Sodium Carbonate → HCID 76695337、化合物

HRID 1868343ノート

反応式

HRID 1868343 の反応式
Br[C:2]1[C:3]([CH:15]=[O:16])=[N:4][N:5]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=1.CC1(C)C(C)(C)OB([CH:25]=[CH:26][C:27]2[CH:28]=[N:29][CH:30]=[CH:31][CH:32]=2)O1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[N:29]1[CH:30]=[CH:31][CH:32]=[C:27]([CH:26]=[CH:25][C:2]2[C:3]([CH:15]=[O:16])=[N:4][N:5]([CH2:7][O:8][CH2:9][CH2:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=2)[CH:28]=1

参加物

7

反応物 3

HCID 10340Sodium CarbonateHCID 57982717HCID 57982717、化合物HCID 667342383-[2-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-YL)-vinyl]-pyridine

生成物 1

HCID 76695337HCID 76695337、化合物

試薬・触媒・溶媒 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
120 °C

実験手順

After the solution of 4-bromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazole-3-carbaldehyde Compound 3a (570 mg, 1.87 mmol) and 3-[2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-vinyl]-pyridine Compound 3c (863 mg, 3.74 mmol) in dioxane (35 mL) was degassed by evacuating and purging with nitrogen. [1,1′-Bis(diphenylphosphino)-ferrocene]dichloropalladium(II) complex (Pd(dppf)2Cl2) (273 mg, 0.374 mmol) and sodium carbonate in water (3.74 mL, 2M) were added to the reaction mixture. The resultant suspension was purged again with nitrogen and heated at 120° C. for 30 min in a microwave reactor. After the solvent was removed in vacuo, the residue was dissolved in methanol and loaded to silica gel directly. The crude compound was eluted with a gradient of 4:1 to 2:1 hexane/ethyl acetate by flush chromatography to yield 4-(2-pyridin-3-yl-vinyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrazole-3-carbaldehyde Compound 3d (385.6 mg, 0.624 mmol, 72% yield) as a white solid. 1H NMR (300 MHz, CDCl3) δ 10.26 (s, 1H), 8.75 (s, 1H), 8.55 (d, 1H), 7.91 (m, 3H), 7.54 (d, 1H), 7.50 (t, 2H), 7.34 (dd, 2H), 7.11 (d, 1H), 5.82 (s, 2H), 3.62 (t, 2H), 0.94 (t, 2H), 0 (s, 9H); MS (ESI) m/z: 330.1 (M+H+).

後処理

  1. customby evacuating
  2. custompurging with nitrogen
  3. customThe resultant suspension was purged again with nitrogen
  4. customAfter the solvent was removed in vacuo
  5. dissolutionthe residue was dissolved in methanol
  6. washThe crude compound was eluted with a gradient of 4:1 to 2:1 hexane/ethyl acetate
  7. customby flush chromatography

出典と根拠

ORDレコード
ord-29ced1bcafd943899af28d4e043b491e
出典データセット
uspto-grants-2009_12
特許番号
US07635703B2

反応ノート

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