4-(2-(2-(2-(2-(5-Cyano-2-(2-methoxyethoxy)-4-nitrophenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-5-(2-methoxyethoxy)-2-nitrobenzonitrile → 2-Amino-5-(2-(2-(2-(2-(5-amino-4-cyano-2-(2-methoxyethoxy)phenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-4-(2-methoxyethoxy)benzonitrile

HRID 1405968Notes

Reaction equation

HRID 1405968 reaction equation
[C:1]([C:3]1[C:4]([N+:43]([O-])=O)=[CH:5][C:6]([O:38][CH2:39][CH2:40][O:41][CH3:42])=[C:7]([CH:37]=1)[O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][C:21]1[C:28]([O:29][CH2:30][CH2:31][O:32][CH3:33])=[CH:27][C:24]([C:25]#[N:26])=[C:23]([N+:34]([O-])=O)[CH:22]=1)#[N:2]>CC(O)=O.CC(O)C.[Fe]>[NH2:43][C:4]1[CH:5]=[C:6]([O:38][CH2:39][CH2:40][O:41][CH3:42])[C:7]([O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][C:21]2[CH:22]=[C:23]([NH2:34])[C:24]([C:25]#[N:26])=[CH:27][C:28]=2[O:29][CH2:30][CH2:31][O:32][CH3:33])=[CH:37][C:3]=1[C:1]#[N:2]

Participants

5

Reactant 1

HCID 867011944-(2-(2-(2-(2-(5-Cyano-2-(2-methoxyethoxy)-4-nitrophenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-5-(2-methoxyethoxy)-2-nitrobenzonitrile

Product 1

HCID 867011962-Amino-5-(2-(2-(2-(2-(5-amino-4-cyano-2-(2-methoxyethoxy)phenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-4-(2-methoxyethoxy)benzonitrileYield 99.4%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 3776IsopropanolSolvent

Procedure

To a solution of 4-(2-(2-(2-(2-(5-cyano-2-(2-methoxyethoxy)-4-nitrophenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-5-(2-methoxyethoxy)-2-nitrobenzonitrile (0.2 g) in AcOH (10 mL) and i-PrOH (10 mL) was added iron powder (0.5 g). The resulting mixture was heated to reflux for 1 h. After reaction finished, the mixture was cooled to room temperature, filtered, the precipitate washed with EA (10 mL). The combined washings and filtrate were concentrated under reduced pressure and purification by silica chromatography to give 0.18 g of 2-amino-5-(2-(2-(2-(2-(5-amino-4-cyano-2-(2-methoxyethoxy)phenoxy)ethoxy)ethoxy)ethoxy)ethoxy)-4-(2-methoxyethoxy)benzonitrile. 1H-NMR (400 MHz, CDCl3): δ: 6.91 (s, 1H), 6.88 (s, 1H), 6.34 (s, 1H), 6.25 (s, 1H), 4.30 (br, 2H), 4.22-4.05 (m, 10H), 3.88-3.65 (m, 16H), 3.43 (s, 6H).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureto reflux for 1 h
  3. customAfter reaction
  4. filtrationfiltered
  5. washthe precipitate washed with EA (10 mL)
  6. concentrationThe combined washings and filtrate were concentrated under reduced pressure and purification by silica chromatography

Sources & evidence

ORD record
ord-d587fb63c2af4920b1209b00f1dfda96
Source dataset
uspto-grants-2014_12
Patent number
US08916572B2

Reaction notes

Loading…