Nitromethane → HCID 11446856, compound

HRID 1297221Notes

Reaction equation

HRID 1297221 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]([C:11]#[N:12])=[C:5]1[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1.[N+]([CH3:17])([O-])=O.C1CCN2C(=NCCC2)CC1>C(#N)C.CCOCC>[CH3:1][O:2][C:3]([C:4]1([C:11]#[N:12])[C:5]2([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10]2)[CH2:17]1)=[O:13]

Participants

6

Reactant 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 11229121CYANO-CYCLOHEXYLIDENE-ACETIC ACID METHYL ESTER

Product 1

HCID 11446856HCID 11446856, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

To a solution of cyano-cyclohexylidene-acetic acid methyl ester (20.0 g, 112 mmol) in acetonitrile (400 mL) was added nitromethane (30 mL, 558 mmol) followed by dropwise addition of DBU (16.9 mL, 113 mmol) over five minutes. The solution went from clear to orange and was stirred at room temperature for 5.5 hours. The solution was diluted with ether (1 L), washed with 1N HCl (2×250 mL) and then brine (2×250 mL). The organic layer was dried over sodium sulfate, filtered and evaporated. The residue was chromatographed on a wet-packed silica gel column (6.5×40 cm) eluting with 95:5 hexanes/ethyl acetate. The appropriate fractions were combined and evaporated to give 18.6 g (86%) of 1-cyano-spiro[2.5]octane-1-carboxylic acid methyl ester as a clear oil: 1H NMR (300 MHz, CDCl3) δ 1.35 (m, 1H), 1.49 (d, J=5.0 Hz, 1H), 1.5-1.75 (m, 9H), 1.82 (d, J=5.0 Hz, 1H), 3.83 (s, 3H).

Workup

  1. washwashed with 1N HCl (2×250 mL)
  2. dry with materialThe organic layer was dried over sodium sulfate
  3. filtrationfiltered
  4. customevaporated
  5. customThe residue was chromatographed on a wet-packed silica gel column (6.5×40 cm)
  6. washeluting with 95:5 hexanes/ethyl acetate
  7. customevaporated

Sources & evidence

ORD record
ord-94133b73468843fb9204de4ca8c17d13
Source dataset
uspto-grants-2007_07
Patent number
US07250433B2

Reaction notes

Loading…