Dichloromethane → HCID 18470043, compound

HRID 2228440Notes

Reaction equation

HRID 2228440 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2[S:8][CH:9]=[C:10]([Cl:13])[C:11]=2[Cl:12])=[N:5][C:4]([C:14]2[C:19]([F:20])=[CH:18][CH:17]=[CH:16][C:15]=2[Cl:21])=[N:3]1.C([O-])(=O)C.[Na+].[Br:27]Br.C(Cl)Cl>C(O)(=O)C>[CH3:1][N:2]1[C:6]([C:7]2[S:8][C:9]([Br:27])=[C:10]([Cl:13])[C:11]=2[Cl:12])=[N:5][C:4]([C:14]2[C:19]([F:20])=[CH:18][CH:17]=[CH:16][C:15]=2[Cl:21])=[N:3]1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 24408BromineHCID 517045Sodium AcetateHCID 59876984HCID 59876984, compound

Product 1

HCID 18470043HCID 18470043, compoundYield 96.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
70 °C

Procedure

To a mixture of 1-methyl-3-(2-chloro-6-fluorophenyl)-5-(3,4-dichlorothien-2-yl) [1,2,4]triazole (33.4 g, 92.1 mmol) and sodium acetate (7.6 g, 92.1 mmol) in acetic acid (250 mL) was added bromine (58.9 g, 368.4 mmol) dropwise at a rate which maintained the reaction temperature below 35° C. The resulting mixture was slowly heated to 70° C. and stirred for 2.5 hours, cooled to 50° C. and stirred overnight, and cooled to room temperature. TLC analysis (methylene chloride) indicates full consumption of the starting material. The reaction was slowly poured into a mixture of 10% aqueous sodium bisulfite and ice (300 mL), and the resulting pale yellow suspension was stirred for 20 minutes. The solids were collected by vacuum filtration, washed with water, and dissolved in methylene chloride. The organics were dried (sodium sulfate), filtered, and the solvent evaporated at reduced pressure to give 39.3 g (96%) of desired product as a tan solid: mp 178-180° C. 1H NMR (CDCl3) δ4.04 (s, 3H), 7.08-7.14 (Ar-m, 1H), 7.29-7.40 (Ar-m, 2H).

Workup

  1. temperaturemaintained the reaction temperature below 35° C
  2. temperaturecooled to 50° C.
  3. stirringstirred overnight
  4. temperaturecooled to room temperature
  5. customconsumption of the starting material
  6. additionThe reaction was slowly poured into a mixture of 10% aqueous sodium bisulfite and ice (300 mL)
  7. stirringthe resulting pale yellow suspension was stirred for 20 minutes
  8. filtrationThe solids were collected by vacuum filtration
  9. washwashed with water
  10. dissolutiondissolved in methylene chloride
  11. dry with materialThe organics were dried (sodium sulfate)
  12. filtrationfiltered
  13. customthe solvent evaporated at reduced pressure

Sources & evidence

ORD record
ord-13844da80a9f42959a954b633a7dd012
Source dataset
uspto-grants-2002_07
Patent number
US06417187B2

Reaction notes

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