Water → (R)-(-)-3,4-Dihydro-2-(4-methoxybenzyl)-2H-benzopyran

HRID 2253969

反応式

HRID 2253969 の反応式
FC(F)(F)S(O[CH2:7][C@H:8]1[CH2:13][CH2:12][C:11]2[CH:14]=[CH:15][CH:16]=[CH:17][C:10]=2[O:9]1)(=O)=O.C([Mg]Br)[C:21]1[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=1.O.[Cl-].[NH4+]>O1CCCC1.C(Cl)Cl>[CH3:28][O:27][C:24]1[CH:25]=[CH:26][C:21]([CH2:7][C@H:8]2[CH2:13][CH2:12][C:11]3[CH:14]=[CH:15][CH:16]=[CH:17][C:10]=3[O:9]2)=[CH:22][CH:23]=1

参加物

7

反応物 4

HCID 962WaterHCID 25517Ammonium ChlorideHCID 15740458(R)-(-)-3,4-Dihydro-2-trifluoromethanesulfonyloxymethyl-2H-benzopyranHCID 178418276HCID 178418276、化合物

生成物 1

HCID 18653186(R)-(-)-3,4-Dihydro-2-(4-methoxybenzyl)-2H-benzopyran収率 92%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-10 °C

実験手順

(R)-(-)-3,4-Dihydro-2-trifluoromethane-sulfonyloxymethyl-2H-benzopyran(23.0 g, 78 mmol) and copper (I) bromide dimethyl sulfide complex (2.8 g, 12 mmol) were dissolved in tetrahydrofuran (400 ml) under a nitrogen atmosphere and cooled to -10° C. 4-Anisylmagnesium bromide (215 ml of a 1M solution in tetrahydrofuran, 0.215 mol) was added dropwise over 30 minutes, keeping the temperature below -5° C. The solution was stirred for 3 hours at 0° C. and then slowly poured into a mixture of water (800 ml) containing ammonium chloride (96 g, 1.8 mol) and methylene chloride (400 ml). The layers were separated and the aqueous portion was extracted with methylene chloride (400 ml). The combined organics were washed with 10% ammonium chloride (2×400 ml), water (250 ml), and brine (250 ml). The methylene chloride layer was dried (MgSO4), filtered and concentrated in vacuo. The residue was purified on silica gel using hexanes/methylene chloride (1:1 as eluent to afford 18.5 g (92% yield of the title product as an oil. [α]D -99.2° (c 1.7, MeOH); 1H NMR (300 MHz, CLCl3) δ1.6-1.7 (m, 1H), 1.9-2.0 (m, 1H), 2.7-2.8 (m, 3H), 3.1 (dd, 1H), 3.8 (s, 3H), 4.1 (m, 1H), 6.8 (m, 3H), 7.0 (m, 2H), 7.2 (m, 2H).

後処理

  1. customthe temperature below -5° C
  2. customThe layers were separated
  3. extractionthe aqueous portion was extracted with methylene chloride (400 ml)
  4. washThe combined organics were washed with 10% ammonium chloride (2×400 ml), water (250 ml), and brine (250 ml)
  5. dry with materialThe methylene chloride layer was dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified on silica gel

出典と根拠

ORDレコード
ord-08e1dd6446be4951bbd2f023e04a74fb
出典データセット
uspto-grants-1993_08
特許番号
US05232945

関連ノート

読み込み中…