Trimethylsilylacetylene → [4-(3-Trifluoromethyl-5-trimethylsilanylethynyl-benzenesulfonylamino)-4,5,6,7-tetrahydro-indazol-1-yl]-acetic acid ethyl ester

HRID 2387552Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2387552
[CH2:1]([O:3][C:4](=[O:30])[CH2:5][N:6]1[C:14]2[CH2:13][CH2:12][CH2:11][CH:10]([NH:15][S:16]([C:19]3[CH:24]=[C:23]([C:25]([F:28])([F:27])[F:26])[CH:22]=[C:21](Br)[CH:20]=3)(=[O:18])=[O:17])[C:9]=2[CH:8]=[N:7]1)[CH3:2].[C:31]([Si:33]([CH3:36])([CH3:35])[CH3:34])#[CH:32]>C(N(CC)CC)C.C1(C)C=CC=CC=1.O.[Cu]I.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>[CH2:1]([O:3][C:4](=[O:30])[CH2:5][N:6]1[C:14]2[CH2:13][CH2:12][CH2:11][CH:10]([NH:15][S:16]([C:19]3[CH:20]=[C:21]([C:32]#[C:31][Si:33]([CH3:36])([CH3:35])[CH3:34])[CH:22]=[C:23]([C:25]([F:28])([F:27])[F:26])[CH:24]=3)(=[O:18])=[O:17])[C:9]=2[CH:8]=[N:7]1)[CH3:2]

Komponenten

8

Edukt 2

HCID 66111TrimethylsilylacetyleneHCID 44611232[4-(3-Bromo-5-trifluoromethyl-benzenesulfonylamino)-4,5,6,7-tetrahydro-indazol-1-yl]-acetic acid ethyl ester

Produkt 1

HCID 59152887[4-(3-Trifluoromethyl-5-trimethylsilanylethynyl-benzenesulfonylamino)-4,5,6,7-tetrahydro-indazol-1-yl]-acetic acid ethyl esterAusbeute 94,8 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittelHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

To a mixture of [4-(3-bromo-5-trifluoromethyl-benzenesulfonylamino)-4,5,6,7-tetrahydro-indazol-1-yl]-acetic acid ethyl ester (example 1-7) (51 mg, 0.10 mmol) and ethynyl-trimethyl-silane (20 mg, 0.20 mmol) in triethylamine (0.5 mL) and toluene (0.5 mL), was added copper(I) iodide (0.6 mg, 0.003 mmol) and bis(triphenylphosphine)palladium(II) chloride (2.4 mg, 0.003 mmol). The mixture was heated in a microwave oven at 80° C., for 20 minutes. The resulting mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, concentrated and purified by column chromatography (gradient elution, 0-5% methanol in dichloromethane) to afford [4-(3-trifluoromethyl-5-trimethylsilanylethynyl-benzenesulfonylamino)-4,5,6,7-tetrahydro-indazol-1-yl]-acetic acid ethyl ester (50 mg, 94.8%) as a brown oil. MS calcd. for C23H28F3N3O4SSi 527, obsd (ESI+) [(M+H)+] 528.

Aufarbeitung

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with brine
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated
  5. custompurified by column chromatography (gradient elution, 0-5% methanol in dichloromethane)

Quellen und Nachweise

ORD-Eintrag
ord-de5db09c47fe4ed38578f2059e9983ae
Quelldatensatz
uspto-grants-2012_09
Patentnummer
US08268870B2

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