A novel synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement as been described. The route involves a one-pot amidation of diketene with different amines at 70°C in the presence of toluene to form corresponding amides followed by reacting the amides with K2CO3 and DMF at room temperature to form corresponding carboxamides and carboxylates. The carboxamides and carboxylates are then reacted with NH2OH•HCL and NaOAc in presence of ethanol and water to form Ketoximes which are then reacted in one pot synthesis with DAST and dichloromethane at room temperature to form corresponding oxazolines via Beckmann rearrangement. Ketoximes are one of the most popular functional groups and are readily prepared by a number of methods. The initial step of our study was the strategic formation of the ketoxime from carboxamides species which would then be converted to corresponding oxazolines via Beckmann rearrangement. Each new compound has been elucidated through 1H-NMR and 13C-NMR. The Characterization data of compound was also agrees with the molecular masses of HRMS (ESI-TOF). Indeed, all the corresponding products were obtained with a good yield. The studies utilizing this strategy for the production of oxazolines are ongoing in our laboratory. Further expansion of the substrate scope, elucidating the mechanism and exploring the applications of this transformation are now under investigation in our laboratory. We are hopeful; the synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement will be useful in many scientific researches.
| Published in | Modern Chemistry (Volume 10, Issue 2) |
| DOI | 10.11648/j.mc.20221002.14 |
| Page(s) | 56-67 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2022. Published by Science Publishing Group |
2-Oxazoline, DAST, Beckmann Rearrangement
| [1] | Andreasch, R. (1887) zur kenntniss des allylharnstoffs. Monatsh Chem, 5, 33 – 46. https://doi.org/10.1007/BF01526087 |
| [2] | Gabriel, S. (1889) the knowledge of the Bromäthylamins. J A Chem Soc, 22, 1139 – 1154. DOI: 10.1002/cber.188902201248. |
| [3] | Donaldson, W. A. (2001) Synthesis of cyclopropane containing natural products. Tetrahedron, 57, 8589–8591. doi: 10.1016/S0040-4020(01)00777-3. |
| [4] | Fan L, Lobkovsky E and Ganem B. (2007) Bioactive 2-oxazolines: a new approach via one-pot, four-component reaction. Org. Lett, 9, 2015-2017. https://doi:10.1021/ol070694h |
| [5] | Friesen, R. W., Ducharme, R. W., Ball, R. G., Blouin, M., Boulet, L., Côté, B., Frenette, R., Girard, M., Guay, D., Huang, Z., Jones, T R., Laliberté, F., Lynch, J. J., Mancini, J., Martins, E., Masson, P., Muise, E., Pon, D. J., Siegl, P. K. S., Styhler, A., Tsou, N. N., Turner, M. J., Young, R. N., Girard (2003) optimization of a tertiary alcohol series of phosphodiesterase-4 (PDE-4) inhibitors and human ether-a-go-go related gene potassium channel binding affinity. J. Med. Chem, 46, 2413 – 2416. https://doi.org/10.1021/jm0204542 |
| [6] | Park, O. S. (1986) Fluorine labeling in biosynthetic studies (I): Synthesis of fluorfarnesols. Arch. Pharm. Res, 9, 237–242. https://doi.org/10.1007/BF02856639 |
| [7] | Middleton, W. J. (1975) new fluorinating reagents. Dialkylaminosulfur fluorides. J. Org. Chem 40, 574-580. https://doi.org/10.1021/jo00893a007 |
| [8] | Messina, P. A., Mange, K. C., Middleton, W. J. (1989) amino sulphur trifluorides: relative stability. J. Fluorine Chem, 42, 137 – 143. https://doi.org/10.1016/S0022-1139(00)83974-3 |
| [9] | Ojima, I., McCarthy, J. R., Welch, J. T. (1996) Biomedical Frontiers in Fluorine Chemistry. J. A m. Chem. Soc. Symposium Series 639. |
| [10] | Cartwright, D., Banks, R. E., Smart, B. E., Tatlow, J. C. (1994) Recent Developments in Fluorine-Containing Agrochemicals, in Organofluorine Chemistry, Principles and Commercial Applications. https://doi.org/10.1007/978-1-4899-1202-2_11. |
| [11] | Hudlicky, M. (1988) Fluorination with Diethylaminosulfur Trifluoride and related aminosulfuranes. Org Reac, t 25, 513 – 516. doi/abs/10.1002/0471264180.or035.03. |
| [12] | Berkowitz, D. B., Bose, M., Pfannenstiel, T. F., Doukov, T. (2000) α-Fluorinated Phosphonates as Substrate Mimics for Glucose 6-Phosphate Dehydrogenase. J Org Chem, 65, 4498. https://pubs.acs.org/doi/abs/10.1021/jo000220v |
| [13] | Phillips, A. J., Uto, Y., Wipf, P., Reno, M. J., Williams, D. R. (2000) Synthesis of Functionalized Oxazolines and Oxazoles with DAST and Deoxo-Fluor. Org Lett, 2, 1165 – 1168. https://doi.org/10.1021/ol005777b |
| [14] | Monthiller, S., Heck, M.-P., Mioskowski, C., Lafargue, P., Lellouche, J. P., Masella, M. (1997) Bull Soc Chem Fr, 134,145 – 149. |
| [15] | Singh, R. P., Shreeve, J. M. Recent Advances in Nucleophilic Fluorination Reactions of Organic Compounds Using Deoxofluor and DAST (2002) Synthesis, 2561-2578. No. 17, Print: 02 12 2002. Art Id.1437-210X,E;2002,0,17,2561,2578,ftx,en;C05302SS.pdf. © Georg Thieme Verlag Stuttgart • New York ISSN 0039-7881. |
| [16] | Zhou, G-C., Zhu, D-Y. (2000) Bioorg Med. Chem. Lett, 10, 2055 – 2057. |
| [17] | Pierre, L., Pierre G., Jean-Paul L. (1995) Heterocycles, 41: 412- 415. |
| [18] | Adriana, A. O., Daphne, C. A., Fernando C., Lucienir, P. D. (2013) microwave assisted green synthesis of aryl methoxylated benzamides and 2-oxazolines from biomass. Green Process synth, 2, 51–56. |
| [19] | Andrew, J. P., Yoshikazu, U., Peter, W., Michael, J., Reno, D. R., Williams (2000) synthesis of Functionalized Oxazolines and Oxazoles with DAST and Deoxo-Fluor. Org Lett, 8, 1165 – 1168. |
| [20] | Aurelien, B., Judith, B., Chirag, P., Trixie, W., Olivier, L. (2011) DAST-Mediated Cyclization of α,α-Disubstituted-r-acylaminoketones: Efficient and Divergent Synthesis of Unprecedented Heterocycles Org. Lett, 13, 192 – 195. |
| [21] | Burrell, G., Evans, J. M., Jones, G. E., Stemp, G. (1990) the action of diethylaminosulphur trifluoride (DAST) on trans-4-amido-3-chromanols: preparation of cis-amidoalcohols via oxazolines. Tetrahedron Lett 31, 3649 – 3652. |
| [22] | Marie-France P., Laetitia A., Jean-Denys H., Jean-François P. (2012) Synthesis of 2-oxazolines and related N-containing heterocycles using [Et2NSF2]BF4 as a cyclodeshydration agent. Tetrahedron Lett, 53, 4121–4123. |
| [23] | L’Heureux, A., Beaulieu, F., Bennet, C., Bill, D. R., Clayton, S., Laflamme, F., Mirmehrabi, M., Tadayon, S., Tovell, D., Couturier, M. (2010) Aminodifluorosulfinium Salts: Selective Fluorination Reagents with Enhanced Thermal Stability and Ease of Handling. J Org Chem 75, 3401–3411. |
| [24] | Beckmann, E. (1886). Chem Ber, 89, 988. |
| [25] | Wallach O, Justus Liebigs Ann (1889) Chem 1: 309. |
| [26] | Ritz, J., Fuchs, H., Kieczka, H., and Moran, W. C. (2001) Ullmanns Encyclopedia of Industrial Chemistry, 6th edition. |
| [27] | Marco B., Fabian R., and Nathan W. L. (2015) Synthesis of 2-Oxazolines by in Situ Desilylation and Cyclodehydration of β-Hydroxyamides. J. Org. Chem, 80, 1, 40–51. |
| [28] | Guodong S., Zeyou W., Xianqiang H., Min H., Shuhua F., Xin Lv. (2020) Palladium/Copper Cocatalyzed C–H Activation and C–C Bond Regioselective Cleavage Reaction for the Synthesis of Fused Chromeno Quinolines. Organic Letters, 22 (22), 8860-8865. |
| [29] | Sawsan H. A., James R. M. (2021) One-Pot Synthesis of Aminated Benzo-Fused Heterocycles and N-Substituted Dibenzothiophenes via Copper-Catalyzed Ullmann Type Reaction. ACS Omega, 6 (8), 6009-6016. |
APA Style
Tony Wheellyam Pouambeka, Guy Crepin Enoua, Narcisse Nicaise Obaya, Bob Wilfrid Loumouamou, Hubert Makomo, et al. (2022). Synthesis of 2-Oxazolines from Diketene Using DAST via Beckmann Rearrangement. Modern Chemistry, 10(2), 56-67. https://doi.org/10.11648/j.mc.20221002.14
ACS Style
Tony Wheellyam Pouambeka; Guy Crepin Enoua; Narcisse Nicaise Obaya; Bob Wilfrid Loumouamou; Hubert Makomo, et al. Synthesis of 2-Oxazolines from Diketene Using DAST via Beckmann Rearrangement. Mod. Chem. 2022, 10(2), 56-67. doi: 10.11648/j.mc.20221002.14
Share This Article
Twitter
Linked In
Facebook
Copy
Download@article{10.11648/j.mc.20221002.14,
author = {Tony Wheellyam Pouambeka and Guy Crepin Enoua and Narcisse Nicaise Obaya and Bob Wilfrid Loumouamou and Hubert Makomo and Victor N’Goka},
title = {Synthesis of 2-Oxazolines from Diketene Using DAST via Beckmann Rearrangement},
journal = {Modern Chemistry},
volume = {10},
number = {2},
pages = {56-67},
doi = {10.11648/j.mc.20221002.14},
url = {https://doi.org/10.11648/j.mc.20221002.14},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20221002.14},
abstract = {A novel synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement as been described. The route involves a one-pot amidation of diketene with different amines at 70°C in the presence of toluene to form corresponding amides followed by reacting the amides with K2CO3 and DMF at room temperature to form corresponding carboxamides and carboxylates. The carboxamides and carboxylates are then reacted with NH2OH•HCL and NaOAc in presence of ethanol and water to form Ketoximes which are then reacted in one pot synthesis with DAST and dichloromethane at room temperature to form corresponding oxazolines via Beckmann rearrangement. Ketoximes are one of the most popular functional groups and are readily prepared by a number of methods. The initial step of our study was the strategic formation of the ketoxime from carboxamides species which would then be converted to corresponding oxazolines via Beckmann rearrangement. Each new compound has been elucidated through 1H-NMR and 13C-NMR. The Characterization data of compound was also agrees with the molecular masses of HRMS (ESI-TOF). Indeed, all the corresponding products were obtained with a good yield. The studies utilizing this strategy for the production of oxazolines are ongoing in our laboratory. Further expansion of the substrate scope, elucidating the mechanism and exploring the applications of this transformation are now under investigation in our laboratory. We are hopeful; the synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement will be useful in many scientific researches.},
year = {2022}
}
TY - JOUR T1 - Synthesis of 2-Oxazolines from Diketene Using DAST via Beckmann Rearrangement AU - Tony Wheellyam Pouambeka AU - Guy Crepin Enoua AU - Narcisse Nicaise Obaya AU - Bob Wilfrid Loumouamou AU - Hubert Makomo AU - Victor N’Goka Y1 - 2022/06/27 PY - 2022 N1 - https://doi.org/10.11648/j.mc.20221002.14 DO - 10.11648/j.mc.20221002.14 T2 - Modern Chemistry JF - Modern Chemistry JO - Modern Chemistry SP - 56 EP - 67 PB - Science Publishing Group SN - 2329-180X UR - https://doi.org/10.11648/j.mc.20221002.14 AB - A novel synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement as been described. The route involves a one-pot amidation of diketene with different amines at 70°C in the presence of toluene to form corresponding amides followed by reacting the amides with K2CO3 and DMF at room temperature to form corresponding carboxamides and carboxylates. The carboxamides and carboxylates are then reacted with NH2OH•HCL and NaOAc in presence of ethanol and water to form Ketoximes which are then reacted in one pot synthesis with DAST and dichloromethane at room temperature to form corresponding oxazolines via Beckmann rearrangement. Ketoximes are one of the most popular functional groups and are readily prepared by a number of methods. The initial step of our study was the strategic formation of the ketoxime from carboxamides species which would then be converted to corresponding oxazolines via Beckmann rearrangement. Each new compound has been elucidated through 1H-NMR and 13C-NMR. The Characterization data of compound was also agrees with the molecular masses of HRMS (ESI-TOF). Indeed, all the corresponding products were obtained with a good yield. The studies utilizing this strategy for the production of oxazolines are ongoing in our laboratory. Further expansion of the substrate scope, elucidating the mechanism and exploring the applications of this transformation are now under investigation in our laboratory. We are hopeful; the synthesis of 2-oxazolines from diketene by using DAST via Beckmann rearrangement will be useful in many scientific researches. VL - 10 IS - 2 ER -
Information
Email: