Di-tert-butyl azodicarboxylate → Di-tert-butyl 1-(3-methyl-inden-5-yl)hydrazine-1,2-dicarboxylate

HRID 384367Notes

Reaction equation

HRID 384367 reaction equation
C([Li])CCC.Br[C:7]1[CH:15]=[C:14]2[C:10]([CH2:11][CH2:12][CH:13]2[CH3:16])=[CH:9][CH:8]=1.C(=O)=O.CC(C)=O.[N:24]([C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])=[N:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27]>O1CCCC1>[CH3:16][C:13]1[C:14]2[C:10](=[CH:9][CH:8]=[C:7]([N:24]([C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])[NH:25][C:26]([O:28][C:29]([CH3:30])([CH3:31])[CH3:32])=[O:27])[CH:15]=2)[CH2:11][CH:12]=1

Participants

6

Reactant 4

HCID 97268Di-tert-butyl azodicarboxylateHCID 128921496-Bromo-1-methyl-indanHCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 1

HCID 68612829Di-tert-butyl 1-(3-methyl-inden-5-yl)hydrazine-1,2-dicarboxylateYield 46.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

n-Butyllithium (8.6 mL, 13.76 mmol) was added to a three-neck flask under argon atmosphere. Upon cooling by a dry ice-acetone bath, 8 mL of tetrahydrofuran, 6-bromo-1-methyl-indan 38d (1.32 g, 6.26 mmol) were added successively under stirring. The reaction mixture was reacted in the dry ice-acetone bath for 2 hours followed by dropwise addition of a solution of di-tert-butyl azodicarboxylate (1.87 g, 8.14 mmol) in 10 mL of tetrahydrofuran. The mixture was stirred for another 30 minutes and the ice-acetone bath was removed. The mixture was warmed up to room temperature and stirred for 20 hours. The reaction was quenched by addition of 20 mL of saturated ammonium chloride. The mixture was extracted with ethyl acetate (25 mL×3). The combined organic extracts were washed with saturated brine (10 mL×2), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the title compound di-tert-butyl 1-(3-methyl-inden-5-yl)hydrazine-1,2-dicarboxylate 38e (1.05 g, yield 46.7%) as a yellow oil.

Workup

  1. temperatureUpon cooling by a dry ice-acetone bath
  2. stirringThe mixture was stirred for another 30 minutes
  3. customthe ice-acetone bath was removed
  4. stirringstirred for 20 hours
  5. customThe reaction was quenched by addition of 20 mL of saturated ammonium chloride
  6. extractionThe mixture was extracted with ethyl acetate (25 mL×3)
  7. washThe combined organic extracts were washed with saturated brine (10 mL×2)
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-51679dfdf46e4fe3a17a47cfe3f6d768
Source dataset
uspto-grants-2013_02
Patent number
US08367710B2

Reaction notes

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