Methyl dichlorophosphate → 5-Chloro-2-(4-chloro-2-trifluoromethylphenyl)pentanenitrile

HRID 406367

Reaction equation

HRID 406367 reaction equation
P(Cl)(Cl)(OC)=O.[Cl:7][CH2:8][CH2:9][CH2:10][CH:11]([C:15]1[CH:20]=[CH:19][C:18]([Cl:21])=[CH:17][C:16]=1[C:22]([F:25])([F:24])[F:23])[C:12]([NH2:14])=O.N12CCCN=C1CCCCC2.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[Cl:7][CH2:8][CH2:9][CH2:10][CH:11]([C:15]1[CH:20]=[CH:19][C:18]([Cl:21])=[CH:17][C:16]=1[C:22]([F:25])([F:23])[F:24])[C:12]#[N:14]

Participants

6

Reactant 4

HCID 69611Methyl dichlorophosphateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 516892Sodium BicarbonateHCID 666188025-Chloro-2-(4-chloro-2-trifluoromethylphenyl)pentanoic acid amide

Product 1

HCID 666189395-Chloro-2-(4-chloro-2-trifluoromethylphenyl)pentanenitrileYield 79.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Methyl dichlorophosphate (1.9 mL) was added dropwise at 20° C. or less to an ice-cooled solution of 5-chloro-2-(4-chloro-2-trifluoromethylphenyl)pentanoic acid amide (3.0 g) and 1,8-diazabicyclo[5,4,0]undec-7-ene (6.4 mL) in methylene chloride (30 mL). After completion of the dropwise addition, the reaction solution was stirred at room temperature for one hour and 25 minutes. A saturated sodium bicarbonate aqueous solution was added to the reaction solution. After stirring for five minutes, the organic layer was separated. The aqueous layer was reextracted with methylene chloride. The combined organic layers were sequentially washed with 1 N hydrochloric acid, water, a saturated sodium bicarbonate aqueous solution and brine, dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (carrier: Wakogel C-200; elution solvent:heptane:ethyl acetate=49:1→19:1) to obtain 2.25 g of the title compound.

Workup

  1. additionAfter completion of the dropwise addition
  2. stirringAfter stirring for five minutes
  3. customthe organic layer was separated
  4. washThe combined organic layers were sequentially washed with 1 N hydrochloric acid, water
  5. dry with materiala saturated sodium bicarbonate aqueous solution and brine, dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (carrier: Wakogel C-200; elution solvent:heptane:ethyl acetate=49:1→19:1)

Sources & evidence

ORD record
ord-a1c3ad42df04461db79b9e1cc1260091
Source dataset
uspto-grants-2014_06
Patent number
US08754100B2

Linked notes

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