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Potassium Carbonate → Tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinate

HRID 1641075
ノート
印刷プレビュー

反応式

HRID 1641075 の反応式
Br[C:2]1[N:7]=[C:6]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1.[CH3:15][N:16]1[C:25]2[C:20](=[CH:21][C:22](B3OC(C)(C)C(C)(C)O3)=[CH:23][CH:24]=2)[NH:19][CH2:18][CH2:17]1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:15][N:16]1[C:25]2[C:20](=[CH:21][C:22]([C:2]3[N:7]=[C:6]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=3)=[CH:23][CH:24]=2)[NH:19][CH2:18][CH2:17]1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 3

HCID 11430Potassium CarbonateHCID 23432991tert-Butyl 6-bromopicolinateHCID 594187141-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoxaline

生成物 1

HCID 59418755Tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinate収率 38.3%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide
触媒
HCID 178418476HCID 178418476、化合物触媒
HCID 962Water溶媒2 回
HCID 312751,4-Dioxane溶媒2 回

反応条件

温度
100 °C

実験手順

Tert-butyl 6-bromopicolinate (25A) (157 mg, 0.61 mmol) in 1,4-dioxane (1.0 mL) was added dropwise to 1-methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoxaline (25F) (167 mg, 0.61 mmol), K2CO3 (207 mg, 1.52 mmol), tetrabutylammonium bromide (19.5 mg, 0.061 mmol), and dichlorobis(triphenylphosphine)palladium(II) (17.9 mg, 0.024 mmol) in 1,4-dioxane (2.0 mL) and water (1.0 mL) at rt. The mixture was microwave (150W) heated to 100° C. for 50 minutes, cooled to 20° C., diluted with water and extracted with EtOAc. The organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE:EtOAc 100:0-70:30, to provide 76 mg (38%) of the desired product tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinate (25G): 1H NMR (300 MHz, MeOD) δ 7.84-7.78 (3H, m), 7.35 (1H, d), 7.30 (1H, d), 6.62 (1H, d), 3.41 (2H, t), 3.31 (2H, t), 2.92 (3H, bs), 1.64 (9H, s).

後処理

  1. temperaturecooled to 20° C.
  2. extractionextracted with EtOAc
  3. washThe organic phases were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE

出典と根拠

ORDレコード
ord-d0149dbee3e44f219f2fcf4cfe49d03b
出典データセット
uspto-grants-2012_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08114893B2

反応ノート

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