Sulfuric Acid → HCID 10742308, compound

HRID 1107639Notes

Reaction equation

HRID 1107639 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:18]=[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:16]2[C:11](=[CH:12][C:13]([C:27]#[N:28])=[CH:14][CH:15]=2)[CH:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].OS(O)(=O)=O.C1C(=O)N([Br:41])C(=O)C1.CCOCC>C1COCC1>[C:1]([O:5][C:6]([NH:8][C:9]1[CH:18]=[C:17]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C:16]2[C:11](=[CH:12][C:13]([C:27]#[N:28])=[CH:14][CH:15]=2)[C:10]=1[Br:41])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 3283Diethyl EtherHCID 67184N-bromobutanimideHCID 10761938HCID 10761938, compound

Product 1

HCID 10742308HCID 10742308, compoundYield 87.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-60 °C

Procedure

A solution of 15 (137 mg, 0.366 mmol) in freshly distilled THF (7.3 mL) and cooled to -78° C. under Ar was treated with 10 μL of a 1 μL/mL solution of H2SO4 in THF and the solution was stirred for 20 min before the addition of NBS (78 mg, 439 mmol, 1.2 equiv). The reaction mixture was allowed to warm to -60° C. and was stirred for 4 h at which time the reaction was complete by TLC. Et2O (7.3 mL) was added and the resulting organic phase was washed with 5% aqueous NaHCO3 (1×10 mL), saturated aqueous NaCl (1×10 mL), dried (MgSO4), and concentrated in vacuo. Chromatography (SiO2, 2×20 cm, 10% EtOAc-hexane) afforded 16 (145 mg, 166 mg theoretical, 87%) as a white crystalline solid: mp 179° C. dec (white needles, 10% EtOAc-hexane); 1H NMR (CDCl3, 250 MHz) δ8.40 (s, 1H, C8-H), 8.26 (d, 1H, J=8.5 Hz), 8.23 (s 1H, C3-H), 7.5-7.3 (m, 6H), 5.23 (s, 2H), 1.58 (s, 9H); 13C NMR (CDCl3, 75 MHz) δ154.4, 152.4, 137.0, 136.0, 132.2, 132.0, 128.7, 128.6, 128.4, 128.0, 124.9, 124.8, 124.2, 119.1, 111.9, 102.0, 81.9, 70.8, 28.3; IR (KBr) vmax 3416, 2978, 2230, 1738, 1623, 1603, 1570, 1498, 1405, 1364, 1335, 1229, 1158, 990, 970, 878, 850, 823, 758, 696 cm-1 ; FABHRMS (NBA-CsI) m/z 584.9793 (M+ +Cs, C23H21BrN2O3 requires 584.9790).

Workup

  1. washthe resulting organic phase was washed with 5% aqueous NaHCO3 (1×10 mL), saturated aqueous NaCl (1×10 mL)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6eee4e3100b74523b6bf6e5357a46624
Source dataset
uspto-grants-2000_05
Patent number
US06060608

Reaction notes

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