O-Phenylenediamine → HCID 58746641, compound

HRID 724707Notes

Reaction equation

HRID 724707 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH2:9][C@H:10]([NH:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:11]([O:13]CC2C=CC=CC=2)=O)[CH:5]=[CH:6][C:7]=1[I:8].[OH-].[Na+].F[P-](F)(F)(F)(F)F.[N:38]1(O[P+](N(C)C)(N(C)C)N(C)C)[C:42]2[CH:43]=[CH:44][CH:45]=[CH:46][C:41]=2[N:40]=N1.C1(N)C(N)=CC=CC=1.C(N(CC)C(C)C)(C)C>C(#N)C.O.Cl.CN(C=O)C.C(OCC)(=O)C>[NH2:38][C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][C:41]=1[NH:40][C:11](=[O:13])[C@@H:10]([NH:21][C:22](=[O:23])[O:24][C:25]([CH3:26])([CH3:27])[CH3:28])[CH2:9][C:4]1[CH:5]=[CH:6][C:7]([I:8])=[C:2]([Br:1])[CH:3]=1

Participants

11

Reactant 5

HCID 7243O-PhenylenediamineHCID 14798Sodium HydroxideHCID 81531DiisopropylethylamineHCID 151348Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphateHCID 86602082HCID 86602082, compound

Product 1

HCID 58746641HCID 58746641, compoundYield 60%

Reagents, catalysts & solvents 5

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
25 °C

Procedure

Benzyl (2S)-3-(3-bromo-4-iodophenyl)-2-[(tert-butoxycarbonyl)amino]propanoate (1.50 g, 2.68 mmol) was dissolved in acetonitrile (7.5 mL) and treated with 1.0 M of sodium hydroxide in water (5.4 mL). The solution was stirred at 25° C. for 30 min. The reaction was diluted with 1 N HCl solution and extracted with ethyl acetate three times, dried with sodium sulfate, filtered, and concentrated in vacuo. The crude was dissolved in DMF (4.0 mL) and treated with benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (1.03 g, 2.34 mmol) at 0° C. for 15 min. A solution of 1,2-benzenediamine (345 mg, 3.19 mmol) and N,N-diisopropylethylamine (1.85 mL, 10.6 mmol) in DMF (4.0 mL) was added to the reaction. The resulting mixture was warmed to room temperature for 2 h. The reaction was diluted with ethyl acetate and washed with saturated sodium bicarbonate solution (50 mL) and 1 N HCl solution (50 mL). The organic solutions were dried with sodium sulfate, filtered, and concentrated in vacuo. The crude residue was purified by preparative LCMS to yield the desired product (0.71 g, 60%). 1H NMR (400 MHz, CDCl3): δ 7.85 (d, 1H), 7.62 (s, 1H), 7.25–6.98 (m, 5H), 4.40 (t, 1H), 3.11 (dd, 1H), 2.91 (dd, 1H), 1.41 (s, 9H); LCMS found for C20H24BrIN3O3 (M+H)+: m/z=560, 562.

Workup

  1. extractionextracted with ethyl acetate three times
  2. dry with materialdried with sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. dissolutionThe crude was dissolved in DMF (4.0 mL)
  6. temperatureThe resulting mixture was warmed to room temperature for 2 h
  7. washwashed with saturated sodium bicarbonate solution (50 mL) and 1 N HCl solution (50 mL)
  8. dry with materialThe organic solutions were dried with sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe crude residue was purified by preparative LCMS

Sources & evidence

ORD record
ord-59917b1c691d4345b1c7543d2b0fedf7
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Reaction notes

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