Phosgene → HCID 13422307, compound

HRID 979234Notes

Reaction equation

HRID 979234 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH:6]=[C:7]([CH3:13])[C:8]=1[C:9](=[O:12])[CH2:10][CH3:11])[NH2:5].[C:14](Cl)(Cl)=[O:15].C(N(CC)CC)C.[CH:25]#[C:26][CH:27]([OH:29])[CH3:28]>C1(C)C=CC=CC=1>[CH3:13][C:7]1[CH:6]=[C:4]([NH:5][C:14](=[O:15])[O:29][CH:27]([CH3:28])[C:26]#[CH:25])[CH:3]=[C:2]([CH3:1])[C:8]=1[C:9](=[O:12])[CH2:10][CH3:11]

Participants

6

Reactant 4

HCID 6371PhosgeneHCID 8471TriethylamineHCID 162393-Butyn-2-olHCID 20201867HCID 20201867, compound

Product 1

HCID 13422307HCID 13422307, compoundYield 89.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Procedure

3,5-Dimethyl-4-propionylaniline (1.77 g) in toluene (20 ml) was dropwise added to a toluene solution containing 10 g of phosgene at 10° to 20° C. The resulting mixture was gradually heated and, after being refluxed for 30 minutes, cooled to room temperature. The solvent was removed by distillation uner reduced pressure to give crude 3,5-dimethyl-4-propionylphenyl isocyanate. The thus obtained crude substance was added to a toluene solution (50 ml) containing triethylamine (1.0 g) and 1-butyn-3-ol (0.75 g). The resultant mixture was allowed to stand at room temperature for 12 hours, poured into ice-water and extracted with ethyl acetate. The extract was washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using a mixture of toluene and ethyl acetate as the eluent to give 1-methyl-2-propynyl N-(3,5-dimethyl-4-propionylphenyl)carbamate (Compound No. 60) (2.45 g) in a yield of 89.9%. nD23.0 1.5247.

Workup

  1. temperatureThe resulting mixture was gradually heated
  2. temperatureafter being refluxed for 30 minutes
  3. customThe solvent was removed by distillation uner reduced pressure
  4. customto give crude 3,5-dimethyl-4-propionylphenyl isocyanate
  5. customThe thus obtained crude substance
  6. extractionextracted with ethyl acetate
  7. washThe extract was washed with water
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel chromatography
  11. additiona mixture of toluene and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-10a06d1fb7c1400a96ec319287f3da32
Source dataset
uspto-grants-1987_05
Patent number
US04666938

Reaction notes

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