Water → 3-(9,10-Didehydro-2-formyl-6-methyl-8alpha-ergolinyl)-1,1-diethylurea

HRID 569334Notes

Reaction equation

HRID 569334 reaction equation
S1CCS[CH:2]1[C:6]1[NH:20][C:19]2[C:21]3[C:7]=1[CH2:8][C@@H:9]1[C:14]([C:15]=3[CH:16]=[CH:17][CH:18]=2)=[CH:13][C@H:12]([NH:22][C:23](=[O:29])[N:24]([CH2:27][CH3:28])[CH2:25][CH3:26])[CH2:11][N:10]1[CH3:30].O.S(Cl)(Cl)(=O)=[O:33].C(=O)([O-])[O-].[K+].[K+]>C(Cl)(Cl)Cl>[CH:2]([C:6]1[NH:20][C:19]2[C:21]3[C:7]=1[CH2:8][C@@H:9]1[C:14]([C:15]=3[CH:16]=[CH:17][CH:18]=2)=[CH:13][C@H:12]([NH:22][C:23](=[O:29])[N:24]([CH2:27][CH3:28])[CH2:25][CH3:26])[CH2:11][N:10]1[CH3:30])=[O:33]

Participants

6

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 24648Sulfuryl chlorideHCID 867420553-[9,10-Didehydro-2-(1,3-dithiolan-2-yl)-6-methyl-8alpha-ergolinyl]-1,1-diethylurea

Product 1

HCID 867420563-(9,10-Didehydro-2-formyl-6-methyl-8alpha-ergolinyl)-1,1-diethylureaYield 102.3%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

Under argon, 1.10 g (2.5 mmol) of 3-[9,10-didehydro-2-(1,3-dithiolan-2-yl)-6-methyl-8α-ergolinyl]-1,1-diethylurea is dissolved in 25 ml of chloroform and combined with 1.9 g of silica gel of a particle size of 0.063-0.2 mm. Under vigorous agitation, 2 ml of distilled water is added dropwise. Subsequently, within a time period of 15 minutes, a solution of 0.5 ml (0.6 mmol) of sulfuryl chloride in 13 ml of chloroform is added dropwise and the mixture is stirred for 2 hours at room temperature. For working-up purposes, 3 g of potassium carbonate is added and the mixture is vigorously agitated for 20 minutes. The precipitate is filtered off and washed with methylene chloride. The precipitate is moistened with ethanol and made into a slurry with 250 ml of saturated sodium chloride solution. This mixture is repeatedly extracted with methylene chloride. The extracts are dried together with the methylene chloride filtrate over magnesium sulfate and concentrated. The crude product is chromatographed under pressure on silica gel with a chloroform/methanol mixture and the main fraction of 448 mg is recrystallized from diisopropyl ether, thus obtaining 225 mg of 3-(9,10-didehydro-2-formyl-6-methyl-8α-ergolinyl)-1,1-diethylurea (25% yield).

Workup

  1. additionis added
  2. stirringthe mixture is vigorously agitated for 20 minutes
  3. filtrationThe precipitate is filtered off
  4. washwashed with methylene chloride
  5. extractionThis mixture is repeatedly extracted with methylene chloride
  6. dry with materialThe extracts are dried together with the methylene chloride filtrate over magnesium sulfate
  7. concentrationconcentrated
  8. customThe crude product is chromatographed under pressure on silica gel with a chloroform/methanol mixture
  9. customthe main fraction of 448 mg is recrystallized from diisopropyl ether

Sources & evidence

ORD record
ord-8a0c211eb0524c15b9985732493ea7b1
Source dataset
uspto-grants-1988_03
Patent number
US04731367

Reaction notes

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