Sodium hydride → (+/-)-4-[3-(Benzhydrylidene-amino)-4-cyano-benzyl]-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester

HRID 1433008ノート

反応式

HRID 1433008 の反応式
[CH3:1][O:2][C:3]([C@H:5]1[NH:10][C:9](=[O:11])[CH2:8][N:7]([C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13])[CH2:6]1)=[O:4].[C:18](=[N:31][C:32]1[CH:39]=[C:38]([CH2:40]Br)[CH:37]=[CH:36][C:33]=1[C:34]#[N:35])([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.[H-].[Na+]>CN(C=O)C>[CH3:1][O:2][C:3]([CH:5]1[N:10]([CH2:40][C:38]2[CH:37]=[CH:36][C:33]([C:34]#[N:35])=[C:32]([N:31]=[C:18]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[CH:39]=2)[C:9](=[O:11])[CH2:8][N:7]([C:12]([O:14][CH2:15][CH:16]=[CH2:17])=[O:13])[CH2:6]1)=[O:4]

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 179851902-(Benzhydrylideneamino)-4-bromomethylbenzonitrileHCID 53852557(S)-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester

生成物 1

HCID 54080225(+/-)-4-[3-(Benzhydrylidene-amino)-4-cyano-benzyl]-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester収率 39%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

To a solution containing (S)-5-oxo-piperazine-1,3-dicarboxylic acid 1-allyl ester 3-methyl ester (0.43 g, 1.77 mmol), EXAMPLE 56, and 2-(benzhydrylidene-amino)-4-bromomethyl-benzonitrile (0.66 g, 1.77 mmol), EXAMPLE 13, in anhydrous DMF (5 mL) at 0° C. is added 60% NaH (78 mg, 1.95 mmol). After 30 min, the reaction mixture is warmed to ambient temperature and maintained for 6 hours. The reaction mixture is carefully quenched with water and then diluted with water and diethyl ether. The layers are separated and the organic phase is washed twice with water, brine, dried over anhydrous Na2SO4, filtered and concentrated. The crude residue is chromatographed on silica gel (2:1 hexane/ethyl acetate to 1:1 hexane/ethyl acetate) to provide 0.37 g (39%) of the title compound as a glassy solid.

後処理

  1. temperaturemaintained for 6 hours
  2. customThe reaction mixture is carefully quenched with water
  3. additiondiluted with water and diethyl ether
  4. customThe layers are separated
  5. washthe organic phase is washed twice with water, brine
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude residue is chromatographed on silica gel (2:1 hexane/ethyl acetate to 1:1 hexane/ethyl acetate)

出典と根拠

ORDレコード
ord-b0d82d1a45174ff7b1b213040136b578
出典データセット
uspto-grants-2009_11
特許番号
US07612075B2

反応ノート

読み込み中…