Nitromethane → 1-Cyano-2,2-dipropyl-cyclopropanecarboxylic acid benzyl ester

HRID 1796828Notes

Reaction equation

HRID 1796828 reaction equation
[CH2:1]([O:8][C:9](=[O:20])[C:10]([C:18]#[N:19])=[C:11]([CH2:15][CH2:16][CH3:17])[CH2:12][CH2:13][CH3:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N+]([CH3:24])([O-])=O.C1CCN2C(=NCCC2)CC1>C(#N)C>[CH2:1]([O:8][C:9]([C:10]1([C:18]#[N:19])[CH2:24][C:11]1([CH2:12][CH2:13][CH3:14])[CH2:15][CH2:16][CH3:17])=[O:20])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 114257292-Cyano-3-propyl-hex-2-enoic acid benzyl ester

Product 1

HCID 113466791-Cyano-2,2-dipropyl-cyclopropanecarboxylic acid benzyl esterYield 81%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 2-cyano-3-propyl-hex-2-enoic acid benzyl ester (0.91 g, 3.35 mmol) in 50 mL acetonitrile was added nitromethane (0.91 mL, 16.77 mmol), followed by DBU (0.50 mL, 3.35 mmol) resulting in an orange solution. The reaction was stirred at room temperature for 16 hours, then partitioned between Et2O and 1N HCl (aq). The phases were separated, and the organic phase washed with brine, dried (MgSO4), and concentrated. Flash chromatography of the residue (5→10% EtOAc/hexanes) afforded 0.71 g (81%) of 1-cyano-2,2-dipropyl-cyclopropanecarboxylic acid benzyl ester as a pale yellow oil. 1H NMR (CDCl3) δ 7.35 (m, 5H), 5.21 (dd, J=18.3, 12.4 Hz, 2H), 1.79 (d, J=5.1 Hz, 1H), 1.74 (m, 1H), 1.52 (m, 3H), 1.43 (d, J=5.1 Hz, 1H), 1.36 (m, 3H), 1.04 (m, 1H), 0.95 (t, J=7.1 Hz, 3H), 0.73 (t, J=7.1 Hz, 3H). 13C NMR δ 166.40, 135.22, 128.81, 128.69, 128.48, 118.60, 68.23, 41.26, 36.45, 30.27, 29.76, 24.91, 19.74, 19.65, 14.22, 14.10. IR (neat) 2240, 1734 cm−1. Anal. Calcd for C18H23NO2: C, 75.76; H, 8.12; N, 4.91. Found: C, 75.38; H, 8.02; N, 4.97.

Workup

  1. customresulting in an orange solution
  2. custompartitioned between Et2O and 1N HCl (aq)
  3. customThe phases were separated
  4. washthe organic phase washed with brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-37927935019c43c5b7a1b5b692d10ebe
Source dataset
uspto-grants-2006_04
Patent number
US07030267B2

Reaction notes

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