Dichloromethane → HCID 86607174, compound

HRID 2373703Notes

Reaction equation

HRID 2373703 reaction equation
Br[C:2]1[C:3]([CH2:17][C:18]([O-:20])=[O:19])=[C:4]([C:7]2[CH:12]=[CH:11][C:10]([O:13][CH2:14][CH2:15][CH3:16])=[CH:9][CH:8]=2)[S:5][CH:6]=1.[Cl:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1B(O)O.[C:31]([O-])([O-])=O.[K+].[K+].ClCCl>O.CCOC(C)=O.CCCCCC.O1CCOCC1>[Cl:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[C:2]1[C:3]([CH2:17][C:18]([O:20][CH3:31])=[O:19])=[C:4]([C:7]2[CH:12]=[CH:11][C:10]([O:13][CH2:14][CH2:15][CH3:16])=[CH:9][CH:8]=2)[S:5][CH:6]=1

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 27343222-Chlorophenylboronic acidHCID 86607175HCID 86607175, compound

Product 1

HCID 86607174HCID 86607174, compoundYield 86.8%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent2×

Procedure

Into dioxane (5 mL) was dissolved [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate (0.340 g, 0.92 mmol) and 2-chlorophenylboronic acid (0.287 g, 1.84 mmol). K2CO3 (0.381 g, 2.76 mmol) was dissolved in H2O (0.5 mL) and added to the dioxane. The solution was degassed by bubbling argon through the mixture for five minutes. {1,1′-Bis(diphenylphosphino)-ferrocene}dichloropalladium(II) complex with dichloromethane (1:1) (0.027 g, 0.028 mmol) was added and the mixture heated under argon to 70° C. for 3 hours (followed by TLC 15:1 Hexane:EtOAc). The solvents were removed and the mixture partitioned between EtOAc and H2O. The EtOAc layer was dried (MgSO4) and absorbed onto silica gel. The product was purified by flash chromatography (20:1 hexane:EtOAc) to yield methyl [4-(2-chlorophenyl)-2-(4-propoxyphenyl)thien-3-yl]acetate (0.320 g) as a white solid. mp 81-82° C.; 1H NMR (500 MHz, DMSO-d6) δ: 1.00 (t, 3H, J=7.48 Hz), 1.75 (m, 2H), 3.46 (s, 2H), 3.98 (t, 2H, J=6.41 Hz), 7.05 (d, 2H, J=8.85 Hz), 7.31 (dd, 1H, J=1.99 and 7.17 Hz), 7.42 (m, 5H), 7.56 (dd, 1H, J=1.22 and 7.78 Hz). MS (ES) m/z 401.1 ([M+H]+). MS (ES) m/z 418.1 ([M+NH4]+). Anal. calcd for C22H21ClO3S: C, 65.91; H, 5.28; N, 0.00. Found: C, 65.54; H, 5.21; N, 0.00.

Workup

  1. customThe solution was degassed
  2. customby bubbling argon through the mixture for five minutes
  3. customThe solvents were removed
  4. customthe mixture partitioned between EtOAc and H2O
  5. dry with materialThe EtOAc layer was dried (MgSO4)
  6. customabsorbed onto silica gel
  7. customThe product was purified by flash chromatography (20:1 hexane:EtOAc)

Sources & evidence

ORD record
ord-f41ecf444f4443c99c1ed4abb7e37092
Source dataset
uspto-grants-2008_12
Patent number
US07459567B2

Reaction notes

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