Pyridine → (4R,5R)-3-Acetylamino-4,5-dimethyl-(Z)-oct-2-enoic Acid Ethyl Ester

HRID 132668ノート

反応式

HRID 132668 の反応式
[CH2:1]([O:3][C:4](=[O:15])/[CH:5]=[C:6](\[NH2:14])/[C@H:7]([CH3:13])[C@H:8]([CH3:12])[CH2:9][CH2:10][CH3:11])[CH3:2].[C:16](Cl)(=[O:18])[CH3:17].N1C=CC=CC=1>C(Cl)Cl>[CH2:1]([O:3][C:4](=[O:15])/[CH:5]=[C:6](\[NH:14][C:16](=[O:18])[CH3:17])/[C@H:7]([CH3:13])[C@H:8]([CH3:12])[CH2:9][CH2:10][CH3:11])[CH3:2]

参加物

5

反応物 3

HCID 1049PyridineHCID 6367Acetyl chlorideHCID 86597974(4R,5R)-3-Amino-4,5-dimethyl-(Z)-oct-2-enoic Acid Ethyl Ester

生成物 1

HCID 25232468(4R,5R)-3-Acetylamino-4,5-dimethyl-(Z)-oct-2-enoic Acid Ethyl Ester収率 93.1%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
-20 °C

実験手順

To a 1 L 3-necked round bottom flask equipped with an overhead stirrer, thermocouple, addition funnel, and nitrogen inlet, was charged 150 g (0.70 mol) of (4R,5R)-3-amino-4,5-dimethyl-(Z)-oct-2-enoic acid ethyl ester and 50 mL of dry CH2Cl2. The reaction mixture was cooled to −20° C. To the mixture was added, successively, acetyl chloride (60 mL, 0.84 mol) and pyridine (66.8 g, 0.84 mol) over 0.5-hour time intervals. After the additions, the mixture was stirred at −20° C. to 0° C. for 2 hours and then filtered to remove the pyridine.HCl salt. The filtrate was diluted with 200 mL of CH2Cl2 and washed 2× with aliquots of aq NH4Cl. The organic solution was treated with silica gel (50 g), MgSO4 (20 g) and charcoal (20 g), and stirred at room temperature for 0.5 hours. The solids were filtered off and the filtrate was concentrated under reduced pressure to give 166.5 g (93% yield) of the titled compound as an oil: 1H NMR (400 MHz, CHLOROFORM-D) 0.85 (t, J=7.4 Hz, 3H), 0.95 (d, J=6.8 Hz, 3H), 1.00 (d, J=7.0 Hz, 3H), 1.11 (m, 1H) 1.29 (t, J=5.8 Hz, 3H), 1.40-1.25 (m, 2H), 1.65 (m, 1H) 2.13 (s, 3H), 3.80 (m, 1H) 4.2-4.14 (m, 3H), 5.01 (s, 1H), 11.28 (s, 1H).

後処理

  1. customTo a 1 L 3-necked round bottom flask equipped with an overhead stirrer
  2. additionthermocouple, addition funnel, and nitrogen inlet
  3. additionTo the mixture was added
  4. filtrationfiltered
  5. customto remove the pyridine
  6. additionThe filtrate was diluted with 200 mL of CH2Cl2
  7. washwashed 2× with aliquots of aq NH4Cl
  8. additionThe organic solution was treated with silica gel (50 g), MgSO4 (20 g) and charcoal (20 g)
  9. stirringstirred at room temperature for 0.5 hours
  10. filtrationThe solids were filtered off
  11. concentrationthe filtrate was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-64d14dd1af1d4f3191ec19ab7a303163
出典データセット
uspto-grants-2008_06
特許番号
US07388023B2

反応ノート

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