Dichloromethane → ethyl 8-methyl-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 854906Notes

Reaction equation

HRID 854906 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(C(OCC)=O)=[CH:7]2.CB1OB(C)OB(C)O1.C(Cl)Cl.[C:38]([O-])([O-])=O.[Cs+].[Cs+].[CH3:44][CH2:45][O:46][C:47]([CH3:49])=[O:48]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:7][C:6]1[CH:5]=[C:4]([O:21][C:22]([F:23])([F:24])[F:25])[CH:3]=[C:2]2[C:11]=1[O:10][CH:9]([C:12]([F:13])([F:14])[F:15])[C:49]([C:47]([O:46][CH2:45][CH3:44])=[O:48])=[CH:38]2

Participants

8

Reactant 5

HCID 6344DichloromethaneHCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 574072TrimethylboroxineHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599456ethyl 8-methyl-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 83%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Procedure

A mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (0.500 g, 1.04 mmole), trimethylboroxine (145 uL, 1.04 mmole), PdCl2(dppf)2.CH2Cl2 (0.084 mg, 0.104 mmole) and Cs2CO3 (1.01 g, 3.11 mmole) in 10% aqueous dioxane (2.5 mL) was heated to 110° C. under a dry N2 atmosphere for 6 h. The mixture was poured into EtOAc (100 mL), washed with brine (2×50 mL), dried over MgSO4, filtered and concentrated in vacuo to give an oily yellow solid. Purification by silica chromatography (9:1 hexanes:EtOAc) gave 0.320 g (83% yield) of the product as a yellow crystalline solid: EIHRMS m/z 370.0650 (M+, C15H2F6O4, 370.0640).

Workup

  1. washwashed with brine (2×50 mL)
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto give an oily yellow solid
  6. customPurification by silica chromatography (9:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-d274f5e0145c477c8344b93462f72bf7
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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