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

HRID 854907Notes

Reaction equation

HRID 854907 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]1([C:32]#[CH:33])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C(Cl)Cl>C1(C)C=CC=CC=1.[Cl-].[Na+].O.[Cu]I.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]>[C:26]1([C:32]#[C:33][C:2]2[CH:3]=[C:4]([O:21][C:22]([F:23])([F:25])[F:24])[CH:5]=[C:6]3[C:11]=2[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]3)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

8

Reactant 3

HCID 6344DichloromethaneHCID 10821PhenylacetyleneHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599458ethyl 8-(phenylethynyl)-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 85%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolventHCID 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 (1.00 g, 2.07 mmole), phenylacetylene (0.455 mL, 4.15 mmole), CuI (39.5 mg, 0.207 mmole), PdCl2(dppf)2.CH2Cl2 (169 mg, 0.207 mmole) and TEA (0.867 mL, 6.22 mmole) in anhydrous toluene (10 mL) was stirred at room temperature for 18.5 h. The mixture was then poured into brine (100 mL) and extracted with EtOAc. The EtOAc layer was separated, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by silica chromatography (9:1 hexanes:EtOAc) to give 0.802 g (85% yield) of the product as a yellow crystalline solid: EIHRMS m/z 456.0781 (M+, C14H14F6O4, Calc'd 456.0796).

Workup

  1. extractionextracted with EtOAc
  2. customThe EtOAc layer was separated
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica chromatography (9:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-010d82e958fa4bfb919543624bb4f706
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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