HCID 21220292, compound → HCID 15017672, compound

HRID 1584805Notes

Reaction equation

HRID 1584805 reaction equation
Br[C:2]1[C:3]([F:15])=[C:4]([CH:10]=[C:11]([F:14])[C:12]=1[F:13])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH2:16](C([Sn])=C(CCCC)CCCC)[CH2:17]CC>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:15][C:3]1[C:2]([CH:16]=[CH2:17])=[C:12]([F:13])[C:11]([F:14])=[CH:10][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

5

Reactant 2

HCID 21220292HCID 21220292, compoundHCID 53438229Tri(butyl)vinyltin

Product 1

HCID 15017672HCID 15017672, compound

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

In 30 ml of toluene was dissolved 3.04 g of ethyl 3-bromo-2,4,5-trifluorobenzoate, and to the solution were added 5.11 g of tributylvinyltin and 0.25 g of tetrakis(triphenylphosphine) palladium (0), after which the resulting mixture was heated under reflux for two hours under a nitrogen atmosphere. The reaction mixture was concentrated under reduced pressure, and the residue obtained was purified by a column chromatography (eluent: n-hexane:ethyl acetate=100:1), to obtain a colorless, oily ethyl 2,4,5-trifluoro-3-vinylbenzoate. The oily product thus obtained was dissolved in a mixed solvent of 62 ml of methanol and 12 ml of methylene chloride, and thereafter, at -50° C., an ozone gas was blown thereinto for three hours and subsequently a nitrogen gas was blown thereinto for 30 minutes. The temperature of this solution was elevated to -20° C., and thereafter, 0.81 g of sodium borohydride was added thereto, after which the resulting mixture was stirred at room temperature for 12 hours. The reaction mixture was added to a mixed solvent of 400 ml of ethyl acetate and 600 ml of ice water and the pH was adjusted to 1 with 6N hydrochloric acid, after which the organic layer formed was separated, washed with a saturated saline solution and then dried over anhydrous magnesium sulfate. The solvent was then removed by distillation under reduced pressure. The residue thus obtained was purified by a column chromatography (eluent: n-hexane:ethyl acetate=4:1), to obtain 1.70 g of a colorless, oily ethyl 3-hydroxymethyl-2,4,5-trifluorobenzoate.

Workup

  1. temperatureafter which the resulting mixture was heated
  2. temperatureunder reflux for two hours under a nitrogen atmosphere
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. customthe residue obtained
  5. customwas purified by a column chromatography (eluent: n-hexane:ethyl acetate=100:1)

Sources & evidence

ORD record
ord-edddce5d27b74f95aefd5ed6989390cb
Source dataset
uspto-grants-1999_08
Patent number
US05935952

Reaction notes

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