Tetrahydrofuran → 8-isopropenyl-9,10-dimethoxy-13-methyl-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinoline

HRID 2381198Notes

Reaction equation

HRID 2381198 reaction equation
[CH3:1][O:2][C:3]1[C:23]2[CH2:22][NH+:10]3[CH2:11][CH2:12][C:13]4[C:18]([C:9]3=[C:8]([CH3:24])[C:7]=2[CH:6]=[CH:5][C:4]=1[O:25][CH3:26])=[CH:17][C:16]1[O:19][CH2:20][O:21][C:15]=1[CH:14]=4.[I-].[C:28]([Mg]Br)([CH3:30])=[CH2:29].O1CCCC1>C(OCC)C>[C:28]([CH:22]1[N:10]2[CH2:11][CH2:12][C:13]3[C:18]([C:9]2=[C:8]([CH3:24])[C:7]2[CH:6]=[CH:5][C:4]([O:25][CH3:26])=[C:3]([O:2][CH3:1])[C:23]1=2)=[CH:17][C:16]1[O:19][CH2:20][O:21][C:15]=1[CH:14]=3)([CH3:30])=[CH2:29]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 30165Iodide IonHCID 866474919,10-Dimethoxy-13-methyl-5,6-dihydro[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-7-yliumHCID 178456138HCID 178456138, compound

Product 1

HCID 498060918-isopropenyl-9,10-dimethoxy-13-methyl-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolineYield 36%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 9,10-dimethoxy-13-methyl-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-7-ylium; iodide (300 mg, 0.63 mmol) in anhydrous diethyl ether (100 mL) at 0° C. was added a solution of isopropenylmagnesium bromide in tetrahydrofuran (0.5 M, 18.8 mL, 9.4 mmol) dropwise. After stirring at 0° C. for 30 min, the reaction was quenched by adding saturated aqueous ammonium chloride solution (20 mL). The mixture was extracted with diethyl ether (2×50 mL), washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was re-crystallized from diethyl ether to afford 8-isopropenyl-9,10-dimethoxy-13-methyl-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinoline (90 mg, 36%). LC/MS m/e calcd for C24H23NO4 (M+H)+: 392.47, observed: 392.2; 1H NMR (400 MHz, DMSO-d6) δ ppm 1.53 (s, 3 H) 2.13 (s, 3 H) 2.62-2.71 (m, 1 H) 2.72-2.79 (m, 1 H) 3.00-3.08 (m, 1 H) 3.13-3.21 (m, 1 H) 3.71 (s, 3 H) 3.80 (s, 3 H) 4.59 (s, 1 H) 4.77 (s, 1 H) 5.12 (s, 1 H) 6.03 (s, 2 H) 6.83 (s, 1 H) 6.93 (s, 2 H) 7.02 (s, 1 H).

Workup

  1. customthe reaction was quenched
  2. additionby adding saturated aqueous ammonium chloride solution (20 mL)
  3. extractionThe mixture was extracted with diethyl ether (2×50 mL)
  4. washwashed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was re-crystallized from diethyl ether

Sources & evidence

ORD record
ord-257d1c8a6f3645249f477247bbcf0e89
Source dataset
uspto-grants-2012_09
Patent number
US08258149B2

Reaction notes

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