Nitrogen → {4-[2-(3,4,5-Trihydroxy-phenyl)-acetyl]piperazin-1-yl}-acetic acid ethyl ester

HRID 383599

反応式

HRID 383599 の反応式
N#N.[CH2:3]([O:5][C:6](=[O:29])[CH2:7][N:8]1[CH2:13][CH2:12][N:11]([C:14](=[O:28])[CH2:15][C:16]2[CH:21]=[C:20]([O:22]C)[C:19]([O:24]C)=[C:18]([O:26]C)[CH:17]=2)[CH2:10][CH2:9]1)[CH3:4].B(Br)(Br)Br.O>C(Cl)Cl>[CH2:3]([O:5][C:6](=[O:29])[CH2:7][N:8]1[CH2:13][CH2:12][N:11]([C:14](=[O:28])[CH2:15][C:16]2[CH:21]=[C:20]([OH:22])[C:19]([OH:24])=[C:18]([OH:26])[CH:17]=2)[CH2:10][CH2:9]1)[CH3:4]

参加物

6

反応物 4

HCID 947NitrogenHCID 962WaterHCID 25134Boron tribromideHCID 59785709{4-[2-(3,4,5-Trimethoxy-phenyl)-acetyl]-piperazin-1-yl}-acetic acid ethyl ester

生成物 1

HCID 59819847{4-[2-(3,4,5-Trihydroxy-phenyl)-acetyl]piperazin-1-yl}-acetic acid ethyl ester収率 40%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-78 °C

実験手順

(The following reaction is done in an anhydrous N2 atmosphere.) Dissolve {4-[2-(3,4,5-Trimethoxy-phenyl)-acetyl]-piperazin-1-yl}-acetic acid ethyl ester (64) (99 mg, 0.26 mmol) in anhydrous DCM (6.0 mL), cool the solution to −78° C. and add dropwise a 1 M BBr3 solution in DCM (2.30 mL, 2.30=101). Stir the reaction mixture for 30 min at −78° C. and after slowly warming up for additional 4 h at −20° C. Add dropwise water and extract the mixture with EtOAc (3 times). Wash the combined organic layer with brine and dry it dry with Na2SO4. Purify the crude product by preparative RP HPLC (gradient, water/CH3CN 95:5 to 5:95) to obtain {4-[2-(3,4,5-Trihydroxy-phenyl)-acetyl]-piperazin-1-yl}-acetic acid ethyl ester (65) (34 mg, 40%) as a sticky brownish solid. 1H NMR (400 MHz, CD3OD): 1.35 (t, 3H, J=7.1 Hz); 3.14-3.24 (br.m, 2H); ca. 3.32 (br.m, 2H); 3.65 (s, 2H); 3.78-4.00 (br.m, 4H); 4.12 (s, 2H); 4.34 (q, 2H, J=7.1 Hz); 6.29 (s, 2H).

後処理

  1. custom(The following reaction
  2. temperatureafter slowly warming up for additional 4 h at −20° C
  3. extractionextract the mixture with EtOAc (3 times)
  4. washWash the combined organic layer with brine
  5. customdry it
  6. dry with materialdry with Na2SO4
  7. customPurify the crude product by preparative RP HPLC (gradient, water/CH3CN 95:5 to 5:95)

出典と根拠

ORDレコード
ord-fc780e3d8f7e47399ef5f69de47faf8f
出典データセット
uspto-grants-2013_02
特許番号
US08367677B2

関連ノート

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