Diethyl (cyanomethyl)phosphonate → 2-(Spiro[3.3]heptan-2-ylidene)acetonitrile

HRID 1853087Notes

Reaction equation

[C:1]([CH2:3]P(=O)(OCC)OCC)#[N:2].CC([O-])(C)C.[K+].[CH2:18]1[C:21]2([CH2:24][CH2:23][CH2:22]2)[CH2:20][C:19]1=O>C1COCC1>[CH2:20]1[C:21]2([CH2:24][CH2:23][CH2:22]2)[CH2:18][C:19]1=[CH:3][C:1]#[N:2]

Participants

Conditions

Temperature: 0 °C

Procedure

Diethyl cyanomethylphosphonate (3.15 mL, 20.0 mmol) was suspended in THF (30 mL) and cooled to 0° C. Potassium 2-methylpropan-2-olate (2.35 g, 21.0 mmol) was added portion-wise and stirred at 0° C. for 15 minutes. Spiro[3.3]heptan-2-one (2.100 g, 19.06 mmol) as a solution in THF (20 mL) was added dropwise and the reaction mixture was allowed to warm to ambient temperature overnight. The reaction mixture was partitioned between water, saturated aqueous NH4Cl and EtOAc. The organic layer was washed with saturated aqueous NH4Cl, brine, dried (MgSO4), filtered and concentrated under reduced pressure to afford the crude material. The crude was purified by flash column chromatography, eluting with 2.5% EtOAc/Hexanes to provide 2-(spiro[3.3]heptan-2-ylidene)acetonitrile (1.40 g, 10.5 mmol, 55% yield). 1H NMR (CDCl3) δ 5.14-5012 (m, 1H), 2.93-2.91 (m, 2H), 2.82-2.80 (m, 2H), 2.10-2.04 (m, 4H), 1.91-1.85 (m, 2H).

Workup

temperatureto warm to ambient temperature overnight
customThe reaction mixture was partitioned between water, saturated aqueous NH4Cl and EtOAc
washThe organic layer was washed with saturated aqueous NH4Cl, brine
dry with materialdried (MgSO4)
filtrationfiltered
concentrationconcentrated under reduced pressure
customto afford the crude material
customThe crude was purified by flash column chromatography
washeluting with 2.5% EtOAc/Hexanes

Sources & evidence

ORD record: ord-2b543f94f7434138a5f9f01e1a1b7622
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962596B2

Reaction notes

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