Benzoyl chloride → HCID 53246613, compound

HRID 1189581

Reaction equation

HRID 1189581 reaction equation
[CH3:1][C:2]1[N:3]([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[C:4]([CH3:22])=[CH:5][C:6]=1[CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[S:14]([N:17]1[CH2:21][CH2:20][CH2:19][CH2:18]1)(=[O:16])=[O:15].[Cl-].[Cl-].C([Al+2])C.[C:34](Cl)(=[O:41])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1>C(Cl)Cl.C1(C)C=CC=CC=1>[C:34]([C:5]1[C:6]([CH2:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[S:14]([N:17]2[CH2:21][CH2:20][CH2:19][CH2:18]2)(=[O:15])=[O:16])=[C:2]([CH3:1])[N:3]([CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[C:4]=1[CH3:22])(=[O:41])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1

Participants

7

Reactant 4

HCID 7412Benzoyl chloride2×HCID 11237Ethylaluminum dichlorideHCID 16686341Ethyl aluminium dichlorideHCID 58310930HCID 58310930, compound

Product 1

HCID 53246613HCID 53246613, compoundYield 91.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

In a small vial charged with ethyl 2-(2,5-dimethyl-3-(2-(pyrrolidin-1-ylsulfonyl)benzyl)-1H-pyrrol-1-yl)acetate (143.7 mg, 0.355 mmol) in DCM (4 mL), at 0° C., was added dropwise a solution of ethylaluminum dichloride (444 μL, 0.444 mmol) in toluene. The reaction mixture turned deep rose color and benzoyl chloride (61.9 μL, 0.533 mmol) was added. The resulting mixture became orange and slowly was allowed to warm to rt. The reaction was stirred 5.25 h and then cooled once again and an additional 800 μL of EtAlCl2 and 150 μL of benzoyl chloride were added. The reaction was once again allowed to warm to room temperature slowly with stirring and stirred an additional 15.25 h at room temperature. The reaction was then quenched by the addition of water and dichloromethane and the water layer was extracted with DCM (3×). The organic layer was dried with MgSO4, and concentrated under vacuum. The crude product was added to a 40 g ISCO silica gel column and purified with a gradient of 0% to 60% EtOAc/hexanes. The product was obtained as a light orange foam (165.2 mg, 0.325 mmol, 91% yield). 1H NMR (CDCl3/400 MHz) δ (ppm) 7.92 (dd, 1H), 7.68 (dd, 2H), 7.46 (t, 1H), 7.38-7.32 (m, 3H), 7.20 (t, 1H), 7.10 (d, 1H), 4.56 (s, 2H), 4.30 (s, 2H), 4.24 (q, 2H), 3.23-3.17 (m, 4H), 2.03 (s, 3H), 1.98 (s, 3H), 1.84-1.78 (m, 4H), 1.29 (t, 3H). MS m/z: 509.40 (M+1).

Workup

  1. additionwas added
  2. temperaturecooled once again
  3. temperatureto warm to room temperature slowly
  4. stirringwith stirring
  5. stirringstirred an additional 15.25 h at room temperature
  6. customThe reaction was then quenched by the addition of water and dichloromethane
  7. extractionthe water layer was extracted with DCM (3×)
  8. dry with materialThe organic layer was dried with MgSO4
  9. concentrationconcentrated under vacuum
  10. additionThe crude product was added to a 40 g ISCO silica gel column
  11. custompurified with a gradient of 0% to 60% EtOAc/hexanes

Sources & evidence

ORD record
ord-9359d4907be14199a04f8db13c62be8f
Source dataset
uspto-grants-2014_03
Patent number
US08674115B2

Linked notes

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