In this communication a series of ionic reactions is advanced in order to explain not only indigo blue formation but also the continuous presence of indigo red as companion, and why this compound is always found in minority. Indican is the glycoside found in Indigofera tinctoria from which the mixture of indigo blue and indigo red is obtained by means of air oxidation in alkaline medium. A reaction mechanism for the hydrolysis of indican, which was advanced decades ago, is criticized in this paper. Fifty years ago a radical mechanism was suggested for indigo formation. However, the supposed reactive species, indoxyl radical, was not detected by electron spin resonance. Besides, there is no free radical promoter, and indirubin (indigo red) was not considered. A series of ionic reactions explain the formation of both indigoids, and why indigo red occurs in minor proportion. Indoxyl, 3-hydroxyindole, is the aglycone from indican. Reaction of indoxyl with oxygen is catalyzed by calcium hydroxide, indoxyl hydroperoxide being formed. Internal reaction in this intermediate produces 3-oxo-indolenine, which reacts with indoxyl carbanion to give leucoindigo. Further steps lead to indigo blue. Indirubin is formed from indoxyl hydroperoxide by dehydration to isatin, a keto lactam. Condensation of isatin salt with 3-indolinone affords indigo red. This step is retarded due to electric hindrance.
| Published in | Modern Chemistry (Volume 9, Issue 4) |
| DOI | 10.11648/j.mc.20210904.14 |
| Page(s) | 88-91 |
| 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), 2024. Published by Science Publishing Group |
Indigo Blue, Indirubin, Indican, Indoxyl, Organic Hydroperoxide, 3-Oxoindolenine, PeroxyHemiaminal
| [1] | F. Sánchez. Viesca, and R. Gómez, “On the chemistry of Sonnenschein test for strychnine”, Am. J. Chem., vol. 11 (3), pp. 49-51, 2021. |
| [2] | F. Sánchez. Viesca, and R. Gómez, “The chemistry of the Wellcome test for morphine”, OAR J. Chem. & Pharm., vol. 01 (02), pp. 001-004, 2021. |
| [3] | F. Sánchez. Viesca, and R. Gómez, “The chemistry of Weyl-Salkowsky test for creatinine”, Am. J. Chem., vol. 11 (1), pp. 18-21, 2021. |
| [4] | F. Sánchez. Viesca, and R. Gómez, “The chemistry of Marchand’s test for strychnine identification”, Magna Scientia Adv. Res. & Rev., vol. 01 (01), pp. 018-022, 2020. |
| [5] | F. Sánchez. Viesca, and R. Gómez, “On the mchanism of the oxido-degradation of uric acid by ferric chloride”, Int. J. Chem. Sci., vol. 4 (2), pp. 43-45, 2020. |
| [6] | C. E. Ballou, “Alkali-sensitive glycosides“, Adv. Carbohydr. Chem., vol. 9, pp. 59-75, 1954. |
| [7] | G. A. Russell, and G. Kaupp, “Reactions of stabilized carbanions. Oxidation of carbanions”, J. Am. Chem. Soc., vol. 91 (14), pp. 3851-3859, 1969. |
| [8] | N. R. Krishnaswamy, and C. N. Sundaresan, “Fascinating Organic Molecules from Nature”, Resonance-Journal of Science Education (Bangalore, India), November 2012, pp. 1022-1026. |
| [9] | F. Sánchez. Viesca, M. Berros, and R. Gómez, “On the mechanism of the Baeyer-Drewsen synthesis of indigo”, Am. J. Chem., vol. 6 (1), pp. 18-22, 2016. |
| [10] | F. Sánchez. Viesca, and R. Gómez, “On the Baeyer-Emmerling synthesis of indigo”, World J. Org. Chem., vol. 6 (1), pp. 6-12, 2018. |
| [11] | F. Sánchez. Viesca, and R. Gómez, “On the mechanism of indirubin formation in the Baeyer-Emmerling synthesis”, Am. J. Chem., vol. 8 (4), pp. 85-89, 2018. |
| [12] | W. Hsieh, “Indirubin, an acting component of indigo naturalis”, J. Dematol. Sci., vol. 67 (2), pp. 140-146, 2012. |
| [13] | “Fármacos de la familia de la indirrubina pueden mejorar la supervivencia en el glioblastoma”, Revista de Neurología/online. Redacción, Julio 2011. Available: https://www.neurologia.com/noticia/2978/noticia Accessed: November 3, 2021. |
| [14] | S. P. Williams, M. O. Nowicki, F. Liu, R. Press, J. Goldlewski, and M. Abbdel-Rasoul, “Indirubin decrease glioma invasion by blocking migratory phenotypes in both the tumor and stromal endothelial cell compartments”, Cancer Res., 2011. |
| [15] | N. G. Kolar, S. Nam, and A. L. Skaltsounis, “A colorful history: The evolution of indigoids”, Progress in Chem. of Org. Nat. Prods., vol. 99, pp. 69-145, 2014. |
| [16] | K. Schmidt-Rohr, “Oxygen is the high energy molecule powering complex multicellular life”, ACS Omega, vol. 5 (5), pp. 2221-2233, 2020. |
| [17] | V. B. Borisov, and M. I. Verkhovsky, “Oxygen as acceptor”, Eco Sal Plus, vol. 3 (2), Pub Med ID: 26443754, Aug. 2009. |
| [18] | M. Sh. Singh, Reactive Intermediates in Organic Chemistry, London, J. Wiley & Sons, 2014, Chapter 3, p. 22. |
| [19] | W. F. Luder, and S. Zuffanti, The Electronic Theory of Acids and Bases, 2nd ed. New York, Dover, 1961, p. 71. |
| [20] | E. E. Royals, Advanced Organic Chemistry, Englewood Cliffs, N. J., Prentice-Hall, 1961, p. 141. |
| [21] | P. Sykes, Mechanism in Organic Chemistry, 2nd ed. London, Longmans, 1965, p. 100. |
| [22] | W. A. Waters, Mechanisms of Oxidation of Organic Compounds, London, Methuen & Co., 1964, p. 46. |
| [23] | F. Sánchez. Viesca, and R. Gómez, “On the mechanism of the Neumann-Wender glucose test”, Am. J. Chem., vol. 9 (4), pp. 123-126, 2019. |
| [24] | I. Heilbron, and H. M. Bunbury, Eds., Dictionary of Organic Compounds, London, Eyre & Spotiswoode, 1953, vol. 3, p. 55. |
| [25] | National Institutes of Health, 2020, sodiumurate/C5H3N4O3/Chem Spider On line, access with the title, Last login: November 3, 2021. |
| [26] | A. H. Morton, The Chemistry of Heterocyclic Compounds, New York, McGraw-Hill, 1946, p. 137. |
| [27] | S. Miall, and M. Miall, Diccionario de Química, 2ª. ed., Mexico City, Atlante, 1953, p. 573. |
| [28] | F. Sánchez. Viesca, M. Berros, and R. Gómez, “Impedimento eléctrico y otros factores en la nitración de la 2-aminopiridina”, TIP Rev, Esp. Cienc. Quím. Biol., vol. 16 (1), pp. 36-41, 2013. |
| [29] | F, Sánchez. Viesca, R. Gómez, and M. Berros, “Electric hindrance and precursor complexes in the regiochemistry of some nitrations”, J. Chem. Ed. (ACS), vol. 88 (7), pp. 944-946, 2011. |
| [30] | F. Sánchez-Viesca, M. Berros, and R. Gómez, “Recent advances in several organic reaction mechanisms”, Modern Chemistry, vol. 7 (1), pp. 18-26, 2019. |
APA Style
Francisco Sánchez-Viesca, Reina Gómez. (2021). On the Formation Mechanism of Indigo Blue and Indigo Red from Vegetable Source. Modern Chemistry, 9(4), 88-91. https://doi.org/10.11648/j.mc.20210904.14
ACS Style
Francisco Sánchez-Viesca; Reina Gómez. On the Formation Mechanism of Indigo Blue and Indigo Red from Vegetable Source. Mod. Chem. 2021, 9(4), 88-91. doi: 10.11648/j.mc.20210904.14
AMA Style
Francisco Sánchez-Viesca, Reina Gómez. On the Formation Mechanism of Indigo Blue and Indigo Red from Vegetable Source. Mod Chem. 2021;9(4):88-91. doi: 10.11648/j.mc.20210904.14
Share This Article
Twitter
Linked In
Facebook
Copy
Download@article{10.11648/j.mc.20210904.14,
author = {Francisco Sánchez-Viesca and Reina Gómez},
title = {On the Formation Mechanism of Indigo Blue and Indigo Red from Vegetable Source},
journal = {Modern Chemistry},
volume = {9},
number = {4},
pages = {88-91},
doi = {10.11648/j.mc.20210904.14},
url = {https://doi.org/10.11648/j.mc.20210904.14},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.mc.20210904.14},
abstract = {In this communication a series of ionic reactions is advanced in order to explain not only indigo blue formation but also the continuous presence of indigo red as companion, and why this compound is always found in minority. Indican is the glycoside found in Indigofera tinctoria from which the mixture of indigo blue and indigo red is obtained by means of air oxidation in alkaline medium. A reaction mechanism for the hydrolysis of indican, which was advanced decades ago, is criticized in this paper. Fifty years ago a radical mechanism was suggested for indigo formation. However, the supposed reactive species, indoxyl radical, was not detected by electron spin resonance. Besides, there is no free radical promoter, and indirubin (indigo red) was not considered. A series of ionic reactions explain the formation of both indigoids, and why indigo red occurs in minor proportion. Indoxyl, 3-hydroxyindole, is the aglycone from indican. Reaction of indoxyl with oxygen is catalyzed by calcium hydroxide, indoxyl hydroperoxide being formed. Internal reaction in this intermediate produces 3-oxo-indolenine, which reacts with indoxyl carbanion to give leucoindigo. Further steps lead to indigo blue. Indirubin is formed from indoxyl hydroperoxide by dehydration to isatin, a keto lactam. Condensation of isatin salt with 3-indolinone affords indigo red. This step is retarded due to electric hindrance.},
year = {2021}
}
TY - JOUR T1 - On the Formation Mechanism of Indigo Blue and Indigo Red from Vegetable Source AU - Francisco Sánchez-Viesca AU - Reina Gómez Y1 - 2021/12/07 PY - 2021 N1 - https://doi.org/10.11648/j.mc.20210904.14 DO - 10.11648/j.mc.20210904.14 T2 - Modern Chemistry JF - Modern Chemistry JO - Modern Chemistry SP - 88 EP - 91 PB - Science Publishing Group SN - 2329-180X UR - https://doi.org/10.11648/j.mc.20210904.14 AB - In this communication a series of ionic reactions is advanced in order to explain not only indigo blue formation but also the continuous presence of indigo red as companion, and why this compound is always found in minority. Indican is the glycoside found in Indigofera tinctoria from which the mixture of indigo blue and indigo red is obtained by means of air oxidation in alkaline medium. A reaction mechanism for the hydrolysis of indican, which was advanced decades ago, is criticized in this paper. Fifty years ago a radical mechanism was suggested for indigo formation. However, the supposed reactive species, indoxyl radical, was not detected by electron spin resonance. Besides, there is no free radical promoter, and indirubin (indigo red) was not considered. A series of ionic reactions explain the formation of both indigoids, and why indigo red occurs in minor proportion. Indoxyl, 3-hydroxyindole, is the aglycone from indican. Reaction of indoxyl with oxygen is catalyzed by calcium hydroxide, indoxyl hydroperoxide being formed. Internal reaction in this intermediate produces 3-oxo-indolenine, which reacts with indoxyl carbanion to give leucoindigo. Further steps lead to indigo blue. Indirubin is formed from indoxyl hydroperoxide by dehydration to isatin, a keto lactam. Condensation of isatin salt with 3-indolinone affords indigo red. This step is retarded due to electric hindrance. VL - 9 IS - 4 ER -
Information
Email: