Synthesis of Urea Derivatives from CO₂ and Amines Catalyzed by Polyethylene Glycol Supported Potassium Hydroxide without Dehydrating Agents

Abstract

Polyethylene glycol supported potassium hydroxide (KOH/PEG1000) was developed as a recyclable catalyst for facile synthesis of urea derivatives from amines and CO₂ without utilization of additional dehydrating agents. Primary aliphatic amines, secondary aliphatic amines, and diamines can be converted into the corresponding urea derivatives in moderate yields. Furthermore, the catalyst can be recovered after a simple separation procedure, and reused over 5 times with retention of high activity.

Key words

amine - carbon dioxide - polyethylene glycol - urea - supported catalyst

References and Notes

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11

In the ^¹H NMR spectra, the chemical shift for NH peak of Et₂NH/CDCl₃/CO₂ was shifted to upfield from δ = 5.947 to 5.194 ppm after adding PEG to the solution. The ^¹H NMR charts were provided on pS15 in the Supplementary Information.

13

General Procedure for the Synthesis of Urea from Amines and CO ₂
A 50 mL autoclave reactor was charged with amine (4 mmol), KOH/PEG1000 (0.4 mmol). CO₂ was introduced into the autoclave, and then the mixture was stirred at desired temperature for 15 min to allow equilibration. Finally, the pressure was adjusted to the reaction pressure (e.g., 8 MPa), and the mixture was stirred continuously. When the reaction finished, the reactor was cooled in ice-water and CO₂ was ejected slowly. An aliquot of sample was taken from the resultant mixture for GC analysis. The catalyst (KOH/PEG1000) was separated by adding Et₂O and cooling and recovered by a simple filtration. The products were further identified by ^¹H NMR and ^¹³C NMR spectroscopy, which are consistent with those reported in the literature^¹4 and in good agreement with the assigned structures (see electronic Supplementary Information).

1,3-Dibutylurea (Table 3, Entry 1)
^¹H NMR (300 MHz, CDC1₃): δ = 0.91 (t, 6 H, J = 7.2 Hz), 1.30-1.40 (m, 4 H), 1.41-1.51 (m, 4 H), 3.14 (q, 4 H), 4.61 (br d, NH). ^¹³C {^lH} NMR (75.5 MHz, CDCl₃): δ = 158.5, 40.3, 32.4, 20.0, 13.8.