Water → Fenoxanil

HRID 1586278Notes

Reaction equation

HRID 1586278 reaction equation
[Cl:1][C:2]1[CH:13]=[C:12]([Cl:14])[CH:11]=[CH:10][C:3]=1[O:4][C@H:5]([CH3:9])[C:6](Cl)=[O:7].[NH2:15][C:16]([CH3:22])([CH:19]([CH3:21])[CH3:20])[C:17]#[N:18].C(N(CC)CC)C.O>C1(C)C=CC=CC=1>[C:17]([C:16]([NH:15][C:6](=[O:7])[CH:5]([O:4][C:3]1[CH:10]=[CH:11][C:12]([Cl:14])=[CH:13][C:2]=1[Cl:1])[CH3:9])([CH3:22])[CH:19]([CH3:21])[CH3:20])#[N:18]

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 943552-Amino-2,3-dimethylbutyronitrileHCID 11118592(R)-2-(2,4-Dichlorophenoxy)propionyl chloride

Product 1

HCID 11262655FenoxanilYield 88%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-5 °C

Procedure

A stirred solution of (R)-2-(2,4-dichlorophenoxy)propionyl chloride (380.25 g, 1.5 mol) in toluene is cooled to -10° C. and treated simultaneously, with cooling, with 2-amino-2,3-dimethylbutyronitrile (168.3 g, 1.5 mol) and triethylamine (181.8 g, 1.8 mol) so as to maintain a reaction temperature range of -5° C. to -10° C. When the simultaneous addition of amines is complete, the reaction mixture is stirred at -5° C. for 2 hours, allowed to warm to room temperature in the absence of external heating, and treated with water. The phases are separated. The organic phase is cooled to 0° C., treated with 10% NaOH, and stirred for 1 hour at 0° C. The phases are separated. The organic phase is again washed with fresh 10% NaOH for 1 hour at 0° C., separated and washed a third time at 0° C. for 1 hour with fresh 10% NaOH. The organic phase is then washed sequentially with water, brine and water, dried over MgSO4 and concentrated in vacuo to give a residue. The residue is crystallized in petroleum ether to give the title product as a white solid, 435 g (88% yield) identified by NMR analysis.

Workup

  1. additiontreated simultaneously
  2. temperatureto maintain a reaction temperature range of -5° C. to -10° C
  3. temperatureto warm to room temperature in the absence of external heating
  4. customThe phases are separated
  5. temperatureThe organic phase is cooled to 0° C.
  6. additiontreated with 10% NaOH
  7. stirringstirred for 1 hour at 0° C
  8. customThe phases are separated
  9. washThe organic phase is again washed with fresh 10% NaOH for 1 hour at 0° C.
  10. customseparated
  11. washwashed a third time at 0° C. for 1 hour with fresh 10% NaOH
  12. washThe organic phase is then washed sequentially with water, brine and water
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated in vacuo
  15. customto give a residue
  16. customThe residue is crystallized in petroleum ether

Sources & evidence

ORD record
ord-920e1aa016cb4190b582ddffd1b4f4cd
Source dataset
uspto-grants-1999_08
Patent number
US05942640

Reaction notes

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