Specifics of cross-aldol condensation of acetaldehyde with formaldehyde in presence of aminoacids and their derivatives
Abstract
Reaction of cross-aldol condensation of acetaldehyde with formaldehyde at presence of aminoacids and their ether- and benzoil-derivatives were studied in pyridine, N, N-dymethylacetamide, water and toluene. It was shown that aminoacids are capable to catalyse cross- and homocondensation of acetaldehyde. The yield of acrolein in presence of aminoacids is much lower than with use of its derivatives. The selectivity of cross-condensation is dependent from acid-base properties of catalyst and the reaction media. It is found that the main contribute to catalysis of cross-condensation is introduced by amino-group of aminoacid and it basic properties determine the yield of acrolein
Keywords
541. 128. 3:542. 952:541. 124:547. 257. 4. -386:547. 952. 3
About the Authors
L. V. Dashko
МИТХТ им. М.В. Ломоносова, 119571, Москва, пр-т Вернадского, д. 86
Russian Federation
Russian Federation
D. V. Dmitriev
МИТХТ им. М.В. Ломоносова, 119571, Москва, пр-т Вернадского, д. 86
Russian Federation
Russian Federation
V. R. Flid
МИТХТ им. М.В. Ломоносова, 119571, Москва, пр-т Вернадского, д. 86
Russian Federation
Russian Federation
References
1. Mestres, R. A green look at the aldol reaction / R. Mestres // Green Chem. - 2004. - Vol. 6. - P. 583-603.
2. Northrup, A. B. The first direct and enantioselective cross-aldol reaction of aldehydes / A. B. Northrup, D. W. C. MacMillan // J. Am. Chem. Soc. - 2002. - Vol. 124. - P. 6798-6799.
3. Вопросы селективности альдольной гомо- и кросс-конденсации низших альдегидов в присутствии различных солей аминов / Л. В. Дашко, В. В. Медведев, Д. В. Дмитриев, В. Р. Флид // Вестник МИТХТ. - 2008. - Т. 3, № 4. - С. 23-31.
4. Гордон, А. Спутник химика / А. Гордон, Р. Форд. - М. : Мир, 1976. - 541 с.
5. Титце, Л. Препаративная органическая химия / Л. Титце, Т. Айхер. - М. : Мир, 1999. - 704 с.
6. Proline-catalysed Mannich reactions of acetaldehyde / Yang Jung Woon, С. Chandler, М. Stadler, D. Kampen, B. List // Nature. - 2008. - Vol. 452. - Р. 453-455.
7. Enantioselective organocatalytic direct aldol reactions of α-oxyaldehydes: step one in a two-step synthesis of carbohydrates / A. B. Northrup, I. K. Mangion, F. Hettche, D. W. C. MacMillan // Angew. Chem. Int. Ed. - 2004. - Vol. 43. - P. 2152-2154.
8. Erkkilä, A. Rapid organocatalytic aldehyde-aldehyde condensation reaction / A. Erkkilä, P. M. Pihko // Eur. J. Org. Chem. - 2007. - P. 4205-4216
9. Samanta, S. Asymmetric direct aldol reaction of 1,2-diketones and ketones mediated by proline derivatives // S. Samanta, C.-G. Zhao / Tetrahedron Lett. - 2006. - Vol. 47. - P. 3383-3386.
10. Cordova, A. Direct catalytic asymmetric cross-aldol reactions in ionic liquid media / A. Cordova // Tetrahedron Lett. - 2004. - Vol. 45. - P. 3949-3952.
11. Cordova, A. Catalyzed one-step asymmetric synthesis of 5-hydroxy-(2E)-hexenal from acetaldehyde / A. Cordova, W. Notz, C. F. Barbas III // J. Org. Chem. - 2002. - Vol. 67. - P. 301-303.
12. Vapor phase aldol condensation over fully ion-exchanged montmorillonite-rich catalysts / A. Azzouz, D. Messad, D. Nistor, C. Catrinescu, A. Zvolinschi, S. Asaftei // Appl. Catalysis. A. - 2003. - Vol. 241. - P. 1-13.
Review
For citations:
Dashko L.V., Dmitriev D.V., Flid V.R. Specifics of cross-aldol condensation of acetaldehyde with formaldehyde in presence of aminoacids and their derivatives. Fine Chemical Technologies. 2009;4(4):49-54. (In Russ.)
Views: 353
Email this article 
