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

HRID 2381203Notes

Reaction equation

HRID 2381203 reaction equation
[CH2:1]([C:4]1[C:5]2[CH:6]=[CH:7][C:8]([O:27][CH3:28])=[C:9]([O:25][CH3:26])[C:10]=2[CH2:11][NH+:12]2[CH2:21][CH2:20][C:19]3[C:14](=[CH:15][C:16]4[O:24][CH2:23][O:22][C:17]=4[CH:18]=3)[C:13]=12)[CH:2]=[CH2:3].[Br-].[C:30]([Mg]Br)([CH3:32])=[CH2:31].O1CCCC1>C(OCC)C>[CH2:1]([C:4]1[C:5]2[CH:6]=[CH:7][C:8]([O:27][CH3:28])=[C:9]([O:25][CH3:26])[C:10]=2[CH:11]([C:30]([CH3:32])=[CH2:31])[N:12]2[CH2:21][CH2:20][C:19]3[C:14](=[CH:15][C:16]4[O:24][CH2:23][O:22][C:17]=4[CH:18]=3)[C:13]=12)[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 259Bromide ionHCID 8028TetrahydrofuranHCID 8664749313-Allyl-9,10-dimethoxy-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-7-yliumHCID 178456138HCID 178456138, compound

Product 1

HCID 4980621413-allyl-8-isopropenyl-9,10-dimethoxy-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolineYield 27%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 13-allyl-9,10-dimethoxy-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinolin-7-ylium; bromide (300 mg, 0.66 mmol) in anhydrous diethyl ether (20 mL) at 0° C. was added a solution of isopropenylmagnesium bromide in tetrahydrofuran (0.5 M, 20 mL, 10 mmol) dropwise. After stirring at 0° C. for 30 min, the reaction was quenched by adding saturated aqueous ammonium chloride solution (50 mL). The mixture was extracted with diethyl ether (2×100 mL), washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was re-crystallized from diethyl ether to afford 13-allyl-8-isopropenyl-9,10-dimethoxy-5,8-dihydro-6H-[1,3]dioxolo[4,5-g]isoquino[3,2-a]isoquinoline (75 mg, 27%). LC/MS m/e calcd for C26H27NO4 (M+H)+: 418.51, observed: 418.2; 1H NMR (400 MHz, DMSO-d6) δ ppm 1.57 (s, 3 H) 2.64-2.80 (m, 2 H) 2.97-3.06 (m, 1 H) 3.18-3.25 (m, 1 H) 3.72 (s, 3 H) 3.79 (s, 3 H) 4.63 (s, 1 H) 4.73 (s, 1 H) 5.06-5.18 (m, 3 H) 6.02 (s, 2 H) 6.05-6.15 (m, 1 H) 6.81 (m, 1 H) 6.86 (s, 1 H) 6.91 (m, 1 H) 6.98 (s, 1 H).

Workup

  1. customthe reaction was quenched
  2. additionby adding saturated aqueous ammonium chloride solution (50 mL)
  3. extractionThe mixture was extracted with diethyl ether (2×100 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-0e5523e32c304ec499b0a1e5b20e31fa
Source dataset
uspto-grants-2012_09
Patent number
US08258149B2

Reaction notes

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