Oxalyl chloride → Methyl 1-(4-oxochroman-6-yl)cyclopropanecarboxylate

HRID 468294ノート

反応式

HRID 468294 の反応式
[CH3:1][O:2][C:3]([C:5]1([C:8]2[CH:13]=[CH:12][C:11]([O:14][CH2:15][CH2:16][C:17]([OH:19])=O)=[CH:10][CH:9]=2)[CH2:7][CH2:6]1)=[O:4].C(Cl)(=O)C(Cl)=O>C(Cl)Cl.CN(C=O)C>[O:19]=[C:17]1[C:10]2[C:11](=[CH:12][CH:13]=[C:8]([C:5]3([C:3]([OH:2])=[O:4])[CH2:6][CH2:7]3)[CH:9]=2)[O:14][CH2:15][CH2:16]1.[O:19]=[C:17]1[C:10]2[C:11](=[CH:12][CH:13]=[C:8]([C:5]3([C:3]([O:2][CH3:1])=[O:4])[CH2:6][CH2:7]3)[CH:9]=2)[O:14][CH2:15][CH2:16]1

参加物

6

反応物 2

HCID 65578Oxalyl chlorideHCID 59129343HCID 59129343、化合物

生成物 2

HCID 591291561-(4-Oxochroman-6-yl)cyclopropanecarboxylic acid収率 19%HCID 59129225Methyl 1-(4-oxochroman-6-yl)cyclopropanecarboxylate収率 38%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 6344Dichloromethane溶媒

反応条件

温度
2.5 °C

実験手順

To a solution of 1-[4-(2-carboxy-ethoxy)-phenyl]-cyclopropanecarboxylic methyl ester (5.0 g, 20 mmol) in CH2Cl2 (50 mL) were added oxalyl chloride (4.8 g, 38 mmol) and two drops of DMF at 0° C. The mixture was stirred at 0-5° C. for 1 h and then evaporated under vacuum. To the resulting mixture was added CH2Cl2 (50 mL) at 0° C. and stirring was continued at 0-5° C. for 1 h. The reaction was slowly quenched with water and was extracted with EtOAc (50 mL×3). The combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum to give the crude product, which was purified by column chromatography on silica gel (petroleum ether/ethyl acetate 20:1-2:1) to give 1-(4-oxochroman-6-yl)cyclopropanecarboxylic acid (830 mg, 19%) and methyl 1-(4-oxochroman-6-yl)cyclopropanecarboxylate (1.8 g, 38%). 1-(4-oxochroman-6-yl)cyclopropane-carboxylic acid: 1H NMR (400 MHz, DMSO) δ 12.33 (br s, 1H), 7.62 (d, J=2.0 Hz, 1H), 7.50 (dd, J=2.4, 8.4 Hz, 1H), 6.95 (d, J=8.4 Hz, 1H), 4.50 (t, J=6.4 Hz, 2H), 2.75 (t, J=6.4 Hz, 2H), 1.44-1.38 (m, 2H), 1.10-1.07 (m, 2H). MS (ESI) m/z (M+H+) 231.4. 1-(4-oxochroman-6-yl)cyclopropanecarboxylate: 1H NMR (400 MHz, CDCl3) δ 7.83 (d, J=2.4 Hz, 1H), 7.48 (dd, J=2.4, 8.4 Hz, 1H), 6.93 (d, J=8.4 Hz, 1H), 4.55-4.52 (m, 2H), 3.62 (s, 3H), 2.80 (t, J=6.4 Hz, 2H), 1.62-1.56 (m, 2H), 1.18-1.15 (m, 2H).

後処理

  1. customevaporated under vacuum
  2. additionTo the resulting mixture was added CH2Cl2 (50 mL) at 0° C.
  3. stirringstirring
  4. waitwas continued at 0-5° C. for 1 h
  5. customThe reaction was slowly quenched with water
  6. extractionwas extracted with EtOAc (50 mL×3)
  7. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  8. customevaporated under vacuum
  9. customto give the crude product, which
  10. customwas purified by column chromatography on silica gel (petroleum ether/ethyl acetate 20:1-2:1)

出典と根拠

ORDレコード
ord-a45236ef315647999681b570f097b684
出典データセット
uspto-grants-2014_01
特許番号
US08623905B2

反応ノート

読み込み中…