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

HRID 591065ノート

反応式

HRID 591065 の反応式
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

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
95 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-b53374957af946358cd3c222fe4ba0bb
出典データセット
uspto-grants-2016_01
特許番号
US09238026B2

反応ノート

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