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

Reaktionsgleichung

Reaktionsgleichung von HRID 538990
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

Komponenten

8

Edukt 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

Produkt 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-triazoleAusbeute 98 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

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]+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-8fe734810f74453ca4058948523960ef
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08865726B2

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