Phosgene → Ethoxysulfuron

HRID 840342Notes

Reaction equation

HRID 840342 reaction equation
[C:1](Cl)(Cl)=[O:2].[NH2:5][C:6]1[N:11]=[C:10]([O:12][CH3:13])[CH:9]=[C:8]([O:14][CH3:15])[N:7]=1.C(N(CC)CC)C.[CH2:23]([O:25][C:26]1[CH:36]=[CH:35][CH:34]=[CH:33][C:27]=1[O:28][S:29]([NH2:32])(=[O:31])=[O:30])[CH3:24]>C(OCC)(=O)C.O>[CH3:13][O:12][C:10]1[CH:9]=[C:8]([O:14][CH3:15])[N:7]=[C:6]([NH:5][C:1](=[O:2])[NH:32][S:29]([O:28][C:27]2[CH:33]=[CH:34][CH:35]=[CH:36][C:26]=2[O:25][CH2:23][CH3:24])(=[O:31])=[O:30])[N:11]=1

Participants

7

Reactant 4

HCID 6371Phosgene2×HCID 8471Triethylamine2×HCID 1189462-Amino-4,6-dimethoxypyrimidineHCID 145806752-Ethoxyphenyl sulfamate

Product 1

HCID 3623881Ethoxysulfuron

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent4×

Conditions

Temperature
-10 °C

Procedure

Ethyl acetate (16 ml) was introduced and cooled to −10° C. under nitrogen. Phosgene (4.0 g, 0.04 mol) was passed in at this temperature and then a solution of 2-amino-4,6dimethoxypyrimidine (2.86 g, 0.0185 mol) and triethylamine (3.73 g, 0.037 mol) in ethyl acetate (20 ml) was added dropwise in the course of 2 h. After 1 h, the reaction was warmed to 20° C., nitrogen was blown through until there was no longer phosgene in the solution, and then a solution of 2-ethoxyphenoxysulfonamide (4.0 g, 0.0184 mol) in ethyl acetate (10 ml) and triethylamine (1.86 g, 0.0184 mol) in ethyl acetate (10 ml) were successively added dropwise in the course of 30 min. After 30 min, water (100 ml) was added, the phases were separated and the organic phase was extracted with 2×25 ml of 1.5M sodium hydroxide solution. The aqueous phases were combined, washed with xylene (20 ml), adjusted to pH=2 using 6M hydrochloric acid and the product was filtered off and dried; yield: 5.57 g, 70.7% of theory.

Workup

  1. temperaturethe reaction was warmed to 20° C.
  2. waitAfter 30 min
  3. customthe phases were separated
  4. extractionthe organic phase was extracted with 2×25 ml of 1.5M sodium hydroxide solution
  5. washwashed with xylene (20 ml)
  6. filtrationthe product was filtered off
  7. customdried

Sources & evidence

ORD record
ord-473ef57d8f1e42a2bc4a143b6eac40a0
Source dataset
uspto-grants-2002_04
Patent number
US06365739B1

Reaction notes

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