, J3,4 = 7.5 Hz, J4,6 = 2.3 Hz, 1 H, 4-H),
2-Iodophenyl 4-(tosyloxy)butanoate (8a)
3
6.82 – 6.84 (m, 2H, 5-H, 6-H), 7.49 (d, J3,4 = 7.8 Hz, 1 H,
AgOTs (1.02 g, 3.64 mmol) was added to a solution of 7b
(1.08 g, 2.60 mmol) in dry acetonitrile (2 mL) under an argon
atmosphere, and the mixture was stirred at r. t. overnight in
the dark. After the removal of the solvent the residue was pu-
rified via column chromatography (petroleum ether/EtOAc
40 : 1 → 10 : 1 → 1 : 1) to yield 8a as a pale-yellow liquid
(1.13 g, 94 %). Rf = 0.20 (petroleum ether/EtOAc 8 : 1). – 1H
NMR (400 MHz, C6D6): δ = 1.61 – 1.68 (m, 2 H, H-β), 1.81
3-H). – 13C NMR (101 MHz, C6D6): δ = 30.1 (d, JC,F
=
2
3
19.6 Hz, C-β), 34.2 (d, JC,F = 4.7 Hz, C-α), 82.3 (d,
1JC,F = 165.3 Hz, C-γ), 93.6 (C-2), 123.4 (C-6), 126.7 (C-4),
130.0 (C-5), 139.6 (C-3), 152.2 (C-1), 170.9 (C=O). – 19F
NMR (376 MHz, C6D6): δ = −220.7. – MS ((+)-ESI): m/z
(%) = 332 (10) [M+Na+H]+. – C10H10FIO2 (308.09): calcd.
C 38.98, H 3.27; found C 38.66, H 3.09.
3
3
(s, 3H, CH3), 2.29 (t, J = 7.0 Hz, 2 H, H-α), 3.86 (t, J =
2-Iodophenyl 6-fluorohexanoate (9b)
3
4
6.3 Hz, 2 H, H-γ), 6.38 (dt, J3,4 = 7.8 Hz, J4,6 = 1.6 Hz,
1 H, 4-H), 6.67 (d, 3J = 7.8 Hz, 2H, Hmeta), 6.80 – 6.88 (m,
AgF (205 mg, 1.62 mmol) was added to a solution of 7b
(362 mg, 0.81 mmol) in dry acetonitrile (2 mL) under an ar-
gon atmosphere, and the mixture was stirred at r. t. overnight
in the dark. After the removal of the solvent the residue was
purified via bulb tube distillation to yield 9b as a colorless
liquid (137 mg, 90 %). B. p. 95 ◦C/5 × 10−3 mbar. Rf = 0.52
(petroleum ether/EtOAc 8 : 1). – 1H NMR (400 MHz, C6D6):
δ = 1.17 – 1.22 (m, 2 H, H-γ), 1.31 – 1.36 (m, 2 H, H-β),
3
2 H, 5-H, 6-H), 7.47 (d, J3,4 = 7.8 Hz, 1H, 3-H), 7.74 (d,
3J = 8.6 Hz, 2H, Hortho). – 13C NMR (101 MHz, C6D6): δ =
21.1 (CH3), 24.3 (C-β), 30.2 (C-α), 68.9 (C-γ), 90.9 (C-2),
123.3 (C-6), 127.6 (C-4), 128.2 (Cortho), 129.4 (C-5), 129.9
(Cmeta), 134.3 (Cipso), 139.5 (C-3), 144.3 (Cpara), 151.8
(C-1), 169.8 (C=O). – MS ((+)-ESI): m/z (%) = 289 (20)
[M–TsO]+, 483 (100) [M+Na]+. – C17H17IO5S (460.28):
calcd. C 44.36, H 3.72; found C 44.19, H 3.79.
3
1.49 – 1.55 (m, 2 H, H-δ), 2.29 (t, J = 7.6 Hz, 2 H, H-α),
3
4.04 (dt,3JH,F = 47.7 Hz, J = 5.9 Hz, 2 H, H-ε), 6.41 (dt,
2-Iodophenyl 5-(tosyloxy)pentanoate (8b)
3J3,4 = 7.5 Hz, 4J4,6 = 1.6 Hz, 1 H, 4-H), 6.83 – 6.92 (m, 2 H,
3
5-H, 6-H), 7.51 (d, J3,4 = 7.1 Hz, 1 H, 3-H). – 13C NMR
AgOTs (1.06 g, 3.79 mmol) was added to a solution of
7c (1.17 g, 2.71 mmol) in dry acetonitrile (10 mL) under
an argon atmosphere, and the mixture was stirred at r. t.
overnight in the dark. After the removal of the solvent the
residue was purified via column chromatography (petroleum
ether/EtOAc 20 : 1 → 8 : 1) to yield 8b as a pale-yellow liq-
uid (1.22 g, 95 %). Rf = 0.26 (petroleum ether/EtOAc 8:1). –
1H NMR (400 MHz, C6D6): δ = 1.31 – 1.36 (m, 2 H, H-β),
(101 MHz, C6D6): δ = 24.5 (C-β), 25.0 (d, 3JC,F = 5.2 Hz,
2
C-γ), 30.3 (d, JC,F = 19.6 Hz, C-δ), 34.2 (C-α), 83.4 (d,
1JC,F = 165.9 Hz, C-ε), 91.0 (C-2), 123.4 (C-6), 127.5 (C-4),
129.4 (C-5), 139.6 (C-3), 151.9 (C-1), 170.5 (C=O). – 19F
NMR (376 MHz, C6D6): δ = −218.4. – MS ((+)-ESI): m/z
(%) = 359 (80) [M+Na]+. – C12H14FIO2 (336.14): calcd.
C 42.88, H 4.20; found C 43.04, H 4.29.
3
1.42 – 1.49 (m, 2 H, H-γ), 1.82 (s, 3 H, CH3), 2.14 (t, J =
7.4 Hz, 2 H, H-α), 3.77 (t, 3J = 6.0 Hz, 2 H, H-δ), 6.38
2-(Diphenylphosphano)phenyl 4-fluorobutanoate (10)
KOAc (38 mg, 0.39 mmol), HPPh2 (60 µL, 0.32 mmol)
4
3
(dt, 3J3,4 = 7.8 Hz, J4,6 = 2.3 Hz, 1 H, 4-H), 6.69 (d, J =
7.8 Hz, 2 H, Hmeta), 6.83 – 6.85 (m, 2 H, 5-H, 6-H), 7.49
(d, J3,4 = 8.6 Hz, 1 H, 3-H), 7.76 (d, 3J = 8.6 Hz, 2 H, and Pd(OAc)2 in catalytical amount were added to a solu-
Hortho). – 13C NMR (101 MHz, C6D6): δ = 20.9 (C-β), tion of 2-iodophenyl benzoate (9a) (100 mg, 0.32 mmol)
21.2 (CH3), 28.3 (C-γ), 33.5 (C-α), 69.6 (C-δ), 91.0 (C-2), in dry DMA (2 mL) under an argon atmosphere. The mix-
3
◦
123.4 (C-6), 127.5 (C-4), 128.2 (Cortho), 129.4 (C-5), 129.9 ture was stirred at 90 C for 3 h. Afterwards water (15 mL)
(Cmeta), 134.5 (Cipso), 139.6 (C-3), 144.2 (Cpara), 151.8 and CH2Cl2 (15 mL) were added, the organic layer was
(C-1), 170.1 (C=O). – MS ((+)-ESI): m/z (%) = 303 (50) separated, and the aqueous layer was extracted with 3×
[M–TsO]+, 497 (100) [M+Na]+. – C18H19IO5S (474.31): 10 mL CH2Cl2. The combined organic layers were dried
calcd. C 45.58, H 4.04; found C 45.56, H 4.01.
over Na2SO4, and the solvent was removed under reduced
- 10.1515/znb-2010-0912
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