Trifluoroacetic acid → HCID 12146505, compound

HRID 1836433Notes

Reaction equation

HRID 1836433 reaction equation
[CH2:1]([O:3][C:4](=[O:30])[CH2:5][S:6][C:7]1[CH:12]=[CH:11][C:10]([C:13](=[O:29])[NH:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([NH:21]C(OC(C)(C)C)=O)[CH:16]=2)=[CH:9][N:8]=1)[CH3:2].C(O)(C(F)(F)F)=O.N([O-])=O.[Na+].[N-:42]=[N+:43]=[N-].[Na+]>C(Cl)Cl.O>[CH2:1]([O:3][C:4](=[O:30])[CH2:5][S:6][C:7]1[CH:12]=[CH:11][C:10]([C:13](=[O:29])[NH:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([N:21]=[N+:42]=[N-:43])[CH:16]=2)=[CH:9][N:8]=1)[CH3:2]

Participants

7

Reactant 4

HCID 6422Trifluoroacetic acidHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 69587923HCID 69587923, compound

Product 1

HCID 12146505HCID 12146505, compoundYield 118.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. solution of [5-(3-tert-butoxycarbonylaminophenyl-carbamoyl)pyridin-2-ylsulfanyl]-acetic acid ethyl ester (41 mg, 0.10 mmol) in DCM (3 mL) was added TFA (3 mL) followed by stirring for 15 minutes. The mixture was concentrated in vacuo and was taken up in a mixture of acetic acid (3 mL) and water (1 mL), cooled to 0° C., and treated with a solution of sodium nitrite (15 mg, 0.23 mmol) in water (1 mL). After 5 minutes, the mixture was treated with neat sodium azide (15 mg, 0.22 mmol) and the solution was allowed to warm to an ambient temperature over 30 minutes. The mixture was poured into water and was extracted with ethyl acetate (3×25 mL) and the combined extracts were washed with water and brine and dried over magnesium sulfate. Filtration and concentration gave 42.4 mg (100%) of the [5-(3-azido-phenylcarbamoyl)-pyridin-2-ylsulfanyl]-acetic acid ethyl ester as a solid: 1H NMR (300 MHz, acetone-d6) δ 9.73 (bs, 1H), 8.98 (m, 1H), 8.18 (m, 1H), 7.75 (m, 1H), 7.60 (m, 1H), 7.45 (m, 1H, 7.39 (m, 1H), 6.85 (m, 1H), 4.15 (m, 2H), 4.07 (s, 2H), 1.22 (m, 3H); MS (EI) m/z 356.11 (M−H)−.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. additionwas taken up in a mixture of acetic acid (3 mL) and water (1 mL)
  3. waitAfter 5 minutes
  4. temperatureto warm to an ambient temperature over 30 minutes
  5. extractionwas extracted with ethyl acetate (3×25 mL)
  6. washthe combined extracts were washed with water and brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-c855a75472ed4f1f864b1bb117dfd2e5
Source dataset
uspto-grants-2004_08
Patent number
US06777432B1

Reaction notes

Loading…