Sodium Hydroxide → HCID 14822404, compound

HRID 1587762Notes

Reaction equation

HRID 1587762 reaction equation
CO[C:3]([C@@H:5]1[CH2:19][C@H:18]2[C@@H:8]([CH2:9][C:10]3[C:20]4[C:13](=[CH:14][CH:15]=[CH:16][C:17]2=4)[NH:12][C:11]=3[CH3:21])[N:7]([CH2:22][CH2:23][CH3:24])[CH2:6]1)=O.[H-].[Al+3].[Li+].[H-].[H-].[H-].[OH-].[Na+].[CH3:33][S-:34].[Na+]>O1CCOCC1.O>[CH3:21][C:11]1[NH:12][C:13]2[C:20]3[C:10]=1[CH2:9][C@@H:8]1[C@@H:18]([C:17]=3[CH:16]=[CH:15][CH:14]=2)[CH2:19][C@@H:5]([CH2:3][S:34][CH3:33])[CH2:6][N:7]1[CH2:22][CH2:23][CH3:24]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 4378561Sodium methanethiolateHCID 14822401HCID 14822401, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 14822404HCID 14822404, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

345 mg of 2-methyl-6-n-propyl-8beta-ergoline-carboxylic acid methyl ester (1.06 mmol) is dissolved in 10 ml of anhydrous dioxane and heated with 150 mg of lithium aluminum hydride for 90 minutes to 80° C. After the cooling, 0.15 ml of water, 0.15 ml of 15% sodium hydroxide solution and 0.45 ml of water are added in succession, the precipitate is filtered off and the filtrate is concentrated by evaporation, quantitative yield. The crude alcohol is dissolved in 5 ml of pyridine and stirred with 0.25 ml of methanesulfonyl chloride for one hour at room temperature. Ice is added, it is stirred for another 30 minutes, and it is made alkaline with ammonia. The mixture is extracted with dichloromethane, the organic phase is dried and concentrated by evaporation. The residue of 388 mg is dissolved in 5 ml of N,N-dimethylacetamide and 720 mg of sodium methyl mercaptide (10 mmol) is stirred for an hour at room temperature. Ice is added to the mixture and it is extracted with dichloromethane. The organic phases are dried and concentrated by evaporation. 175 mg is crystallized from methanol, yield 50% [α]D =-80° (0.5% in chloroform).

Workup

  1. filtrationthe precipitate is filtered off
  2. concentrationthe filtrate is concentrated by evaporation, quantitative yield
  3. dissolutionThe crude alcohol is dissolved in 5 ml of pyridine
  4. additionIce is added
  5. stirringit is stirred for another 30 minutes
  6. extractionThe mixture is extracted with dichloromethane
  7. customthe organic phase is dried
  8. concentrationconcentrated by evaporation
  9. dissolutionThe residue of 388 mg is dissolved in 5 ml of N,N-dimethylacetamide
  10. additionIce is added to the mixture and it
  11. extractionis extracted with dichloromethane
  12. customThe organic phases are dried
  13. concentrationconcentrated by evaporation
  14. custom175 mg is crystallized from methanol, yield 50% [α]D =-80° (0.5% in chloroform)

Sources & evidence

ORD record
ord-4503e8e8692f4cf79e8f0de179babba5
Source dataset
uspto-grants-1993_06
Patent number
US05219862

Reaction notes

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