4,4'-(Pentamethylenedioxy)-bis-(nitrobenzene) → 1,5-Bis(p-aminophenoxy)pentane

HRID 8417

Reaction equation

HRID 8417 reaction equation
[N+:1]([C:4]1[CH:25]=[CH:24][C:7]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][O:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-])=O)=[CH:17][CH:16]=2)=[CH:6][CH:5]=1)([O-])=O.[H][H]>O1CCCC1.[Pd]>[NH2:21][C:18]1[CH:17]=[CH:16][C:15]([O:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][O:8][C:7]2[CH:6]=[CH:5][C:4]([NH2:1])=[CH:25][CH:24]=2)=[CH:20][CH:19]=1

Participants

5

Reactant 2

HCID 5505304,4'-(Pentamethylenedioxy)-bis-(nitrobenzene)HCID 178418361HCID 178418361, compound

Product 1

HCID 141731,5-Bis(p-aminophenoxy)pentaneYield 90%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 1,5-bis(4-nitrophenoxy)pentane (32.7 grams, 94.4 mmol; prepared as described in Part A of this Example) and Pd/C 10% (1.00 gram, obtained from Aldrich Chemical Co.) was stirred for 20 hours in tetrahydrofuran (400 milliliters) under 200 pounds per square inch of hydrogen gas. The mixture was then filtered over CELITE, and the solvent was removed by evaporation under reduced pressure. The resulting crude solid was recrystallized from ethanol to afford pure 1,5-bis(4-aminophenoxy)pentane (24.4 grams, 85.1 mmol, 90 percent yield) as small colorless crystals: mp 78–79° C.; IR (KBr) 3433, 3353, 3217, 2949, 2868, 1856, 1632, 1511, 1473, 1396, 1228, 1031, 1002, 825, 517 cm−1; 1H NMR (300 MHz, CDCl3) δ 6.76 (d, 4H, 3J=8.8 Hz), 6.64 (d, 4H, 3J=8.8 Hz), 3.92 (td, 4H, 3J=6.4 Hz, 4J=1.4 Hz), 3.40 (s, 4H), 1.82 (q, 4H, 3J=6.8 Hz), 1.62 (q, 2H, 3J=6.8 Hz); 13C NMR (75 MHz, CDCl3) δ 151.31, 140.06, 116.51, 115.78, 68.58, 29.32, 22.83; MS (FAB, 3-nitrobenzyl alcohol) m/e 286.7; Anal. Calcd for C17H22N2O2: C, 71.30; H, 7.74; N, 9.78. Found: C, 71.11; H, 8.22; N, 9.85.

Workup

  1. customprepared
  2. filtrationThe mixture was then filtered over CELITE
  3. customthe solvent was removed by evaporation under reduced pressure
  4. customThe resulting crude solid was recrystallized from ethanol

Sources & evidence

ORD record
ord-a7f7ae6390344917803d662834d38ff3
Source dataset
uspto-grants-2006_08
Patent number
US07087752B2

Linked notes

Loading…