Reaction of aromatic amines and ethyl acetoacetate promoted by zeolite HSZ-360. Phosgene-free synthesis of symmetric diphenylureas

Abstract

Reaction of aromatic amines 1 with ethyl acetoacetate 2 in the presence of the commercially available acid zeolite HSZ-360 gives symmetric diphenylureas 3 in good yields and excellent selectivities.

References

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9. Zeolite HSZ-360 is a commercial (Tosoh Corp.) acid faujasitic-type catalyst with 13.9 SiO₂–Al₂O₃ molar ratio, pore size 7.4 Å, surface area 500 ± 10 m² g^–1(determined in our laboratory by the BET method: S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309), acidity 0.51 mequiv. H⁺ g^–1[determined in our laboratory by temperature programmed desorption of ammonia gas (NH₃-TPD): P. Berteau and B. Delmon, Catal. Today, 1989, 5, 121] and with the following chemical composition (wt% dry basis): SiO₂ 89.0, Al₂O₃ 10.9, Na₂O 0.06.
10. Zeolite HSZ-330 is a commercial (Tosoh Corp.) acid faujasitic-type catalyst with 5.9 SiO₂–Al₂O₃ molar ratio, pore size 7.4 Å, surface area 460 ± 10 m² g^–1(determined in our laboratory by the BET method), acidity 1.59 mequiv. H⁺ g^–1[determined in our laboratory by temperature programmed desorption of ammonia gas (NH₃-TPD)] and with the following chemical composition (wt% dry basis): SiO₂ 86.1, Al₂O₃ 13.7, Na₂O 0.19.
11. KSF is a commercial (Fluka) montmorillonite with surface area 15 ± 10 m² g^–1, acidity 0.85 mequiv. H⁺ g^–1[determined in our laboratory by temperature programmed desorption of ammonia gas (NH₃-TPD)] and with the following chemical composition (average value): SiO₂(54.0%), Al₂O₃(17.0%), Fe₂O₃(5.2%), CaO (1.5%), MgO (2.5%), Na₂O (0.4%), K₂O (1.5%); K10 is a commercial (Fluka) montmorillonite with surface area 200 ± 10 m² g^–1, acidity 0.70 mequiv. H⁺ g^–1[determined in our laboratory by temperature programmed desorption of ammonia gas (NH₃-TPD)] and with the following chemical composition (average value): SiO₂(73.0%), Al₂O₃(14.0%), Fe₂O₃(2.7%), CaO (0.2%), MgO (1.1%), Na₂O (0.6%), K₂O (1.9%).
12. See for example: R. A. Sheldon, Chem. Ind. (London), 1992, 903; R. A. Sheldon, J. Mol. Catal., A, 1996, 107, 75; D. C. Dittmer, Chem. Ind. (London), 1997, 779.
13. By carrying out the reaction for longer times the same value of yield (∼70%) was observed.
14. A. F. M. Iqbal, Helv. Chim. Acta, 1976, 59, 655 3g: pale brown solid, mp 237–238 °C (lit., 236–238 °C); 3h: pale brown solid, mp 237–283.5 °C (lit., 239 °C); 3i: pale brown solid, mp 218–220 °C (lit., 219–220 °C); 3j: pale brown solid, mp 263–264 °C (lit., 263–265 °C); 3k: pale brown solid, mp 283–284.5 °C (lit., 284 °C).