Formaldehyde → HCID 66905586, compound

HRID 1437616Notes

Reaction equation

HRID 1437616 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([CH:14]([C:22]#[N:23])[C:15](=[O:21])C(OCC)=O)=[CH:10][CH:9]=1.C=O>O.C(Cl)Cl>[OH:21][CH2:15][CH:14]([C:11]1[CH:10]=[CH:9][C:8]([Cl:7])=[CH:13][CH:12]=1)[C:22]#[N:23]

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 10340Sodium CarbonateHCID 359722HCID 359722, compound

Product 1

HCID 66905586HCID 66905586, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

Sodium carbonate (204 mg, 1.9 mmol) dissolved in water (1.2 mL) was added dropwise over 10 min to a vigorously stirred mixture of the above ethyl 3-(4-chlorophenyl)-3-cyano-2-oxopropanoate (400 mg 1.59 mmol), 37% HCHO (131 μL 1.75 mmol) and methylene chloride (2 mL). After an additional 2 min, the mixture was diluted with ˜one mL each of water and methylene chloride and phase separated. Acidification of the aqueous phase and filtration of the precipitated solid recovered 68 mg (17%) of the starting material. The organic phase was washed twice with water, dried and stripped to give a colorless oil. Flash chromatography on 10 g of silica gel eluting with 5-50% ethyl acetate in hexane recovered 43 mg of a higher Rf product assumed to be 4-chloroatroponitrile, and 210 mg (75%) of the desired alcohol, Rf 0.09 (silica gel, ethyl acetate:hexane=1:4).

Workup

  1. customseparated
  2. filtrationAcidification of the aqueous phase and filtration of the precipitated solid
  3. customrecovered 68 mg (17%) of the starting material
  4. washThe organic phase was washed twice with water
  5. customdried
  6. customto give a colorless oil
  7. customFlash chromatography on 10 g of silica gel eluting with 5-50% ethyl acetate in hexane recovered 43 mg of a higher Rf product

Sources & evidence

ORD record
ord-789aa33ceaed4450aed932596342500f
Source dataset
uspto-grants-2009_11
Patent number
US07622504B2

Reaction notes

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