Potassium Cyanide → ethyl 8-cyano-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 854915Notes

Reaction equation

HRID 854915 reaction equation
I[C:2]1[CH:3]=[C:4]([O:21][C:22]([F:25])([F:24])[F:23])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2.[C-:26]#[N:27].[K+]>C1COCC1.[Cl-].[Na+].O.[Cu]I.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:26]([C:2]1[CH:3]=[C:4]([O:21][C:22]([F:24])([F:23])[F:25])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:14])([F:15])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2)#[N:27]

Participants

7

Reactant 2

HCID 9032Potassium CyanideHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599465ethyl 8-cyano-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 82%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (2.00 g, 4.15 mmole), CuI (158 mg, 0.830 mmole), KCN (1.08 g, 16.6 mmole) and Pd(PPh3)4 (480 mg, 0.415 mmole) in anhydrous THF (5.0 mL) were refluxed under a dry N2 atmosphere for 2.5 days. The mixture was then poured into brine (100 mL), extracted with EtOAc (100 mL), dried over MgSO4 and concentrated in vacuo. Purification by silica chromatography followed by crystallization from EtOAc-hexanes gave 1.30 g (82% yield) of the product a yellow crystalline solid: EIHRMS m/z 399.0812 (M+NH4, C15H9NO4F6NH4, Calc'd 399.0774).

Workup

  1. temperaturewere refluxed under a dry N2 atmosphere for 2.5 days
  2. extractionextracted with EtOAc (100 mL)
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customPurification by silica chromatography
  6. customfollowed by crystallization from EtOAc-hexanes

Sources & evidence

ORD record
ord-68ba58866bf441889605ac0f99e9631b
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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