Aniline → 3-(4-Methyl-3-oxo-7-phenylamino-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-azetidine-1-carboxylic acid tert-butyl ester

HRID 519109

Reaktionsgleichung

Reaktionsgleichung von HRID 519109
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([NH:12][C:13]2[CH:14]=[C:15]3[C:24](=[CH:25][C:26]=2Br)[O:23][CH2:22][C:21]2[N:16]3[CH:17]([CH3:29])[C:18](=[O:28])[NH:19][N:20]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=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.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.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]>[C:1]([O:5][C:6]([N:8]1[CH2:11][CH:10]([NH:12][C:13]2[CH:14]=[C:15]3[C:24](=[CH:25][C:26]=2[NH:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[O:23][CH2:22][C:21]2[N:16]3[CH:17]([CH3:29])[C:18](=[O:28])[NH:19][N:20]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Komponenten

7

Edukt 4

HCID 6115AnilineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 867272933-(7-Bromo-4-methyl-3-oxo-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-azetidine-1-carboxylic acid tert-butyl ester

Produkt 1

HCID 867274883-(4-Methyl-3-oxo-7-phenylamino-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-azetidine-1-carboxylic acid tert-butyl esterAusbeute 14 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

A solution of 3-(7-bromo-4-methyl-3-oxo-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-azetidine-1-carboxylic acid tert-butyl ester (Example #1, Step B, 0.1 g, 0.21 mmol), aniline (0.06 g, 0.64 mmol), Pd2(dba)3 (0.039 g, 0.04 mmol), Xantphos (0.0496 g, 0.09 mmol), and Cs2CO3 (0.14 g, 0.43 mmol) in anhydrous dioxane (10 mL) was heated at 130° C. for 14 h. The reaction mixture was cooled to ambient temperature and concentrated in vacuo, The residue was purified by chromatography on silica gel (eluting with 50% EtOAc in petroleum ether) to give 3-(4-methyl-3-oxo-7-phenylamino-2,3,4,10-tetrahydro-9-oxa-1,2,4a-triaza-phenanthren-6-ylamino)-azetidine-1-carboxylic acid tert-butyl ester (0.014 g, 14%) as brown solid. LC/MS (Table 1, Method 2) Rt=1.205 min; MS m/z: 542 [M+23+41]+

Aufarbeitung

  1. concentrationconcentrated in vacuo
  2. customThe residue was purified by chromatography on silica gel (eluting with 50% EtOAc in petroleum ether)

Quellen und Nachweise

ORD-Eintrag
ord-e351f5ce8d4b4645969edc2f11bd03a5
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09115151B2

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