Cesium carbonate → 4-{4-[7-(2,6-Dichloro-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamino]-benzenesulfonyl}-piperazine-1-carboxylic acid tert-butyl ester

HRID 273530ノート

反応式

HRID 273530 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[C:9]1[CH:19]=[C:18]([CH3:20])[C:12]2[N:13]=[C:14]([NH2:17])[N:15]=[N:16][C:11]=2[CH:10]=1.[C:21]([O:25][C:26]([N:28]1[CH2:33][CH2:32][N:31]([S:34]([C:37]2[CH:42]=[CH:41][C:40](Br)=[CH:39][CH:38]=2)(=[O:36])=[O:35])[CH2:30][CH2:29]1)=[O:27])([CH3:24])([CH3:23])[CH3:22].C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[C:21]([O:25][C:26]([N:28]1[CH2:33][CH2:32][N:31]([S:34]([C:37]2[CH:42]=[CH:41][C:40]([NH:17][C:14]3[N:15]=[N:16][C:11]4[CH:10]=[C:9]([C:3]5[C:4]([Cl:8])=[CH:5][CH:6]=[CH:7][C:2]=5[Cl:1])[CH:19]=[C:18]([CH3:20])[C:12]=4[N:13]=3)=[CH:39][CH:38]=2)(=[O:36])=[O:35])[CH2:30][CH2:29]1)=[O:27])([CH3:24])([CH3:22])[CH3:23]

参加物

6

反応物 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 166655764-(4-BOC-piperazinosulfonyl)bromobenzeneHCID 248227577-(2,6-Dichlorophenyl)-5-methylbenzo[e][1,2,4]triazin-3-amine

生成物 1

HCID 116502904-{4-[7-(2,6-Dichloro-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamino]-benzenesulfonyl}-piperazine-1-carboxylic acid tert-butyl ester収率 44%

試薬・触媒・溶媒 1

HCID 9832798Tris(dibenzylideneacetone) dipalladium触媒

実験手順

In a dry 25 mL round bottom flask, 7-(2,6-dichloro-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamine (0.205 g, 0.672 mmol, 1 equiv), 4-(4-bromo-benzenesulfonyl)-piperazine-1-carboxylic acid tert-butyl ester (0.408 g, 1.01 mmol, 1.5 equiv), cesium carbonate (0.657 g, 2.02 mmol, 3 equiv); 4,5-bis(diphenylphosphino)-9,9-dimethyl xanthene (0.078 g, 0.134 mmol, 0.2 equiv) and tris(dibenzylideneacetone) dipalladium (0.0615 g, 0.067 mmol, 0.1 equiv) were combined. The reactants were flushed with argon, diluted with dioxane (20 mL) and outfitted with a reflux condenser. The reaction was heated to reflux for 2 hours, then filtered hot, and the solvents were evaporated. Purification on silica gel flash column provided desired product as a yellow solid (0.185 g, 44% yield). MS (ESI+): m/z=529.0 (M−100), LC retention time: 3.51 min. 1H NMR (DMSO-d6): δ 1.33 (s, 9H), 2.72 (s, 3H), 2.87 (m, 4H), 3.4 (m, 4H), 7.5 (m, 1H), 7.67 (d, J=8.7 Hz, 2H), 7.78 (m, 3H), 8.18 (d, J=1.7 Hz, 1H), 8.30 (d, J=8.8 Hz, 2H), 11.53 (s, 1H).

後処理

  1. customThe reactants were flushed with argon
  2. additiondiluted with dioxane (20 mL)
  3. customoutfitted with a reflux condenser
  4. temperatureThe reaction was heated
  5. temperatureto reflux for 2 hours
  6. filtrationfiltered hot
  7. customthe solvents were evaporated
  8. customPurification on silica gel flash column

出典と根拠

ORDレコード
ord-4fc8c850d2a34b2fbc1313e0ed371d11
出典データセット
uspto-grants-2008_11
特許番号
US07456176B2

反応ノート

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