Sodium Azide → HCID 178428301, compound

HRID 530408Notes

Reaction equation

HRID 530408 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([C:25]#[N:26])[CH:20]=2)[CH:5]=[C:6]([NH:8][C:9]2[N:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[CH:11][N:10]=2)[CH:7]=1.[N-:27]=[N+:28]=[N-:29].[Na+]>O.C(OCC)(=O)C.Cl.[Br-].[Zn+2].[Br-]>[CH3:1][C:2]1[CH:7]=[C:6]([NH:8][C:9]2[N:14]=[C:13]([C:15]([F:18])([F:17])[F:16])[CH:12]=[CH:11][N:10]=2)[CH:5]=[C:4]([C:19]2[CH:24]=[CH:23][CH:22]=[C:21]([C:25]3[NH:29][N:28]=[N:27][N:26]=3)[CH:20]=2)[CH:3]=1

Participants

7

Reactant 2

HCID 33557Sodium AzideHCID 90042323HCID 90042323, compound

Product 1

HCID 178428301HCID 178428301, compound

Reagents, catalysts & solvents 4

HCID 10421208Zinc bromideCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
115 °C

Procedure

A suspension of 3′-methyl-5′-{[4-(trifluoromethyl)pyrimidin-2-yl]amino}biphenyl-3-carbonitrile (354 mg, 1.00 mmol), zinc bromide (225 mg, 1.00 mmol), and sodium azide (68.3 mg, 1.05 mmol) in water (2 mL) was heated to 115° C. for 24 hours. The reaction mixture was then diluted with ethyl acetate (15 mL) and aqueous 2 M hydrochloric acid (2.25 mL) to give two layers. The layers were separated and the aqueous layer was extracted with ethyl acetate (15 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified via reverse phase HPLC to yield N-[5-methyl-3′-(1H-tetrazol-5-yl)biphenyl-3-yl]-4-(trifluoromethyl)pyrimidin-2-amine MS ESI calc'd. for C19H15F3N7 [M+H]+ 398, found 398. 1H NMR (500 MHz, DMSO-d6) δ 10.28 (s, 1H), 8.83 (d, J=4.9 Hz, 1H), 8.30 (s, 1H), 8.02 (d, J=7.8 Hz, 1H), 7.99 (s, 1H), 7.82 (d, J=7.9 Hz, 1H), 7.70 (t, J=7.8 Hz, 1H), 7.59 (s, 1H), 7.27 (d, J=4.9 Hz, 1H), 7.24 (s, 1H), 2.38 (s, 3H).

Workup

  1. customto give two layers
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with ethyl acetate (15 mL)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified via reverse phase HPLC

Sources & evidence

ORD record
ord-63512d158d514ac8b74f864fac41daba
Source dataset
uspto-grants-2016_05
Patent number
US09353066B2

Reaction notes

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