Sulfuric Acid → Aminocyclopyrachlor-methyl

HRID 218305Notes

Reaction equation

HRID 218305 reaction equation
O.[NH2:2][C:3]1[N:8]=[C:7]([CH:9]2[CH2:11][CH2:10]2)[N:6]=[C:5]([C:12]([OH:14])=[O:13])[C:4]=1[Cl:15].[C:16](=O)(OC)OC.S(=O)(=O)(O)O.[OH-].[Na+]>O.CO>[NH2:2][C:3]1[N:8]=[C:7]([CH:9]2[CH2:11][CH2:10]2)[N:6]=[C:5]([C:12]([O:14][CH3:16])=[O:13])[C:4]=1[Cl:15]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 12021Dimethyl CarbonateHCID 14798Sodium HydroxideHCID 670843376-Amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monohydrate

Product 1

HCID 16725794Aminocyclopyrachlor-methylYield 93.5%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

A 500 mL multi-neck flask equipped with nitrogen bubbler, addition funnel, reflux condenser, and thermocouple was charged with 6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid monohydrate (47.8 g, 0.206 mol), methanol (32 g) and dimethyl carbonate (94.5 g, 1.05 mol). Concentrated sulfuric acid (50.0 g, 0.500 mol) was added over about 30 minutes with cooling to maintain the temperature below 60° C., and then the reaction mixture was heated at 70° C. for 10 h. The resulting mixture was cooled to 15° C. and diluted with 250 mL of water. The pH of the reaction mass was raised to 5-8 by adding about 42.7 g (0.534 mol) of 50 wt % aqueous NaOH over 30 minutes with cooling to maintain the temperature in the range of 10-15° C. The resulting slurry was cooled to 5° C. and filtered. The filtered wet cake was washed with water and dried to constant weight at 50° C. to give 43.3 g (93.5% yield) of the title compound with 98% purity as a solid melting at 147-148° C.

Workup

  1. customA 500 mL multi-neck flask equipped with nitrogen bubbler, addition funnel
  2. temperaturereflux condenser
  3. temperaturewith cooling
  4. temperatureto maintain the temperature below 60° C.
  5. temperatureThe resulting mixture was cooled to 15° C.
  6. temperatureThe pH of the reaction mass was raised to 5-8
  7. temperaturewith cooling
  8. temperatureto maintain the temperature in the range of 10-15° C
  9. temperatureThe resulting slurry was cooled to 5° C.
  10. filtrationfiltered
  11. washThe filtered wet cake was washed with water
  12. customdried to constant weight at 50° C.

Sources & evidence

ORD record
ord-d2fc09284873476aab34e568f5a6a0d7
Source dataset
uspto-grants-2012_06
Patent number
US08198442B2

Reaction notes

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