Ethanol → methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-5-phenylthiophen-3-yl]acetate

HRID 590995노트

반응식

HRID 590995 반응식
Br[C:2]1[S:3][C:4]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[CH:5][C:6]=1[CH:7]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[C:8]([O:10][CH3:11])=[O:9].CC1(C)C(C)(C)OB([C:31]2[CH:32]=[C:33]3[C:38](=[CH:39][CH:40]=2)[O:37][CH2:36][CH2:35][CH2:34]3)O1.C(=O)([O-])[O-].[Na+].[Na+].C(O)C>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].O>[C:13]([O:12][CH:7]([C:6]1[CH:5]=[C:4]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[S:3][C:2]=1[C:31]1[CH:40]=[CH:39][C:38]2[O:37][CH2:36][CH2:35][CH2:34][C:33]=2[CH:32]=1)[C:8]([O:10][CH3:11])=[O:9])([CH3:16])([CH3:15])[CH3:14]

참가 물질

8

반응물 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70819299Methyl 2-(2-bromo-5-phenylthiophen-3-yl)-2-(tert-butoxy)acetate

생성물 1

HCID 70855249methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-5-phenylthiophen-3-yl]acetate수율 70%

시약·촉매·용매 3

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 962Water용매2회HCID 1140Toluene용매

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온도
95 °C

실험 절차

A solution of methyl 2-(2-bromo-5-phenylthiophen-3-yl)-2-(tert-butoxy)acetate (11i) (77 mg, 0.20 mmol), 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (94 mg, 0.36 mmol) and sodium carbonate (85 mg, 0.80 mmol) in a mixture of toluene (1.26 mL), ethanol (0.6 mL) and water (0.5 mL) was bubbled with nitrogen for 5 minutes. Palladium tetrakis(triphenylphosphine) (12 mg, 0.01 mmol) was added and the reaction mixture was heated a 95° C. for 4 h. After cooling to room temperature, water (2 mL) was added. The aqueous layer was extracted with toluene (2×8 mL). The organic layers were washed with brine (5 mL), dried over sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 85/15) to provide the desired product (11j) (60 mg, 0.14 mmol, 68%).

후처리

  1. customwas bubbled with nitrogen for 5 minutes
  2. temperatureAfter cooling to room temperature
  3. extractionThe aqueous layer was extracted with toluene (2×8 mL)
  4. washThe organic layers were washed with brine (5 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 85/15)

출처 및 근거

ORD 기록
ord-1c16a4ca101442f995469fb7b5201df4
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09238026B2

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