p-Toluenesulfonic acid → HCID 18434078, compound

HRID 1636749Notes

Reaction equation

HRID 1636749 reaction equation
[CH2:1]([N:4]([CH3:26])[CH2:5]/[CH:6]=[CH:7]/[CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:24])[CH2:17][CH:18](O)[CH:19]=[C:20]([CH3:22])[CH3:21])=[CH:12][C:11]=1[F:25])[CH:2]=[CH2:3].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1(C)C=CC=CC=1>[CH2:1]([N:4]([CH3:26])[CH2:5]/[CH:6]=[CH:7]/[CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16](=[O:24])/[CH:17]=[CH:18]/[CH:19]=[C:20]([CH3:21])[CH3:22])=[CH:12][C:11]=1[F:25])[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 18434225HCID 18434225, compound

Product 1

HCID 18434078HCID 18434078, compoundYield 71.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 4.1 g of (E)-(RS)-1-[4-[4-(allyl-methyl-amino)-but-2-enyloxy]-3-fluoro-phenyl]-3-hydroxy-5-methyl-hex-4-en-1-one (Ex. 21) in 280 ml of toluene is added to 2.6 g of p-toluenesulphonic acid and stirred at room temperature for 2.5 hrs. The reaction mixture is concentrated, the residue is dissolved in methylene chloride, extracted with saturated sodium bicarbonate solution, dried and the residue is concentrated and purified over silica gel with 97.5% methylene chloride/methanol. The free amine is dissolved in methylene chloride/methanol with 0.75 g of fumaric acid, evaporated and recrystallized from ethyl acetate/methanol/ether. There are obtained 2.77 g of (E)-1-[4-[(E)-4-(allyl-methyl-amino)-but-2-enyloxy]-3-fluoro-phenyl]-5-methyl-hexa-2,4-dien-1-one.fumarate (1:1), MS: m/e 344 (M+H+).

Workup

  1. concentrationThe reaction mixture is concentrated
  2. dissolutionthe residue is dissolved in methylene chloride
  3. extractionextracted with saturated sodium bicarbonate solution
  4. customdried
  5. concentrationthe residue is concentrated
  6. custompurified over silica gel with 97.5% methylene chloride/methanol
  7. dissolutionThe free amine is dissolved in methylene chloride/methanol with 0.75 g of fumaric acid
  8. customevaporated
  9. customrecrystallized from ethyl acetate/methanol/ether

Sources & evidence

ORD record
ord-36017d46a5ca47fbb08cc0bc02ad2533
Source dataset
uspto-grants-2000_03
Patent number
US06034275

Reaction notes

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