Hydrochloric Acid → 2,2,4,4,7-Pentamethyl-6-ethynyl-chroman

HRID 6552

反応式

HRID 6552 の反応式
[Li]CCCC.[CH3:6][C:7]1([CH3:23])[CH2:16][C:15]([CH3:18])([CH3:17])[C:14]2[C:9](=[CH:10][C:11]([CH3:22])=[C:12]([C:19](=O)[CH3:20])[CH:13]=2)[O:8]1.P(Cl)(OCC)(OCC)=O.C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.Cl>C1COCC1.CCCCCC.O>[CH3:6][C:7]1([CH3:23])[CH2:16][C:15]([CH3:17])([CH3:18])[C:14]2[C:9](=[CH:10][C:11]([CH3:22])=[C:12]([C:19]#[CH:20])[CH:13]=2)[O:8]1

参加物

10

反応物 6

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 13139Diethyl chlorophosphateHCID 2724682Lithium diisopropylamideHCID 156611372,2,4,4,7-Pentamethyl-6-acetylchroman2 回HCID 178418339Butyllithium2 回

生成物 1

HCID 156611392,2,4,4,7-Pentamethyl-6-ethynyl-chroman

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒2 回

反応条件

温度
-78 °C

実験手順

To a solution of 455 mg (4.5 mmol) of disopropylamine in 5 ml of dry THF at -78 degrees C. was added under argon 3 ml of 1.5 M n-BuLi in hexane. The mixture was stirred at -78 degrees C. for a further 45 min and then treated with a solution of 1.07 g (4.3 mmol) of 2,2,4,4,7-pentamethyl-6-acetyl-chroman (Compound 90) in 4 ml of dry THF. The reaction mixture was stirred at -78 degrees C. for 1 h and then treated with 776 mg (4.5 mmol) of diethyl chlorophosphate. The mixture was allowed to warm to room temperature and then transferred by a double-ended needle into a solution of lithium diisopropyl amide in 10 ml dry THF at -78 degrees C. which was prepared as described above using 910 mg (9.0 mmol) of diisopropylamine and 6 ml of 1.5 M (9.0 mmol) n-BuLi in hexane. The mixture was stirred at room temperature for 15 h and then poured into 10 ml of iced water The mixture was acidified to pH=2 with 10% HCl solution. The organic layer was separated and the aqueous layer extracted with pentane. The organic extracts were combined and washed successively with water, saturated NaHCO3 and saturated NaCl solutions and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by Kugelrohr distillation (82 degrees C. 0.3 mm) to give the title compound as a pale yellow oil. PMR (CDCl3): δ 1.32 (6H, s), 1.34 (6H, s), 1.81 (2H, s), 2.36 (3H, s), 3.18 (1H, s), 6.64 (1H, s), 7.40 1H (s). MS exact mass, m/e 228.1520 (calcd. for C16H20O, 228.1514).

後処理

  1. customat -78 degrees C
  2. stirringThe reaction mixture was stirred at -78 degrees C
  3. waitfor 1 h
  4. temperatureto warm to room temperature
  5. customwhich was prepared
  6. stirringThe mixture was stirred at room temperature for 15 h
  7. customThe organic layer was separated
  8. extractionthe aqueous layer extracted with pentane
  9. washwashed successively with water, saturated NaHCO3 and saturated NaCl solutions
  10. dry with materialdried (MgSO4)
  11. customThe solvent was removed in vacuo
  12. distillationthe residue purified by Kugelrohr distillation (82 degrees C. 0.3 mm)

出典と根拠

ORDレコード
ord-8ab7f252cbf94f38a7c5fa1c66be5d0f
出典データセット
uspto-grants-1993_09
特許番号
US05248777

関連ノート

読み込み中…