Hydrochloric Acid → HCID 58935008, compound

HRID 855113Notes

Reaction equation

HRID 855113 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(OCC)=O)=[CH:7]2.[CH3:26][CH2:27]OCC.C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:60]([O-:63])([O-])=[O:61].[K+].[K+].Cl.[OH2:67]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:26]([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:14])([F:15])[F:13])[C:8]([C:60]([OH:63])=[O:61])=[CH:7]2)(=[O:67])[CH3:27]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 962WaterHCID 3283Diethyl EtherHCID 11430Potassium CarbonateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 86599457ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 58935008HCID 58935008, compoundYield 47%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of ethyl 8-iodo-6-(trifluoromethoxy)-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 21a, Step 2 (2.41 g, 5.00 mmole), n-buytylvinyl ether (3.22 mL, 25.0 mmole), Pd(OAc)2 (33.4 mg, 0.150 mmole), DPPP (136 mg, 0.330 mmole) and K2CO3 (0.830 g, 6.00 mmole), in a mixture of DMF (12.5 mL) and H2O (1.5 mL) was stirred at 100° C. for 17 hrs. After the mixture was cooled to room temperature, 1N HCl (20 mL) was then added and the mixture was stirred for 30 minutes and then was extracted with EtOAc (2×200 mL). The extracts were combined and washed with H2O (200 mL), brine (100 mL), dried over MgSO4, and filtered. The solvent was removed in vacuo to give the crude product as a dark brown oil. Purification by silica chromatography (20% EtOAc in hexanes with 1% HOAc) gave 0.940 g (47% yield) of the product as a tan crystalline solid: EIHRMS m/z 370.0258 (M+, C14H8F6O5, Calc'd 370.0276). 1H NMR (dmso-d6/300 MHz) 13.59 (brs, 1H), 7.95 (s, 1H), 7.85 (d, 1H, J=2.8 Hz), 7.58 (dd, 1H, J=4.0, 2.2 Hz), 6.19 (q, 1H, J=7.0 Hz), 2.58 (s, 3H).

Workup

  1. temperatureAfter the mixture was cooled to room temperature
  2. stirringthe mixture was stirred for 30 minutes
  3. extractionwas extracted with EtOAc (2×200 mL)
  4. washwashed with H2O (200 mL), brine (100 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customThe solvent was removed in vacuo
  8. customto give the crude product as a dark brown oil
  9. customPurification by silica chromatography (20% EtOAc in hexanes with 1% HOAc)

Sources & evidence

ORD record
ord-6efd81b97ffd4005991c731e4b494cd1
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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