Tributylphosphine → Methyl(4,7-dichloro-6-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)methoxy)-1-benzothiophen-3-yl)acetate

HRID 591432Notes

Reaction equation

HRID 591432 reaction equation
C(P(CCCC)CCCC)CCC.[CH3:14][O:15][C:16](=[O:30])[CH2:17][C:18]1[C:22]2[C:23]([Cl:29])=[CH:24][C:25]([OH:28])=[C:26]([Cl:27])[C:21]=2[S:20][CH:19]=1.[CH3:31][N:32]1[C:36]([CH2:37]O)=[CH:35][C:34]([C:39]([F:42])([F:41])[F:40])=[N:33]1.C1CCN(C(N=NC(N2CCCCC2)=O)=O)CC1>C1COCC1>[CH3:14][O:15][C:16](=[O:30])[CH2:17][C:18]1[C:22]2[C:23]([Cl:29])=[CH:24][C:25]([O:28][CH2:37][C:36]3[N:32]([CH3:31])[N:33]=[C:34]([C:39]([F:42])([F:40])[F:41])[CH:35]=3)=[C:26]([Cl:27])[C:21]=2[S:20][CH:19]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 58456726(1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)methanolHCID 121006406Methyl(4,7-dichloro-6-hydroxy-1-benzothiophen-3-yl)acetate

Product 1

HCID 89768823Methyl(4,7-dichloro-6-((1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)methoxy)-1-benzothiophen-3-yl)acetateYield 88.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of tri-n-butylphosphine (0.193 mL), methyl(4,7-dichloro-6-hydroxy-1-benzothiophen-3-yl)acetate (150 mg), (1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)methanol (102 mg) and THF (5.0 mL) was added ADDP (195 mg) at room temperature. The mixture was stirred at room temperature under nitrogen atmosphere overnight. The mixture was concentrated in vacuo. To the residue was added IPE and the precipitate was filtered off. The filtrate was concentrated in vacuo. The residue was purified by silica gel column chromatography (NH, EtOAc/hexane) to give the title compound (205.9 mg). The solid was crystallized from EtOAc-hexane to give the title compound.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. additionTo the residue was added IPE
  3. filtrationthe precipitate was filtered off
  4. concentrationThe filtrate was concentrated in vacuo
  5. customThe residue was purified by silica gel column chromatography (NH, EtOAc/hexane)

Sources & evidence

ORD record
ord-072036c0b9d54d3aa7658c3544c426c6
Source dataset
uspto-grants-2016_01
Patent number
US09238639B2

Reaction notes

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