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Dimethylformamide → (2-Chloro-7-cyano-naphthalen-1-yl)-acetic acid ethyl ester

HRID 1968711
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HRID 1968711 반응식
[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13](OS(C(F)(F)F)(=O)=O)[CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2].[CH3:26][N:27](C=O)C>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[C-]#N.[Zn+2].[C-]#N>[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([C:26]#[N:27])[CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2]
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참가 물질

5

반응물 2

HCID 6228DimethylformamideHCID 86623472(2-Chloro-7-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester

생성물 1

HCID 66869743(2-Chloro-7-cyano-naphthalen-1-yl)-acetic acid ethyl ester

시약·촉매·용매 2

HCID 11186Zinc cyanide (Zn(CN)2)촉매HCID 11979704Tetrakis(triphenylphosphine)palladium
촉매

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온도
125 °C

실험 절차

(2-Chloro-7-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester (9.30 g, 23.43 mmol) is dissolved in DMF (80 ml) under an atmosphere of argon. Palladium(0) tetrakis(triphenylphosphane) (1.08 g, 0.9375 mmol) and zinc(II) cyanide (5.50 g, 46.87 mmol) are added. The reaction mixture is heated to 125° C. After 1 h, TLC analysis indicates complete consumption of starting material. The suspension is cooled to RT and poured onto water. After stirring for 15 minutes, filtration and concentration affords the crude reaction product. Purification by FCC (hexane/EtOAc 4:1) affords the title compound. 1H NMR (CDCl3, 400 MHz): δ 1.26 (t, J=8.8 Hz, 3H), 4.19 (q, J=8.8 Hz, 2H), 4.28 (s, 2H), 7.62-7.66 (m, 2H), 7.79 (d, J=9.9 Hz, 1H), 7.92 (d, J=9.9 Hz, 1H), 8.32 (s, 1H). ES+-MS: 274.2 [M+H]+.

후처리

  1. customconsumption of starting material
  2. temperatureThe suspension is cooled to RT
  3. additionpoured onto water
  4. filtrationfiltration and concentration
  5. customaffords the crude
  6. customreaction product
  7. customPurification by FCC (hexane/EtOAc 4:1)

출처 및 근거

ORD 기록
ord-333d7a78e3c042cf9d6b4aecca740a65
출처 데이터셋
uspto-grants-2013_04
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08426440B2

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