1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 89761414, Verbindung

HRID 528589Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 528589
[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1I.[CH3:12][O:13][C:14]1[CH:39]=[CH:38][C:17]([CH2:18][N:19]([C:33]2[S:34][CH:35]=[CH:36][N:37]=2)[S:20]([C:23]2[CH:24]=[CH:25][C:26]3[NH:31][CH2:30][CH2:29][O:28][C:27]=3[CH:32]=2)(=[O:22])=[O:21])=[CH:16][CH:15]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1[N:31]1[CH2:30][CH2:29][O:28][C:27]2[CH:32]=[C:23]([S:20]([N:19]([CH2:18][C:17]3[CH:38]=[CH:39][C:14]([O:13][CH3:12])=[CH:15][CH:16]=3)[C:33]3[S:34][CH:35]=[CH:36][N:37]=3)(=[O:21])=[O:22])[CH:24]=[CH:25][C:26]1=2

Komponenten

7

Edukt 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23676156Sodium t-butoxideHCID 448911892-Bromo-1-iodo-4-(1-methylethyl)benzeneHCID 89761436N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide2×

Produkt 1

HCID 89761414HCID 89761414, VerbindungAusbeute 79,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

A microwave vial was charged with 2-bromo-1-iodo-4-isopropylbenzene (Oakwood, 0.117 g, 0.359 mmol), N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide (INTERMEDIATE M, 0.150 g, 0.359 mmol), Xantphos (0.042 g, 0.072 mmol), Pd2(dba)3 (0.033 g, 0.036 mmol) and sodium tert-butoxide (0.069 g, 0.719 mmol). The mixture was diluted with toluene (3.59 ml), and purged with nitrogen, and stirred at 130° C. in the microwave for 30 minutes, until clean conversion to the desired product. After completion, the reaction was filtered over a plug of Celite, washing well with DCM. The filtrate was concentrated in vacuo. The crude material was purified using a 5-g SCX column (product eluted with methanol wash to yield 4-(2-bromo-4-isopropylphenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide (0.175 g, 0.285 mmol, 79% yield) as an orange oil. m/z (ESI) 614.0 (M+H)+.

Aufarbeitung

  1. custompurged with nitrogen
  2. filtrationAfter completion, the reaction was filtered over a plug of Celite
  3. washwashing well with DCM
  4. concentrationThe filtrate was concentrated in vacuo
  5. customThe crude material was purified
  6. washeluted with methanol
  7. washwash

Quellen und Nachweise

ORD-Eintrag
ord-f1ba8034d6184b85b45ee083b9344418
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09346798B2

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