3-Bromopropionitrile → 1-Tert-butyl 4-ethyl 4-(2-cyanoethyl)piperidine-1,4-dicarboxylate

HRID 41536

反応式

HRID 41536 の反応式
[C:1]([N:8]1[CH2:13][CH2:12][CH:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:10][CH2:9]1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[Li+].CC([N-]C(C)C)C.Br[CH2:28][CH2:29][C:30]#[N:31]>C1COCC1>[C:30]([CH2:29][CH2:28][C:11]1([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:12][CH2:13][N:8]([C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])[CH2:9][CH2:10]1)#[N:31]

参加物

5

反応物 3

HCID 170203-BromopropionitrileHCID 2724682Lithium diisopropylamideHCID 27588121-Tert-butyl 4-ethyl piperidine-1,4-dicarboxylate

生成物 1

HCID 672523241-Tert-butyl 4-ethyl 4-(2-cyanoethyl)piperidine-1,4-dicarboxylate収率 41.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of ethyl N-Boc-piperidine-4-carboxylate (10.0 g, 38.86 mmol) in THF (200 mL) was added LDA (2 M solution in Hexane, 38.86 mL, 77.72 mmol) at −78° C. and stirred for 30 min. 3-bromo propionitrile (6.25 g, 46.63 mmol) was then added at −78° C. The resulting reaction mixture was stirred at −60° C. for 4 h and quenched with saturated NH4Cl solution. Ethyl acetate was added and the organic layer was extracted with water and brine. The organic layer was dried over Na2SO4, filtered and concentrated. The crude product was purified by column chromatography using 10% ethyl acetate in hexane to yield the title compound as a pale yellow liquid (5.0 g, 40%). [1H-NMR (DMSO-d6, 300 MHz): δ 4.15 (q, 2H), 3.78-3.54 (m, 2H), 2.93-2.72 (m, 2H), 2.43 (t, 2H), 2.02-1.78 (m, 4H), 1.45-1.29 (m, 11H), 1.22 (t, 3H); HPLC RtA=4.703 min (93%); LCMS RtA=1.881, [M+H-Boc]+=211.1].

後処理

  1. customThe resulting reaction mixture
  2. stirringwas stirred at −60° C. for 4 h
  3. customquenched with saturated NH4Cl solution
  4. additionEthyl acetate was added
  5. extractionthe organic layer was extracted with water and brine
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by column chromatography

出典と根拠

ORDレコード
ord-b130606dece64225852ec4b295a7726a
出典データセット
uspto-grants-2013_09
特許番号
US08530648B2

関連ノート

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