Carbamates are molecules that have different types of biological activities and provide a particular chemical control against ticks. The new structures of the proposed compounds were optimized and synthetized respectively, through a molecular model using the methods:PM3, HF and DFT applying the B3LYP functional, with the basis 6-31+G(d) and 6-311+G(d,p), BVP86 and PBEPBE with 6-31+G(d) and the vibrational frequencies computed. These calculated frequencies were compared with the experimental ones to determine the most accurate level of theory for the prediction of vibrational frequencies of the compounds. The best results were obtained through HF/631+G(d). Additionally, we report a modification to obtain this type of compounds, and based on the amino-dehalogenation of ethyl chloroformate, different benzyl ethyl carbamates were synthesized modifying the base molecule. The performances obtained were compared to others already reported. The methodology used allowed us to synthesize new carbamates using benzylamine derivatives through a modification on the basic catalysis of the addition-elimination reaction.
KeywordsN-CarbamatesIxodicideMolecular Modeling
The Center for the Food Security & Public Health (2007) Rhipicephalus microplus. Iowa State University. http://www.cfsph.iastate.edu/Factsheets/pdfs/boophilus_microplus.pdf
Servicio Nacional de Sanidad, Inocuidad y Calidad Agroalimentaria (2013) Garrapata Boophilus spp.
http://www.senasica.gob.mx/?id=4373
Rodriguez, V. (2011) Epidemiologia y Control de Rhipicephalus (Boophilus microplus) en Mexico. Epidemiologia de Enfermedades Parasitarias en Animales Domesticos. Electronic pressMexico.
SAGARPA (2015) Secretaría de agricultura, ganadería, desarrollo rural pesca y alimentación.
https://www.gob.mx/sagarpa
Perez, L.C., Rodriguez, V.R.I., Ramirez, C.G.T. and Miller, R.J. (2010) First Report of the Cattle Tick Rhipicephalus microplus Resistant to Ivermectin in Mexico. Veterinary Parasitology, 168, 165-169. https://doi.org/10.1016/j.vetpar.2009.10.021
George, J.E., Pound, J.M. and Davey, R.B. (2004) Chemical Control of Ticks on Cattle and the Resistance of these Parasites to Acaricides. Parasitology, 129, S353-S366. https://doi.org/10.1017/S0031182003004682
Iturbe, R.S.L. (2014) Evaluacion de la Eficacia in vivo de Dos Carbamatos de Nueva Sintesis sobre Rhipicephalus microplus. MSc dissertation, UNAM. FES Cuautitlán, Mexico.
Helguera, A.M., Alfonso, P.G., Alexandra, G., Joana, R., Fernando, C., Dolores, V., Cordeiro, M. and Fernanda, B. (2013) Combining QSAR Classification Models for Predictive Modeling of Human Monoamine Oxidase Inhibitors. European Journal of Medicinal Chemistry, 59, 75. https://doi.org/10.1016/j.ejmech.2012.10.035
Prado, O.M.G., Alba, H.F., Angeles E., Velazquez, S.A.M., Ramirez, N.P., Diaz, T.R. and Munoz, G.M.A. (2014) The Action of Two Ethyl Carbamates on Acetylcholinesterase and Reproductive Organs of Rhipicephalus microplus. Veterinary Parasitology, 199, 215. https://doi.org/10.1016/j.vetpar.2013.10.028
Gaussian 16, Revision B.01, Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R.; Scalmani, G.; Barone, V.; Petersson, G.A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A.V.; Bloino, J., Janesko, B.G., Gomperts, R., Mennucci, B., Hratchian, H.P., Ortiz, J.V., Izmaylov, A.F., Sonnenberg, J.L., Williams-Young, D., Ding, F., Lipparini, F., Egidi, F., Goings, J., Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V.G., Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Throssell, K., Montgomery Jr., J.A., Peralta, J.E., Ogliaro, F., Bearpark, M.J., Heyd, J.J., Brothers, E.N., Kudin, K.N., Staroverov, V.N., Keith, T.A., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A.P., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Millam, J.M., Klene, M., Adamo, C., Cammi, R., Ochterski, J.W., Martin, R.L., Morokuma, K., Farkas, O., Foresman, J.B., Fox, D.J. Gaussian, Inc., Wallingford CT (2016) GaussView 5.0. Wallingford, E.U.A.
Lewars, E.G. (2011) Computational Chemistry: Introduction to the Theory and Applications of Molecular and Quantum Mechanics. Springer. Netherlands.
Cuevas, G. and Cortes, F. (2003) Introducción a la Química Computacional (1a ed.). Fondo de Cultura Economica, Mexico.
Andersson, M.P. and Uvdal, P. (2005) New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-Z Basis Set 6-311+(d,p). Journal of Physical Chemistry A, 109, 2937. https://doi.org/10.1021/jp045733a
Scott, A.P. and Radom, L. (1996) Harmonic Vibrational Frequencies: An Evaluation of Hartree-Fock, Moller-Plesset, Quadratic Configuration Interaction, Density Functional Theory, and Semiempirical Scale Factors. Journal of Physical Chemistry, 100, 16502-16513. https://doi.org/10.1021/jp960976r
Merrick, J.P., Moran, D. and Radom, L. (2007) An Evaluation of Harmonic Vibrational Frequency Scale Factors. Journal of Physical Chemistry A, 111, 11683-11700. https://doi.org/10.1021/jp073974n
Sheldrick, G.M. (2008) A Short History of SHELX. Acta Crystallographica A, 64, 112-122. https://doi.org/10.1107/S0108767307043930
Casadei, M.A., Moracci, F.M., Zappia, G. and Rossi, L. (1997) Electrogenerated Superoxide-Activated Carbon Dioxide. A New Mild and Safe Approach to Organic Carbamates. Journal of Organic Chemistry, 62, 6754-6759. https://doi.org/10.1021/jo970308h
(1980) Monograph, Food and Cosmetics Toxicology. 657.
(1975) Monograph, Food and Cosmetics Toxicology. 99.
Stille, G., Wagner-Jauregg, T. and Haering, M. (1963) Central Muscle Relaxants. Drug Research. 856.
Setsuro, F., Toshihiro, H., Kazuo, O., Yoshiyuki, M. and Sadao, H. (1981). https://chem.nlm.nih.gov/chemidplus/rn/101-97-3
(1975) Monograph, Food and Cosmetics Toxicology. 723.
Gaines, T. and Linder, L. (1986) Acute Toxicity of Pesticides in Adult and Weanling Rats. Fundamental and Applied Toxicology, 7, 299-308. https://doi.org/10.1016/0272-0590(86)90160-0
(1979) Monograph, Food and Cosmetics Toxicology. 873.
(1970) World Review of Pest Control. 119. https://chem.nlm.nih.gov/chemidplus/rn/3060-89-7
(1988) Monograph, Food and Chemical Toxicology. 287.
(1997) Chinese Pharmaceutical Journal, 135. https://chem.nlm.nih.gov/chemidplus/rn/5465-00-9
(1975) Monograph, Food and Cosmetics Toxicology. 773.
(1976) Monograph, Food and Cosmetics Toxicology. 835.
(1970) World Review of Pest Control. 119. https://chem.nlm.nih.gov/chemidplus/rn/1746-81-2
Stormann, H. (1964) Choleretic and Other Pharmacological Properties of 2-(3-chloro-6-pyridazinylthio)-acetic Acid Diethylamide, Drug Research. 266.
(1974) Food and Cosmetics Toxicology. Monographs. Fragrance Raw Materials Monographs: Phenylpropyl Acetate. 965.
March, J. and Smith, M.B. (2007) March’s Advanced Organic Chemistry. Reactions, Mechanisms, and Structure. Wiley, Hoboken.
Fukuoka, S., Chono, M. and Kohno, M. (1984) A Novel Catalytic Synthesis of Carbamates by Oxydative Alkoxycarbonylation of Amines in the Presence of Palladium and Iodide. Journal of the Chemical Society, Chemical Communications, 399-400. https://doi.org/10.1039/c39840000399
Chatuverdi, D., Mishra, N. and Mishra, V. (2007) An Efficient, One-Pot Synthesis of Carbamates from the Corresponding Alcohols Using Mitsunobu’s Reagent. Monatshetfte für Chemie, 138, 57-60. https://doi.org/10.1007/s00706-006-0557-2
Inesi, A., Feroci, M. and Rossi, L. (2000) The Reaction of Amines with an Electrogenerated Base. Improved Synthesis of Arylcarbamic Esters. Tetrahedron Letters, 41, 963-966. https://doi.org/10.1016/S0040-4039(99)02180-2
Perez, E., da Silv, M.O., Costa, V., Rodrigues-Fihlo, U. and Franco, D. (2002) Efficient and Clean Synthesis of N-Alkyl Carbamates by Transcarboxylation and O-Alkylation Coupled Reactions Using a DBU-CO2 Zwitterionic Carbamic Complex in Aprotic Polar Media. Tetrahedron Letters, 43, 4091-4093. https://doi.org/10.1016/S0040-4039(02)00697-4
Chaturvedi, D. and Ray, S. (2006) Versatile Use of Carbon Dioxide. Monatshefte für Chemie, 137, 127-145. https://doi.org/10.1007/s00706-005-0423-7
Cenini, S. and Ragaini, F. (2013) Catalytic Reductive Carbonylation of Organic Nitro Compounds (Vol. 20 of Catalysis by Metal Complexes). Springer Science & Business Media, Berlin.
Fu, X., Zhang, Z., Li, C., Wang, L., Ji, H., Yang, Y. and Gao, G. (2009) N-Heterocyclic Carbomethoxylation Catalized by Ionic Liquids in the Presence of Dimethyl Carbonate. Catalysis Communications, 10, 665-668. https://doi.org/10.1016/j.catcom.2008.11.012
Zhou, H., Shi, F., Tian, X., Zhang, Q. and Deng, Y. (2007) Synthesis of Carbamates from Aliphatic Amines and Dimethyl Carbonate Catalyzed by Acid Functional Ionic Liquids. Journal of Molecular Catalysis A: Chemical, 271, 89-92. https://doi.org/10.1016/j.molcata.2007.02.017
Yang, X., Zhang, Y. and Ma, D. (2012) Synthesis of Aryl Carbamates via Copper-Catalyzed Coupling ofAryl Halides with Potassium Cyanate. Advanced Synthesis & Catalysis, 354, 2443-2446. https://doi.org/10.1002/adsc.201200296
Kainmehr, E. and Baghersad, M.H. (2011) Copper-Catalyzed Coupling of Arylboronic Acids with Potassium Cyanate: A New Approach to the Synthesis of Aryl Carbamates. Advanced Synthesis & Catalysis, 353, 2599-2603. https://doi.org/10.1002/adsc.201100153
Sandler, S.R. and Karo, W. (2013) Organic Functional Group Preparations. Elsevier, Berlin.
Santi, R., Romano, A., Panella, F., Mestroni, G., Sessanti, A. and Santi, O. (1999) Reductive Carbonylation of 2,4-Dinitrotoluene to 2,4-Toluendiurethane with Palladium(1,10-phenanthroline)2(hexafluorophosphate)2, as Catalyst, and 1,10-Phenan-throlinium Hexafluorophosphate, as Cocatalyst. Journal of Molecular Catalysis A: Chemical, 144, 41-45. https://doi.org/10.1016/S1381-1169(98)00379-3
Krogul, A., Skupińska, J. and Litwinienko, G. (2011) Catalytic Activity of PdCl2 Complexes with Pyridines in Nitrobenzene Carbonylation. Journal of Molecular Catalysis A: Chemical, 337, 9-16. https://doi.org/10.1016/j.molcata.2011.01.007
Chaturvedi, D. (2012) Perspectives on the Synthesis of Organic Carbamates. Tetrahedron, 68, 15-45. https://doi.org/10.1016/j.tet.2011.10.001
D’Addona, D. and Bochet, C.G. (2001) Preparation of Carbamates from Amines and Alcohols under Mild Conditions. Tetrahedron Letters, 42, 5227-5229. https://doi.org/10.1016/S0040-4039(01)00991-1
Chassaing, C., Berger, M., Heckeroth, A., Ilg, T., Jager, M., Kern, C. and Uphoff, M. (2008) Highly Water-Soluble Prodrugs of Anthelmintic Benzimidazole Carbamates: Synthesis, Pharmacodynamics, and Pharmacokinetics. Journal of Medicinal Chemistry, 51, 1111-1114. https://doi.org/10.1021/jm701456r
Cooper, C.S., Peyton, A.L. and Weinkam, R.J. (1983) Formation Nitrosamines by Alkylation of Diazotates. Journal of Organic Chemistry, 48, 4116-4119. https://doi.org/10.1021/jo00170a052
Pandey, R.K., Dagade, S.P., Dongare, M.K. and Kumar, P. (2003) Synthesis of Carbamates Using Yttria-Zirconia Based Lewis Acid Catalyst. Synthetic Communications, 33, 4019-4027. https://doi.org/10.1081/SCC-120026337
Yadav, J.S., Reddy, G.S., Reddy, M.M. and Meshram, H.M. (1998) Zinc Promoted Simple and Convenient Synthesis of Carbamates: An Easy Access for Amino Group Protection. Tetrahedron Letters, 39, 3259-3262. https://doi.org/10.1016/S0040-4039(98)00464-X
Solomons, G., Fryhle, C. and Snyder, S. (2014) Organic Chemistry. John Wiley & Sons, Hoboken.
Bach, A., Stuhr-Hansen, N., Thorsen, T.S., Bork, N., Moreira, I.S., Frydenvang, K. and Weinstein, H. (2010) Structure-Activity Relationships of a Small-Molecule Inhibitor of the PDZ Domain of PICK1. Organic & Biomolecular Chemistry, 8, 4281-4288. https://doi.org/10.1039/c0ob00025f
Wang, X., Lou, Q., Guo, Y., Xu, Y., Zhang, Z. and Liu, J. (2006) The Design and Synthesis of 9-Phenylcyclohepta[d]pyrimidine-2,4-dione Derivatives as Potent Non-Nucleoside Inhibitors of HIV Reverse Transcriptase. Organic & Biomolecular Chemistry, 4, 3252-3258. https://doi.org/10.1039/b607972p
Mu?oz, C.C.E. (2012) Sintesis de Derivados del Acido Carbamico de la Serie LQM-900, los cuales han Mostrado Actividad Ixodicida. Undergraduate Dissertation, UNAM, FES Cuautitlan, Mexico.
Avila, S.B.L. (2014) Sintesis de 5 Nuevos Carbamatos con Actividad Ixodicida en Garrapatas del Genero Boophilus. Tesis de Licenciatura, Undergraduate Dissertation, UNAM, FES Cuautitlan, Mexico.