Sodium Chloride → 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol

HRID 13900

Reaction equation

HRID 13900 reaction equation
C1(NC2CCCCC2)CCCCC1.Br[C:15]1[CH:23]=[CH:22][C:18]([N:19]([CH3:21])[CH3:20])=[CH:17][CH:16]=1.[CH3:24][C:25]([OH:29])([C:27]#[CH:28])[CH3:26].[Cl-].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I.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>[CH3:20][N:19]([C:18]1[CH:22]=[CH:23][CH:15]=[CH:16][C:17]=1[C:28]#[C:27][C:25]([CH3:26])([OH:29])[CH3:24])[CH3:21]

Participants

10

Reactant 4

HCID 5234Sodium ChlorideHCID 7582DicyclohexylamineHCID 82582-Methyl-3-butyn-2-olHCID 114654-bromo-N,N-dimethylaniline

Product 1

HCID 667723334-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-olYield 86.1%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 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, 0.019 g (0.1 mmol) of copper (I) iodide, 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. 1.000 g (5 mmol) of 4-bromo-N,N-dimethylaniline 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 0.875 g of 4-(N,N-dimethylaminophenyl)-2-methyl-3-butyne-2-ol (yield: 86 mol % based on 4-bromo-N,N-dimethylaniline). The identification of the product was made by mass spectroscopy, 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-d5c69cc3df2046e18eec2d2369bacffe
Source dataset
uspto-grants-2010_06
Patent number
US07728176B2

Linked notes

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