Chlorotrimethylsilane → [(Cyclooct-1-en-1-yl)oxy](trimethyl)silane

HRID 1256926ノート

反応式

HRID 1256926 の反応式
[C:1]1(=[O:9])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.C(N(CC)CC)C.Cl[Si:18]([CH3:21])([CH3:20])[CH3:19]>CN(C=O)C>[C:1]1([O:9][Si:18]([CH3:21])([CH3:20])[CH3:19])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=1

参加物

5

反応物 3

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 10403Cyclooctanone

生成物 1

HCID 54080585[(Cyclooct-1-en-1-yl)oxy](trimethyl)silane収率 93%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

To a solution of cyclooctanone (40.0 g, 316 mmol) in 200 mL of anhydrous DMF were added triethylamine (TEA, 93.0 mL, 666 mmol) and chlorotrimethylsilane (84.0 mL, 666 mmol). The reaction was heated to reflux. After 15 h, the reaction was quenched with 20 mL of H2O and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (300 mL), washed with H2O (3×100 mL) and brine (1×50 mL), and dried over MgSO4. Distillation under reduced pressure (20 torr) yielded 58.1 g (93%) of the desired product as a colorless oil, by 108° C. (20 torr) (lit. 106° C. at 25 torr). Nakamura, et al. J. Am. Chem. Soc. (1976) 98, 2346-2348. IR: 2926, 2851, 1661 cm−1. 1H NMR (CDCl3, 300 MHz): δ 0.20 (s, 9H), 1.39-1.58 (m, 8H), 2.02 (m, 2H), 2.19 (m, 2H), 4.75 (t, 1H, J=9.0 Hz). (Lit: 1H NMR (CDCl3, 600 MHz): δ 0.16 (s, 9H), 1.46 (m, 4H), 1.49 (m, 2H), 1.55 (m, 2H), 1.97 (m, 2H), 2.14 (m, 2H), 4.70 (t, 1H, J=8.0 Hz) (Frimer et al. J. Org. Chem. (2000) 65, 1807-1817.) 13C NMR (CDCl3, 75 MHz): δ 0.4, 25.5, 26.3, 26.4, 27.8, 30.9, 31.0, 105.41, 152.99. (Lit: 13C NMR (CDCl3, 150 MHz): δ 0.45, 25.52, 26.36, 26.40, 27.83, 30.98, 31.05, 105.45, 153.05) Frimer et al. (2000) supra) FAB-HRMS: Calcd. for C11H23OSi+ [M+H]+: 199.1518, found 199.1520.

後処理

  1. temperatureThe reaction was heated to reflux
  2. customthe reaction was quenched with 20 mL of H2O
  3. customthe DMF was removed on a rotary evaporator
  4. additionThe residue was diluted with hexanes (300 mL)
  5. washwashed with H2O (3×100 mL) and brine (1×50 mL)
  6. dry with materialdried over MgSO4
  7. distillationDistillation under reduced pressure (20 torr)

出典と根拠

ORDレコード
ord-1d7addb2429d4f2e90c67f3a19689613
出典データセット
uspto-grants-2013_06
特許番号
US08461298B2

反応ノート

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