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2,2,6,6-Tetramethylpiperidine → 6-Chloro-9-(tetrahydro-2H-pyran-2-yl)-2-(tributylstannyl)-9H-purine

HRID 1876502
ノート
印刷プレビュー

反応式

HRID 1876502 の反応式
CC1(C)CCCC(C)(C)N1.[Cl:11][C:12]1[N:20]=[CH:19][N:18]=[C:17]2[C:13]=1[N:14]=[CH:15][N:16]2[CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][O:22]1.[CH2:27]([Sn:31](CCCC)([CH2:36][CH2:37][CH2:38][CH3:39])[CH2:32][CH2:33][CH2:34][CH3:35])[CH2:28][CH2:29][CH3:30].[Cl-].[Cl-].[NH4+]>O1CCCC1.C([Li])CCC.C(OCC)(=O)C>[Cl:11][C:12]1[N:20]=[C:19]([Sn:31]([CH2:32][CH2:33][CH2:34][CH3:35])([CH2:36][CH2:37][CH2:38][CH3:39])[CH2:27][CH2:28][CH2:29][CH3:30])[N:18]=[C:17]2[C:13]=1[N:14]=[CH:15][N:16]2[CH:21]1[CH2:26][CH2:25][CH2:24][CH2:23][O:22]1
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

8

反応物 4

HCID 130352,2,6,6-TetramethylpiperidineHCID 25517Ammonium ChlorideHCID 977406-chloro-9-(tetrahydro-2H-pyran-2-yl)-9H-purineHCID 86641992Tetrabutyltin chloride

生成物 1

HCID 112263006-Chloro-9-(tetrahydro-2H-pyran-2-yl)-2-(tributylstannyl)-9H-purine収率 80.3%

試薬・触媒・溶媒 3

HCID 8028
Tetrahydrofuran
溶媒
2 回
HCID 8857Ethyl Acetate溶媒
HCID 178418339Butyllithium溶媒

反応条件

温度
-78 °C

実験手順

2,2,6,6-Tetramethylpiperidine (26.5 ml, 157 mmol) was dissolved in tetrahydrofuran (200 ml) in an argon atmosphere and n-butyl lithium (2.6 M hexane solution, 54 ml) was added dropwise at room temperature. After the completion of dropwise addition, the resulting mixture was stirred for 15 minutes. The reaction mixture was cooled to −78° C. followed by the dropwise addition of a tetrahydrofuran (30 ml) solution of 6-chloro-9-(tetrahydro-2H-pyran-2-yl)-9H-purine (7.5 g, 31.4 mmol) and the resulting mixture was stirred at the same temperature for 40 minutes. Tetrabutyltin chloride (26 ml, 94.3 mmol) was added dropwise to this solution and the resulting mixture was stirred for 30 minutes. An aqueous ammonium chloride solution was added, the resulting mixture was heated to room temperature followed by the addition of ethyl acetate, and the organic layer was fractionated. The organic layer was washed with water and saturated brine and dried over magnesium sulfate and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate=9:1 to 8:2 to 7:3 to 6:4 to 5:5) to give the title compound (13.3 g, 80%) as a pale yellow oil.

後処理

  1. additionwas added dropwise at room temperature
  2. additionAfter the completion of dropwise addition
  3. stirringthe resulting mixture was stirred at the same temperature for 40 minutes
  4. stirringthe resulting mixture was stirred for 30 minutes
  5. temperaturethe resulting mixture was heated to room temperature
  6. washThe organic layer was washed with water and saturated brine
  7. dry with materialdried over magnesium sulfate
  8. customthe solvent was evaporated under reduced pressure
  9. customThe residue was purified by silica gel chromatography (hexane:ethyl acetate=9:1 to 8:2 to 7:3 to 6:4 to 5:5)

出典と根拠

ORDレコード
ord-78e4ffec75624cb6ab403495dd927902
出典データセット
uspto-grants-2012_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08309546B2

反応ノート

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