Di-tert-butyl azodicarboxylate → di-tert-butyl 1-(3-ethyl-2,3-dihydro-1H-inden-5-yl)hydrazine-1,2-dicarboxylate

HRID 384374Notes

Reaction equation

HRID 384374 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][CH:8]2[CH2:11][CH3:12])=[CH:4][CH:3]=1.C([Li])(C)(C)C.C(=O)=O.CC(C)=O.[N:25]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])=[N:26][C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28]>O1CCCC1.C1CCCCC1>[CH2:11]([CH:8]1[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([N:25]([C:34]([O:36][C:37]([CH3:40])([CH3:39])[CH3:38])=[O:35])[NH:26][C:27]([O:29][C:30]([CH3:31])([CH3:32])[CH3:33])=[O:28])[CH:10]=2)[CH2:6][CH2:7]1)[CH3:12]

Participants

7

Reactant 4

HCID 97268Di-tert-butyl azodicarboxylateHCID 18522661Acetone cardice2×HCID 574838336-Bromo-1-ethyl-indanHCID 178418306HCID 178418306, compound

Product 1

HCID 57483834di-tert-butyl 1-(3-ethyl-2,3-dihydro-1H-inden-5-yl)hydrazine-1,2-dicarboxylateYield 81.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8078CyclohexaneSolvent

Procedure

Upon cooling by a dry ice-acetone bath, a solution of 6-bromo-1-ethyl-indan 41b (2.52 g, 11.2 mmol) in 15 mL of tetrahydrofuran was added dropwise to a solution of t-butyllithium in cyclohexane (18.1 mL, 1.3 N) under argon atmosphere. Upon completion of the addition, the mixture was stirred for 2 hours in the dry ice-acetone bath. A solution of di-tert-butyl azodicarboxylate in 15 mL of tetrahydrofuran was added dropwise to the above mixture at the same temperature. Upon completion of the addition, the reaction mixture was stirred for another 1.5 hours in the dry ice-acetone bath. Then the dry ice-ethanol bath was removed. The mixture was warmed up to room temperature and stirred for 18 hours. The reaction was monitored by TLC until the disappearance of the starting materials and quenched by addition of 25 mL of saturated ammonium chloride. The mixture was extracted with ethyl acetate (30 mL×3). The combined organic extracts were dried over anhydrous sodium sulfate, filtered to remove the drying agent and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the title compound di-tert-butyl 1-(3-ethyl-2,3-dihydro-1H-inden-5-yl)hydrazine-1,2-dicarboxylate 41c (3.43 g, 81.5%) as a brown oil.

Workup

  1. temperatureUpon cooling by a dry ice-acetone bath
  2. additionUpon completion of the addition
  3. additionUpon completion of the addition
  4. customThen the dry ice-ethanol bath was removed
  5. customquenched by addition of 25 mL of saturated ammonium chloride
  6. extractionThe mixture was extracted with ethyl acetate (30 mL×3)
  7. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. customto remove the drying agent
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-fcfec18b34c442119d6df051c7b08a17
Source dataset
uspto-grants-2013_02
Patent number
US08367710B2

Reaction notes

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