Sodium Chloride → (4-Fluorophenyl)-2-methyl-3-butyne-2-ol

HRID 13901

Reaction equation

HRID 13901 reaction equation
C1(NC2CCCCC2)CCCCC1.Br[C:15]1[CH:20]=[CH:19][C:18]([F:21])=[CH:17][CH:16]=1.[CH3:22][C:23]([OH:27])([C:25]#[CH:26])[CH3:24].[Cl-].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC([B-](C2C=CC(C)=CC=2)(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.C1(C)C=CC=CC=1.O1CCCC1>[F:21][C:18]1[CH:19]=[CH:20][C:15]([CH2:22][C:23]([CH3:24])([OH:27])[C:25]#[CH:26])=[CH:16][CH:17]=1

Participants

9

Reactant 4

HCID 5234Sodium ChlorideHCID 7582DicyclohexylamineHCID 82582-Methyl-3-butyn-2-olHCID 99931-Bromo-4-fluorobenzene

Product 1

HCID 23136659(4-Fluorophenyl)-2-methyl-3-butyne-2-olYield 96.7%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 23136639Tri-tert-butylphosphonium tetra-para-tolylborateCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A 50-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.034 g (0.15 mmol) of palladium (II) acetate, 1.088 g (6 mmol) of dicyclohexylamine and 5 ml of tetrahydrofuran were weighed in the flask, followed by stirring. Further, 0.174 g (0.3 mmol) of tri-tert-butylphosphonium tetra-para-tolylborate obtained in Example B-3 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 30° C. for 30 minutes. 0.875 g (5 mmol) of 1-bromo-4-fluorobenzene and 0.505 g (6 mmol) of 2-methyl-3-butyne-2-ol were added, followed by stirring at 30° C. for 17 hours. After the completion of the reaction, 10 ml of tetrahydrofuran, 5 ml of toluene and 15 ml of saturated sodium chloride solution were added, followed by separation. The organic phase was purified by column chromatography to afford 0.862 g of (4-fluorophenyl)-2-methyl-3-butyne-2-ol (yield: 97 mol % based on 1-bromo-4-fluorobenzene). The identification of the product was made by 1H-NMR and 13C-NMR.

Workup

  1. customA 50-ml four-necked flask was equipped with a stirrer
  2. additionadded into the flask
  3. customThe flask was purged with argon
  4. stirringby stirring at 30° C. for 30 minutes
  5. stirringby stirring at 30° C. for 17 hours
  6. additionwere added
  7. customfollowed by separation
  8. customThe organic phase was purified by column chromatography

Sources & evidence

ORD record
ord-49b94118ff304fdab21d7c1daff66385
Source dataset
uspto-grants-2010_06
Patent number
US07728176B2

Linked notes

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