Carbon tetrabromide → HCID 19360624, compound

HRID 376980Notes

Reaction equation

HRID 376980 reaction equation
O[CH2:2][CH2:3][CH:4]1[CH2:9][CH2:8][N:7]([C:10]([CH3:22])([CH3:21])[C:11]([C:13]2[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=2)=[O:12])[CH2:6][CH2:5]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)Br.C([O-])(=[S:49])C.[K+]>C(Cl)Cl.CC(N(C)C)=O.C(O)C>[SH:49][CH2:2][CH2:3][CH:4]1[CH2:9][CH2:8][N:7]([C:10]([CH3:22])([CH3:21])[C:11]([C:13]2[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=2)=[O:12])[CH2:6][CH2:5]1

Participants

8

Reactant 4

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 19360589HCID 19360589, compoundHCID 23670855Potassium ethanethioate

Product 1

HCID 19360624HCID 19360624, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent2×HCID 31374DimethylacetamideSolvent

Procedure

9.81 g (30.5 mmol) of 2-[4-(2-hydroxy-ethyl)-piperidin-1-yl]-2-methyl-1-[4-(methylthio)-phenyl]-propan-1-one and 8.0 g of triphenylphosphine are dissolved in 100 ml of methylene chloride. 10.1 g of carbon tetrabromide is dissolved in 50 ml of methylene chloride and is added dropwise to the above solution at 5 ° C. After stirring for 1 h, the resulting solution is concentrated to give a slurry, this material is purified by column chromatography on silica gel with ethyl acetate-hexane (10:90) as an eluent, and an oily product is obtained. The resulting material is used for the next reaction. 13.0 g of the above oily product are dissolved in 100 ml of dried dimethylacetamide and 4.56 g of potassium thioacetate are added. After stirring for 2.5 h at 50° C., the reaction mixture is poured into ice-water and extracted with ethyl acetate. The combined organic layers are washed with saturated sodium chloride solution and dried over MgSO4. The solvent is removed by evaporator and the crude oil is further purified by column chromatography on silica gel with ethyl acetate-hexane (10:90) as an eluent, and an oily product is obtained. The product is dissolved in 40 ml of ethanol and the solution is bubbled by nitrogen for 10 min. to remove oxygen. To the solution are added 10 ml of 2N sodium hydroxide solution and stirred at 0° C. for 1 h. After the reaction mixture is neutralized by adding 2N hydrochloric acid solution, the resulting solution is poured into 10 ml of water and extracted with ethyl acetate. The organic layer is washed with water and saturated sodium chloride solution, and dried over MgSO4. After ethyl acetate is distilled off, the residue is purified by means of column chromatography on silica gel with ethyl acetate-hexane (5-95) as an eluent, and an oily product is obtained. The structure is confirmed by the 1H-NMR spectrum (CDCl3): δ [ppm] 1.16 (m, 2H), 1.28 (s, 6H), 1.31 (t, 1H), 1.42 (m, 1H), 1.56 (q, 2H), 1.63 (d, 2H), 2.24 (t, 2H), 2.52 (s, 3H), 2.53 (m, 2H), 2.79 (d, 2H), 7.21 (d, 2H), 8.53 (d, 2H).

Workup

  1. additionis added dropwise to the above solution at 5 ° C
  2. concentrationthe resulting solution is concentrated
  3. customto give a slurry
  4. customthis material is purified by column chromatography on silica gel with ethyl acetate-hexane (10:90) as an eluent
  5. customan oily product is obtained
  6. customThe resulting material is used for the next reaction
  7. stirringAfter stirring for 2.5 h at 50° C.
  8. extractionextracted with ethyl acetate
  9. washThe combined organic layers are washed with saturated sodium chloride solution
  10. dry with materialdried over MgSO4
  11. customThe solvent is removed by evaporator
  12. customthe crude oil is further purified by column chromatography on silica gel with ethyl acetate-hexane (10:90) as an eluent
  13. customan oily product is obtained
  14. customthe solution is bubbled by nitrogen for 10 min.
  15. customto remove oxygen
  16. additionTo the solution are added 10 ml of 2N sodium hydroxide solution
  17. stirringstirred at 0° C. for 1 h
  18. additionby adding 2N hydrochloric acid solution
  19. additionthe resulting solution is poured into 10 ml of water
  20. extractionextracted with ethyl acetate
  21. washThe organic layer is washed with water and saturated sodium chloride solution
  22. dry with materialdried over MgSO4
  23. distillationAfter ethyl acetate is distilled off
  24. customthe residue is purified by means of column chromatography on silica gel with ethyl acetate-hexane (5-95) as an eluent
  25. customan oily product is obtained

Sources & evidence

ORD record
ord-bf89be74c10f403a986ea6915b659961
Source dataset
uspto-grants-2000_02
Patent number
US06022906

Reaction notes

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