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

HRID 468294노트

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HRID 468294 반응식
[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

참가 물질

6

반응물 2

HCID 65578Oxalyl chlorideHCID 59129343HCID 59129343, 화합물

생성물 2

HCID 591291561-(4-Oxochroman-6-yl)cyclopropanecarboxylic acid수율 19%HCID 59129225Methyl 1-(4-oxochroman-6-yl)cyclopropanecarboxylate수율 38%

시약·촉매·용매 2

HCID 6228Dimethylformamide촉매HCID 6344Dichloromethane용매

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온도
2.5 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-a45236ef315647999681b570f097b684
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623905B2

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