Phosphorus oxychloride → HCID 86742125, compound

HRID 649513Notes

Reaction equation

HRID 649513 reaction equation
[Br:1][C:2]1[C:16]2=[C:17]3[C:5]([NH:6][CH:7]=[C:8]3[CH2:9][C@@H:10]3[C@@H:15]2[CH2:14][C@H:13]([NH:18][C:19](=O)[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:12][N:11]3[CH3:26])=[CH:4][CH:3]=1.P(Cl)(Cl)(Cl)=O.C(OC([S-])=[S:36])C.[K+]>C(Cl)Cl>[Br:1][C:2]1[C:16]2=[C:17]3[C:5]([NH:6][CH:7]=[C:8]3[CH2:9][C@@H:10]3[C@@H:15]2[CH2:14][C@H:13]([NH:18][C:19](=[S:36])[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:12][N:11]3[CH3:26])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 2735045Potassium ethylxanthateHCID 13823189HCID 13823189, compound

Product 1

HCID 86742125HCID 86742125, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

At -20° C., 6.29 g of 3-(12-bromo-6-methyl-8α-ergolinyl)-1,1-diethylurea (15 mmol) is dissolved in a mixture of 4.13 g of freshly distilled phosphorus oxychloride (45 mmol) and 50 ml of anhydrous methylene chloride, and the temperature is allowed to rise to +10° C. within 4 hours. The mixture is agitated overnight at room temperature, then for another 2 hours at 40° C., and subsequently the solvent is distilled off under vacuum. The residue is dissolved in 50 ml of anhydrous acetonitrile, cooled to -10° C., combined with 7.2 g of potassium ethylxanthate (45 mmol) and stirred for 20 hours at room temperature. The solvent is extensively distilled off, then the mixture is divided between ethyl acetate and saturated sodium carbonate solution, the organic phase is dried with sodium sulfate, and evaporated. The residue is crystallized from ethyl acetate, thus obtaining 5.03 g (77%) of 3-(12-bromo- 6-methyl-8α-ergolinyl)-1,1-diethylthiourea.

Workup

  1. waitfor another 2 hours at 40° C.
  2. distillationsubsequently the solvent is distilled off under vacuum
  3. dissolutionThe residue is dissolved in 50 ml of anhydrous acetonitrile
  4. temperaturecooled to -10° C.
  5. stirringstirred for 20 hours at room temperature
  6. distillationThe solvent is extensively distilled off
  7. dry with materialthe organic phase is dried with sodium sulfate
  8. customevaporated
  9. customThe residue is crystallized from ethyl acetate

Sources & evidence

ORD record
ord-b16b5f2db41a462db22a99a1d64fea3a
Source dataset
uspto-grants-1988_04
Patent number
US04740509

Reaction notes

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