Chloride → HCID 54507987, compound

HRID 484568Notes

Reaction equation

HRID 484568 reaction equation
Cl[CH2:2][C:3]([CH3:11])=[CH:4][C:5]#[C:6][C:7]([CH3:10])([OH:9])[CH3:8].[CH3:12][C:13]([C:20]#[CH:21])=[CH:14][CH2:15][CH2:16][C:17](=[O:19])[CH3:18].[Cl-]>>[OH:9][C:7]([CH3:10])([CH3:8])[C:6]#[C:5][CH:4]=[C:3]([CH3:11])[CH2:2][C:21]#[C:20][C:13]([CH3:12])=[CH:14][CH2:15][CH2:16][C:17](=[O:19])[CH3:18]

Participants

4

Reactant 3

HCID 312ChlorideHCID 54182571HCID 54182571, compoundHCID 54188136HCID 54188136, compound

Product 1

HCID 54507987HCID 54507987, compound

Procedure

A mixture of 446 mg (2.58 mmoles) of 6-chloromethyl-2-methyl-6-hepten-3-yn-2-ol and 7-chloro-2,6-dimethyl-5-hepten-3-yn-2-ol (produced in accordance with Example X), 264 mg (1.94 mmoles) of 6-methyl-5-octen-7-yn-2-one (produced in accordance with Example II), 539 mg (3.90 mmoles) of anhydrous potassium carbonate, 20 mg (0.20 mmoles) of cuprous chloride, and 46 mg (0.20 mmoles) of benzyltriethylammonium chloride in 2.00 mL of acetonitrile (HPLC-grade) was stirred vigorously at room temperature for 18 hours, during which time the mixture was maintained under a nitrogen atmosphere. Isolation of the product in the manner described in the procedure of Example III afforded 556 mg of material, proton NMR analysis of which indicated the presence of minor amounts of unreacted 7-chloro-2,6-dimethyl-5-hepten-3-yn-2-ol and 6-methyl-5-octen-7-yn-2-one, but not any of the nonconjugated allylic chloride (6-chloromethyl-2-methyl-6 -hepten-3-yn-2-ol) which presumably underwent the coupling reaction more readily. Removal of the C-9 components by evaporative fractional distillation in the presence of a small amount of powdered calcium carbonate, followed by distillation, afforded 211 mg (40% yield, not corrected for recovery of unreacted starting materials) of the two named C-18 ketones: boiling point 130°-145° C. (bath temperature, 0.25 mm).

Workup

  1. customthe coupling reaction more readily
  2. customRemoval of the C-9 components
  3. distillationby evaporative fractional distillation in the presence of a small amount of powdered calcium carbonate
  4. distillationfollowed by distillation
  5. customafforded 211 mg (40% yield

Sources & evidence

ORD record
ord-ceb562fc55d542839da44a708211ff39
Source dataset
uspto-grants-1993_07
Patent number
US05231232

Reaction notes

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