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

HRID 854914Notes

Reaction equation

HRID 854914 reaction equation
I[C:2]1[CH:3]=[C:4]([O:21][C:22]([F:25])([F:24])F)[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.[CH2:26](C([Sn])=C(CCCC)CCCC)[CH2:27]CC.[NH4+].[F-:42]>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>[F:42][C:22]([F:24])([F:25])[O:21][C:4]1[CH:5]=[C:6]2[C:11](=[C:2]([CH:26]=[CH2:27])[CH:3]=1)[O:10][CH:9]([C:12]([F:15])([F:13])[F:14])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2

Participants

6

Reactant 3

HCID 25516Ammonium fluorideHCID 53438229Tri(butyl)vinyltinHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 87870394Ethyl 6-(trifluoromethoxy)-2-(trifluoromethyl)-8-vinyl-2h-chromene-3-carboxylateYield 64%

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 tributylvinyltin (0.665 mL, 2.28 mmole). The mixture was refluxed for 3 h and stirred at r.t for 18 h. After refluxing for and additional 21 h, sat. NH4F solution (50 mL) was added, the mixture was stirred for 30 minutes and extracted with EtOAc (200 mL). The extract was washed with brine (50 mL), dried over MgSO4, filtered and concentrated in vacuo. Purification by silica chromatography (95:5 hexanes:EtOAc) gave 0.510 g (64% yield) of the product as a crystalline solid: EIHRMS m/z 382.0620 (M+, C16H12F6O4, Calc'd 382.0640).

Workup

  1. temperatureThe mixture was refluxed for 3 h
  2. additionwas added
  3. stirringthe mixture was stirred for 30 minutes
  4. extractionextracted with EtOAc (200 mL)
  5. washThe extract was washed with brine (50 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification by silica chromatography (95:5 hexanes:EtOAc)

Sources & evidence

ORD record
ord-08d40af88977455fb0fb8bb7759b8fcb
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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