Acetic Acid → HCID 86611447, compound

HRID 1865120Notes

Reaction equation

HRID 1865120 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.C(O)(=O)C.[N:20]([O-])=[O:21].[Na+]>C1COCC1.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](=[O:15])[CH:9]([NH:20][OH:21])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 2757149Ethyl 3-(4-bromophenyl)-3-oxopropanoateHCID 23668193Sodium Nitrite

Product 1

HCID 86611447HCID 86611447, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 8028TetrahydrofuranSolvent

Procedure

To the solution of ethyl 3-(4-bromophenyl)-3-oxopropanoate in THF (prepared in step A above), add acetic acid (160 L) and water (73 L) at an internal temperature of 8° C. To this mixture, add a solution of sodium nitrite (6.35 kg, 92.00 mol, 1.25 eq) in water (30 L) at an internal temperature of 6 to 9° C. during 90 min and stir at this temperature for 90 min. At an internal temperature of 4 to 7° C., add water (147 L) over 30 min to the reaction mixture and stir the resulting suspension for 30 min. Filter the suspension and wash the filter cake with water (59 L) and heptane (60 L). Dry the filter cake under a constant flow of nitrogen for 13 h to obtain the title compound: 18.731 kg according to loss of drying (23.044 kg wet); white powder; 1H NMR (DMSO-d6, 500.0 MHz): δ 1.22 (t, J=7.1 Hz, 3H), 4.27 (q, J=7.1 Hz, 2H), 7.75 (d, J=8.8 Hz, 2H, 7.83 (d, J=8.8 Hz, 2H), 13.18 (s, 1H); 13C NMR (DMSO-d6, 125.7 MHz): δ 14.36, 62.27, 129.68, 131.09, 133.08, 133.36, 148.44, 161.17, 191.08; Anal. Calcd for C11H10BrNO4: C, 44.02; H, 3.36; Br, 26.63; N, 4.67; O, 21.32. Found: C, 43.98; H, 3.31; Br, 26.65; N, 4.59; MS (ES−) 299; IR (KBr): 3281, 3219, 3049, 2983, 2870, 1728, 1680, 1586, 1446, 1400, 1302, 1262, 1029, 944 cm−1.

Workup

  1. stirringstir the resulting suspension for 30 min
  2. filtrationFilter the suspension
  3. washwash the filter cake with water (59 L) and heptane (60 L)
  4. customDry the filter cake under a constant flow of nitrogen for 13 h

Sources & evidence

ORD record
ord-d2a9ff4e1d8c47c2862aa6e88000f4a7
Source dataset
uspto-grants-2009_12
Patent number
US07625932B2

Reaction notes

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