Acetic Anhydride → Ethyl 3-acetyl-4,5-dimethyl-1H-pyrrole-2-carboxylate

HRID 2361571Notes

Reaction equation

HRID 2361571 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[C:5](OC(=O)C)(=[O:7])[CH3:6].[CH2:12]([O:14][C:15]([C:17]1[NH:18][C:19]([CH3:23])=[C:20]([CH3:22])[CH:21]=1)=[O:16])[CH3:13]>ClC(Cl)C>[CH2:12]([O:14][C:15]([C:17]1[NH:18][C:19]([CH3:23])=[C:20]([CH3:22])[C:21]=1[C:5](=[O:7])[CH3:6])=[O:16])[CH3:13]

Participants

5

Reactant 3

HCID 7918Acetic AnhydrideHCID 137478Ethyl 4,5-dimethyl-1H-pyrrole-2-carboxylateHCID 6451240Aluminum(III) Chloride

Product 1

HCID 12288399Ethyl 3-acetyl-4,5-dimethyl-1H-pyrrole-2-carboxylateYield 60%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent2×

Procedure

To a solution of aluminum chloride (50.19 g, 0.376 mol) in dry dichloroethane (580 mL) at 25° C. was added slowly acetic anhydride (17.75 mL, 0.188 mol). The resulting mixture was stirred at room temp. for 10 minutes, then a solution of pyrrole 3b (10.49 g, 0.0627 mol) in dichloroethane (30 mL) was added and the reaction mixture was stirred at room temp. for 2 hours. After an additional 3 hours at 80° C., the mixture was poured into ice water and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate and concentrated in vacuo to an orange residue. Short plug filtration over silica gel (30% ethyl acetate/70% hexanes) gave 7.5 g (60%) of ethyl-3-acetyl-4,5-dimethyl-2-pyrrole carboxylate 4b. 1H NMR (CDCl3) δ 9.0 (bs, 1H), 4.3 (q, 2H), 2.7 (s, 3H), 2.1 (s, 3H), 1.9 (s, 3H), 1.3 (t, 3H) ppm.

Workup

  1. stirringthe reaction mixture was stirred at room temp. for 2 hours
  2. waitAfter an additional 3 hours at 80° C.
  3. extractionextracted with dichloromethane
  4. dry with materialThe organic layer was dried with anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo to an orange residue
  6. filtrationShort plug filtration over silica gel (30% ethyl acetate/70% hexanes)

Sources & evidence

ORD record
ord-bd02ea81f0254349a10b41d9e2d4ccba
Source dataset
uspto-grants-2014_04
Patent number
US08691758B2

Reaction notes

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