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

HRID 1464819

반응식

HRID 1464819 반응식
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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-10 °C

실험 절차

(R)-(-)-3,4-Dihydro-2-trifluoromethanesulfonyloxymethyl-2H-benzopyran (23.0 g, 78 mmol) and copper (I) bromide dimethyl sulfide complex (2.8 g, 13 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 (MgSC4), 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, CDCl3) 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) .

후처리

  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 (MgSC4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified on silica gel

출처 및 근거

ORD 기록
ord-4ffdb3f9d23d4fabb3d25bd7d2b40d3a
출처 데이터셋
uspto-grants-1994_04
특허 번호
US05306726

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