Triphenylphosphine → Methyl 5-[({4-[(4-butylphenyl)ethynyl]phenyl}sulfonyl)(hexyl)amino]-2-fluorobenzoate

HRID 551986Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 551986
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:12]2[CH:13]=[CH:14][C:15]([F:21])=[C:16]([CH:20]=2)[C:17]([O-:19])=[O:18])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[CH2:28]([C:32]1[CH:37]=[CH:36][C:35]([C:38]#[CH:39])=[CH:34][CH:33]=1)[CH2:29][CH2:30][CH3:31].[C:40]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.CCOCC.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.[I].[Cu]>[CH2:28]([C:32]1[CH:33]=[CH:34][C:35]([C:38]#[C:39][C:2]2[CH:7]=[CH:6][C:5]([S:8]([N:11]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:12]3[CH:13]=[CH:14][C:15]([F:21])=[C:16]([CH:20]=3)[C:17]([O:19][CH3:40])=[O:18])(=[O:10])=[O:9])=[CH:4][CH:3]=2)=[CH:36][CH:37]=1)[CH2:29][CH2:30][CH3:31]

Komponenten

8

Edukt 3

HCID 11776TriphenylphosphineHCID 27751321-Butyl-4-ethynylbenzeneHCID 866265855-[({4-Bromophenyl)sulfonyl](hexyl)amino]-2-fluorobenzoate

Produkt 1

HCID 57554500Methyl 5-[({4-[(4-butylphenyl)ethynyl]phenyl}sulfonyl)(hexyl)amino]-2-fluorobenzoateAusbeute 221,5 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418476HCID 178418476, VerbindungKatalysatorHCID 178505378HCID 178505378, VerbindungKatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

To a solution of 5-[({4-bromophenyl)sulfonyl](hexyl)amino]-2-fluorobenzoate (400 mg; 0.85 mmol) in DMF (15 mL) under nitrogen were added (p-butylphenyl)acetylene (0.16 mL; 0.93 mmol), bis(triphenylphosphine)palladium chloride (29.7 mg; 0.04 mmol), triphenylphosphine (44.4 mg; 0.17 mmol), copper iodine (8.1 mg; 0.04 mmol) and TEA (0.35 mL; 2.54 mmol). The reaction mixture was stirred under MW at 120° C. for 1500 s. The mixture was diluted with Et2O (75 mL) and the precipitate obtained filtrated off. Filtrate was washed with HCl 1N and with brine. The organic layer was dried over magnesium sulfate and the solvent was removed under reduced pressure. Purification by flash chromatography on silicagel (c-Hex/EtOAc, 95:5 then 90:10) gave 207 mg (44.5%) of the title compound as a yellow cream. HPLC, Rt: 6.17 min (purity=98.5%). LC/MS: M+(ESI): 500.3, 1H NMR (CDCl3) δ: 7.55 (m, 6H), 7.32 (m, 1H), 7.10 (m, 4H), 3.91 (s, 3H), 3.52 (t, J=6.9 Hz, 2H), 2.63 (t, J=7.9 Hz, 2H), 1.30 (m, 12H), 0.95 (m, 3H), 0.85 (t, 3H.

Aufarbeitung

  1. customthe precipitate obtained
  2. filtrationfiltrated off
  3. washFiltrate was washed with HCl 1N and with brine
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. customthe solvent was removed under reduced pressure
  6. customPurification by flash chromatography on silicagel (c-Hex/EtOAc, 95:5

Quellen und Nachweise

ORD-Eintrag
ord-1c7390b978cf47a4b64fed4d53339403
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07947851B2

Notizen zur Reaktion

Wird geladen…