Ethylene Glycol → 4-(7-Ethyl-2,7-diaza-spiro[4.4]non-2-yl)-2-methyl-6-nitro-phenylamine

HRID 470302Notes

Reaction equation

HRID 470302 reaction equation
I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:5]([NH2:6])=[C:4]([CH3:12])[CH:3]=1.[CH2:13]([N:15]1[CH2:19][CH2:18][C:17]2([CH2:23][CH2:22][NH:21][CH2:20]2)[CH2:16]1)[CH3:14].C(O)CO.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C(O)(C)C.[Cu]I>[CH2:13]([N:15]1[CH2:19][CH2:18][C:17]2([CH2:20][N:21]([C:2]3[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[C:5]([NH2:6])=[C:4]([CH3:12])[CH:3]=3)[CH2:22][CH2:23]2)[CH2:16]1)[CH3:14]

Participants

7

Reactant 4

HCID 174Ethylene GlycolHCID 62657Potassium Phosphate, TribasicHCID 32399352-Ethyl-2,7-diazaspiro[4.4]nonaneHCID 248996464-Iodo-2-methyl-6-nitroaniline

Product 1

HCID 597852714-(7-Ethyl-2,7-diaza-spiro[4.4]non-2-yl)-2-methyl-6-nitro-phenylamineYield 60%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3776IsopropanolSolvent

Conditions

Temperature
90 °C

Procedure

A suspension of 4-iodo-2-methyl-6-nitroaniline (1.39 g, 5 mmol), 2-ethyl-2,7-diaza-spiro[4.4]nonane (770 mg, 5 mmol), CuI (190.5 mg, 1.0 mmol), ethylene glycol (931 mg, 15 mmol) and K3PO4 (3.2 g, 15 mmol) in isopropanol (40 mL) was sealed and heated at 90° C. for 19 h. After cooled down to room temperature, the reaction mixture was concentrated. The residue was purified by chromatography (16:1 CH2Cl2/MeOH) to afford the title compound (910 mg, 60%). 1H NMR (CDCl3) δ 1.29 (t, J=8 Hz, 3H), 1.96-2.19 (4H), 2.24 (s, 3H), 2.77-3.01 (6H), 3.22-3.40 (4H), 5.78 (br s, 2H NH), 6.80 (s, 1H), 7.06 (s, 1H). ESI-MS m/z 305 (MH+).

Workup

  1. customwas sealed
  2. temperatureAfter cooled down to room temperature
  3. concentrationthe reaction mixture was concentrated
  4. customThe residue was purified by chromatography (16:1 CH2Cl2/MeOH)

Sources & evidence

ORD record
ord-1aaa597bea3e4810a10be8fab931495c
Source dataset
uspto-grants-2014_01
Patent number
US08629147B2

Reaction notes

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