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Hydrochloric Acid → 4-[3-Chloro-4-(pyridin-2-ylmethoxy)-phenylamino]-5,8-dihydro-6H-9-thia-1,3,7-triaza-fluorene-7-carboxylic acid tert-butyl ester

HRID 1887410
ノート
印刷プレビュー

反応式

HRID 1887410 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:20][C:19]2[S:18][C:17]3[N:16]=[CH:15][N:14]=[C:13](Cl)[C:12]=3[C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cl:22][C:23]1[CH:24]=[C:25]([NH2:37])[CH:26]=[CH:27][C:28]=1[O:29][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][N:32]=1.Cl>C(O)(C)C.O1CCOCC1>[C:1]([O:5][C:6]([N:8]1[CH2:20][C:19]2[S:18][C:17]3[N:16]=[CH:15][N:14]=[C:13]([NH:37][C:25]4[CH:26]=[CH:27][C:28]([O:29][CH2:30][C:31]5[CH:36]=[CH:35][CH:34]=[CH:33][N:32]=5)=[C:23]([Cl:22])[CH:24]=4)[C:12]=3[C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 313Hydrochloric AcidHCID 167812123-Chloro-4-(2-pyridylmethoxy)anilineHCID 49788563tert-Butyl 4-chloro-5,6-dihydropyrido(4',3':4,5)thieno(2,3-d)pyrimidine-7(8H)-carboxylate

生成物 1

HCID 595869744-[3-Chloro-4-(pyridin-2-ylmethoxy)-phenylamino]-5,8-dihydro-6H-9-thia-1,3,7-triaza-fluorene-7-carboxylic acid tert-butyl ester収率 95.4%

試薬・触媒・溶媒 2

HCID 3776
Isopropanol
溶媒
HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

To a 4-Chloro-5,8-dihydro-6H-9-thia-1,3,7-triaza-fluorene-7-carboxylic acid tert-butyl ester (3.08 g, 9.40 mmol, 1.05 equiv) in 40 mL of isopropyl alcohol solution was added 3-Chloro-4-(pyridin-2-ylmethoxy)phenylamine (2.10 g, 9.0 mmol, 1 equiv) at rt. 4 N HCl in dioxane (0.1 mL) was added to the reaction mixture to accelerate the reaction. The reaction mixture was heated at 80° C. for 16 h. The mixture was allowed to cool to rt then filtered and washed with IPA (50 mL). DCM (100 mL) and sat. sodium bicarbonate (100 mL) were added to the solid. The mixture was stirred at rt for 1 h before separated the layers. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to yield 4.50 g of crude material. The crude material was purified by flash chromatography (50% THF/DCM) to yield a light yellow (3.60 g, 6.87 mmol, 76%) as product. 1H-NMR (DMSO-d6) δ 9.32 (broad s, 1H), 8.67 (d, J=4.0 Hz, 1H), 8.40 (s, 1H), 8.27 (s, 1H), 8.05 (t, 1H), 7.79 (d, J=2.7 Hz, 1H), 7.70 (d, J=8.0 Hz, 1H), 7.53 (t, 1H), 7.24 (d, J=8.9 Hz, 1H), 5.35 (s, 2H), 4.66 (s, 2H), 3.66 (t, 2H), 3.19 (t, 2H), 1.43 (s, 9H); LCMS RT=3.39 min, [M+H]+=524.0.

後処理

  1. customthe reaction
  2. temperatureto cool to rt
  3. filtrationthen filtered
  4. washwashed with IPA (50 mL)
  5. additionDCM (100 mL) and sat. sodium bicarbonate (100 mL) were added to the solid
  6. custombefore separated the layers
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-8d14335fcf474156b0fa274675c55c97
出典データセット
uspto-grants-2013_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08501755B2

反応ノート

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