Diethyl (cyanomethyl)phosphonate → 3-(Cyanomethylene)-1-(methoxymethyl)cyclobutanecarbonitrile

HRID 1966148Notes

Reaction equation

HRID 1966148 reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[CH3:18][O:19][CH2:20][C:21]1([C:26]#[N:27])[CH2:24][C:23](=O)[CH2:22]1>O1CCCC1>[C:7]([CH:9]=[C:23]1[CH2:24][C:21]([CH2:20][O:19][CH3:18])([C:26]#[N:27])[CH2:22]1)#[N:8]

Participants

5

Reactant 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 23665647Potassium tert-butoxideHCID 668243301-(Methoxymethyl)-3-oxocyclobutane-1-carbonitrile

Product 1

HCID 668245123-(Cyanomethylene)-1-(methoxymethyl)cyclobutanecarbonitrile

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of 1.0000 M of potassium tert-butoxide in tetrahydrofuran (2.25 mL) at 0° C. was added dropwise a solution of diethyl cyanomethylphosphonate (0.381 mL, 0.00236 mol) in tetrahydrofuran (4 mL, 0.05 mol). The reaction was warmed to rt and then cooled to 0° C. again. To the reaction mixture was added a solution of 1-(methoxymethyl)-3-oxocyclobutanecarbonitrile (0.298 g, 0.00214 mol) in tetrahydrofuran (2 mL, 0.02 mol). The reaction was allowed to warm up to rt and stirred at rt overnight. After quenching with water, the mixture was extracted with ether. The combined organic layers were washed with water, brine, dried and evaporated to dryness. The crude mixture was used directly in next step. LCMS calculated for C9H11N2O(M+H)+: 163.1. Found: 163.1.

Workup

  1. temperaturecooled to 0° C. again
  2. temperatureto warm up to rt
  3. customAfter quenching with water
  4. extractionthe mixture was extracted with ether
  5. washThe combined organic layers were washed with water, brine
  6. customdried
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-27f688aa7bf54ad28d3e367115842a69
Source dataset
uspto-grants-2013_04
Patent number
US08420629B2

Reaction notes

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