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

HRID 1584642Notes

Reaction equation

HRID 1584642 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) was added 1-dimethylamino-2-propyne (2.82 g), bis(triphenylphosphine)palladium(II) chloride (400 mg), and cuprous iodide (54 mg). The mixture was stirred at room temperature under an atmosphere of argon for approximately 6 hours, heated briefly (ca. 10 minutes) to 60° C. The reaction mixture was cooled, filtered through diatomaceous earth, and the solvent was removed by evaporation in vacuo. The residue was dissolved in ethyl acetate, washed three times with water, once with saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. The solvent was removed by evaporation in vacuo, and the residue was purified by chromatography over silica gel (80% ethyl acetate in hexanes was used as the eluant) to give the product as an amber oil that solidified on standing. MS (+ES) m/z: 309 (M+H)+.

Workup

  1. temperatureheated briefly (ca. 10 minutes) to 60° C
  2. temperatureThe reaction mixture was cooled
  3. filtrationfiltered through diatomaceous earth
  4. customthe solvent was removed by evaporation in vacuo
  5. dissolutionThe residue was 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 was removed by evaporation in vacuo
  9. customthe residue was purified by chromatography over silica gel (80% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-b8b15d39790948818bf9474df185c606
Source dataset
uspto-grants-1999_08
Patent number
US05932745

Reaction notes

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