Nitromethane → Ethyl 1-cyanospiro[2.5]octane-1-carboxylate

HRID 1796814Notes

Reaction equation

HRID 1796814 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[C:5]([C:12]#[N:13])=[C:6]1[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]1)[CH3:2].[N+]([CH3:18])([O-])=O.N12CCCN=C1CCCCC2>C(#N)C>[CH2:1]([O:3][C:4]([C:5]1([C:12]#[N:13])[C:6]2([CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]2)[CH2:18]1)=[O:14])[CH3:2]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 81256Ethyl cyanocyclohexylideneacetate

Product 1

HCID 54753996Ethyl 1-cyanospiro[2.5]octane-1-carboxylateYield 75%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of cyano-cyclohexylidene-acetic acid ethyl ester (1.37 g, 7.09 mmol) in 30 mL acetonitrile was added nitromethane (1.92 mL, 35.5 mmol), followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (1.06 mL, 7.09 mmol) resulting in an orange solution. The reaction was stirred for 2.5 hours, then partitioned between ethyl ether (Et2O) and 1N hydrochloric acid (HCl) (aq). The phases were separated, and the organic phase washed with brine, dried over magnesium sulfate (MgSO4), and concentrated. Flash chromatography of the residue (5% ethyl acetate (EtOAc)/hexanes) afforded 1.1 g (75%) of 1-cyano-spiro[2.5]octane-1-carboxylic acid ethyl ester as a colorless oil. 1H NMR (CDCl3) δ 4.22 (m, 2H), 1.77 (d, J=5.1 Hz, 1H), 1.42–1.72 (m, 10H), 1.40 (d, J=5.1 Hz, 1H), 1.30 (t, J=7.1 Hz, 3H). 13C NMR δ 166.40, 118.60, 62.72, 40.20, 34.67, 29.01, 28.75, 25.69, 25.54, 25.28, 24.66, 14.38. LRMS: m/z 208.0 (M+1). IR: 2239, 1732 cm−1. Anal. Calcd for C12H17NO2: C, 69.54; H, 8.27; N, 6.76. Found: C, 69.41; H, 8.33; N, 6.75.

Workup

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

Sources & evidence

ORD record
ord-a28203d337674daa8c14abfe50ee213f
Source dataset
uspto-grants-2006_04
Patent number
US07030267B2

Reaction notes

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