Sodium Azide → 2-[(S)-1-Phenylethylamino]-4-[6-azidobenzimidazol-1-yl]pyrimidine

HRID 2300811Notes

Reaction equation

HRID 2300811 reaction equation
N([O-])=O.[Na+].[C:5]1([C@@H:11]([NH:13][C:14]2[N:19]=[C:18]([N:20]3[C:24]4[CH:25]=[C:26]([NH2:29])[CH:27]=[CH:28][C:23]=4[N:22]=[CH:21]3)[CH:17]=[CH:16][N:15]=2)[CH3:12])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[N-:30]=[N+:31]=[N-].[Na+]>O.C(O)(=O)C.C(OCC)(=O)C>[C:5]1([C@@H:11]([NH:13][C:14]2[N:19]=[C:18]([N:20]3[C:24]4[CH:25]=[C:26]([N:29]=[N+:30]=[N-:31])[CH:27]=[CH:28][C:23]=4[N:22]=[CH:21]3)[CH:17]=[CH:16][N:15]=2)[CH3:12])[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1

Participants

7

Reactant 3

HCID 33557Sodium AzideHCID 98188992-[(S)-1-phenylethylamino]-4-[6-aminobenzimidazol-1-yl]pyrimidineHCID 23668193Sodium Nitrite

Product 1

HCID 599246882-[(S)-1-Phenylethylamino]-4-[6-azidobenzimidazol-1-yl]pyrimidineYield 73.7%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 16.3 mg of NaNO2 in 0.5 mL of H2O was added to a 5° C. solution of 78 mg of 2-[(S)-1-phenylethylamino]-4-[6-aminobenzimidazol-1-yl]pyrimidine in 2 mL acetic acid. The solution was cooled to 0° C. and stirred for 0.5 hours. A solution of 23 mg of NaN3 in 0.5 mL H2O was added and stirred for one hour. The solution was diluted with 100 mL of ethyl acetate and washed with water, saturated NaHCO3 and brine. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography eluting with methanol in methylene chloride to give 62 mg of the title compound. RF: 0.6 (5% MeOH in CH2Cl2). 1H NMR (300 MHz, CD3OD): δ1.57 (d, J=7 Hz, 3H), 5.18 (q, J=8 Hz, 1H), 6.88 (d, J=6 Hz, 1H), 7.05 (dd, J=2.5, 9 Hz, 1H), 7.18 (m, 1H), 7.29 (t, J=6 Hz, 2H), 7.43 (d, J=9 Hz, 2H), 7.65 (d, J=9 Hz, 1H), 8.02 (m, 1H), 8.3 (d, J=6 Hz, 1H), 8.69 (b s, 1H). Mass Spectrum (CH3CN-TFA-NH4HCO2-ESI): 357.2 (M+1).

Workup

  1. stirringstirred for one hour
  2. washwashed with water, saturated NaHCO3 and brine
  3. dry with materialThe organic phase was dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by flash chromatography
  7. washeluting with methanol in methylene chloride

Sources & evidence

ORD record
ord-4d4bb7cd158440c09144ad9f76ae622d
Source dataset
uspto-grants-2002_12
Patent number
US06498165B1

Reaction notes

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