1-Bromo-4-iodobenzene → 1-(4-Bromophenyl)-cis-3,5-dimethylpiperazine

HRID 447317

反応式

HRID 447317 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.C1C=CC2C(C3C(O)=CC=C4C=3C=CC=C4)=C(O)C=CC=2C=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[CH3:39][C@H:40]1[CH2:45][NH:44][CH2:43][C@@H:42]([CH3:46])[NH:41]1>CCOC(C)=O.[Cu]I.CN(C=O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N:44]2[CH2:43][C@H:42]([CH3:46])[NH:41][C@H:40]([CH3:39])[CH2:45]2)=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 115221-Bromo-4-iodobenzeneHCID 11762BinolHCID 62657Potassium Phosphate, TribasicHCID 6950261rel-(2R,6S)-2,6-dimethylpiperazine

生成物 1

HCID 667303611-(4-Bromophenyl)-cis-3,5-dimethylpiperazine収率 60.2%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A microwave vial was charged with 1-bromo-4-iodobenzene (1.0 g, 3.5 mmol), CuI (0.135 g, 0.707 mmol), BINOL (0.202 g, 0.707 mmol), and K3PO4 (1.5 g. 7.1 mmol). The vial was capped and then evacuated and backfilled with Ar. Cis-2,6-dimethylpiperazine (0.605 g, 5.30 mmol) and DMF (4 mL) were then added. The resulting mixture was stirred at rt for 4 d. The mixture was diluted with EtOAc, filtered through a cake of Celite and the filtrate was concentrated to give the crude product. Crude product was purified by flash chromatography using MeOH/CH2Cl2 (2:98 to 15:85) to give the title compound as a red solid (567 mg, 59%). 1H NMR (400 MHz, MeOD) δ 7.33 (d, J=8.8 Hz, 2H), 6.89 (d, J=8.8 Hz, 2H), 3.63-3.60 (m, 2H), 3.18-3.07 (m, 2H), 2.40 (t, J=11.6 Hz, 2H), 1.23 (d, J=6.4 Hz, 6H); MS ESI 269.0 [M+H]+, calcd for [C12H17BrN2+H]+ 269.06.

後処理

  1. customThe vial was capped
  2. customevacuated
  3. filtrationfiltered through a cake of Celite
  4. concentrationthe filtrate was concentrated
  5. customto give the crude product
  6. customCrude product was purified by flash chromatography

出典と根拠

ORDレコード
ord-c652735f6b6d4920a38ce1c2f3fd31a9
出典データセット
uspto-grants-2013_07
特許番号
US08481533B2

関連ノート

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