O-Phenylenediamine → HCID 86689298, compound

HRID 537324Notes

Reaction equation

HRID 537324 reaction equation
[C:1]1([NH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[NH2:7].[CH2:9]([O:13][C:14]1[CH:15]=[C:16]([CH:22]=[CH:23][CH:24]=1)[O:17][CH2:18][C:19](O)=O)[CH:10]([CH3:12])[CH3:11]>Cl>[N:7]1[C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=2[NH:8][C:19]=1[CH2:18][O:17][C:16]1[CH:22]=[CH:23][CH:24]=[C:14]([O:13][CH2:9][CH:10]([CH3:11])[CH3:12])[CH:15]=1

Participants

4

Reactant 2

HCID 7243O-PhenylenediamineHCID 4067614HCID 4067614, compound

Product 1

HCID 86689298HCID 86689298, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

A 250 mL flask fitted with a stir-bar and condenser was charged with 1,2-phenylenediamine (2.46 g, 22.7 mmol), acid 72 (5.10 g, 22.7 mmol), and 4M HCl (50 mL). The resultant suspension was heated in a 125° C. bath for 72 hr. The mixture was cooled, and concentrated in vacuo to a green solid. The solid was triturated with acetone (50 mL), filtered, and rinsed with acetone (2×20 mL). The solid was then triturated with H2O (50 mL) and filtered. The material was next taken up in MeOH:H2O 1:1 (75 mL), and the pH was adjusted to 11 with 2M NaOH (10 mL). The mixture was then extracted with EtOAc (100 mL). The organic phase was washed with saturated aqueous NH4Cl (50 mL) and brine (50 mL), filtered through phase separation paper, and concentrated in vacuo to a light pink glass. The material crystallized to give 3.95 g of 73 as a white solid (59%). 1H NMR (60 MHz, CDCl3): δ 7.8-7.6 (m, 2H), 7.5-7.0 (m, 3H), 6.6-6.4 (m, 3H), 5.4 (s, 2H), 3.5 (d, 2H), 1.9 (nonet, 1H), 0.9 (d, 6H) ppm. HPLC analysis (15:10:75 H2O:A1:MeOH) showed a purity of 99% with a retention time of 8.5 min.

Workup

  1. customA 250 mL flask fitted with a stir-bar and condenser
  2. temperatureThe mixture was cooled
  3. concentrationconcentrated in vacuo to a green solid
  4. customThe solid was triturated with acetone (50 mL)
  5. filtrationfiltered
  6. washrinsed with acetone (2×20 mL)
  7. customThe solid was then triturated with H2O (50 mL)
  8. filtrationfiltered
  9. extractionThe mixture was then extracted with EtOAc (100 mL)
  10. washThe organic phase was washed with saturated aqueous NH4Cl (50 mL) and brine (50 mL)
  11. filtrationfiltered through phase separation paper
  12. concentrationconcentrated in vacuo to a light pink glass
  13. customThe material crystallized

Sources & evidence

ORD record
ord-c73ab2c6bb354a66a7131a216ce3e138
Source dataset
uspto-grants-2014_10
Patent number
US08859780B2

Reaction notes

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