Ammonium fluoride → Ethyl 8-allyl-6-(trifluoromethoxy)-2-(trifluoromethyl)-2h-chromene-3-carboxylate

HRID 854918Notes

Reaction equation

HRID 854918 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)[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2.[CH2:26]([CH:30]([Sn])C=C(CCCC)CCCC)[CH2:27]CC.[NH4+].[F-:43]>C1(C)C=CC=CC=1.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>[CH2:30]([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:14])([F:15])[F:43])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2)[CH:26]=[CH2:27]

Participants

6

Reactant 3

HCID 25516Ammonium fluorideHCID 86589045TributylallyltinHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 87870734Ethyl 8-allyl-6-(trifluoromethoxy)-2-(trifluoromethyl)-2h-chromene-3-carboxylateYield 94%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

To a mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (1.00 g, 2.07 mmole) and Pd(PPh3)4 (0.239 g, 0.207 mmole) in anhydrous toluene (50 mL) under a dry N2 atmosphere was added tributylallyltin (0.707 mL, 2.28 mmole). The mixture was refluxed for 16 h and 20% NH4F solution (50 mL) was added. The mixture was stirred for 1 h and extracted with EtOAc (200 mL). The extract was washed with brine (100 mL), dried over Na2SO4, filtered and concentrated in vacuo. Purification by silica chromatography (9:1 hexanes:EtOAc) gave 0.770 g (94% yield) of the product as a yellow oil: EIHRMS m/z 396.0769 (M+, C17H14F6O4, Calc'd 396.0796).

Workup

  1. temperatureThe mixture was refluxed for 16 h
  2. extractionextracted with EtOAc (200 mL)
  3. washThe extract was washed with brine (100 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by silica chromatography (9:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-c7396466f8424b1b8561efa7db04ad2e
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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