Acetic Acid → (2R, 3S)-3-Benzyloxy-2-[(4-ethyl-2,3-dioxopiperazin-1-yl)carbonylamino]butyric acid

HRID 64761ノート

反応式

HRID 64761 の反応式
[CH2:1]([O:8][C@@H:9]([CH3:15])[C@H:10]([C:12]([OH:14])=[O:13])[NH2:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:16]([N:18]1[CH2:23][CH2:22][N:21]([C:24](Cl)=[O:25])[C:20](=[O:27])[C:19]1=[O:28])[CH3:17].CO.C(O)(=O)C>O.CC(C)=O.C(Cl)(Cl)Cl>[CH2:1]([O:8][C@@H:9]([CH3:15])[C@@H:10]([NH:11][C:24]([N:21]1[CH2:22][CH2:23][N:18]([CH2:16][CH3:17])[C:19](=[O:28])[C:20]1=[O:27])=[O:25])[C:12]([OH:14])=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 176Acetic AcidHCID 887MethanolHCID 1088134-Ethyl-2,3-dioxopiperazinecarbonyl chlorideHCID 22869571O-Benzyl-D-threonine

生成物 1

HCID 56624685(2R, 3S)-3-Benzyloxy-2-[(4-ethyl-2,3-dioxopiperazin-1-yl)carbonylamino]butyric acid

試薬・触媒・溶媒 3

HCID 180Acetone溶媒HCID 962Water溶媒HCID 6212Chloroform溶媒

反応条件

温度
0 °C

実験手順

O-Benzyl-D-threonine (0.92 g, 4.4 mmole) (prepared by the method of T. Mizoguchi, G. Levin, D. W. Woolley, and J. M. Stewart, J. Org. Chem., 1968, 33, 903, who described the L-isomer) was suspended in water (20 ml) and the pH adjusted to 9.5 , giving a virtually complete solution. This was cooled to 0° C. and stirred while 4-ethyl-2,3-dioxopiperazine-1-carbonyl chloride (1.00 g, 4.9 m mole) in AR acetone (10 ml) was added dropwise. The pH was kept at 9.5 by the addition of further base while the solution was allowed to regain room temperature. After 2 h the solution was acidified to pH 2 and the bulk of the acetone removed by evaporation. The oily product was extracted into ethyl acetate (3×50 ml), then the total organic phase was washed once with brine and dried over sodium sulphate. Evaporation gave the title acid (1.36 g, 82%) as a colourless non-crystalline foam which retained solvent traces tenaciously; Rf 0.35 in chloroform:methanol:acetic acid, 17:2:1; δ(CDCl3) 0.75-1.35 (5H, m, CH3CH and NCH2CH3), 3.1-3.7 (4H, m, 2 NCH2), 3.9-4.25 (2H, m, NCH2), 4.50 (2H, m, CH--CH), 6.25 (1H, brs, D2O exch, OH), 7.25 (5H, s, aryl), 9.50 (1H, brd), J 7 Hz, D2O exch, NH), 9.70 (1H, brs, D2O exch, CO2H).

後処理

  1. customgiving a virtually complete solution
  2. additionwas added dropwise
  3. additionThe pH was kept at 9.5 by the addition of further base while the solution
  4. customto regain room temperature
  5. customthe bulk of the acetone removed by evaporation
  6. extractionThe oily product was extracted into ethyl acetate (3×50 ml)
  7. washthe total organic phase was washed once with brine
  8. dry with materialdried over sodium sulphate
  9. customEvaporation
  10. customgave the title acid (1.36 g, 82%) as a colourless non-crystalline foam which

出典と根拠

ORDレコード
ord-f93372bc37bc4fb7b57e864a1433b923
出典データセット
uspto-grants-1986_09
特許番号
US04609652

反応ノート

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