Ammonia → 1,1-Diethyl-3[2-(1,3-dithiolan-2-yl)-1,6-dimethyl-8alpha-ergolinyl]urea

HRID 2352068Notes

Reaction equation

HRID 2352068 reaction equation
[CH2:1](OC=O)[CH3:2].[CH:6]([SH:9])([SH:8])[CH3:7].[CH2:10]([N:12]([CH2:34][CH3:35])[C:13]([NH:15][C@H:16]1[CH2:30][C@H:29]2[C@@H:19]([CH2:20][C:21]3[C:31]4[C:24](=[CH:25][CH:26]=[CH:27][C:28]2=4)[N:23](C)[CH:22]=3)[N:18]([CH3:33])[CH2:17]1)=[O:14])[CH3:11].N>C(Cl)(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl.O.CO>[CH2:34]([N:12]([CH2:10][CH3:11])[C:13]([NH:15][C@H:16]1[CH2:30][C@H:29]2[C@@H:19]([CH2:20][C:21]3[C:31]4[C:24](=[CH:25][CH:26]=[CH:27][C:28]2=4)[N:23]([CH3:22])[C:7]=3[CH:6]2[S:9][CH2:2][CH2:1][S:8]2)[N:18]([CH3:33])[CH2:17]1)=[O:14])[CH3:35]

Participants

9

Reactant 4

HCID 222AmmoniaHCID 8025Ethyl formateHCID 336451,1-EthanedithiolHCID 136545951,1-Diethyl-3-(1,6-dimethyl-8alpha-ergolinyl)urea

Product 1

HCID 867434611,1-Diethyl-3[2-(1,3-dithiolan-2-yl)-1,6-dimethyl-8alpha-ergolinyl]ureaYield 37%

Reagents, catalysts & solvents 4

HCID 24193Titanium TetrachlorideCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolvent2×

Procedure

At room temperature under argon, 7 ml of formic acid ethyl ester and 3.6 ml (44 mmol) of ethanedithiol are added in succession to a solution of 6.9 g of 1,1-diethyl-3-(1,6-dimethyl-8α-ergolinyl)urea in 200 ml of chloroform. Then, 8.8 ml (80 mmol) of titanium(IV) chloride dissolved in 100 ml of chloroform is added gradually dropwise to the reaction mixture and the latter is stirred for 20 hours at room temperature. Although the starting material at this point in time has not as yet been completely reacted, the reaction mixture is worked up to avoid further formation of the disubstituted compound. For this purpose, the reaction mixture is cooled in an ice bath and combined, in succession, dropwise with 50 ml of methanol and 40 ml of water. Then the mixture is made alkaline with 25% strength ammonia solution and extracted with methylene cloride. The organic phases are washed with water and dried over magnesium sulfate. The evaporated residue is crystallized under boiling heat from methanol/ethyl acetate, thus obtaining 3.0 g of 1,1-diethyl-3[2-(1,3-dithiolan-2-yl)-1,6-dimethyl-8α-ergolinyl]urea (37% yield).

Workup

  1. additionis added gradually dropwise to the reaction mixture
  2. customas yet been completely reacted
  3. temperatureFor this purpose, the reaction mixture is cooled in an ice bath
  4. extractionextracted with methylene cloride
  5. washThe organic phases are washed with water
  6. dry with materialdried over magnesium sulfate
  7. customThe evaporated residue is crystallized
  8. temperatureunder boiling heat from methanol/ethyl acetate

Sources & evidence

ORD record
ord-86d085658a734553ab7fc234029502fa
Source dataset
uspto-grants-1989_10
Patent number
US04874768

Reaction notes

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