N-Alkylation of sulfonamides by alkyl halides in the presence of electrophilic catalysts and transformations of alkylated compounds

Larysa V. Dmitrikova, Svetlana D. Kopteva, Victor I. Markov

Abstract


Vicinal halo amines constitute an important class of compounds due to their diverse biological activity and a broad application as synthones in the production of pharmaceutical agents. The reaction of aryl- and alkylsulfonamides with 1,2-dibromo-2-phenylethane in the presence of Lewis acids (such as FeCl3 and ZnCl2) in 1,2-dichloroethane can represent one of the most efficient ways of halo amine synthesis. It has been shown that methanesulfonamides and benzylsulfonamides starting materials produced the alkylation products with good yields while p-toluenesulfonamides appeared to be less active and 6-methyl-3-nitrobenzylsulfonamides did not give the expected compounds. It has been found that synthesized vicinal halo amides can easily cyclize in alkaline conditions to give 1-sulfonylaziridines. The regioselectivity of aziridine ring opening has also been studied. It was established that strong nucleophile attacks terminal carbon which leads to the breaking-up of 1–3 bond and subsequent aziridine ring opening. In contrast, weak nucleophiles (water, potassium rhodanide, hydrogen bromide) trigger the cleavage of aziridine cycle by breaking-up of 1–2 bond under acidic conditions which is in accordance with molecular orbital theory. Substituents at the aromatic ring of sulfonyl fragment do not influence on the pathway of aziridine ring opening.

Keywords


aryl sulfonamides; alkyl sulfonamides; sulfonyl aziridines; Lewis acids

References


Kasyan, L. I., Kasyan, A. O., Okovityy, S. I., & Tarabara, I. N. (2009). [Amine-containing scaffolds and their derivatives]. Dnepropetrovsk, Ukraine: Dnepr. Nats. Univ. (in Russian).

Kasyan, L. I., Palchikov, V. A., & Tokar A. V. (2012). [Oxazaheterocycles generated from amino alcohols, epoxides and aziridines]. Dnepropetrovsk, Ukraine: Izd. Dnepr. nats. univ (in Russian).

Burmistrov, S. I., Markov, V. I., & Doroshenko V. A. (1965). USSR Patent no. 172773 Byul. izobret. (in Russian).

Huang, J., & O’Brien, P. (2006). Two-Step Synthesis of N-sulfonyl aziridines from epoxides. Synthesis, 3, 425–434. doi:10.1055/s-2006-926282 CrossRef

Martinez-Asencio, A., Ramon, D., & Yus, M. (2010). N-Alkylation of poor nucleophilic amine and sulfonamide derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate. Tetrahedron Lett., 51, 325−327. doi:10.1016/j.tetlet.2009.11.009 CrossRef

Shi, W., Bai, C., Zhu, K., Cui, D., & Zhang, C. (2014). Bronsted acid-assisted N-alkylation of sulfonamides using ethers as the alkylation reagents. Tetrahedron, 70, 434−438. doi:10.1016/j.tet.2013.11.036 CrossRef

Demir, S., Coşkun, F. Özdemir, İ. (2014). The first used half sandwich ruthenium(II) complexes bearing benzimidazole moiety for N-alkylation of amines with alcohols. J. Organomet. Chem., 755, 134−140. doi:10.1016/j.jorganchem.2014.01.007 CrossRef

Demir, S., Damarhan,Y., Özdemir, I. (2015) Functionalized ionic liquids based onimidazolium cation: Synthesis, characterization and catalytic activity for N-alkylation reaction. J. Mol. Liq., 204, 210−215. doi:10.1016/j.molliq.2015.01.051 CrossRef

Sun, J., Jin, X., Zhang, F., Hu, W., Liu, J., & Li R. (2012). Ni–Cu/γ-Al2O3 catalyzed N-alkylation of amines with alcohols. Catal. Commun., 24, 30–33. doi:10.1016/j.catcom.2012.03.010 CrossRef

Zhang, Ya., Qi, X.., Cui, X., Shi, F., & Deng, Yo. (2011). Palladium catalyzed N-alkylation of amines with alcohols. Tetrahedron Lett., 52, 1334–1338. doi:10.1016/j.tetlet.2011.01.059 CrossRef

Kuznetsova, N. G. (2010). [Synthesis of aziridines and cyclic propanes with dialkylphosphate fragment]. Nizhny Novgorod, Russian Federation (in Russian).

Elderfild, R. (1961) [Heterocyclic compounds (Vol. 1)] Moskow, USSR (in Russian).

Markov, V. I., & Burmistrov, S. I. (1965). [1-Arenesulfonyl-2,2-dimethylethylenimides. Reactions with hydrochloric acid, hydrogen sulphide, methanol]. Zhurn. obshch. khimii – J. Gen. Chem., 35(1), 153–158 (in Russian).

Baldwin, J. E., Spivey, A. C., Schofield, C. J., & Sweeney, J. B. (1993). Amino acid synthesis via ring opening of N-sulphonyl aziridine-2-carboxylate esters with organometallic reagents. Tetrahedron, 49(28), 6309–6330. doi:10.1016/S0040-4020(01)87968-0 CrossRef

Dewar, M., & Ford G. (1979). Relationship between olefinic π-complexes and three-membered rings. J. Am. Chem. Soc., 101(4), 783–791. doi:10.1021/ja00498a001 CrossRef




DOI: http://dx.doi.org/10.15421/081610

Refbacks

  • There are currently no refbacks.




Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

______________________________________________________
BULLETIN OF DNIPROPETROVSK NATIONAL UNIVERSITY
eISSN: 2313-4984 | pISSN: 2306-871X
Contact:chem.dnu@gmail.com
The journal publishes research papers on terms: Creative Commons Attribution 4.0 International License
Founder: Oles Honchar Dnipropetrovsk National University