Dibromomaleimide → 2-bromo-3-(5,6-methylenedioxy-1H-indol-3-yl)maleinimide

HRID 440172Notes

Reaction equation

HRID 440172 reaction equation
[CH2:1]1[O:12][C:11]2[CH:10]=[C:9]3[C:5]([CH:6]=[CH:7][NH:8]3)=[CH:4][C:3]=2[O:2]1.C([Mg]Br)C.Br[C:18]1[C:23](=[O:24])[NH:22][C:20](=[O:21])[C:19]=1[Br:25].[Cl-].[NH4+]>C1(C)C=CC=CC=1.O1CCCC1>[Br:25][C:19]1[C:20]([NH:22][C:23](=[O:24])[C:18]=1[C:6]1[C:5]2[C:9](=[CH:10][C:11]3[O:12][CH2:1][O:2][C:3]=3[CH:4]=2)[NH:8][CH:7]=1)=[O:21]

Participants

7

Reactant 4

HCID 14279DibromomaleimideHCID 25517Ammonium ChlorideHCID 2607975H-[1,3]dioxolo[4,5-f]indoleHCID 178418443HCID 178418443, compound

Product 1

HCID 148557092-bromo-3-(5,6-methylenedioxy-1H-indol-3-yl)maleinimideYield 56.8%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

6.44 g (40 mmol) 5,6-methylenedioxyindole are dissolved in 300 ml anhydrous toluene and mixed dropwise at 60° C. with 20 ml of a 2M solution of ethyl magnesium bromide in tetrahydrofuran (Aldrich). After completion of the addition, there is added dropwise thereto a solution of 1.7 g (6.67 mmol) dibromomaleinimide in 50 ml toluene, with the addition of the minimum amount of tetrahydrofuran required for solution, and then heated under reflux for 18 hours. After cooling, the reaction mixture is mixed with a saturated aqueous solution of ammonium chloride, the organic phase is separated off and the aqueous phase is extracted three times with toluene and once with ethyl acetate. The combined organic phases are dried, rotary evaporated and chromatographed in silica gel (elution agent: dichloromethane/ethyl acetate 30:1 v/v). There is obtained 1.27 g (56% of theory) 2-bromo-3-(5,6-methylenedioxy-1H-indol-3-yl)-maleinimide; m.p. about 185° C. (decomp.); RF=0.50 (dichloromethane/ethyl acetate 3:1 v/v); and 0.63 g (22.5% of theory) 2,3-bis-(5,6-methylenedioxy-1H-indol-3-yl)-maleinimide in the form of red crystals; m.p, about 270° C. (decomp.), after recrystallisation from propanol; RF=0.36 (dichloromethane/ethyl acetate 3:1 v/v).

Workup

  1. additionAfter completion of the addition, there
  2. additionis added dropwise
  3. temperatureheated
  4. temperatureunder reflux for 18 hours
  5. temperatureAfter cooling
  6. customthe organic phase is separated off
  7. extractionthe aqueous phase is extracted three times with toluene
  8. customThe combined organic phases are dried
  9. customrotary evaporated
  10. customchromatographed in silica gel (elution agent: dichloromethane/ethyl acetate 30:1 v/v)

Sources & evidence

ORD record
ord-9f8009b99c3f4ba2a24170c1571e59f6
Source dataset
uspto-grants-1996_05
Patent number
US05516915

Reaction notes

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