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Triethylamine → 5-(2,4-dichlorophenyl)-N-[(cis)-4-ethoxypyrrolidin-3-yl]-3,6-diethylpyrazin-2-amine

HRID 1297290
ノート
印刷プレビュー

反応式

HRID 1297290 の反応式
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[N:10]=[C:11]([CH2:36][CH3:37])[C:12]([NH:17][C@H:18]2[C@@H:22]([O:23][CH2:24][CH3:25])[CH2:21][N:20](C(OCC3C=CC=CC=3)=O)[CH2:19]2)=[N:13][C:14]=1[CH2:15][CH3:16].C(N(CC)CC)C.C([SiH](CC)CC)C>C(Cl)Cl.[Pd](Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:9]1[N:10]=[C:11]([CH2:36][CH3:37])[C:12]([NH:17][C@H:18]2[C@@H:22]([O:23][CH2:24][CH3:25])[CH2:21][NH:20][CH2:19]2)=[N:13][C:14]=1[CH2:15][CH3:16]
参加物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 8471TriethylamineHCID 12052Triethylsilane2 回HCID 10196417Benzyl (cis)-3-{[5-(2,4-dichlorophenyl)-3,6-diethylpyrazin-2-yl]amino}-4-ethoxypyrrolidine-1-carboxylate

生成物 1

HCID 103098205-(2,4-dichlorophenyl)-N-[(cis)-4-ethoxypyrrolidin-3-yl]-3,6-diethylpyrazin-2-amine収率 92%

試薬・触媒・溶媒 2

HCID 24290
Palladium Chloride
触媒
HCID 6344Dichloromethane溶媒

実験手順

To a solution of benzyl (3R,4S)-3-{[5-(2,4-dichlorophenyl)-3,6-diethylpyrazin-2-yl]amino}4-ethoxypyrrolidine-1-carboxylate (8.60 g, 15.8 mmole) in CH2Cl2 (0.1M, 158 ml) under N2 was added Palladium chloride (279 mg, 1.58 mmole) and triethyl amine (3.29 ml, 1.5 eq.). Triethylsilane (3.78 ml, 1.5 eq.) was added dropwise over 15 min. After one hour an additional 8.74 ml of triethylsilane was added dropwise. After 2 additional hours, the reaction mixture was filtered through celite. Trifluoroacetic acid (8 ml) was added and the reaction mixture was stirred for 30 min. Quenched to pH 10 with 2N NaOH and extracted 3×300 ml of CH2Cl2, dried MgSO4, filtered and concentrated. Vacuum chromatography was run on a 1 L frit funnel with 5–15% MeOH/CH2Cl2 with 0.5% NH4OH to give 5.95 g (92%) of an oil. 1H NMR (400 MHz, CDCl3) δ) 7.49, 7.33–7.26, 5.38, 4.54, 4.07, 3.68, 3.52, 3.22, 2.95, 2.71, 2.46, 1.29, 1.15; HRMS (FAB) calcd for C20H26Cl2N4O+H 409.1562. found 409.1567. Anal. Calcd for C20H26Cl2N4O: C, 58.68; H, 6.40; N, 13.69. Found: C, 58.42; H, 6.43; N, 13.50.

後処理

  1. filtrationAfter 2 additional hours, the reaction mixture was filtered through celite
  2. additionTrifluoroacetic acid (8 ml) was added
  3. customQuenched to pH 10 with 2N NaOH
  4. extractionextracted 3×300 ml of CH2Cl2, dried MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customVacuum chromatography was run on a 1 L frit funnel with 5–15% MeOH/CH2Cl2 with 0.5% NH4OH

出典と根拠

ORDレコード
ord-defa2b06d8fb42b59edd18616bdf2fab
出典データセット
uspto-grants-2007_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07250418B2

反応ノート

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