Hydrochloric Acid → HCID 10970645, compound

HRID 2081274Notes

Reaction equation

HRID 2081274 reaction equation
[CH:1](Br)=[CH2:2].[Mg].Cl[C:6]1[CH:24]=[C:23]([C:25]([F:28])([F:27])[F:26])[CH:22]=[CH:21][C:7]=1[O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:14](=[O:15])[O:13][C:12]2(O)[CH3:19].[ClH:29]>C1COCC1>[Cl:29][C:6]1[CH:24]=[C:23]([C:25]([F:26])([F:27])[F:28])[CH:22]=[CH:21][C:7]=1[O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[C:14](=[O:15])[O:13][C:12]2([CH3:19])[CH:1]=[CH2:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11641BromoetheneHCID 5462224Magnesium2×HCID 11068325HCID 11068325, compound

Product 1

HCID 10970645HCID 10970645, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Vinyl bromide (112.4 g, 1.05 mol) in THF (500 ml) was added to magnesium (24 g, 1.0 mol) in THF (500 ml) under a nitrogen blanket over 1 hour. The temperature was maintained below 60° during addition and stirring continued for a further 30 minutes during which all the magnesium dissolved. The reaction mixture was cooled to 0° C. and then a solution of 5-(2-chloro-4-trifluoromethylphenoxy)-3-hydroxy-3-methylphthalide, prepared as described in Example 2, (119.5 g, 0.33 mol) in THF (500 ml) was run in while maintaining a temperature of 0° to 5° C. After stirring for a further 1 hour, during which the temperature rose to 20° C., dilute hydrochloric acid (1.1 mol in 250 ml) was added very cautiously over 30 minutes. The solution separated into two layers and the aqueous layer was run off. Toluene (500 ml) was added and the solution washed twice with water. The solvent was stripped and the residual oil dissolved in ethyl acetate/60°-80° petroleum spirit and eluted over silica. The desired product, 5-(2-chloro-4-trifluoromethylphenoxy)-3-methyl-3-vinyl phthalide, was crystallised from hexane, m.p.=71°-73° C. Yield=122.2 g (96%).

Workup

  1. temperatureThe temperature was maintained below 60° during addition
  2. temperaturewhile maintaining a temperature of 0° to 5° C
  3. stirringAfter stirring for a further 1 hour, during which the temperature
  4. customrose to 20° C.
  5. customThe solution separated into two layers
  6. additionToluene (500 ml) was added
  7. washthe solution washed twice with water
  8. dissolutionthe residual oil dissolved in ethyl acetate/60°-80° petroleum spirit
  9. washeluted over silica
  10. customThe desired product, 5-(2-chloro-4-trifluoromethylphenoxy)-3-methyl-3-vinyl phthalide, was crystallised from hexane, m.p.=71°-73° C

Sources & evidence

ORD record
ord-f5219edce6c84a7eb4419ec74341fb55
Source dataset
uspto-grants-1993_02
Patent number
US05183907

Reaction notes

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