HCID 11089657, compound → HCID 86599498, compound

HRID 855123Notes

Reaction equation

HRID 855123 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]CC)=[O:17])=[CH:7]2.C([Sn](CCCC)(CCCC)[C:31]#[C:32][O:33][CH2:34][CH3:35])CCC.[Cl-].C([NH+]([CH2:50][CH3:51])CC)C>CN(C=O)C.O>[CH2:34]([O:33][C:32]#[C:31][C:2]1[CH:3]=[C:4]([O:21][C:22]([F:24])([F:25])[F:23])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:13])([F:14])[F:15])[C:8]([C:16]([O:18][CH2:50][CH3:51])=[O:17])=[CH:7]2)[CH3:35]

Participants

6

Reactant 3

HCID 11089657HCID 11089657, compoundHCID 12698378Triethylazanium chlorideHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599498HCID 86599498, compoundYield 44%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (01597/1 PR) (10.6 g, 21.9 mmole), crude tributyl(ethoxyethynyl)stannane prepared as in Step 1 (10.4 g, 28.5 mmole assumed), triethylammonium chloride (3.63 g, 21.9 mmole) and Pd (PPh3)2 (0.769 g, 1.10 mmole) in DMF (140 mL) was stirred at room temperature overnight. The mixture was hen diluted with H2O and extracted with ethyl ether (2×200 mL). The combined extracts were washed with brine, dried over MgSO4, filtered and concentrated in vacuo. Purification by silica chromatography (5%-6.5% EtOAc:hexanes gradient) gave 4.06 g (44% yield) of the product as a yellow crystalline solid: 1H NMR (dmso-d6/300 MHz) 7.95 (s, 1H), 7.55 (d, 1H, J=2.0 Hz), 7.37 (d, 1H, J=2.2 Hz), 6.11 (q, 1H, J=7.3 Hz), 4.32-4.20 (m, 4H), 1.39 (t, 3H, J=7.1 Hz), 1.26 (t, 3H, J=7.2 Hz).

Workup

  1. extractionextracted with ethyl ether (2×200 mL)
  2. washThe combined extracts were washed with brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification by silica chromatography (5%-6.5% EtOAc:hexanes gradient)

Sources & evidence

ORD record
ord-81de58a7daa9498a96d0d45aa8ff21f6
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

Loading…