Diphosgene → 3-(4-Chloro-6-fluoro-2-methoxy-3-nitrophenyl)-1,5-dimethyl-6-thioxo-[1,3,5]triazinane-2,4-dione

HRID 394440Notes

Reaction equation

HRID 394440 reaction equation
O=C(Cl)[O:3][C:4](Cl)(Cl)Cl.[Cl:9][C:10]1[CH:15]=[C:14]([F:16])[C:13]([NH2:17])=[C:12]([O:18][CH3:19])[C:11]=1[N+:20]([O-:22])=[O:21].CNC(=[S:28])NC.[C:29](N1C=CN=C1)([N:31]1[CH:35]=[CH:34][N:33]=[CH:32]1)=[O:30]>C1(C)C=CC=CC=1.C(N(CC)CC)C>[Cl:9][C:10]1[CH:15]=[C:14]([F:16])[C:13]([N:17]2[C:29](=[O:30])[N:31]([CH3:35])[C:32](=[S:28])[N:33]([CH3:34])[C:4]2=[O:3])=[C:12]([O:18][CH3:19])[C:11]=1[N+:20]([O-:22])=[O:21]

Participants

7

Reactant 4

HCID 10426DiphosgeneHCID 682631,1'-CarbonyldiimidazoleHCID 2723631N,N'-DimethylthioureaHCID 181760194-Chloro-6-fluoro-2-methoxy-3-nitrophenylamine

Product 1

HCID 181760083-(4-Chloro-6-fluoro-2-methoxy-3-nitrophenyl)-1,5-dimethyl-6-thioxo-[1,3,5]triazinane-2,4-dione

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 3.0 g (15.0 mmol) of diphosgene in 5 ml of toluene was added dropwise at approximately 20° C. to a solution of 3.0 g (13.6 mmol) of 4-chloro-6-fluoro-2-methoxy-3-nitrophenylamine in 15 ml of toluene. Then, the mixture was slowly heated to reflux temperature and stirred for 6 hours under reflux. After the reaction mixture had been concentrated and dried, the crude isocyanate was redissolved in 5 ml of toluene to be used in the next reaction. 6 ml of triethylamine and a solution of 3.55 g (14.4 mmol) of dimethylthiourea were added dropwise to this solution at approximately 20° C. 4.7 g (28.8 mmol) of carbonyldiimidazole were subsequently added to the reaction mixture. The mixture was heated at 80° C. for 5 hours and then allowed to cool. For work-up, it was firstly washed four times with water. Then, the organic phase was dried over magnesium sulfate and concentrated under reduced pressure. The crude product (6.58 g) was purified by silica gel chromatography (mobile phase: cyclohexane/ethyl acetate=10:1). Yield: 1.31 g (24%);

Workup

  1. temperatureThen, the mixture was slowly heated
  2. temperatureto reflux temperature
  3. temperatureunder reflux
  4. concentrationAfter the reaction mixture had been concentrated
  5. customdried
  6. dissolutionthe crude isocyanate was redissolved in 5 ml of toluene
  7. customto be used in the next reaction
  8. temperatureto cool
  9. washFor work-up, it was firstly washed four times with water
  10. dry with materialThen, the organic phase was dried over magnesium sulfate
  11. concentrationconcentrated under reduced pressure
  12. customThe crude product (6.58 g) was purified by silica gel chromatography (mobile phase: cyclohexane/ethyl acetate=10:1)

Sources & evidence

ORD record
ord-ac4b319ced2046b99950b95e610109ee
Source dataset
uspto-grants-2003_08
Patent number
US06602825B1

Reaction notes

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