Reaktion #45419

Reaktionsgleichung

mixture

7-iodo-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-4-amine

tert-butyl acrylate

PPh3

Na2CO3

→

desired product

Ausbeute 76.0%

tert-butyl (2E)-3-[4-amino-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-7-yl]acrylate

Ausbeute 76.0%

Lösungsmittel

DMF

Reaktionsbedingungen

Aufarbeitung

1. 1
   EinengenThe mixture was concentrated to half its original volume
2. 2
   workup.ADDITIONpoured into 10% NaCl (300 mL)
3. 3
   ExtraktionThe product was extracted with ethyl acetate (3×70 mL)
4. 4
   WaschenThe combined organic extracts were washed with brine
5. 5
   Trocknendried (MgSO4)
6. 6
   Filtrationfiltered
7. 7
   Einengenconcentrated
8. 8
   workup.DISSOLUTIONThe residue was dissolved in dichloromethane (300 mL)
9. 9
   workup.ADDITIONtreated with silica gel (25 g)
10. 10
    Einengenconcentrated
11. 11
    Sonstigechromatographed with ethyl acetate/heptane (1:6)

Vorschrift

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.

Quelle