Abstract and References
Transactions on Science and Technology Vol. 4, No. 2, 84 - 91, 2017

Synthesis of 6-bromo-2-oxindole from 2,5-dibromonitrobenzene: A more detailed and modified pathway

Shu Er Tan, Mohd Sani Sarjadi
ABSTRACT: This present work reports a modified and more detailed experimental and purification procedure to synthesize 6-bromo-2-oxindole (2). The cost to obtain (2) in commercial is relatively more expensive than to synthesize from its precursor, known as 2,5-dibromonitrobenzene (1). This synthesis procedure involved two consecutive steps. The first step involved the nucleophilic attacked of (1) by diethyl malonate and formed an intermediate, i.e. diethyl-2-(4-bromo-2-nitrophenyl) malonate. For the second step, this intermediate undergone acid hydrolysis, decarboxylation, reesterification, radical reduction, and finally ring closure to obtain the desired (2).

KEYWORDS: 6-Bromo-2-oxindole; Nucleophilic attack; Decarboxylation; Radical Reduction; Ring Closure
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REFERENCES

Ashraf, R. S., Kronemeijer, A. J., James, D. I., Sirringhaus, H. & McCulloch, I. (2012). A new thiophene substituted isoindigo based copolymer for high performance ambipolar transistors. Chemical Communications, 48 (33), 3939.

Bogdanov, A. V. & Mironov, V. F. (2011). A convenient synthetic route from isatin N-Mannich bases to nitrogen-containing derivatives of isoindigo. Monatshefte für Chemie - Chemical Monthly, 142, 81–85.

Bogdanov, A. V, Mironov, V. F. & Musin, L. I. (2012). Facile and Convenient Synthesis of Functionalized Aryl-Containing Isoindigo Derivatives via Substituted Indolin-2-one Carbene Dimerization. Synthetic Communications, 42, 2388–2395.

Bogdanov, A. V, Musin, L. I. & Mironov, V. F. (2011). Regiochemistry of the Reaction of Deoxygenation of 1-Tosylisatin with Hexaethyltriamidophosphite. Russian Journal of General Chemistry, 81 (5), 964–965.

Trost, B.M. & Brennan, M.K. (2009). Asymmetric syntheses of oxindole and indole spirocyclic alkaloid natural products. Synthesis, 2009(18), 3003-3025.

Deng, P., Lei, Y., Zheng, X., Li, S., Wu, J., Zhu, F., Ong, B. S. & Zhang, Q. (2016). Polymer based on benzothiadiazole-bridged bis-isoindigo for organic field-effect transistor applications. Dyes and Pigments, 125, 407–413.

Grenier, F., Berrouard, P., Pouliot, J.-R., Tseng, H.-R., Heeger, A. J. & Leclerc, M. (2012). Synthesis of new n-type isoindigo copolymers. Polymer Chemistry, 4(6), 1836–1841.

Jia, Y. & Kündig, E. P. (2009). Oxindole Synthesis by Direct Coupling of C sp 2 À H and C sp 3 À H Centers. Angewandte Chemie, 121(9), 1664-1667.

Jiang, Y., Gao, Y., Tian, H., Ding, J., Yan, D., Geng, Y. & Wang, F. (2016). Synthesis and Characterization of Isoindigo [7, 6-g] isoindigo-Based Donor–Acceptor Conjugated Polymers. Macromolecules, 49(6), 2135-2144.

Kim, G., Han, A., Lee, H. R., Lee, J., Oh, J. H. & Yang, C. (2014). Acceptor–acceptor type isoindigo-based copolymers for high-performance n-channel field-effect transistors. Chemical Communications, 50 (17), 2180.

Kumar, P. & Lokanatha Rai, K. (2012). Reduction of aromatic nitro compounds to amines using zinc and aqueous chelating ethers: Mild and efficient method for zinc activation. Chemical Papers, 66(8), 772–778.

Lei, T., Wang, J. Y. & Pei, J. (2014). Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers. Accounts of Chemical Research, 47(4), 1117–1126.

Marti, C. & Carreira, E.M., 2003. Construction of Spiro [pyrrolidine‐3, 3′‐oxindoles]− Recent Applications to the Synthesis of Oxindole Alkaloids. European Journal of Organic Chemistry, 2003 (12), 2209-2219.

Mei, J., Graham, K. R., Stalder, R. & Reynolds, J. R. (2010). Synthesis of Isoindigo-Based Oligothiophenes for Molecular Bulk Heterojunction Solar Cells. Organic Letters, 12(4), 660–663.

Papageorgiou, C. & Borer, X. (1988). Acid-Catalyzed Rearrangements for a Diastereoselective Entry into a New Fused Hexacyclic Heterocycle: (5RS,7aRS,12RS,14aRS,)-4,5,7a,11,12,14,14a-octahydro-5,12-dimethyl-diindolo [1,7-bc: 1?,7?-gh][2,6] naphthyridine. Helvetica Chimica Acta, 71 (5), 1079–1083.

Peddibhotla, S. (2009). 3-Substituted-3-hydroxy-2-oxindole, an emerging new scaffold for drug discovery with potential anti-cancer and other biological activities. Current Bioactive Compounds, 5(1), 20-38.

Raju, B., Ragul, R. & Sivasankar, B. N. (2009). A new reagent for selective reduction of nitro group. Indian Journal of Chemistry, 48B, 1315–1318.

Stalder, R., Mei, J., Graham, K. R., Estrada, L. A. & Reynolds, J. R. (2013). Isoindigo, a Versatile Electron-Deficient Unit For High-Performance Organic Electronics. Chemistry of Materials, 26(1), 664–678.

Wang, E., Ma, Z., Zhang, Z., Vandewal, K., Henriksson, P., Inganäs, O., Zhang, F.L. & Andersson, M. R. (2011). An Easily Accessible Isoindigo-Based Polymer for High-Performance Polymer Solar Cells. Journal of the American Chemical Society, 133(36), 14244–14247.

Wang, E., Mammo, W. & Andersson, M. R. (2014). Isoindigo-based polymers and small molecules for bulk heterojunction solar cells and field effect transistors. Advanced Materials, 26(12), 1801–1826.

Zhang, G., Fu, Y., Xie, Z. & Zhang, Q. (2011). Synthesis and Photovoltaic Properties of New Low Bandgap Isoindigo-Based Conjugated Polymers. Macromolecules, 44 (6), 1414–1420.