Arylboronic Acid-Catalyzed Direct Condensation of Carboxylic Acids with Ureas

Abstract

The first example of the catalytic direct condensation of carboxylic acids with ureas to give N-acylureas, N,N′-diacyl-2-imidazolidones, and poly(N,N′-diacyl-2-imidazolidone)s is described. Arylboronic acids bearing electron-withdrawing substituents are highly effective as catalysts for this condensation. Furthermore, a new and efficient one-pot procedure for the conversion of carboxylic acids and urea to nitriles via N-acylurea intermediates was accomplished by using arylboronic acid and rhenium(VII) oxo complexes as hybrid catalysts.

acylations - catalysis - condensation - green chemistry - nitriles

References

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<A NAME="RY01604ST-21">21</A>

A commercially available 65-70 wt% aq solution of perrhenic acid was used.

<A NAME="RY01604ST-22">22</A>

Procedure for the Direct Polycondensation of 1,10-Decanedicarboxylic Acid with 2-Imidazolidone . A reaction mixture of 1,10-decanedicarboxylic acid (4 mmol), 2-imidazolidone (4.08 mmol), and 2 (0.4 mmol) in mesitylene (4 mL) was heated at azeotropic reflux with the removal of H₂O. After 1 d, the resulting solution was cooled to ambient temperature and concentrated under reduced pressure. The reaction mixture was cooled to precipitate polymeric acylureas and diluted with toluene (ca 20 mL), and the solvents were removed by filtration. The product was dissolved in CHCl₃, precipitated into MeOH, and dried at 100 °C under reduced pressure to obtain the desired poly(acylurea) in 95% yield. The DP value, n = 34, was determined by ¹H NMR analysis. ¹H NMR (300 MHz, CDCl₃): δ = 1.18-1.44 (m, 12n H, [O=C(CH₂)₂ (CH ₂)₆ (CH₂)₂C=O) _n ], 1.56-1.75 (m, 4n H, [O=CCH₂CH ₂ (CH₂)₆CH ₂CH₂C=O) _n ], 2.33 (t, J = 8.4 Hz, 2 H, CH ₂CO₂H), 2.91 [t, J = 7.8 Hz, 4n H, (O=CCH ₂ (CH₂)₈CH ₂C=O) _n ], 3.49 (t, J = 8.4 Hz, 2 H, HNCH ₂CH₂N), 3.83 {s, 4n H, [N(CH ₂)₂N] _n }, 3.95 (t, J = 8.4 Hz, 2 H, HNCH₂CH ₂N).

<A NAME="RY01604ST-23">23</A>

Two linear GPC columns of TSK-gel-SuperHZM-M (4.6 mmID × 15 cm) and TSK-gel-HZ2000 (4.6 mm ID × 15 cm) were employed. The polymer was run at 20 µL (1 mg/mL) in CHCl₃ with a polystyrene standard.