Triphenylphosphine → {1-[3-cyano-5-(trifluoromethyl)phenyl]-1H-tetrazol-5-yl}methyl acetate

HRID 517716Notes

Reaction equation

[C:1]([O:4][CH2:5][C:6]([NH:8][C:9]1[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[C:11]([C:19]#[N:20])[CH:10]=1)=O)(=[O:3])[CH3:2].C[Si]([N:25]=[N+:26]=[N-:27])(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.CCOC(C)=O>[C:1]([O:4][CH2:5][C:6]1[N:8]([C:9]2[CH:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[C:11]([C:19]#[N:20])[CH:10]=2)[N:27]=[N:26][N:25]=1)(=[O:3])[CH3:2]

Participants

Conditions

Temperature: 50 °C

Procedure

To a solution of 2-{[3-cyano-5-(trifluoromethyl)phenyl]amino}-2-oxoethyl acetate (Intermediate 29, 3.38 g, 11.8 mmol) in tetrahydrofuran (100 mL) was added trimethylsilylazide (3.14 mL, 23.6 mmol), triphenylphosphine (6.20 g, 23.6 mmol) then di-isopropylazodicarboxylate (4.60 mL, 23.6 mmol). The reaction was warmed to 50° C. and stirred for 6 hours. The reaction was cooled and diluted with EtOAc (150 mL). The solution was washed with water (100 mL), passed through a hydrophobic frit and the solvent removed under vacuum. The residue was purified by silica chromatography (Biotage SP4, eluting 10% EtOAc in iso-hexane (4 column volumes) then a gradient from 10-35% EtOAc in iso-hexane (over 8 column volumes)) to yield the title compound as a yellow solid (3.33 g)

Workup

temperatureThe reaction was cooled
washThe solution was washed with water (100 mL)
customthe solvent removed under vacuum
customThe residue was purified by silica chromatography (Biotage SP4
washeluting 10% EtOAc in iso-hexane (4 column volumes)

Sources & evidence

ORD record: ord-54583ebcb45e409bb56df18aef411072
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09115132B2

Reaction notes

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