Tributylstannane → 4-Chloro-2-(tributylstannyl)pyrimidine

HRID 634100ノート

反応式

HRID 634100 の反応式
[Li+].CC([N-]C(C)C)C.[SnH:9]([CH2:18][CH2:19][CH2:20][CH3:21])([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:10][CH2:11][CH2:12][CH3:13].Cl[C:23]1[N:28]=[C:27]([Cl:29])[CH:26]=[CH:25][N:24]=1>C1COCC1>[Cl:29][C:27]1[CH:26]=[CH:25][N:24]=[C:23]([Sn:9]([CH2:14][CH2:15][CH2:16][CH3:17])([CH2:18][CH2:19][CH2:20][CH3:21])[CH2:10][CH2:11][CH2:12][CH3:13])[N:28]=1

参加物

5

反応物 3

HCID 5948TributylstannaneHCID 775312,4-DichloropyrimidineHCID 2724682Lithium diisopropylamide

生成物 1

HCID 149763044-Chloro-2-(tributylstannyl)pyrimidine収率 24%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-20 °C

実験手順

To a solution of LDA (251 ml, 502 mmol) in THF (650 mL) at −20° C. was added SnBu3H (108.5 ml, 402 mmol) dropwise. The mixture was maintained at −20° C. for 15 min, then cooled to −78° C. 2,4-dichloro pyrimidine (50 g, 335 mmol) was added and the reaction was stirred at −78° C. for 5 h. The cooling bath was removed and the reaction was slowly warmed to 0° C. within 30 min. The mixture was poured into 10% NH4Cl at 0° C., and the aqueous layer was extracted with Et2O. The combined organic layers were washed with brine, dried, filtered and concentrated. The residue was purified with silica gel chromatography (eluting with 1% EtOAc in Hex) to give 4-chloro-2-(tributylstannyl)pyrimidine (18.5 g, 24%) as a pale yellow color syrup. MS (ESI, pos. ion) m/z: 405.1 (M+1); 1H-NMR (400 MHz, CDCl3): δ 8.54 (d, J=8 Hz, 1H), 7.17 (d, J=8 Hz, 1H), 1.61-1.54 (m, 6H), 1.37-1.28 (m, 6H), 1.21-1.17 (m, 6H), 0.90 (m, 9H).

後処理

  1. temperaturecooled to −78° C
  2. customThe cooling bath was removed
  3. temperaturethe reaction was slowly warmed to 0° C. within 30 min
  4. additionThe mixture was poured into 10% NH4Cl at 0° C.
  5. extractionthe aqueous layer was extracted with Et2O
  6. washThe combined organic layers were washed with brine
  7. customdried
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified with silica gel chromatography (eluting with 1% EtOAc in Hex)

出典と根拠

ORDレコード
ord-5ddfb110bfdb4f97adfc2b9b2924af16
出典データセット
uspto-grants-2016_04
特許番号
US09321756B2

反応ノート

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