2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → [5-Bromo-4-(4-chlorobenzyl)-7-fluoro-1-oxo-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl]acetic acid methyl ester

HRID 1436216Notes

Reaction equation

HRID 1436216 reaction equation
[Br:1][C:2]1[C:10]2[N:9]([CH2:11][C:12]3[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=3)[C:8]3[CH:19](CC(O)=O)[CH2:20][CH2:21][C:7]=3[C:6]=2[CH:5]=[C:4]([F:26])[CH:3]=1.[N+](=C)=[N-].C(C1C(=O)C(Cl)=C(Cl)C(=[O:35])C=1C#N)#N.C[CH2:45][O:46][C:47]([CH3:49])=[O:48]>C1COCC1.O.[Cl-].[Na+].O>[CH3:45][O:46][C:47](=[O:48])[CH2:49][CH:19]1[C:8]2[N:9]([CH2:11][C:12]3[CH:13]=[CH:14][C:15]([Cl:18])=[CH:16][CH:17]=3)[C:10]3[C:2]([Br:1])=[CH:3][C:4]([F:26])=[CH:5][C:6]=3[C:7]=2[C:21](=[O:35])[CH2:20]1

Participants

7

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8857Ethyl AcetateHCID 9550DiazomethaneHCID 18476687[4-(4-Chlorobenzyl)-7-fluoro-5-bromo-1,2,3,4-tetrahydrocyclopenta[B]indol-3-YL]acetic acid

Product 1

HCID 67021498[5-Bromo-4-(4-chlorobenzyl)-7-fluoro-1-oxo-1,2,3,4-tetrahydrocyclopenta[b]indol-3-yl]acetic acid methyl ester

Reagents, catalysts & solvents 2

HCID 21881883Oxolane--water (1/1)SolventHCID 57417360Sodium chloride; waterSolvent

Procedure

The methyl ester of the compound of Example 1 step 5 (1.00 g, prepared by treating the corresponding acid with excess diazomethane) in 10 mL of a 9:1 THF/H2O solution was treated with 2.52 g of DDQ. The reaction mixture was allowed to stir at room temperature overnight. The reaction mixture at this time was poured into a separatory funnel containing EtOAc and brine. The combined organic layers were washed with water, brine, dried over anhydrous MgSO4 and concentrated. The resulting material was further purified by flash chromatography eluting with 30% EtOAc/hexane. The chromatography procedure was repeated an additional two times. 350 mg of the above ketone was obtained as a grey solid.

Workup

  1. additionThe reaction mixture at this time was poured into a separatory funnel
  2. washThe combined organic layers were washed with water, brine
  3. dry with materialdried over anhydrous MgSO4
  4. concentrationconcentrated
  5. customThe resulting material was further purified by flash chromatography
  6. washeluting with 30% EtOAc/hexane

Sources & evidence

ORD record
ord-ca9b3fdba3864890873b407a1113a4c5
Source dataset
uspto-grants-2009_11
Patent number
US07618994B2

Reaction notes

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