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34547747925
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Preparation of 10: Pyridine (59 mg, 0.74 mmol) and 2-fluoroethyltosylate (100 mg, 0.46 mmol) were heated at 110°C for 20 h. The solvent was removed, and HCl in ether was added to give a solid, which was recrystallized from ether/ethanol (37, yield, M.p. 207-210°C; 1H NMR (D2O, 300.06 MHz, δ, 2.24 (3 H, s, CH 3, 4.82 (4 H, dm, NCH2, CH2F, 7.20 (2 H, d, CH, 7.53 (2 H, d, CH, 7.94 (2 H, t, CH, 8.44 (1 H, t, CH, 8.71 ppm (2 H, d, CH, 13C NMR (D2O, 75.5 MHz, δ, 20.4 (CH 3, 61.4, d, J, 18.1 Hz, NCH2, 81.8 (d, J, 169.8 Hz, CH2F, 125.3, 128.3, 129.4, 139.4, 142.4, 144.7, 146.3 ppm; 19F NMR (D2O, 282.3 MHz, δ, 224.2 m, for NCH2CH2F, 2JHF, 47.1 Hz, 3JHF, 26.4 Hz, 3JHH, 4.3 Hz by simulation, Br
-
+.
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-
-
-
10
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34547740089
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Preparation of 12: Pyridine (1.3 mL, 15.9 mmol) and 2-chloroethanol (0.95 mL, 14.2 mmol) were heated at 110°C for 16 h. The residual pyridine was removed under vacuum, giving a light brown solid. Colorless crystalline needles were obtained after recrystallization in ether/ethanol at 4°C (98, yield, M.p. 66-68°C; 1H NMR (CD3OD, 300.06 MHz, δ, 4.05 (2 H, t, 3JHH, 4.9 Hz, CH2OH, 4.79 (2 H, t, 3JHH, 4.9 Hz, NCH2, 8.18 (2 H, d, CH, 8.67 (1 H, t, CH, 9.04 ppm (2 H, d, CH, 13C NMR (CD 3OD, 75.47 MHz, δ, 62.1 (OCH2, 65.5 (NCH 2, 129.6, 146.9, 147.5 ppm CH, HRMS: m/z: calcd for C 7H10NO: 124.0762; found: 124.0763 [M
-
+.
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-
-
-
11
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34547821982
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Crystal data for 10: C21H23FNNaO 6S2, Mr, 491.51, triclinic, space group P1, a, 9.7646(17, b, 9.8148(16, c, 13.290(2) Å, α, 78.499(8, β, 80.851(8, γ, 66.472(7)°, V, 1139.9(3) Å3, F(000, 512, Z, 2, ρcalcd, 1.432 Mg m-3, μ, 2.716 mm-1, CuKα radiation (λ, 1.54178 Å, T, 173 K, 14680 reflections, 3.41 < θ < 67.61°, Rigaku Saturn 92 detector with 007 generator, 3712 unique data, Rmerg, 0.1643, final R, 0.0948 (for 2642 reflections with I ≥ 2σI, GOF, 1.090, 292 refined parameters, max. residual electron density: 0.525 e Å-3. Crystal data for 11: C16H 21FN2O3S, Mr, 340.41, triclinic, s
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-3. CCDC 652 106 (10), CCDC 652 101 (11), and CCDC 652 108 (12) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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HH values of 26 and 4.3 Hz, respectively.
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See the Supporting Information for a full list. CSD reference codes: 13a: NOFFAP; 13b: NOWDUY.
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