Water → HCID 86599470, compound

HRID 854928Notes

Reaction equation

HRID 854928 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10](I)[CH:11]=1)[O:8][CH:7]([C:13]([F:16])([F:15])[F:14])[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:5]2.[CH3:22][C:23]([C:25]#[CH:26])=[CH2:24].O.CCOC(C)=O>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.[Cu]I>[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([C:26]#[C:25][C:23]([CH3:24])=[CH2:22])[CH:11]=1)[O:8][CH:7]([C:13]([F:16])([F:15])[F:14])[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:5]2

Participants

8

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 62323IsopropenylacetyleneHCID 21883552ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 86599470HCID 86599470, compoundYield 53%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

To a solution of ethyl 6-chloro-8-iodo-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in U.S. Pat. No. 6,271,253 B1 Example 73, Step 2 (0.342 g, 0.790 mmole) in degassed anhydrous toluene was added Pd(PPh3)4 (54 mg, 0.47 mmole), CuI (15 mg, 0.079 mmole), TEA (0.275 mg, 2.72 mmole) and 2-methylbut-1-en-3-yne (0.247 g, 3.74 mmole) and the mixture was stirred under a N2 atmosphere. After the reaction was determined to be complete by GCMS, H2O and EtOAc were added and the layers were separated. The EtOAc layer was washed with 10% HCl, twice with H2O, twice with aqueous NH4Cl, dried over Na2SO4 and concentrated in vacuo. Purification of the crude product by silica chromatography (95:5 hexanes:EtOAc) gave 155 mg (53% yield) of the product as a white crystalline solid: 1H NMR (CDCl3/300 MHz) 7.62 (s, 1H), 7.37 (d, 1H, J=2.4 Hz), 7.14 (d, 1H, J=2.4 Hz), 5.80 (q, 1H, J=6.6 Hz), 5.44 (m, 1H), 5.35-5.36 (m, 1H), 4.31-4.34 (m, 2H), 1.99 (s, 3H), 1.36 (t, 3H, J=7.1 Hz).

Workup

  1. additionwere added
  2. customthe layers were separated
  3. washThe EtOAc layer was washed with 10% HCl, twice with H2O, twice with aqueous NH4Cl
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customPurification of the crude product by silica chromatography (95:5 hexanes:EtOAc)

Sources & evidence

ORD record
ord-da907920755d4f7ea5a6044781b62877
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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