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

反応式

HRID 519109 の反応式
[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]

参加物

7

反応物 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

生成物 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 ester収率 14%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒

実験手順

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]+

後処理

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

出典と根拠

ORDレコード
ord-e351f5ce8d4b4645969edc2f11bd03a5
出典データセット
uspto-grants-2015_08
特許番号
US09115151B2

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