Nuevo método para la sÃntesis de N,N-dietil-m-metilbenzamida
Resumen
Objetivos: Presentar un procedimiento factible para sintetizar DEET a partir de ácido m-toluico y dietilamina.
Métodos: El ácido m-toluico fue activado con 1,1'-carbonil-diimidazol, para obtener el producto intermedio 1- (m-toluoil) imidazol que continúa reaccionando con dietilamina, para producir DEET. De este modo, se mejoran los factores que afectan la sÃntesis de N, N-dietil-m-toluamida.
Resultados: Se obtuvo DEET mediante un procedimiento óptimo. Los subproductos de la reacción son solubles en agua; se eliminan fácilmente mediante el método de extracción lÃquido-lÃquido con agua y diclorometano. La mayor parte del DEET obtenido tiene gran pureza. Los rendimientos fueron del 94 al 95 %.
Conclusiones: Se ha proporcionado una ruta mejorada para una sÃntesis simple y eficaz de DEET a partir de ácido m-toluico y dietilamina en presencia de 1,1'-carbonil-diimidazol. El procedimiento de sÃntesis se realizó en un solo reactor y el aislamiento de DEET se logró mediante extracción lÃquido-lÃquido. El tiempo total de procedimiento se redujo significativamente. Este método de sÃntesis es fácilmente escalable y factible industrialmente.
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Referencias
Kitchen LW, Lawrence KL, Coleman RE. The role of the United States military in the development of vector control products, including insect repellents, insecticides, and bed nets, J. Vector. Ecol. 2009 [access: 18/12/2019] 34: 50-61. Available from: https://onlinelibrary.wiley.com/doi/full/10.1111/j.1948-7134.2009.00007.x
Zhu Y, Wang X, inventor. Cangzhou Panshi Chemical Co., Ltd. Method for continuous water removal production of amide product. Chinese Patent CN 104418760. 2015 Mar 18. Available from: https://patents.google.com/patent/CN104418760A/en?oq=CN+104418760
Warren J, Westphal D, Zoubek S. Pfizer Inc. Process for the production of amides. Wipo Patent WO 2002036559. 2002 Sep 6. Available from: https://patents.google.com/patent/WO2002036559A3/en?oq=WO+2002036559
Khalafi-Nezhad A, Parhami A, Soltani R, Navid M, Zarea A. Efficient method for the direct preparation of amides from carboxylic acids using tosyl chloride under solvent-free conditions, Tetrahedron Letters. 2005 [access: 10/03/2020]; 46(40): 6879-82. Available from: https://www.sciencedirect.com/science/article/abs/pii/S0040403905017399
Krull M, Morschhaeuser R, Lerch A, Ritter H, Schmitz S. Clariant International Ltd. Process for the preparation of tertiary amides of alkylphenylcarboxylic acids. Germany Patent DE 102006047620. 2008 Nov 27. Available from: https://patents.google.com/patent/DE102006047620B4/en?oq=DE+102006047620
Zhang F. Tianjin Chemical Reagent Research Institute. Method for preparing of N,N-diethyl-m-methylbenzoyl amide, Chinese Patent CN 101,914,034. 2010 Dec 15. Available from: https://patents.google.com/patent/CN101914034A/en?oq=CN+101%2c914%2c034
Croud VB, Maltas PJ, McCallien DWJ. Johnson Matthey Public Limited Company. Identifiable chemical product, Wipo Patent WO 2016185177. 2016 Nov 24. Available from: https://patents.google.com/patent/WO2016185177A1/en?oq=WO+2016185177
Peter KH, Edward G, Neeland. A Modified Synthesis of Insect Repellent DEET. Journal of Chemical Education. 1998 [access: 22/12/2019]; 75(10): 1267-1268. Available from: https://pubs.acs.org/doi/10.1021/ed075p1267
Zhuang Z, Zhi-Peng H, Liao, Wei-Wei. Asymmetric Synthesis of Functionalized Dihydronaphthoquinones Containing Quaternary Carbon Centers via a Metal-Free Catalytic Intramolecular Acylcyanation of Activated Alkenes. Organic Letters. 2014 [access: 08/01/2020]; 16(12): 3380-3. Available from: https://pubs.acs.org/doi/abs/10.1021/ol501427h
Habeck JC, Diop L, Dickman M. Synthesis of N,N-Diethyl-3-methylbenzamide (DEET): Two Ways to the Same Goal. Journal of Chemical Education. 2010 [access: 03/03/2020]; 87(5): 528-9. Available from: https://pubs.acs.org/doi/10.1021/ed800169h
Xie S, Lin H, Liu D, Shi C, Li L, Shen B, Zhang L. Guangzhou Liby Enterprise Group Co Ltd. A kind of mite-assistant fabricses care composition. Chinese Patent CN 104988725. 2015 Oct 21. Available from: https://patents.google.com/patent/CN104988725B/en?oq=CN+104988725
Ellis LC, Kise MA. Virginia Chemicals Inc. Process for the manufacture of N,N-diethyl-m-toluamide by aqueous caustic procedure. United State Patent US 3,870,756. 1975 Mar 11. Available from: https://patents.google.com/patent/US3870756A/en
Nery MS, Ribeiro RP, Lopes CC, Lopes RSC. Niobium pentachloride promoted conversion of carboxylic acids to carboxamides: Synthesis of the 4-aryl-1,2,3,4-tetrahydroisoquinoline alkaloid structures. Synthesis. 2003 [access: 05/03/2020]; 2: 272-6. Available from: https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-2003-36823
Chaysripongkul S, Pluempanupat W, Jang DO, Chavasiri W. Application of Cl3CCONH2/PPh3 towards the synthesis of bioactive amides. Bulletin of the Korean Chemical Society. 2009 [access: 08/03/2020]; 30(9): 2066-70. Available from: https://koreascience.or.kr/article/JAKO200902727494345.page
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