Toluene → Mandipropamid

HRID 2112301Notes

Reaction equation

HRID 2112301 reaction equation
[CH2:1](Br)[C:2]#[CH:3].[C:5]1(C)[CH:10]=CC=C[CH:6]=1.[Cl:12][C:13]1[CH:18]=[CH:17][C:16]([CH:19]([OH:34])[C:20]([NH:22][CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([OH:31])=[C:27]([O:32][CH3:33])[CH:26]=2)=[O:21])=[CH:15][CH:14]=1.[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.ClC(Cl)C>[Cl:12][C:13]1[CH:14]=[CH:15][C:16]([CH:19]([O:34][CH2:10][C:5]#[CH:6])[C:20]([NH:22][CH2:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([O:31][CH2:1][C:2]#[CH:3])=[C:27]([O:32][CH3:33])[CH:26]=2)=[O:21])=[CH:17][CH:18]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 7842Propargyl bromideHCID 14798Sodium HydroxideHCID 179554462-(4-Chlorophenyl)-2-hydroxy-N-[2-(4-hydroxy-3-methoxyphenyl)ethyl]acetamide

Product 1

HCID 11292824Mandipropamid

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 63651,1-DichloroethaneSolvent

Procedure

A 80% solution of propargyl bromide in toluene (39,1 g, 0,263 mol) is added slowly at room temperature to a mixture of 2-(4-chloro-phenyl)-2-hydroxy-N-[2-(4-hydroxy-3-methoxy-phenyl)-ethyl]-acetamide (35.25 g, 0,105 mol), 30% sodium hydroxide solution (52,4 ml, 0,524 mmol) and tetrabutylammonium bromide (1,8 g) in 180 ml of dichloroethane. The reaction mixture is stirred for 16 hours at +40° C. Subsequently the mixture is evaporated and the residue is diluted with water (100 ml) and dichloroethane (100 ml). The organic phase is separated and the aqueous layer is extracted with dichloroethane. The combined organic phases are washed with brine (150 ml), dried over sodium sulfate and evaporated. The remaining oil is purified by chromatography on silica gel (ethyl acetate/hexane 1:1) to yield 2-(4-chloro-phenyl)-N-[2-(3-methoxy-4-prop-2-ynyloxy-phenyl)-ethyl]-2-prop-2-ynyloxy-acetamide, m.p. 90-92° C.

Workup

  1. customSubsequently the mixture is evaporated
  2. additionthe residue is diluted with water (100 ml) and dichloroethane (100 ml)
  3. customThe organic phase is separated
  4. extractionthe aqueous layer is extracted with dichloroethane
  5. washThe combined organic phases are washed with brine (150 ml)
  6. dry with materialdried over sodium sulfate
  7. customevaporated
  8. customThe remaining oil is purified by chromatography on silica gel (ethyl acetate/hexane 1:1)

Sources & evidence

ORD record
ord-4eed6f6ef4484de0a2bb28667add143f
Source dataset
uspto-grants-2009_04
Patent number
US07521579B2

Reaction notes

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