Fumaric Acid → HCID 19095372, compound

HRID 486563Notes

Reaction equation

HRID 486563 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]2[N:15]3[CH2:16][CH2:17][N:18]=[C:19]([CH3:20])[C:14]3=[CH:13][CH:12]=2)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10].[BH4-].[Na+].[C:23]([OH:30])(=[O:29])/[CH:24]=[CH:25]/[C:26]([OH:28])=[O:27]>CO.O.C(O)C>[C:23]([OH:30])(=[O:29])/[CH:24]=[CH:25]/[C:26]([OH:28])=[O:27].[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:11]2[N:15]3[CH2:16][CH2:17][NH:18][CH:19]([CH3:20])[C:14]3=[CH:13][CH:12]=2)[CH:6]=[CH:7][C:8]=1[O:9][CH3:10]

Participants

7

Reactant 3

HCID 444972Fumaric AcidHCID 4311764Sodium borohydrideHCID 19095339HCID 19095339, compound

Product 1

HCID 19095372HCID 19095372, compoundYield 37%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

6-(3,4-Dimethoxyphenyl)-3,4-dihydro-1-methylpyrrolo[1,2-a]pyrazine (1.3 g) was dissolved in a mixture of 80 ml of methanol and 8 ml of water under argon. The solution was treated portionwise with 0.6 g of sodium borohydride while stirring and stirred at room temperature overnight. Thereafter, the methanol was removed in a vacuum, the residue was taken up in 100 ml of methylene chloride and washed with 100 ml of 10% ammonia solution. The phases were separated and the aqueous phase was extracted twice with 50 ml of methylene chloride each time. The organic phases were combined, dried with MgSO4 and freed from solvent. The crude product, 1.3 g of yellow-brown oil, was chromatographed on 60 g of silica gel with methylene chloride/methanol (49:1) as the eluent. The product, 0.9 g of yellow oil was dissolved in a 20-fold amount of ethanol, treated with 1.1 equivalents of a saturated solution of fumaric acid in ethanol, concentrated to 10 ml and treated with 40 ml of ethyl acetate. There was obtained 0.5 g (37%) of 6-(3,4-dimethoxyphenyl)-1,2,3,4-tetrahydro-1-methylpyrrolo[1,2-a]pyrazine fumarate (1:0.6); m.pt.: 172°-175° C. (dec.). A sample was recrystallized from a 40-fold amount of ethanol and yielded the (2:1) fumarate; m.pt.: 178°-180° C. (dec.).

Workup

  1. stirringstirred at room temperature overnight
  2. customThereafter, the methanol was removed in a vacuum
  3. washwashed with 100 ml of 10% ammonia solution
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted twice with 50 ml of methylene chloride each time
  6. dry with materialdried with MgSO4
  7. customThe crude product, 1.3 g of yellow-brown oil, was chromatographed on 60 g of silica gel with methylene chloride/methanol (49:1) as the eluent
  8. dissolutionThe product, 0.9 g of yellow oil was dissolved in a 20-fold amount of ethanol
  9. concentrationconcentrated to 10 ml
  10. additiontreated with 40 ml of ethyl acetate

Sources & evidence

ORD record
ord-eff5747f50074c4e847398ba14dd634c
Source dataset
uspto-grants-1994_03
Patent number
US05292732

Reaction notes

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