Butanedioic acid, 2-acetyl-, 1,4-diethyl ester → HCID 86753278, compound

HRID 355404Notes

Reaction equation

HRID 355404 reaction equation
[C:1]([CH:4]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:5](OCC)=[O:6])(=O)[CH3:2].[F:16][C:17]1[C:23]([OH:24])=[C:22]([F:25])[CH:21]=[CH:20][C:18]=1[OH:19]>CS(O)(=O)=O>[F:25][C:22]1[CH:21]=[C:20]2[C:18](=[C:17]([F:16])[C:23]=1[OH:24])[O:19][C:5](=[O:6])[C:4]([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:1]2[CH3:2]

Participants

4

Reactant 2

HCID 66197Butanedioic acid, 2-acetyl-, 1,4-diethyl esterHCID 108445152,4-Difluororesorcinol

Product 1

HCID 86753278HCID 86753278, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 6395Methanesulfonic AcidSolvent

Procedure

Diethyl acetylsuccinate (2.4 g, 11.1 mmol) is added to a solution of Compound 4 (1.3 g, 8.9 mmol) in 20 mL methanesulfonic acid at 20° C. The reaction is stirred for 16 hours and poured into 200 mL ice water. The product is extracted with EtOAc (80 mL×2), washed with brine (40 mL), dried over anhydrous MgSO4, and concentrated in vacuo to yield a brown oil. The crude oil is purified by column chromatography on silica gel eluted with CHCl3 /MeOH (95:5 to 90:10) to yield 1.06 g (40%) of Compound 10 as an off-white solid. 1H-NMR (DMSO-d6) δ 7.56 (d, 1H), 4.08 (q, 2H), 3.67 (s, 2H), 2.34 (s, 3H), 1.19 (t, 3H). 19F-NMR (DMSO-d6) Φ 130.13 (t, 1F), 148.87 (d, 1F). Also isolated from the column is 0.50 g (20%) of 6,8-difluoro-7-hydroxy-4-methylcoumarin 3-acetic acid (Compound 11).

Workup

  1. extractionThe product is extracted with EtOAc (80 mL×2)
  2. washwashed with brine (40 mL)
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated in vacuo
  5. customto yield a brown oil
  6. customThe crude oil is purified by column chromatography on silica gel
  7. washeluted with CHCl3 /MeOH (95:5 to 90:10)

Sources & evidence

ORD record
ord-31efe3a9e7944717b6abdb03f0f724f2
Source dataset
uspto-grants-1998_11
Patent number
US05830912

Reaction notes

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