Acetic Anhydride → HCID 140557999, compound

HRID 889659Notes

Reaction equation

HRID 889659 reaction equation
[CH3:1][O:2][C:3]([CH:5]1[C:10]([Cl:12])([Cl:11])[C:9](=[N:13][OH:14])[CH2:8][CH:7]([C:15]2[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([O:22][CH3:23])[C:16]=2[F:24])[NH:6]1)=[O:4].[C:25]([O:28]C(=O)C)(=[O:27])[CH3:26]>C(O)(=O)C>[CH3:1][O:2][C:3]([CH:5]1[C:10]([Cl:11])([Cl:12])/[C:9](=[N:13]/[O:14][O:28][C:25](=[O:27])[CH3:26])/[CH2:8][CH:7]([C:15]2[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([O:22][CH3:23])[C:16]=2[F:24])[NH:6]1)=[O:4]

Participants

4

Reactant 2

HCID 7918Acetic AnhydrideHCID 86648305HCID 86648305, compound

Product 1

HCID 140557999HCID 140557999, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
80 °C

Procedure

3-Chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-3-chloro-4-hydroxyimino-1,4,5,6-tetrahydropyridine-2-carboxylic acid methyl ester (34, 756 mg, 2.08 mmol) was slurried in glacial acetic acid (10 mL). Acetic anhydride (241 mg, 2.36 mmol) was added dropwise at room temperature. The reaction mixture was heated at 80° C. for 2 h. The solution was concentrated under vacuum, and the residue was dissolved in CH2Cl2 (50 mL) and washed with saturated aqueous NaHCO3 solution. The extracts were washed with brine, dried (MgSO4) and evaporated to give 3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-4-[(E)-acetoxyoximino]-3-chloro-1,4,5,6-tetrahydropyridine-2-carboxylic acid methyl ester (35; 842 mg, 99%) as a light orange solid: 1H NMR (400 MHz, CDCl3) δ 7.21 (dd, JF-H=1.5 Hz, JH-H=8.4 Hz, 1H, aromatic), 7.11 (dd, JF-H=6.9 Hz, JH-H=8.4 Hz, 1H, aromatic), 5.24 (br s, 1H, NH), 4.76 (dd, J=4.2, 12.3 Hz, 1H, H5a), 3.98 (d, JF-H=1.5 Hz, 3H, OMe), 3.94 (s, 3H, CO2Me), 3.40 (ddd, JF-H=1.8 Hz, JH-H=4.2, 16.5 Hz, 1H, H6), 2.72 (dd, J=12.3, 16.5 Hz, 1H, H5b), 2.23 (s, 3H, NOAc). HRMS calcd for C16H15Cl2FN2O5: 404.034. Found: 404.034.

Workup

  1. concentrationThe solution was concentrated under vacuum
  2. dissolutionthe residue was dissolved in CH2Cl2 (50 mL)
  3. washwashed with saturated aqueous NaHCO3 solution
  4. washThe extracts were washed with brine
  5. dry with materialdried (MgSO4)
  6. customevaporated

Sources & evidence

ORD record
ord-274b856083d943d98e7f69f1803a394d
Source dataset
uspto-grants-2012_08
Patent number
US08252938B2

Reaction notes

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