Abstract
Trimerization of 2-methylpropanal (isobutyraldehyde) is a simple and effective method to synthesize 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol-3-monoisobutyrate which are often used as film forming auxiliaries in paints. The use of solid sodium hydroxide as a catalyst provides an excellent yield of above 85 % after the optimization of the reaction time and the catalyst dosage. Furthermore, trimerization of four other aldehydes with one α-hydrogen catalyzed by solid sodium hydroxide can also take place and the yield of 1,3-diol monoesters reaches 50–70 %. Trimerization of aldehydes with one α-hydrogen can be explained by a three-step reaction mechanism: (i) aldol condensation of aldehyde; (ii) crossed Cannizzaro reaction; and (iii) esterification of carboxylic acid and alcohol.
References
Bikbaeva, G. G., Kislina, I. S., & Vinnik, M. I. (1975). Mechanism of cross Cannizzaro reaction of 2,4-dimethoxybenzaldehyde with formaldehyde in aqueous KOH solutions. Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 24, 1861–1865. DOI: 10.1007/bf00930152.
Duccini, Y., Sanfilippo, A., & Ugazio, S. P. J. (2007). European Patent No. EP 1547573. Munich, Germany: European Patent Office.
Fouquet, G., Merger, F., & Platz, R. (1979). Über die Tischtschenko-Reantion von Aldolen. Liebigs Annalen der Chemie, 10, 1591–1601. DOI: 10.1002/jlac.197919791019. (in German)
Gallagher, M., Dalton, P., Sitvarin, L., & Preti, G. (2008). Sensory and analytical evaluations of paints with and without texanol. Environment Science & Technology, 42, 243–248. DOI: 10.1021/es071555y.
Han, Z. F., Yorimitsu, H., Shinokubo, H., & Oshima, K. (2000). A highly effective aldol reaction mediated by Ti(O-n-Bu)4/t-BuOK combined reagent. Tetrahedron Letters, 41, 4415–4418. DOI: 10.1016/s0040-4039(00)00642-0.
Ito, K., Kamiyama, N., Nakanishi, S., & Otsuji, Y. (1983). Selective trimerization of aliphatic aldehydes catalyzed by polynuclear carbonylferrates. Chemistry Letters, 12, 657–660. DOI: 10.1246/cl.1983.657.
Jian, X. J., Zhang, J., Zhen, L. L., Liu, F. S., & Liu, Y. (2003a). Chinese Patent No. 1429809A. Beijing, China: State Intellectual Property Office of China.
Jian, X. J., Zhang, J., Zhen, L. L., Liu, F. S., & Liu, Y. (2003b). Chinese Patent No. 1429659A. Beijing, China: State Intellectual Property Office of China.
Kulpinski, M. S., & Nord, F. F. (1943). Essential steps in the catalytic condensation of aldehydes; New synthesis of glycol esters. Journal of Organic Chemistry, 8, 256–270. DOI: 10.1021/jo01191a007.
Mahrwald, R., Costisella, B., & Gündogan, B. (1998). Stereocontrol in aldol addition-synthesis of syn and anti 3-hydroxy aldehydes. Synthesis, 1998, 262–264. DOI: 10.1055/s-1998-2031.
Miyano, A., Tashiro, D., Kawasaki, Y., Sakaguchi, S., & Ishii, Y. (1998). Trimerization of aliphatic aldehydes to 1,3-diol monoesters catalyzed by Cp*2Sm(thf)2. Tetrahedron Letters, 39, 6901–6902. DOI: 10.1016/s0040-4039 (98)01447-6.
Swain, C. G., Powell, A. L., Sheppard, W. A., & Morgan, C. R. (1979). Mechanism of the Cannizzaro reaction. Journal of the American Chemical Society, 101, 3576–3583. DOI: 10.1021/ja00507a023.
Swan, P. (2005). An introduction to coalescing aids and Eastman film forming technologies. In Proceedings of the 36th International Conference on Coatings Technology, May 23–25, 2005 (pp. 265–278). Pardubice: Czech Republic. Univerzita Pardubice.
Takasu, T., Sasaki, T., & Yamamoto, A. (1972). U.S. Patent No. 3,703,541. Washington, DC, USA: United States Patent and Trademark Office.
Tic, W. J., Guzialowska-Tic, J., Sutor, E., & Bulanda, W. (2012). European Patent No. EP 2436667. Munich, Germany: European Patent Office.
Törmäkangas, O. P., & Koskinen, A. M. P. (2001). Fast aldol-Tishchenko reaction utilizing 1,3-diol monoalcoholates as the catalysts. Organic Process Research & Development, 5, 421–425. DOI: 10.1021/op0001335.
Villacorta, G. M., & Filippo, J. S., Jr. (1983). Lithium tungsten dioxide promoted Claisen-Tishchenko condensation of aromatic and aliphatic-aldehydes. Journal of Organic Chemistry, 48, 1151–1154. DOI: 10.1021/jo00156a001.
Villani, F. J., & Nord, F. F. (1947). Essential steps in the catalytic condensation of carbonyl compounds. III. The action of metallic alkoxides. Journal of the American Chemical Society, 69, 2605–2607. DOI: 10.1021/ja01203a011.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, YG., Luo, CX., Qian, C. et al. Trimerization of aldehydes with one α-hydrogen catalyzed by sodium hydroxide. Chem. Pap. 68, 422–426 (2014). https://doi.org/10.2478/s11696-013-0450-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2478/s11696-013-0450-5