beta-Bromostyrene → (S)-1,4-Dibenzyl-2-(4-phenyl-but-3-enyl)-piperazine

HRID 1350391

反応式

HRID 1350391 の反応式
[CH:1]12B[CH:5]([CH2:6][CH2:7][CH2:8]1)[CH2:4][CH2:3][CH2:2]2.[CH2:10]([N:17]1[CH2:22][CH2:21][N:20]([CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:19][C@@H:18]1[CH:30]=[CH2:31])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.BrC=CC1C=CC=CC=1.[OH-].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:10]([N:17]1[CH2:22][CH2:21][N:20]([CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:19][C@@H:18]1[CH2:30][CH2:31][CH:1]=[CH:8][C:7]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

参加物

7

反応物 5

HCID 7667beta-BromostyreneHCID 11776TriphenylphosphineHCID 14798Sodium HydroxideHCID 789669-Borabicyclo(3.3.1)nonaneHCID 17759473(S)-1,4-dibenzyl-2-vinylpiperazine

生成物 1

HCID 69487542(S)-1,4-Dibenzyl-2-(4-phenyl-but-3-enyl)-piperazine収率 56%

試薬・触媒・溶媒 1

HCID 178418397HCID 178418397、化合物触媒

実験手順

Combine 9-borabicyclo[3.3.1]nonane (81.6 mL, 40.3 mmol, 0.5 M in THF) and (S)-1,4-dibenzyl-2-vinyl-piperazine (2.0 g, 6.8 mmol)and stir at ambient temperature. After 16 hours, take half volume of it, add triphenylphosphine (143 mg, 0.55 mmol), tetrakis(triphenylphosphine)palladium(0) (78.5 mg, 0.068 mmol), and beta-bromostyrene (0.93 g, 5.08 mmol). Add 3N NaOH (2.8 mL, 8.8 mmol) slowly, gas evolution will occur. Heat to reflux. After 24 hours, cool to ambient temperature. Remove the solvent under reduced pressure, dilute with diethyl ether, wash with 1N HCl, 1N NaOH, H2O and brine, dry the organic layer over Na2SO4, filter and concentrate under reduced pressure. Purification by flash chromatography on silica gel using 2N ammonia in methanol-methylene chloride (0.5%–3%) as the eluent, collect compound and pass through 10 g SCX column, using MeOH, 0.2 N NH3 in MeOH as eluent to give the title compound (750 mg, 56%): mass spectrum (electrospray): m/z=397.3 (M+1); 1H NMR (300 MHz, CDCl3): δ7.35–7.16 (m, 15H), 6.36–6.12 (m, 2H), 4.01 (d, 1H, J=13.2), 3.56–3.43 (m, 2H), 3.25 (d, 1H, J=13.4 Hz), 2.75–2.68 (m, 2H), 2.56–2.48 (m, 2H), 2.29–2.13 (m, 5H), 1.82–1.76 (m, 2H).

後処理

  1. temperatureHeat to reflux
  2. waitAfter 24 hours
  3. customRemove the solvent under reduced pressure
  4. additiondilute with diethyl ether
  5. washwash with 1N HCl, 1N NaOH, H2O and brine
  6. dry with materialdry the organic layer over Na2SO4
  7. filtrationfilter
  8. concentrationconcentrate under reduced pressure
  9. customPurification by flash chromatography on silica gel using 2N ammonia in methanol-methylene chloride (0.5%–3%) as the eluent
  10. customcollect compound

出典と根拠

ORDレコード
ord-915ff01d467d4dcd90feda8425405fd4
出典データセット
uspto-grants-2007_05
特許番号
US07214673B2

関連ノート

読み込み中…