Potassium Acetate → 5-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole

HRID 538990

反応式

HRID 538990 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[CH:11][N:10]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])[N:9]=2)=[CH:4][CH:3]=1.Br[C:22]1[CH:27]=[CH:26][C:25]([C:28]2[N:32]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[N:31]=[CH:30][N:29]=2)=[CH:24][CH:23]=1.C([O-])(=O)C.[K+].[CH3:46][C:47]1([CH3:63])[C:51]([CH3:53])([CH3:52])[O:50][B:49]([B:54]2[O:58][C:57]([CH3:60])([CH3:59])[C:56]([CH3:62])([CH3:61])[O:55]2)[O:48]1>O1CCOCC1.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.[Fe+2]>[CH3:46][C:47]1([CH3:63])[C:51]([CH3:53])([CH3:52])[O:50][B:49]([C:2]2[CH:7]=[CH:6][C:5]([C:8]3[N:12]=[CH:11][N:10]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])[N:9]=3)=[CH:4][CH:3]=2)[O:48]1.[CH3:60][C:57]1([CH3:59])[C:56]([CH3:61])([CH3:62])[O:55][B:54]([C:22]2[CH:23]=[CH:24][C:25]([C:28]3[N:32]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[N:31]=[CH:30][N:29]=3)=[CH:26][CH:27]=2)[O:58]1

参加物

8

反応物 4

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 595259995-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazoleHCID 595262653-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole

生成物 2

HCID 595255703-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazoleHCID 680888445-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole収率 98%

試薬・触媒・溶媒 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

In a sealed tube, a mixture of 3-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole and 5-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole (5.00 g, 14.1 mmol), DPPF (0.469 g, 0.847 mmol), PdCl2dppf-dichloromethane (1.38 g, 1.69 mmol), potassium acetate (4.15 g, 42.3 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (7.17 g, 28.2 mmol) in dioxane (141 mL) was heated at 90° C. under N2 for 18 hours. The crude product was filtered through a pad of Celite, washed with saturated NaHCO3, brine, dried over MgSO4, filtered, and concentrated. Purification of the crude material by column chromatography, eluting with 0-30% EtOAc/Hexanes, afforded 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole and 5-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole (5.55 g, 98%) as a mixture of two regioisomers. LCMS (APCI+) m/z 402 [M+H]+.

後処理

  1. filtrationThe crude product was filtered through a pad of Celite
  2. washwashed with saturated NaHCO3, brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification of the crude material by column chromatography
  7. washeluting with 0-30% EtOAc/Hexanes

出典と根拠

ORDレコード
ord-8fe734810f74453ca4058948523960ef
出典データセット
uspto-grants-2014_10
特許番号
US08865726B2

関連ノート

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