Methanol → di-tert-butyl 1-(3,3-dimethyl-1H-inden-5-yl)hydrazine-1,2-dicarboxylate

HRID 238702Notes

Reaction equation

HRID 238702 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C:8]2([CH3:12])[CH3:11])=[CH:4][CH:3]=1.C([Li])CCC.[N:18]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])=[N:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21].CO>O1CCCC1>[CH3:11][C:8]1([CH3:12])[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([N:18]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[NH:19][C:20]([O:22][C:23]([CH3:24])([CH3:25])[CH3:26])=[O:21])[CH:10]=2)[CH:6]=[CH:7]1.[CH3:11][C:8]1([CH3:12])[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([N:18]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[NH:19][C:20]([O:22][C:23]([CH3:24])([CH3:25])[CH3:26])=[O:21])[CH:10]=2)[CH2:6][CH2:7]1

Participants

7

Reactant 4

HCID 887MethanolHCID 97268Di-tert-butyl azodicarboxylateHCID 124417856-bromo-1,1-dimethyl-2,3-dihydro-1H-indeneHCID 178418339Butyllithium

Product 2

HCID 59615676di-tert-butyl 1-(3,3-dimethyl-1H-inden-5-yl)hydrazine-1,2-dicarboxylateYield 37.2%HCID 67128578Di-tert-butyl 1-(3,3-dimethyl-inden-5-yl)hydrazine-1,2-dicarboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

6-Bromo-1,1-dimethyl-indan (prepared by using a well-known method: patent application WO2005066115) 4a (4.32 g, 19.27 mmol) was dissolved in 40 mL of tetrahydrofuran and then butyllithium (15.67 mL, 1.6 M, 25.05 mmol) was added dropwise at −78° C. After the reaction mixture was reacted for 40 minutes, a solution of di-tert-butyl azodicarboxylate (5.32 g, 23.12 mmol) in 30 mL of tetrahydrofuran was then added. The reaction mixture was reacted for another 3 hours at −78° C. The reaction mixture was added with 5 mL of methanol, then warmed up to room temperature and filtered by silica gel. The filtrate was concentrated under reduced pressure and the resulting residue was purified by silica gel column chromatography to obtain the title compound di-tert-butyl 1-(3,3-dimethyl-1H-inden-5-yl)hydrazine-1,2-dicarboxylate 4b (2.70 g, yield 37.2%) as a yellow solid.

Workup

  1. customAfter the reaction mixture was reacted for 40 minutes
  2. customThe reaction mixture was reacted for another 3 hours at −78° C
  3. filtrationfiltered by silica gel
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customthe resulting residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-d45e3196c34e4864bc7999bb43e546fe
Source dataset
uspto-grants-2014_02
Patent number
US08642637B2

Reaction notes

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