Ethanol → 2-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetic acid

HRID 591065노트

반응식

HRID 591065 반응식
Br[C:2]1[C:3]([C:9](=[O:15])[C:10]([O:12]CC)=[O:11])=[C:4]([CH3:8])[S:5][C:6]=1[CH3:7].C(=O)([O-])[O-].[Na+].[Na+].CC1(C)C(C)(C)OB([C:30]2[CH:31]=[C:32]3[C:37](=[CH:38][CH:39]=2)[O:36][CH2:35][CH2:34][CH2:33]3)O1.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>[O:36]1[C:37]2[CH:38]=[CH:39][C:30]([C:2]3[C:3]([C:9](=[O:15])[C:10]([OH:12])=[O:11])=[C:4]([CH3:8])[S:5][C:6]=3[CH3:7])=[CH:31][C:32]=2[CH2:33][CH2:34][CH2:35]1

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 70818387Ethyl (4-bromo-2,5-dimethyl-thiophen-3-yl)-oxo-acetate

생성물 1

HCID 708551932-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetic acid수율 100%

시약·촉매·용매 3

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 962Water용매2회HCID 1140Toluene용매

반응 조건

온도
95 °C

실험 절차

A solution of ethyl 2-(4-bromo-2,5-dimethylthiophen-3-yl)-2-oxoacetate (17c) (1.0 g, 3.43 mmol), sodium carbonate (1.46 g, 13.7 mmol), and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (1.16 g, 4.46 mmol) in a mixture of toluene (9 mL), ethanol (3 mL) and water (3.5 mL) was bubbled with nitrogen for 5 minutes. Palladium tetrakis(triphenylphosphine) (0.2 g, 0.17 mmol) was added and the reaction mixture was heated at 95° C. overnight. Water (5 mL) was added and the organic layer was extracted with 1N sodium hydroxide (5 mL). The combined aqueous layers were washed with ethyl acetate (10 mL), acidified with 1M hydrochloric acid until pH 2 and extracted with dichloromethane (2×10 mL). The organic layer was dried over sodium sulfate and concentrated in vacuo to provide the desired product (42a) (1.09 g, 3.43 mmol, 100%) which was used without further purification.

후처리

  1. customwas bubbled with nitrogen for 5 minutes
  2. extractionthe organic layer was extracted with 1N sodium hydroxide (5 mL)
  3. washThe combined aqueous layers were washed with ethyl acetate (10 mL)
  4. extractionextracted with dichloromethane (2×10 mL)
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. concentrationconcentrated in vacuo

출처 및 근거

ORD 기록
ord-b53374957af946358cd3c222fe4ba0bb
출처 데이터셋
uspto-grants-2016_01
특허 번호
US09238026B2

반응 노트

불러오는 중…