2-Bromopyridine → HCID 67608577, 화합물

HRID 1779134노트

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HRID 1779134 반응식
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:8][O:9][C:10]1[C:15](B(O)O)=[CH:14][CH:13]=[C:12]([O:19][CH3:20])[N:11]=1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:8][O:9][C:10]1[C:15]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][N:3]=2)=[CH:14][CH:13]=[C:12]([O:19][CH3:20])[N:11]=1

참가 물질

6

반응물 3

HCID 79732-BromopyridineHCID 11430Potassium CarbonateHCID 2762707(2,6-Dimethoxypyridin-3-yl)boronic acid

생성물 1

HCID 67608577HCID 67608577, 화합물

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 8028Tetrahydrofuran용매

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온도
90 °C

실험 절차

2-Bromopyridine (0.475 mL, 0.78 g, 4.9 mmol) and 2,6-dimethoxy-3-pyridineboronic acid (1.09 g, 6.0 mmol, excess) were dissolved in THF (25 mL) at RT. Aqueous solution of K2CO3 (1.65 g in 10 mL of water, 12 mmol, excess) was added, followed by Pd(PPh3)4 (295 mg, 0.25 mmol). The mixture was stirred at 90° C. for 20 h under argon to give yellow solution. Organic solvent was removed under reduced pressure and the residue was extracted with dichloromethane and water. Evaporation of organic phase provided red oil that was purified by chromatography on silica gel eluting with CH2Cl2/MeOH 0 to 0.2%. The fractions containing pure product were collected, while those containing impurities were again purified by chromatography using the same conditions. After three chromatographic purifications the total yield was 965 mg (4.39 mmol; 90%) of yellow oil that crystallized as yellow solid on standing. Anal. Calcd for C12H12N2O2.0.2H2O (MW 219.84): C, 65.56; H, 5.69; N, 12.74. Found: C, 65.74; H, 5.63; N, 12.53. 1H NMR (400 MHz, CD2Cl2): 8.64 (d, J 4.0, 1H), 8.32 (d, J 8.0, 1H), 8.03 (d, J 8.0, 1H), 7.74 (t, J 8.0, 1H), 7.19 (m, 1H), 6.47 (d, J 8.0, 1H), 4.06 (s, 3H), 4.00 (s, 3H). 13C NMR (100 MHz, CD2Cl2): 163.24, 160.16, 154.36, 149.44, 142.44, 136.01, 123.97, 121.38, 114.30, 102.02, 53.75, 53.52.

후처리

  1. customto give yellow solution
  2. customOrganic solvent was removed under reduced pressure
  3. extractionthe residue was extracted with dichloromethane and water
  4. customEvaporation of organic phase
  5. customprovided red oil that
  6. customwas purified by chromatography on silica gel eluting with CH2Cl2/MeOH 0 to 0.2%
  7. additionThe fractions containing pure product
  8. customwere collected, while those containing impurities
  9. customwere again purified by chromatography
  10. customAfter three chromatographic purifications the total yield was 965 mg (4.39 mmol; 90%) of yellow oil that crystallized as yellow solid

출처 및 근거

ORD 기록
ord-589a05158f3f46f9a14d40c381ae79a6
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09269912B2

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