2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 1-Methyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)piperazine

HRID 216713ノート

反応式

HRID 216713 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:13][CH2:12][N:11]([CH3:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[Li]CCCC.C(O[B:24]1[O:28][C:27]([CH3:30])([CH3:29])[C:26]([CH3:32])([CH3:31])[O:25]1)(C)C>C1COCC1.[NH4+].[Cl-]>[CH3:14][N:11]1[CH2:12][CH2:13][N:8]([C:5]2[CH:6]=[CH:7][C:2]([B:24]3[O:28][C:27]([CH3:30])([CH3:29])[C:26]([CH3:32])([CH3:31])[O:25]3)=[CH:3][CH:4]=2)[CH2:9][CH2:10]1

参加物

6

反応物 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 118176751-(4-Bromophenyl)-4-methylpiperazineHCID 178418339Butyllithium

生成物 1

HCID 179989051-Methyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)piperazine

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒3 回HCID 25517Ammonium Chloride溶媒

実験手順

To a cooled (−78° C.) solution of 1-(4-Bromo-phenyl)-4-methyl-piperazine (8.05 g, 31.54 mmol, CAS 130307-08-3) in dry THF (500 ml) are added dropwise 28 ml of a solution of n-BuLi (2.5M in hexanes, 69 mmol). After 1 h, of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13.1 ml, 63.1 mmol) in solution in dry THF (20 ml) are introduced. After complete addition, the reaction mixture is allowed to slowly warm up to RT. The reaction mixture is then diluted with 200 ml of a saturated solution of NH4Cl and most of the THF is removed by evaporation. The residue is diluted with EtOAc and the phases are separated. The aqueous phase is re-extracted three times with EtOAc and the combined organic extracts are washed twice with de-ionized water, once with saturated brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue is purified by chromatography (silicagel, CH2Cl2/EtOH 9:1) to afford the title compound as a colorless solid, Rt=0.851 min (Acquity HPLC BEH C18, 2.1×50 mm, 1.7 micron, detection 215 nM, 0.1 min 2% CH3CN in H2O, 2% to 100% CH3CN in H2O in 1.5 min, 0.4 min 100% CH3CN+0.1% TFA, flow rate 1.0 ml/min); MS: 303 (M+1)+.

後処理

  1. additionAfter complete addition
  2. customis removed by evaporation
  3. additionThe residue is diluted with EtOAc
  4. customthe phases are separated
  5. extractionThe aqueous phase is re-extracted three times with EtOAc
  6. washthe combined organic extracts are washed twice with de-ionized water, once with saturated brine
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue is purified by chromatography (silicagel, CH2Cl2/EtOH 9:1)

出典と根拠

ORDレコード
ord-35d49eea4f44401390691136571ed0e3
出典データセット
uspto-grants-2012_06
特許番号
US08193189B2

反応ノート

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