Acetic Acid → {Benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl ester

HRID 2381922ノート

反応式

HRID 2381922 の反応式
[CH2:1]([O:3][C:4](=[O:31])[CH2:5][N:6]([C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22])[CH2:7]/[CH:8]=[N:9]/[N:10]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]1=[O:20])[CH3:2].C([BH3-])#N.[Na+].C(O)(=O)C>CC#N.CCOC(C)=O>[CH2:1]([O:3][C:4](=[O:31])[CH2:5][N:6]([C:21]([O:23][CH2:24][C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)=[O:22])[CH2:7][CH2:8][NH:9][N:10]1[C:18](=[O:19])[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]1=[O:20])[CH3:2]

参加物

6

反応物 3

HCID 176Acetic AcidHCID 5003444Sodium cyanoborohydrideHCID 87496342ethyl 2-[[(2E)-2-(1,3-dioxoisoindol-2-yl)iminoethyl]-phenylmethoxycarbonylamino]acetate

生成物 1

HCID 68557343{Benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl ester収率 81.2%

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of (benzyloxycarbonyl-{2-[(E)-1,3-dioxo-1,3-dihydro-isoindol-2-ylimino]ethyl}-amino)-acetic acid ethyl ester (7.7 mmol) in CH3CN (65 mL) is treated with sodium cyanoborohydride (1.92 g, 30.5 mmol), and acetic acid (6.8 mL, 118.8 mmol) is added with stirring under N2. After 5.5 h, the reaction solution is diluted with EtOAc (150 mL) and washed with saturated aqueous KHCO3 (3×50 mL) and saturated aqueous NaCl (50 mL). The organic phase is dried (MgSO4), filtered, and concentrated in vacuo. The residue is purified by silica gel chromatography (75:25 to 50:50 heptane:ethyl acetate gradient elution) to afford {benzyloxycarbonyl-[2-(1,3-dioxo-1,3-dihydro-isoindol-2-ylamino)-ethyl]-amino}-acetic acid ethyl ester as an oil (2.66 g, 81%). MS: 426 (M+H); 1H NMR (300 MHz, CDCl3) δ 7.79-7.91 (m, 2H), 7.69-7.79 (m, 2H), 7.17-7.39 (m, 5H), 5.04-5.21 (m, 2H), 4.87-5.04 (m, 1H), 4.04-4.23 (m, 4H), 3.48-3.59 (m, 2H), 3.18-3.38 (m, 2H), 1.10-1.30 (m, 3H).

後処理

  1. additionis added
  2. washwashed with saturated aqueous KHCO3 (3×50 mL) and saturated aqueous NaCl (50 mL)
  3. dry with materialThe organic phase is dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue is purified by silica gel chromatography (75:25 to 50:50 heptane:ethyl acetate gradient elution)

出典と根拠

ORDレコード
ord-110ae9cb1f6243f985e93cca7577e535
出典データセット
uspto-grants-2012_09
特許番号
US08258130B2

反応ノート

読み込み中…