5-Bromo-2,4-dimethoxybenzaldehyde → 2,4-Dimethoxy-5-thien-2-ylbenzaldehyde

HRID 10623

反応式

HRID 10623 の反応式
Br[C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].[S:14]1[CH:18]=[CH:17][CH:16]=[C:15]1B(O)O>C1COCC1>[CH3:11][O:10][C:5]1[CH:4]=[C:3]([O:12][CH3:13])[C:2]([C:15]2[S:14][CH:18]=[CH:17][CH:16]=2)=[CH:9][C:6]=1[CH:7]=[O:8]

参加物

4

反応物 2

HCID 6683465-Bromo-2,4-dimethoxybenzaldehydeHCID 27339602-Thiopheneboronic acid

生成物 1

HCID 161161832,4-Dimethoxy-5-thien-2-ylbenzaldehyde収率 94%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
60 °C

実験手順

Ex-6A: 5-bromo-2,4-dimethoxybenzaldehyde (20.3 g), thiophene-2-boronic acid (11.6 g) and THF (200 mL) were sequentially charged into a clean reaction vessel fitted with a reflux condenser, mechanical stirrer and nitrogen inlet adapter. Nitrogen was bubbled into the resulting solution for 20 min followed by the sequential addition of KF (10.1 g), and Pd(tBu3P)2 (0.424 g). The solution was immediately heated to 60° C. and aged for 1.5 h. The reaction was diluted with H2O (200 mL) and transferred to a separatory funnel containing EtOAc (200 mL) and H2O (200 mL). The layers were cut and the aqueous layer was extracted with EtOAc (100 mL). The combined organic cuts were filtered through a pre-washed pad of solka floc (5 g). The pad of solka floc and spent catalyst were washed with fresh EtOAc (200 mL) and this wash combined with the batch. The resultant filtrate was concentrated to dryness. The crude product was dissolved in THF (38 mL) and crystallized upon heptane (152 mL) addition. The product was filtered and then dried to a constant weight in the vacuum oven (38° C., 20 inHg) affording 19.32 g (94% yield) of desired 2,4-dimethoxy-5-thiophen-2-yl-benzaldehyde as a light off-white solid, m.p. 125–126° C. 1H-NMR (300 MHz, CDCl3): 10.34 (s, 1H), 8.12 (s, 1H), 7.44 (dd, 1H, J=3.5 and 1.5 Hz), 7.31 (dd, 1H, J=5.2 and 1.5 Hz), 7.07 (dd, 1H, J=5.2 and 3.5 Hz), 6.51 (s, 1H), 4.02 (s, 3H), 3.99 (s, 3H).

後処理

  1. customfitted with a reflux condenser, mechanical stirrer and nitrogen inlet adapter
  2. customNitrogen was bubbled into the resulting solution for 20 min
  3. additionfollowed by the sequential addition of KF (10.1 g), and Pd(tBu3P)2 (0.424 g)
  4. additionThe reaction was diluted with H2O (200 mL)
  5. customtransferred to a separatory funnel
  6. additioncontaining EtOAc (200 mL) and H2O (200 mL)
  7. extractionthe aqueous layer was extracted with EtOAc (100 mL)
  8. filtrationThe combined organic cuts were filtered through a pre-washed pad of solka floc (5 g)
  9. washwere washed with fresh EtOAc (200 mL)
  10. concentrationThe resultant filtrate was concentrated to dryness
  11. dissolutionThe crude product was dissolved in THF (38 mL)
  12. customcrystallized upon heptane (152 mL) addition
  13. filtrationThe product was filtered
  14. customdried to a constant weight in the vacuum oven (38° C., 20 inHg)

出典と根拠

ORDレコード
ord-f16ab514fd824af09929b4295ce2adb4
出典データセット
uspto-grants-2006_08
特許番号
US07094801B2

関連ノート

読み込み中…