Acetic Acid → Tert-butyl 4-((2-bromo-5,5-dimethylcyclohex-1-enyl)methyl)piperazine-1-carboxylate

HRID 410340ノート

反応式

HRID 410340 の反応式
[Br:1][C:2]1[CH2:7][CH2:6][C:5]([CH3:9])([CH3:8])[CH2:4][C:3]=1[CH:10]=O.C(O)(=O)C.[C:16]([O:20][C:21]([N:23]1[CH2:28][CH2:27][NH:26][CH2:25][CH2:24]1)=[O:22])([CH3:19])([CH3:18])[CH3:17].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].[OH-].[Na+]>ClCCl>[C:16]([O:20][C:21]([N:23]1[CH2:28][CH2:27][N:26]([CH2:10][C:3]2[CH2:4][C:5]([CH3:8])([CH3:9])[CH2:6][CH2:7][C:2]=2[Br:1])[CH2:25][CH2:24]1)=[O:22])([CH3:19])([CH3:17])[CH3:18]

参加物

7

反応物 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 143452tert-Butyl piperazine-1-carboxylateHCID 5049666Sodium triacetoxyborohydrideHCID 251391912-Bromo-5,5-dimethylcyclohex-1-enecarbaldehyde

生成物 1

HCID 67422645Tert-butyl 4-((2-bromo-5,5-dimethylcyclohex-1-enyl)methyl)piperazine-1-carboxylate収率 73%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a solution of 2-bromo-5,5-dimethyl-cyclohex-1-ene carbaldehyde (1 g, 4.61 mmol) in dichloromethane (70 ml) at rt under nitrogen was added glacial acetic acid (0.29 ml, 5.1 mmol) followed by piperazine-1-carboxylic acid tert-butyl ester (0.94 g, 5.07 mmol). The reaction was stirred for 1 h before sodium triacetoxyborohydride (2.05 g, 9.68 mmol) was introduced. After 16 h, a solution of 5% NaOH (20 ml) was added and the mixture was extracted with dichloromethane. The organic layer was separated and washed with H2O, dried (Na2SO4), filtered and concentrated under reduced pressure to give the crude product. Purification by column chromatography on silica eluting with 5% EtOAc/heptane provided 4-(2-bromo-5,5-dimethyl-cyclohex-1-enylmethyl)-piperazine-1-carboxylic acid tert-butyl ester (1.3 g, 73%).-1H NMR (MeOD) δ 3.44 (4H, br t), 3.14 (2H, br s), 2.55 (2H, br m), 2.40 (4H, br t), 2.08 (2H, br s), 1.51 (2H, t), 1.48 (9H, s), 0.93 (6H, s).

後処理

  1. additionwas introduced
  2. extractionthe mixture was extracted with dichloromethane
  3. customThe organic layer was separated
  4. washwashed with H2O
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto give the crude product
  9. customPurification by column chromatography on silica eluting with 5% EtOAc/heptane

出典と根拠

ORDレコード
ord-dc9c4351f6e2462ba08a73f4ded1809d
出典データセット
uspto-grants-2014_06
特許番号
US08759520B2

反応ノート

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