Dimethyl oxalate → HCID 69655528、化合物

HRID 2214643ノート

反応式

HRID 2214643 の反応式
[F:1][C:2]1[CH:20]=[CH:19][C:5]([CH2:6][N:7]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)[C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.[CH3:21][O:22][C:23](=[O:28])[C:24](OC)=[O:25].[Li+].C[Si]([N-][Si](C)(C)C)(C)C>C1COCC1>[CH3:21][O:22][C:23](=[O:28])[C:24]([OH:25])=[CH:9][C:8](=[O:10])[N:7]([CH2:11][C:12]1[CH:13]=[CH:14][C:15]([F:18])=[CH:16][CH:17]=1)[CH2:6][C:5]1[CH:4]=[CH:3][C:2]([F:1])=[CH:20][CH:19]=1

参加物

5

反応物 3

HCID 11120Dimethyl oxalateHCID 2733832Lithium HexamethyldisilazideHCID 21947396HCID 21947396、化合物

生成物 1

HCID 69655528HCID 69655528、化合物収率 53%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

N,N-Bis-(4-fluoro-benzyl)-acetamide (15.0 grams, 54.5 mmol) and dimethyloxalate (9.6 grams, 81.3 mmol) were dissolved in 54 mL of THF. After cooling to 0° C. 108 mL of 1N LiHMDS (THF) was added dropwise. The reaction mixture was stirred 1 hr then quenched with 1N HCl. The resulting mixture was extracted with CH2Cl2, dried over Na2SO4, filtered and the solvent removed under vacuum. The product was purified by flash column chromatography (SiO2, 80:20 hexanes/EtOAc) to yield 10 grams (53% yield) of 3-[bis-(4-fluoro-benzyl)-carbamoyl]-2-hydroxy-acrylic acid methyl ester as a solid. Mp=118–120° C. Anal. calcd for C19H17F2NO4: C, 63.15; H, 4.74; N, 3.87. found: C, 62.97; H, 4.72; N, 3.81. 1H NMR (500 MHz, CDCl3) δ: 3.87 (s, 3), 4.46 (s, 2), 4.58 (s, 2), 6.32 (s, 1), 7.00–7.26 (overlapping m, 8). 13C NMR (125 MHz, CDCl3) δ: 47.34, 49.35, 53.03, 93.34, 115.66, 115.83, 116.00, 116.18, 128.45, 128.52, 130.03, 130.10, 131.09, 131.93, 131.95, 160.29, 161.44, 161.51, 163.10, 163.41, 163.47, 171.36.

後処理

  1. customthen quenched with 1N HCl
  2. extractionThe resulting mixture was extracted with CH2Cl2
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. customthe solvent removed under vacuum
  6. customThe product was purified by flash column chromatography (SiO2, 80:20 hexanes/EtOAc)

出典と根拠

ORDレコード
ord-35d684e30ce548869cdcb96c9bef2c9e
出典データセット
uspto-grants-2006_09
特許番号
US07109186B2

反応ノート

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