Tributylphosphine → Methyl(4,7-dimethyl-6-((2-methyl-6-(trifluoromethyl)pyridin-3-yl)methoxy)-1-benzothiophen-3-yl)acetate

HRID 591422Notes

Reaction equation

HRID 591422 reaction equation
C(P(CCCC)CCCC)CCC.[CH3:14][C:15]1[C:20]([CH2:21][OH:22])=[CH:19][CH:18]=[C:17]([C:23]([F:26])([F:25])[F:24])[N:16]=1.[CH3:27][O:28][C:29](=[O:43])[CH2:30][C:31]1[C:35]2[C:36]([CH3:42])=[CH:37][C:38](O)=[C:39]([CH3:40])[C:34]=2[S:33][CH:32]=1.C1CCN(C(N=NC(N2CCCCC2)=O)=O)CC1>C1COCC1>[CH3:27][O:28][C:29](=[O:43])[CH2:30][C:31]1[C:35]2[C:36]([CH3:42])=[CH:37][C:38]([O:22][CH2:21][C:20]3[C:15]([CH3:14])=[N:16][C:17]([C:23]([F:24])([F:26])[F:25])=[CH:18][CH:19]=3)=[C:39]([CH3:40])[C:34]=2[S:33][CH:32]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 2760122(2-Methyl-6-(trifluoromethyl)pyridin-3-yl)methanolHCID 121004271Methyl(6-hydroxy-4,7-dimethyl-1-benzothiophen-3-yl)acetate

Product 1

HCID 118667005Methyl(4,7-dimethyl-6-((2-methyl-6-(trifluoromethyl)pyridin-3-yl)methoxy)-1-benzothiophen-3-yl)acetateYield 71.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of tri-n-butylphosphine (0.196 mL), (2-methyl-6-(trifluoromethyl)pyridin-3-yl)methanol (105 mg), methyl(6-hydroxy-4,7-dimethyl-1-benzothiophen-3-yl)acetate (130.9 mg) and THF (5.0 mL) was added ADDP (198 mg) at room temperature. The mixture was stirred at room temperature overnight under nitrogen atmosphere. 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 (EtOAc/hexane) to give the title compound (159 mg) as solid. The solid was crystallized from EtOAc-hexane.

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 (EtOAc/hexane)

Sources & evidence

ORD record
ord-6ee8ad386e8b49789e726bac523dd442
Source dataset
uspto-grants-2016_01
Patent number
US09238639B2

Reaction notes

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