Dimethylformamide → 2-Formyl-3-(4-methylphenyl)pyrrole

HRID 1183160노트

반응식

HRID 1183160 반응식
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:12]=[CH:11][NH:10][CH:9]=2)=[CH:4][CH:3]=1.O=P(Cl)(Cl)Cl.CN([CH:21]=[O:22])C>C(Cl)Cl>[CH:21]([C:9]1[NH:10][CH:11]=[CH:12][C:8]=1[C:5]1[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][CH:6]=1)=[O:22]

참가 물질

5

반응물 3

HCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 105349353-(4-Methylphenyl)pyrrole

생성물 1

HCID 467385812-Formyl-3-(4-methylphenyl)pyrrole

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

Following a standard procedure (Balasubramanian, T. et al., J. Org. Chem. 2000, 65, 7919-7929), a solution of 7 (472 mg, 3.00 mmol) in DMF (0.96 mL) and CH2Cl2 (30 mL) under argon was cooled to 0° C. and then POCl3 (340 μL, 3.60 mmol) was added dropwise. After 1 h, the flask was warmed to room temperature and stirred overnight (˜18 h). The reaction was quenched at 0° C. with 2.5 M NaOH (25 mL). The mixture was poured into water (50 mL), extracted with CH2Cl2, and the combined organic layers were washed with water, brine, dried (Na2SO4), and concentrated. The residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)] to give a brown solid. 1H NMR spectroscopy showed two regioisomers in ˜13:1 ratio. Cooling of the solution (ethyl acetate/hexanes) at ˜−16° C. resulted in precipitation of an orange solid, which proved to be a single regioisomer (354 mg, 64%): mp 149-150° C.; 1H NMR δ 2.41 (s, 3H), 6.42-6.44 (m, 1H), 7.10-7.13 (m, 1H), 7.26 (d, J=8.0 Hz, 2H), 7.40 (d, J=8.0 Hz, 2H), 9.63-9.64 (m, 1H), 9.52-9.78 (br, 1H); 13C NMR δ 21.4, 111.6, 126.2, 128.9, 129.3, 129.7, 130.9, 137.7, 137.9, 180.2; FAB-MS obsd 186.0907, calcd 186.0919 (C12H11NO).

후처리

  1. customThe reaction was quenched at 0° C. with 2.5 M NaOH (25 mL)
  2. additionThe mixture was poured into water (50 mL)
  3. extractionextracted with CH2Cl2
  4. washthe combined organic layers were washed with water, brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customThe residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)]
  8. customto give a brown solid
  9. customresulted in precipitation of an orange solid, which

출처 및 근거

ORD 기록
ord-178c41883ef54e3eb7282834b09c25fe
출처 데이터셋
uspto-grants-2014_03
특허 번호
US08664260B2

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