Dimethyl oxalate → HCID 69655739、化合物

HRID 2214510ノート

反応式

HRID 2214510 の反応式
[Cl:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][C:13]=1[Cl:14])[CH2:5][N:6]([CH3:10])[C:7](=[O:9])[CH3:8].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:25](OC)(=[O:30])[C:26]([O:28][CH3:29])=[O:27]>O1CCCC1>[CH3:29][O:28][C:26](=[O:27])[C:25]([OH:30])=[CH:8][C:7](=[O:9])[N:6]([CH2:5][C:4]1[CH:11]=[CH:12][C:13]([Cl:14])=[C:2]([Cl:1])[CH:3]=1)[CH3:10]

参加物

5

反応物 3

HCID 11120Dimethyl oxalateHCID 2733832Lithium HexamethyldisilazideHCID 21947496n-(3,4-Dichlorobenzyl)-n-methyl-acetamide

生成物 1

HCID 69655739HCID 69655739、化合物収率 61.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-78 °C

実験手順

A solution of N-(3,4-dichlorobenzyl)-N-methyl-acetamide (0.83 g, 3.57 mmol) in tetrahydrofuran (15 ml) was cooled to −78° C. and treated dropwise with 7.1 ml (7.1 mmol) of 1M lithium bis(trimethylsilyl)amide in tetrahydrofuran. After 20 min, the mixture was treated dropwise with a solution of dimethyl oxalate (0.63 g, 5.35 mmol) in tetrahydrofuran (3 ml), stirred at −78° C. for 1 h and then at 5° C. for another 45 min. The reaction mixture was then quenched by the addition of 1 N hydrochloric acid and ethyl acetate. The organic phase was washed successively with water, saturated sodium bicarbonate and brine and dried over anhydrous sodium sulfate. Evaporation of the solvent under reduced pressure and chromatography of the residue on silica gel (elution toluene-ethyl acetate, 85:15) gave 0.70 g (61% yield) of the title ester as clear oil. 1HNMR 400 MHz (C6D6) δ (ppm); mixture of rotamers: 2.01 and 2.49 (3H, 2 s, NCH3), 3.43 and 3.5 (3H, 2 s, OCH3), 4.0 and 4.4 (2H, 2 s, NCH2), 6.26 and 6.33 (1H, 2 s, CH), 6.62–7.2 (3H, m, aromatics). Anal. calcd for C13H13Cl2NO4: C, 49.08; H, 4.12; N, 4.40. Found: C, 49.38; H, 4.23; N, 4.30.

後処理

  1. waitat 5° C. for another 45 min
  2. customThe reaction mixture was then quenched by the addition of 1 N hydrochloric acid and ethyl acetate
  3. washThe organic phase was washed successively with water, saturated sodium bicarbonate and brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. customEvaporation of the solvent under reduced pressure and chromatography of the residue on silica gel (elution toluene-ethyl acetate, 85:15)

出典と根拠

ORDレコード
ord-4b4bbcb0330c4146ade56dbd7827e38a
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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