Yield:611-53-0 63%

Reaction Conditions:

with iodine;3-chloro-benzenecarboperoxoic acid in N,N-dimethyl-formamide at 20; for 2 h;

Steps:

dC 1 In a flame dried round bottom flask 10.0 g dC (44.0 mmol, 1.0 eq), 7.70 g iodine (26.4 mmol, 0.6 eq) and 1 1.4 g mCPBA (70 %, 46.2 mmol, 1 .05 eq) were dissolved in 120 mL DMF. The reaction mixture was stirred 2 h at room temperature and subsequently evaporated to dryness, (small amounts of DMF are tolerable during subsequent column chromatography) Purification by column chromatography (DCM/MeOH/H₂0/NH₃ 190:10:0.6:0.6 → 90:10:0.6:0.6) yielded 9.71 g (63 %) of 1 as an orange solid. ¹H NMR (400 MHz, CDCI₃/MeOD) δ (ppm) = 8.46 (s, 1 H), 6.13 (t, ³J=6.0, 1 H), 4.34 (dt, ³J=4.7, ³J=6.3 , 1 H), 3.93 (dt, ³J=3.0, ³J=4.3, 1 H), 3.84 (dd, ³J=3.0 Hz, ²J=12.1 , 1 H), 3.72 (dd, ³ =3.2, ²J=12.1 , 1 H), 2.39 (ddd, ³J=4.8, ³J=6.3, ²J=13.7, 1 H), 2.20 - 2.09 (m, 1 H). ¹³C NMR (101 MHz, MeOD) δ (ppm) = 163.9, 153.9, 150.9, 89.5, 88.3, 71 .5, 62.2, 56.2, 42.5. HRMS (ESI +) calculated for C₉H₁₃IN₃0₄⁺ [M+H]⁺: 353.9945, found: 353.9944. melting range: 133°C - 135 °C (decomposition) IR (ATR): 3191 (w), 1718 (m), 1642 (s), 1286 (m), 1087 (s), 957 (s), 750 (m).

References:

WO2012/62907,2012,A1 Location in patent:Page/Page column 13; 14