N-Methylmaleimide → 3-(2H-1,3-Benzodioxol-5-yl)-1-methyl-1H-pyrrole-2,5-dione

HRID 371135Notes

Reaction equation

HRID 371135 reaction equation
Cl.[CH2:2]1[O:11][C:10]2[CH:9]=[CH:8][C:6](N)=[CH:5][C:4]=2[O:3]1.N([O-])=O.[Na+].[CH3:16][N:17]1[C:21](=[O:22])[CH:20]=[CH:19][C:18]1=[O:23].C(=O)(O)[O-].[Na+]>O.Cl.CC(C)=O>[O:11]1[C:10]2[CH:9]=[CH:8][C:6]([C:19]3[C:18](=[O:23])[N:17]([CH3:16])[C:21](=[O:22])[CH:20]=3)=[CH:5][C:4]=2[O:3][CH2:2]1

Participants

8

Reactant 4

HCID 70261N-MethylmaleimideHCID 516892Sodium BicarbonateHCID 189500312H-1,3-Benzodioxol-5-amine--hydrogen chloride (1/1)HCID 23668193Sodium Nitrite

Product 1

HCID 135195713-(2H-1,3-Benzodioxol-5-yl)-1-methyl-1H-pyrrole-2,5-dione

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

A 30.9 g amount of 3,4-methylenedioxyaniline hydrochloride was dissolved in 90 ml of water and 40 ml of concentrated hydrochloric acid. The solution was cooled to 5° C. in an ice-salt bath and a solution of 12.3 g of sodium nitrite in 35 ml of water was added dropwise to the reaction mixture over a 25 minute period. A solution of 20.0 g of N-methylmaleimide and 2.4 g of cupric chloride in 150 ml of acetone was added to the reaction mixture portionwise with stirring. The reaction mixture temperature was maintained at 3° C. and the pH was adjusted to 3.2 by the addition of about 30 g of sodium bicarbonate. After standing at room temperature for 16 hours the mixture was filtered to collect a black solid. The solid was dried. Then the solid was dissolved in 500 ml of isopropanol containing 19.5 g of 2,6-lutidine. The mixture was heated to boiling and filtered hot to collect 4.8 g of isoluble material. The filtrate was cooled and an additional 2.6 g of precipitate was collected. This filtrate was reduced in volume to 200 ml and cooled and filtered to collect 2.7 g more of precipitate. The final filtrate was diluted with water and filtered to collect 0.9 g of additional material. The precipitates were combined and subjected to preparative liquid chromatography using a silica gel column and ethyl acetate:hexane (1:1) as eluent. The second cut, 0.6 g was recrystallized from ethyl acetate to give 0.1 g of 3-(1,3-benzodioxol-5-yl)-1-methyl-1H-pyrrole-2,5-dione as a brown solid, mp 210°-215° C.

Workup

  1. temperatureThe reaction mixture temperature was maintained at 3° C.
  2. filtrationthe mixture was filtered
  3. customto collect a black solid
  4. customThe solid was dried
  5. dissolutionThen the solid was dissolved in 500 ml of isopropanol containing 19.5 g of 2,6-lutidine
  6. temperatureThe mixture was heated
  7. filtrationfiltered hot
  8. customto collect 4.8 g of isoluble material
  9. temperatureThe filtrate was cooled
  10. customan additional 2.6 g of precipitate was collected
  11. temperaturecooled
  12. filtrationfiltered
  13. customto collect 2.7 g more of precipitate
  14. additionThe final filtrate was diluted with water
  15. filtrationfiltered
  16. customto collect 0.9 g of additional material
  17. customThe second cut, 0.6 g was recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-4009c93cc2a44a3d97b4df341064392d
Source dataset
uspto-grants-1985_07
Patent number
US04529736

Reaction notes

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