Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester → 4-(6-Chloro-2-oxo-2H-1-benzopyran-4-yl)-butyronitrile

HRID 495150노트

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HRID 495150 반응식
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9](=[O:11])[CH:8]=[C:7](OS(C3C=CC(C)=CC=3)(=O)=O)[C:6]=2[CH:23]=1.[Br-].[C:25]([CH2:27][CH2:28][CH2:29][Zn+])#[N:26]>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9](=[O:11])[CH:8]=[C:7]([CH2:29][CH2:28][CH2:27][C:25]#[N:26])[C:6]=2[CH:23]=1

참가 물질

4

반응물 2

HCID 46179801Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl esterHCID 178511034HCID 178511034, 화합물

생성물 1

HCID 118174844-(6-Chloro-2-oxo-2H-1-benzopyran-4-yl)-butyronitrile수율 73%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
60 °C

실험 절차

Toluene-4-sulfonic acid 6-chloro-2-oxo-2H-1-benzopyran-4-yl ester (1.05 g, 3 mmol) is dissolved in THF (30 mL) under nitrogen and [P(o-tolyl)3]2PdCl2 (120 mg, 0.15 mmol) is added 3-cyanopropylzinc bromide (9 mL of a 0.5 M solution in THF, 4.5 mmol) is added and the resulting yellow solution is stirred at 60° C. for 2 hrs. Silica gel is added to the dark red reaction mixture, which is concentrated in vacuo and purified by flash column chromatography eluting with CH2Cl2 and gradually increasing polarity to 1% MeOH—CH2Cl2 to give a residue which is triturated with Et2O to give the title compound (0.54 g, 73%) as a cream solid. 1H NMR (DMSO-d6, 400 MHz) d 7.92 (1H, d, J=2 Hz), 7.68 (1H, dd, J=9, 2 Hz), 7.46 (1H, d, J=9 Hz), 6.47 (1H, s), 2.90 (2H, t, J=7 Hz), 2.63 (2H, t, J=7 Hz), 1.94 (2H, q, J=7 Hz). LCMS (MeCN—H2O, MeCN—H2O, Luna 3 m C18(2) 30×4.6mm; (ESI Pos.) calcd for C13H10ClNO2 m/z [M+H]=248; found [no mass ion detected].

후처리

  1. additionis added
  2. additionSilica gel is added to the dark red reaction mixture, which
  3. concentrationis concentrated in vacuo
  4. custompurified by flash column chromatography
  5. washeluting with CH2Cl2
  6. temperaturegradually increasing polarity to 1% MeOH—CH2Cl2
  7. customto give a residue which
  8. customis triturated with Et2O

출처 및 근거

ORD 기록
ord-a75ea56a91f6433281c39ce7cacd9627
출처 데이터셋
uspto-grants-2009_05
특허 번호
US07538233B2

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