Ethylene Glycol → HCID 21940697, compound

HRID 1883389Notes

Reaction equation

HRID 1883389 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[NH2:17][CH2:18][CH2:19][CH2:20][NH:21][CH2:22][CH2:23][CH2:24][CH2:25][NH2:26].[CH2:27](O)[CH2:28]O.N>O.[Cu]I.C(O)(C)C>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([NH:26][CH2:25][CH2:24][CH2:23][CH2:22][NH:21][CH2:20][CH2:19][CH2:18][NH:17][C:2]2[CH:7]=[CH:6][C:27]([CH3:28])=[CH:4][CH:3]=2)=[CH:3][CH:4]=1

Participants

9

Reactant 5

HCID 174Ethylene GlycolHCID 222AmmoniaHCID 1102SpermidineHCID 122074-IodotolueneHCID 62657Potassium Phosphate, Tribasic

Product 1

HCID 21940697HCID 21940697, compoundYield 73%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 3776IsopropanolSolvent

Conditions

Temperature
80 °C

Procedure

An oven-dried resealable 15 mL Schlenk tube was charged with CuI (9.6 mg, 0.0504 mmol), 4-Iodotoluene (260 mg, 1.19 mmol), K3PO4 (440 mg, 2.07 mmol), evacuated and backfilled with argon. N-(3-Aminopropyl)-1,4-butanediamine (79 μL, 0.503 mmol), ethylene glycol (115 μL, 2.06 mmol), and isopropyl alcohol (1.0 mL) were added under argon. The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred magnetically at 80° C. for 23 h. The resulting thick, gray-brown suspension was allowed to reach room temperature, poured into a solution of 30% aq ammonia (1 mL) in water (20 mL), and extracted with 3×15 mL of CH2Cl2. The organic phase was dried (Na2SO4), concentrated, and the residue was purified by flash chromatography on silica gel (2×15 cm; dichloromethane-dichloromethane saturated with 30% aq ammonia-methanol 30:20:2; 15 mL fractions). Fractions 12-24 were concentrated and the residue was recrystallized from hexanes (2 mL) to give 119 mg (73% yield) of the desired product as fine white crystals. 1H NMR (400 MHz, CDCl3): δ 6.98 (d, J=8.4 Hz, 4H), 6.56−6.50 (m, 4H), 4.04 (br s, 1H), 3.56 (br s, 1), 3.17 (t, J=6.6 Hz, 2H), 3.11 (t, J=6.6 Hz, 2H), 2.74 (t, J=6.6 Hz, 2H), 2.64 (t, J=6.9 Hz, 2H), 2.23 (s, 6H), 1.79 (quintet, J=6.6 Hz, 2H), 1.70−1.54 (m, 4H), 0.95 (br s, 1H). 13C NMR (100 MHz, CDCl3): δ 146.3, 146.1, 129.7, 126.3, 112.89, 112.85, 49.8, 48.5, 44.2, 43.3, 29.6, 27.8, 27.3, 20.4.

Workup

  1. customevacuated
  2. customThe Schlenk tube was sealed with a Teflon valve
  3. customto reach room temperature
  4. extractionextracted with 3×15 mL of CH2Cl2
  5. dry with materialThe organic phase was dried (Na2SO4)
  6. concentrationconcentrated
  7. customthe residue was purified by flash chromatography on silica gel (2×15 cm; dichloromethane-dichloromethane saturated with 30% aq ammonia-methanol 30:20:2; 15 mL fractions)
  8. concentrationFractions 12-24 were concentrated
  9. customthe residue was recrystallized from hexanes (2 mL)

Sources & evidence

ORD record
ord-cf6399fdceb3498ab75493c7ce277a8f
Source dataset
uspto-grants-2004_07
Patent number
US06759554B2

Reaction notes

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