Dichloromethane → Methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate

HRID 2373702ノート

反応式

HRID 2373702 の反応式
Br[C:2]1[S:3][CH:4]=[C:5]([Br:12])[C:6]=1[CH2:7][C:8]([O:10][CH3:11])=[O:9].[CH2:13]([O:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1)[CH2:14][CH3:15].C([O-])([O-])=O.[K+].[K+].ClCCl>O.CCOC(C)=O.CCCCCC.O1CCOCC1>[Br:12][C:5]1[C:6]([CH2:7][C:8]([O:10][CH3:11])=[O:9])=[C:2]([C:20]2[CH:21]=[CH:22][C:17]([O:16][CH2:13][CH2:14][CH3:15])=[CH:18][CH:19]=2)[S:3][CH:4]=1

参加物

9

反応物 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 44564904-Propoxyphenylboronic AcidHCID 86607173Methyl (2,4-dibromothien-3-yl)acetate

生成物 1

HCID 86607172Methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate収率 57.5%

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒2 回

実験手順

Into dioxane (3 mL) was dissolved methyl (2,4-dibromothien-3-yl)acetate (0.355 g, 1.13 mmol) and 4-propoxyphenylboronic acid (0.214 g, 1.19 mmol). K2CO3 (0.195 g, 1.41 mmol) was dissolved in H2O (0.4 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, 0.033 mmol) was added and the mixture heated under argon to 50° C. for 4 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 (25:1 hexane:EtOAc) to yield methyl [4-bromo-2-(4-propoxyphenyl)thien-3-yl]acetate (0.240 g) as a clear oil. 1H NMR (500 MHz, DMSO-d6) δ: 0.99 (t, 3H, J=7.32 Hz), 1.75 (m, 2H), 3.65 (s, 5H), 3.98 (t, 2H, J=6.6 Hz), 7.05 (d, 2H, J=8.2 Hz), 7.33 (d, 2H, J=8.2 Hz), 7.72 (s, 1H). MS (ES) m/z 369.0 ([M+H]+). MS (ES) m/z 386.0 ([M+NH4]+).

後処理

  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 (25:1 hexane:EtOAc)

出典と根拠

ORDレコード
ord-b620c22040d74cdd992425de555f8416
出典データセット
uspto-grants-2008_12
特許番号
US07459567B2

反応ノート

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