Acetone → HCID 59440146, compound

HRID 2403514Notes

Reaction equation

HRID 2403514 reaction equation
[CH2:1]([O:8][C:9]1[C:32]([O:33][CH3:34])=[CH:31][C:12]([C:13]([N:15]2[C:23]3[C:18](=[CH:19][CH:20]=[C:21]([N+:24]([O-:26])=[O:25])[CH:22]=3)[CH2:17][CH:16]2[C:27](OC)=[O:28])=[O:14])=[C:11]([N+:35]([O-:37])=[O:36])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)=O.CC(C)=O.CC(C[AlH]CC(C)C)C>ClCCl.C1(C)C=CC=CC=1.Cl.C(OCC)(=O)C.CO>[CH2:1]([O:8][C:9]1[C:32]([O:33][CH3:34])=[CH:31][C:12]([C:13]([N:15]2[C:23]3[C:18](=[CH:19][CH:20]=[C:21]([N+:24]([O-:26])=[O:25])[CH:22]=3)[CH2:17][CH:16]2[CH:27]=[O:28])=[O:14])=[C:11]([N+:35]([O-:37])=[O:36])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 4

HCID 180AcetoneHCID 280Carbon DioxideHCID 14487Diisobutylaluminum hydrideHCID 59440245HCID 59440245, compound

Product 1

HCID 59440146HCID 59440146, compoundYield 64.5%

Reagents, catalysts & solvents 5

HCID 313Hydrochloric AcidSolventHCID 887MethanolSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 1-(4-(benzyloxy)-5-methoxy-2-nitrobenzoyl)-6-nitroindoline-2-carboxylate (258b) (1.023 g, 2.016 mmol) was dissolved in a mixture of anhydrous dichloromethane (2.5 mL) and toluene (7.5 mL) and cooled to −78° C. in a dry ice and acetone bath. After 15 minutes DIBAL-H (1.0M in THF) (4.03 mL, 4.03 mmol) was added via a syringe pump over about a 20 minute period. The resulting solution was stirred for 2 hrs at −78° C. after which methanol (1 ml) was added dropwise to quench the reaction at −78° C. The reaction was then diluted with 5% HCl and ethyl acetate and warmed to room temperature. The aqueous layer was washed with additional ethyl acetate and the combined organic layers were washed with brine and dried over anhydrous sodium sulfate. The reaction mixture was passed through a layer of celite and concentrated in vacuo. The crude residue was purified by silica gel chromatography using 40% acetone in hexane to give 1-(4-(benzyloxy)-5-methoxy-2-nitrobenzoyl)-6-nitroindoline-2-carbaldehyde (258c) (621 mg, 1.301 mmol, 64.5% yield). 1H NMR (400 Hz, CDCl3): δ 3.15-3.60 (m, 2H), 3.90 (s, 0.6H), 3.92 (s, 1.2H), 3.97 (s, 1.2H), 4.57 (d, 0.2H, J=4.8 Hz), 5.21 (m, 2.4H), 5.5 (m, 0.4H), 6.39 (s, 0.4H), 6.46 (s, 0.2H), 6.76 (s, 0.2H), 6.89 (s, 0.4H), 7.01 (s, 0.4H), 7.19-7.41 (m, 5.6H), 7.60-7.77 (m, 1.6H), 7.86-7.91 (m, 0.8H), 8.94 (s, 0.4H), 9.34 (s, 0.4H), 9.74 (s, 0.4H), 9.90 (s, 0.2H). MS (m/z). found 500.1 ([M]++Na).

Workup

  1. additionwas added dropwise
  2. customto quench
  3. customthe reaction at −78° C
  4. washThe aqueous layer was washed with additional ethyl acetate
  5. washthe combined organic layers were washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe crude residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-5d0e80e95c9b43a980754cd9a57b661f
Source dataset
uspto-grants-2014_08
Patent number
US08802667B2

Reaction notes

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