Dichloromethane → HCID 68844115, compound

HRID 476397Notes

Reaction equation

HRID 476397 reaction equation
[CH3:1][O:2][C:3]1[C:4]([O:15][CH2:16][CH2:17][CH2:18][C:19]([O:21][CH3:22])=[O:20])=[CH:5][C:6]([N+:12]([O-:14])=[O:13])=[C:7]([CH:11]=1)[C:8]([OH:10])=O.[C:23](Cl)(=[O:27])[C:24](Cl)=O.C([N:31]([CH2:34][CH3:35])CC)C.[CH2:36](Cl)Cl>CN(C=O)C>[CH3:22][O:21][C:19](=[O:20])[CH2:18][CH2:17][CH2:16][O:15][C:4]1[CH:5]=[C:6]([N+:12]([O-:14])=[O:13])[C:7]([C:8]([N:31]2[CH2:34][CH2:35][CH2:36][CH:24]2[CH2:23][OH:27])=[O:10])=[CH:11][C:3]=1[O:2][CH3:1]

Participants

6

Reactant 4

HCID 6344Dichloromethane2×HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 589159645-Methoxy-4-(4-methoxy-4-oxobutoxy)-2-nitrobenzoic acid

Product 1

HCID 68844115HCID 68844115, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideCatalyst

Procedure

The methyl ester 13 (30 g, 95.8 mmol) was suspended in dry DCM (300 mL) with stirring in a round-bottomed flask equipped with a drying tube. Oxalyl chloride (13.4 g, 9.20 mL, 1.1 eq) was added followed by a few drops of DMF. The mixture was stirred overnight at room temperature. Triethylamine (21.3 g, 29.3 mL, 2.2 eq), +(S)-pyrrolidine methanol (9.68 g, 9.44 mL, 1.1 eq) were dissolved in dry DCM (150 mL) under nitrogen. The solution was cooled below −30° C. The acid chloride solution was added dropwise over 6 h maintaining the temperature below −30° C. It was then left to stir overnight at room temperature. The resulting solution was extracted with 1N HCl (2×200 mL), twice with water, once with brine. It was dried with magnesium sulfate and concentrated in vacuo to give a yellow/brown oil 14 which solidified on standing. (quantitative yield). It was used in the next step without further purification. 1H NMR (CDCl3) δ 7.70 (1H, s), 6.80 (1H, s), 4.40 (1H, m), 4.16 (2H, t, J=6.2 Hz), 3.97 (3H, s), 3.97-3.70 (2H, m), 3.71 (3H, s), 3.17 (2H, t, J=6.7 Hz), 2.57 (2H, t, J=7.1 Hz), 2.20 (2H, p, J=6.8 Hz), 1.90-1.70 (2H, m); 13C NMR (CDCl3) δ 173.2, 154.8, 148.4, 109.2, 108.4, 68.4, 66.1, 61.5, 56.7, 51.7, 49.5, 30.3, 28.4, 24.4, 24.2; IR (golden gate) vmax 3400, 2953, 1734, 1618, 1517, 1432, 1327, 1271, 1219, 1170, 1051, 995, 647 cm−1; MS (ES+) m/z (relative intensity) 397.07 ([M+H]+, 100); [α]24D=−84° (c=1, CHCl3).

Workup

  1. customequipped with a drying tube
  2. stirringThe mixture was stirred overnight at room temperature
  3. temperatureThe solution was cooled below −30° C
  4. temperaturemaintaining the temperature below −30° C
  5. waitIt was then left
  6. stirringto stir overnight at room temperature
  7. extractionThe resulting solution was extracted with 1N HCl (2×200 mL), twice with water, once with brine
  8. dry with materialIt was dried with magnesium sulfate
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-2dc4680a5ef24b2f8b0617e8452abf93
Source dataset
uspto-grants-2014_01
Patent number
US08637664B2

Reaction notes

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