N,N-Dimethylpropargylamine → [3-Chloro-4-(3-dimethylamino-prop-1-ynyl)-phenyl]-carbamic Acid Tert-butyl Ester

HRID 1533207Notes

Reaction equation

HRID 1533207 reaction equation
[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:13]=[CH:12][C:11](I)=[C:10]([Cl:15])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2].[CH3:17][N:18]([CH3:22])[CH2:19][C:20]#[CH:21]>C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:13]=[CH:12][C:11]([C:21]#[C:20][CH2:19][N:18]([CH3:22])[CH3:17])=[C:10]([Cl:15])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 81643N,N-DimethylpropargylamineHCID 22592440tert-Butyl (3-chloro-4-iodophenyl)carbamate

Product 1

HCID 54484834[3-Chloro-4-(3-dimethylamino-prop-1-ynyl)-phenyl]-carbamic Acid Tert-butyl Ester

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

To a deoxygenated solution of (3-chloro-4-iodo-phenyl)-carbamic acid tert-butyl ester (10.0 g) in triethylamine (120 ml) is added 1-dimethylamino-2-propyne (2.82 g), bis(triphenyl-phosphine)palladium(II) chloride (0.4 g), and cuprous iodide (0.054 g). The mixture is stirred at room temperature under an atmosphere of argon for approximately 6 hours and is then heated briefly (ca. 10 minutes) to 60° C. The reaction mixture is then cooled, filtered through diatomaceous earth, and the solvent is removed by evaporation under reduced pressure. The residue is dissolved in ethyl acetate, washed three times with water, once with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent is removed by evaporation under reduced pressure, and the residue is chromatographed over silica gel (80% ethyl acetate in hexanes is used as the eluant) to give the purified product as an amber oil that solidified on standing.

Workup

  1. temperatureis then heated briefly (ca. 10 minutes) to 60° C
  2. temperatureThe reaction mixture is then cooled
  3. filtrationfiltered through diatomaceous earth
  4. customthe solvent is removed by evaporation under reduced pressure
  5. dissolutionThe residue is dissolved in ethyl acetate
  6. washwashed three times with water
  7. dry with materialonce with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate
  8. customThe solvent is removed by evaporation under reduced pressure
  9. customthe residue is chromatographed over silica gel (80% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-b17cfb1410614960a0876e6f640c5c14
Source dataset
uspto-grants-2001_03
Patent number
US06207715B1

Reaction notes

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