Triphenylphosphine → Di-tert-butyl 1-(cyclopropylmethyl)hydrazine-1,2-dicarboxylate

HRID 883020Notes

Reaction equation

HRID 883020 reaction equation
[CH:1]1([CH2:4]O)[CH2:3][CH2:2]1.[NH:6]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O>O1CCCC1.O.C(OCC)(=O)C>[CH:1]1([CH2:4][N:6]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[NH:7][C:8]([O:10][C:11]([CH3:12])([CH3:13])[CH3:14])=[O:9])[CH2:3][CH2:2]1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 75644CyclopropanemethanolHCID 85431Di-tert-butyl bicarbamateHCID 97268Di-tert-butyl azodicarboxylate

Product 1

HCID 66643119Di-tert-butyl 1-(cyclopropylmethyl)hydrazine-1,2-dicarboxylateYield 486.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of cyclopropylmethanol (10.1 g, 140 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (6.50 g, 28.0 mmol) and triphenylphosphine (44.1 g, 168 mmol) in tetrahydrofuran (100 mL) was added di-tert-butyl azodicarboxylate (38.7 g, 168 mmol) in portions. The mixture was stirred at room temperature for 3 hours then diluted with water and ethyl acetate. The organic extract was washed with brine, dried (MgSO4), filtered, and concentrated. The residue was purified by column chromatography using an Analogix® Intelliflash280™ (SiO2, eluted with a gradient of 0-100% hexanes in ethyl acetate) to provide the title compound (39 g, 97% yield). 1H NMR (300 MHz, CDCl3) δ ppm 0.16-0.27 (m, 2 H), 0.40-0.54 (m, 2 H), 0.94-1.09 (m, 1 H), 1.47 (s, 9 H), 1.48 (s, 9 H), 3.31 (d, J=6.10 Hz, 2 H), 6.38 (s, 1 H).

Workup

  1. extractionThe organic extract
  2. washwas washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography
  7. washeluted with a gradient of 0-100% hexanes in ethyl acetate)

Sources & evidence

ORD record
ord-9ddf7bd010304053b949e79400ae06e1
Source dataset
uspto-grants-2012_08
Patent number
US08236822B2

Reaction notes

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