Hydrochloric Acid → HCID 13455829, compound

HRID 569232Notes

Reaction equation

HRID 569232 reaction equation
[CH2:1]([Mg]Br)[CH3:2].[OH:5][C:6]1[C:23]2[C:22](=[O:24])[C:21]3[C:16](=[CH:17][CH:18]=[C:19]([O:25][CH3:26])[CH:20]=3)[C:15](=[O:27])[C:14]=2[CH:13]=[C:12]2[C:7]=1[CH2:8][CH2:9][C:10](=[O:28])[CH2:11]2.Cl>C(Cl)Cl>[OH:28][C:10]1([C:1]#[CH:2])[CH2:9][CH2:8][C:7]2[C:12](=[CH:13][C:14]3[C:15](=[O:27])[C:16]4[C:21]([C:22](=[O:24])[C:23]=3[C:6]=2[OH:5])=[CH:20][C:19]([O:25][CH3:26])=[CH:18][CH:17]=4)[CH2:11]1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 13455828HCID 13455828, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 13455829HCID 13455829, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-40 °C

Procedure

Acetylene, purified by passing first through a trap cooled with ice and then through a trap containing concentrated sulfuric acid, is bubbled through 40 ml of anhydrous THF for 1 hour. Ethylmagnesium bromide (40 ml, 1M in THF, 40 mmol) is then added dropwise. After the addition, the solution is evaporated under reduced pressure and the residue is taken up with 80 ml of methylene chloride (CH2Cl2) distilled over P2O5. The ketone prepared in Example 1 (386 mg; 1.2 mmol), dissolved in CH2Cl2 (150 ml), is added dropwise to this solution, cooled to -40° C. The reaction mixture is stirred for 1 hour at between -40° C. and -20° C., then hydrolyzed with a 0.1N solution of hydrochloric acid and then extracted in the conventional manner with methylene chloride. Chromatography under pressure (CH2Cl2) makes it possible to separate the unreacted starting ketone (148 mg; 38%) from the ethynylcarbinol formed (165 mg; 43%).

Workup

  1. customAcetylene, purified
  2. customby passing first through a trap
  3. temperaturecooled with ice
  4. additionthrough a trap containing concentrated sulfuric acid
  5. customis bubbled through 40 ml of anhydrous THF for 1 hour
  6. additionAfter the addition
  7. customthe solution is evaporated under reduced pressure
  8. distillationdistilled over P2O5
  9. additionis added dropwise to this solution
  10. extractionextracted in the conventional manner with methylene chloride
  11. customto separate the unreacted starting ketone (148 mg; 38%) from the ethynylcarbinol
  12. customformed (165 mg; 43%)

Sources & evidence

ORD record
ord-8d89693da1694e9f9420bf921cc1bb34
Source dataset
uspto-grants-1988_03
Patent number
US04731468

Reaction notes

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