Ammonia → 1,1-Diethyl,3-(2,6,13-trimethyl-8alpha-ergolinyl)-thiourea

HRID 35860Notes

Reaction equation

HRID 35860 reaction equation
P(Cl)(Cl)(Cl)=O.[CH2:6]([N:8]([CH2:31][CH3:32])[C:9]([NH:11][C@H:12]1[CH2:26][C@H:25]2[C@@H:15]([CH2:16][C:17]3[C:27]4[C:20](=[CH:21][C:22]([CH3:28])=[CH:23][C:24]2=4)[NH:19][C:18]=3[CH3:29])[N:14]([CH3:30])[CH2:13]1)=O)[CH3:7].CCOC([S-])=[S:37].[K+].N>ClCCl.C(#N)C>[CH2:6]([N:8]([CH2:31][CH3:32])[C:9]([NH:11][C@H:12]1[CH2:26][C@H:25]2[C@@H:15]([CH2:16][C:17]3[C:27]4[C:20](=[CH:21][C:22]([CH3:28])=[CH:23][C:24]2=4)[NH:19][C:18]=3[CH3:29])[N:14]([CH3:30])[CH2:13]1)=[S:37])[CH3:7]

Participants

7

Reactant 4

HCID 222AmmoniaHCID 24813Phosphorus oxychlorideHCID 2735045Potassium ethylxanthateHCID 677880861,1-Diethyl-3-(2,6,13-trimethyl-8alpha-ergolinyl)-urea

Product 1

HCID 884231711,1-Diethyl,3-(2,6,13-trimethyl-8alpha-ergolinyl)-thioureaYield 43%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

0.5 M1 of freshly distilled phosphorus oxychloride (5.6 mmol) and 368 mg of 1,1-diethyl-3-(2,6,13-trimethyl-8alpha- ergolinyl)-urea (1 mmol) are dissolved in 20 ml of dichloromethane at -20° C. and the mixture is allowed to stir overnight at room temperature. The volatile portions are now drawn off in a vacuum, the residue is dissolved in 40 ml of acetonitrile and mixed with a solution of 0.8 g of potassium xanthate (5.6 mmol) in 80 ml of acetonitrile. It is stirred for 2 hours at room temperature, then ice and conc. ammonia solution are added and shaken out with dichloromethane. The organic phases are dried with sodium sulfate and concentrated by evaporation, the residue is chromatographed on silica gel with ethyl acetate and crystallized from ethyl acetate/diisopropyl ether, yield 43%.

Workup

  1. stirringIt is stirred for 2 hours at room temperature
  2. dry with materialThe organic phases are dried with sodium sulfate
  3. concentrationconcentrated by evaporation
  4. customthe residue is chromatographed on silica gel with ethyl acetate
  5. customcrystallized from ethyl acetate/diisopropyl ether, yield 43%

Sources & evidence

ORD record
ord-4719f764f83a4b1f9dce88191a7e0933
Source dataset
uspto-grants-1995_05
Patent number
US05411966

Reaction notes

Loading…