Sodium Carbonate → Tert-butyl (2e)-3-[4-amino-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-7-yl]acrylate

HRID 17141

반응식

HRID 17141 반응식
I[C:2]1[C:3]2[S:11][CH:10]=[C:9]([C:12]3[CH:17]=[CH:16][C:15]([O:18][C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)=[CH:14][CH:13]=3)[C:4]=2[C:5]([NH2:8])=[N:6][CH:7]=1.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Na+].[Na+]>CC([O-])=O.CC([O-])=O.[Pd+2].CN(C=O)C>[NH2:8][C:5]1[C:4]2[C:9]([C:12]3[CH:17]=[CH:16][C:15]([O:18][C:19]4[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=4)=[CH:14][CH:13]=3)=[CH:10][S:11][C:3]=2[C:2](/[CH:27]=[CH:26]/[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])=[CH:7][N:6]=1

참가 물질

7

반응물 4

HCID 10340Sodium CarbonateHCID 11776TriphenylphosphineHCID 15458tert-Butyl acrylateHCID 184508787-Iodo-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-4-amine

생성물 1

HCID 69776505Tert-butyl (2e)-3-[4-amino-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-7-yl]acrylate수율 76%

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매

실험 절차

A mixture of Example 221A (2 g, 4.5 mmol), tert-butyl acrylate (1.3 mL, 8.8 mmol), Pd(OAc)2 (100 mg, 0.44 mmol), PPh3 (236 mg, 0.89 mmol), Na2CO3 (0.95 g, 8.9 mmol), and DMF (40 mL) was stirred for 18 hours at 80° C. under a nitrogen atmosphere. The mixture was concentrated to half its original volume and poured into 10% NaCl (300 mL). The product was extracted with ethyl acetate (3×70 mL). The combined organic extracts were washed with brine, dried (MgSO4), filtered, and concentrated. The residue was dissolved in dichloromethane (300 mL), treated with silica gel (25 g), and concentrated. The preabsorbed silica gel was subsequently transferred to a silica gel (200 g) column and chromatographed with ethyl acetate/heptane (1:6) to provide 1.52 g (76%) of the desired product. 1H NMR (CD2Cl2, 400 MHz) δ 8.13 (s, 1H), 7.78 (d, 1H), 7.49-7.43 (m, 4H), 7.32 (s, 1H), 7.22 (t, 1H), 7.15 (d, 4H), 6.46 (d, 1H), 5.18 (br s, 2H), 1.59 (s, 9H); 13C NMR (CD2Cl2, 100 MHz) δ 166.8, 158.5, 156.8, 155.5, 147.1, 146.9, 139.8, 137.5, 131.3, 130.7, 130.4, 124.4, 123.8, 119.9, 119.7, 118.8, 118.7, 117.2, 80.6, 28.4.

후처리

  1. concentrationThe mixture was concentrated to half its original volume
  2. additionpoured into 10% NaCl (300 mL)
  3. extractionThe product was extracted with ethyl acetate (3×70 mL)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in dichloromethane (300 mL)
  9. additiontreated with silica gel (25 g)
  10. concentrationconcentrated
  11. customchromatographed with ethyl acetate/heptane (1:6)

출처 및 근거

ORD 기록
ord-1138159e966a47fabbe6778a9f2cb60a
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07737160B2

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