Ammonia → 3-Chloro-4-cyclohexylethynylbenzene

HRID 236841

Reaction equation

HRID 236841 reaction equation
[Cl:1][CH:2]1[CH:7]([CH2:8][C:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=O)[CH2:6][CH2:5][CH2:4][CH2:3]1.P(Cl)(Cl)(Cl)(Cl)Cl.[NH2-].[Na+].N>C1COCC1.CCOCC.O>[Cl:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:7]=1[C:8]#[C:9][CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1

Participants

8

Reactant 4

HCID 222AmmoniaHCID 24533Sodium amideHCID 24819Phosphorus pentachlorideHCID 569758903-Chloro-4-cyclohexylacetophenone

Product 1

HCID 572867553-Chloro-4-cyclohexylethynylbenzene

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

3-Chloro-4-cyclohexylacetophenone (0.25 moles) and phosphorus pentachloride (0.31 moles) are placed in a 3-necked flask equipped with a mechanical stirrer, a condenser connected to a nitrogen inlet, and a thermometer. The mixture is stirred at 33°-35° C. for 3 days. The cooled reaction mixture is poured onto 800 g. of ice and extracted with 3×500 ml. of ether. The ether fraction is washed with 2×100 ml water 4×100 ml of 5% sodium hydroxide, 3×50 ml water, 2×50 ml of saturated saline and dried over sodium sulfate. The ether is removed to give the chlorinated intermediate. The intermediate is dissolved in anhydrous THF (200 ml) and is added dropwise to a freshly prepared solution of sodamide in liquid ammonia, using a dry-ice condenser. The reaction mixture is allowed to stir at room temperature overnight; then, it is poured into 50 ml of water and 500 ml of ether. The ether fraction is washed with 3×50 ml water and 50 ml of saturated saline and is dried over sodium sulfate. Removal of solvent gives a residue which is distilled to give 3-chloro-4-cyclohexylethynlbenzene.

Workup

  1. customequipped with a mechanical stirrer, a condenser
  2. customconnected to a nitrogen inlet
  3. customThe cooled reaction mixture
  4. additionis poured onto 800 g
  5. extractionof ice and extracted with 3×500 ml
  6. washThe ether fraction is washed with 2×100 ml water 4×100 ml of 5% sodium hydroxide, 3×50 ml water, 2×50 ml of saturated saline
  7. dry with materialdried over sodium sulfate
  8. customThe ether is removed
  9. customto give the chlorinated intermediate
  10. stirringto stir at room temperature overnight
  11. washThe ether fraction is washed with 3×50 ml water and 50 ml of saturated saline
  12. dry with materialis dried over sodium sulfate
  13. customRemoval of solvent
  14. customgives a residue which
  15. distillationis distilled
  16. customto give 3-chloro-4-cyclohexylethynlbenzene

Sources & evidence

ORD record
ord-f4016ba1365043b9852d24eda6e12c58
Source dataset
uspto-grants-1979_06
Patent number
US04157449

Linked notes

Loading…