4-Ethoxy-2-nitroaniline → HCID 86689280, compound

HRID 537288Notes

Reaction equation

HRID 537288 reaction equation
[CH2:1]([O:3][C:4]1[CH:10]=[CH:9][C:7]([NH2:8])=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1)[CH3:2].CCN(C(C)C)C(C)C.[CH2:23]([O:25][C:26]1[CH:27]=[C:28]([CH:34]=[CH:35][CH:36]=1)[O:29][CH2:30][C:31](Cl)=[O:32])[CH3:24]>C(Cl)Cl>[CH2:1]([O:3][C:4]1[CH:10]=[CH:9][C:7]([NH:8][C:31](=[O:32])[CH2:30][O:29][C:28]2[CH:34]=[CH:35][CH:36]=[C:26]([O:25][CH2:23][CH3:24])[CH:27]=2)=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1)[CH3:2]

Participants

5

Reactant 3

HCID 692294-Ethoxy-2-nitroanilineHCID 81531DiisopropylethylamineHCID 86689279HCID 86689279, compound

Product 1

HCID 86689280HCID 86689280, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

A 1 L 3-neck flask fitted with a stir-bar, addition funnel, and an Ar inlet was charged with aniline 46a (9.57 g, 52.6 mmol) and CH2Cl2 (200 mL). The resultant solution was cooled in an ice bath and iPr2NEt (20.4 g, 27.5 mL, 158 mmol) was added followed by acid chloride 47a (14.1 g, 65.7 mmol) in CH2Cl2 (120 mL) over 30 min. The mixture stirred at rt overnight. The red solution was diluted with CH2Cl2 (250 mL) and was washed with saturated aqueous NH4Cl (200 mL), saturated NaHCO3 (200 mL), and brine (200 mL). The organic phase was filtered through phase separation paper and concentrated in vacuo to an orange solid. The solid was triturated with EtOH (75 mL), filtered, pressed with a rubber dam, and rinsed with EtOH (3×20 mL). The solid dried to give 14.3 g of 48a as a yellow solid (80%). 1H NMR (300 MHz, CDCl3): δ 11.36 (s, 1H), 8.78 (d, 1H), 7.72 (d, 1H), 7.30-7.20 (m, 2H), 6.67-6.59 (m, 3H), 4.66 (s, 2H), 4.09 (qt, 2H), 4.07 (qt, 2H), 1.44 (t, 3H), 1.42 (t, 3H) ppm. HPLC analysis (0:10:90 H2O:A1:MeOH) showed a purity of 98% with a retention time of 4.8 min.

Workup

  1. customA 1 L 3-neck flask fitted with a stir-bar, addition funnel
  2. washwas washed with saturated aqueous NH4Cl (200 mL), saturated NaHCO3 (200 mL), and brine (200 mL)
  3. filtrationThe organic phase was filtered through phase separation paper
  4. concentrationconcentrated in vacuo to an orange solid
  5. customThe solid was triturated with EtOH (75 mL)
  6. filtrationfiltered
  7. washrinsed with EtOH (3×20 mL)
  8. customThe solid dried

Sources & evidence

ORD record
ord-a73d8e44cac34cbe8dbfd4e9d714864c
Source dataset
uspto-grants-2014_10
Patent number
US08859780B2

Reaction notes

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