Potassium Cyanide → HCID 68906716, compound

HRID 217295Notes

Reaction equation

HRID 217295 reaction equation
N([O-])=O.[Na+].[CH3:5][O:6][C:7]([CH2:9][C:10]1[CH:19]=[C:18](N)[C:17]([Cl:21])=[CH:16][C:11]=1[C:12]([O:14][CH3:15])=[O:13])=[O:8].COC(CC1C(Cl)=[C:35]([NH2:38])C=CC=1C(OC)=O)=O.[Cu]C#N.[C-]#N.[K+]>O.Cl.C(OCC)(=O)C>[CH3:5][O:6][C:7]([CH2:9][C:10]1[CH:19]=[C:18]([C:35]#[N:38])[C:17]([Cl:21])=[CH:16][C:11]=1[C:12]([O:14][CH3:15])=[O:13])=[O:8]

Participants

9

Reactant 5

HCID 9032Potassium CyanideHCID 23668193Sodium NitriteHCID 57898840HCID 57898840, compoundHCID 68906482HCID 68906482, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 68906716HCID 68906716, compoundYield 29%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent3×HCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of sodium nitrite (40 mg, 0.6 mmol) in water (0.25 mL) was added to a solution of a mixture (100 mg, 0.39 mmol) of methyl 2-methoxycarbonylmethyl-4-amino-5-chlorobenzoate and methyl 2-methoxycarbonylmethyl-4-amino-3-chlorobenzoate in 2N hydrochloric acid (0.5 mL) under the ice cold condition. The reaction solution was stirred at 0° C. for 1.5 hour. The resulting suspension was dissolved by adding water (0.1 mL) and ethyl acetate (0.2 mL). This solution was added to a suspension of copper (I) cyanide (45 mg, 0.5 mmol) and potassium cyanide (38 mg, 0.6 mmol) in a mixture of water (0.4 mL) and ethyl acetate (0.8 mL) at 0° C. The reaction solution was stirred at 0° C. for 1 hour. The resulting insoluble material was collected by Celite filtration, and washed with a mixed solvent of water and ethyl acetate (1:2). The filtrate and washing solution were combined together. The organic layer was separated, and dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give crude product. The crude product was purified by silica gel column chromatography using n-hexane-ethyl acetate (mixing ratio 10:1), and dried under reduced pressure to give a 0.7:1 mixture (30 mg, 29%) of the title compound and methyl 2-methoxycarbonylmethyl-4-cyano-3-chlorobenzoate.

Workup

  1. dissolutionThe resulting suspension was dissolved
  2. stirringThe reaction solution was stirred at 0° C. for 1 hour
  3. filtrationThe resulting insoluble material was collected by Celite filtration
  4. washwashed with a mixed solvent of water and ethyl acetate (1:2)
  5. washThe filtrate and washing solution
  6. customThe organic layer was separated
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customto give crude product
  10. customThe crude product was purified by silica gel column chromatography
  11. customdried under reduced pressure

Sources & evidence

ORD record
ord-4dd658675f04416da90d200808f4c93a
Source dataset
uspto-grants-2012_06
Patent number
US08193351B2

Reaction notes

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