Hydrochloric Acid → 4-(1,4-Oxazepan-4-yl)cyclohexanone

HRID 552260ノート

反応式

HRID 552260 の反応式
O1[C:5]2([CH2:10][CH2:9][CH:8]([N:11]3[CH2:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12]3)[CH2:7][CH2:6]2)[O:4]CC1.Cl.[OH-].[Na+].CCCCCC>C1COCC1>[O:14]1[CH2:15][CH2:16][CH2:17][N:11]([CH:8]2[CH2:9][CH2:10][C:5](=[O:4])[CH2:6][CH2:7]2)[CH2:12][CH2:13]1

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 8058HexaneHCID 14798Sodium HydroxideHCID 592386344-(1,4-Dioxaspiro[4.5]dec-8-yl)hexahydro-1,4-oxazepine

生成物 1

HCID 592386984-(1,4-Oxazepan-4-yl)cyclohexanone収率 85.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a cooled (<15° C.) solution of 3 (10.31 g, 42.75 mmol) in THF (216 mL) was added 7 N aqueous HCl (86 mL, 0.602 mol) over a period of 5 min. Cooling bath was then removed and the reaction mixture was stirred overnight at r.t. Then, the reaction mixture was basified to pH 8 by dropwise addition of 50% aqueous NaOH (48 g, 0.602 mol) over a period of 30 min while maintaining the internal temperature at 10-13° C. using an external cooling bath (0° C.). Hexane (50 mL) was added and the organic layer was separated, dried over MgSO4 and concentrated to afford yellowish liquid (7.21 g). The aqueous layer was extracted with AcOEt (4×50 mL). The extracts were combined, dried (MgSO4) and concentrated to afford the second portion of crude product (1.58 g). Both portions of crude product were combined and distilled in vacuum to afford ketone (VII-b) (7.27 g, 86%) as colorless liquid b.p. 98° C./5.3·10−3 mbar; 1H NMR (400 MHz, CDCl3) δ 1.73-1.85 (m, 2H), 1.89 (quintet, J=5.9 Hz, 2H), 2.05-2.15 (m, 2H), 2.30-2.42 (m, 2H), 2.43-2.52 (m, 2H), 2.79-2.85 (m, 4H), 3.03 (tt, J=10.4, 6.6 Hz, 1H), 3.72-3.77 (m, 2H), 3.82 (t, J=6.0 Hz, 2H).

後処理

  1. temperatureCooling bath
  2. customwas then removed
  3. temperaturewhile maintaining the internal temperature at 10-13° C.
  4. custom(0° C.)
  5. customthe organic layer was separated
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-251ce96a028249fb92a340c50abf8e1e
出典データセット
uspto-grants-2011_05
特許番号
US07951802B2

反応ノート

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