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Cornforth and Corey-Suggs Reagents As Efficient Catalysts for Sulfonation of Aromatic and Heteroaromatic Compounds Using Nahso3

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Cornforth and Corey-Suggs Reagents As Efficient Catalysts for Sulfonation of Aromatic and Heteroaromatic Compounds Using Nahso3 Phosphorus, Sulfur, and Silicon and the Related Elements ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20 Cornforth and Corey-Suggs reagents as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 under solvent free and microwave conditions Touheeth Fatima, Govardhan Duguta, Venkanna Purugula, Hemanth Sriram Yelike & Chinna Rajanna Kamatala To cite this article: Touheeth Fatima, Govardhan Duguta, Venkanna Purugula, Hemanth Sriram Yelike & Chinna Rajanna Kamatala (2020): Cornforth and Corey-Suggs reagents as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 under solvent free and microwave conditions, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2020.1782909 To link to this article: https://doi.org/10.1080/10426507.2020.1782909 View supplementary material Published online: 22 Jul 2020. Submit your article to this journal Article views: 9 View related articles View Crossmark data Full Terms & Conditions of access and use can be found at https://www.tandfonline.com/action/journalInformation?journalCode=gpss20 PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS https://doi.org/10.1080/10426507.2020.1782909 Cornforth and Corey-Suggs reagents as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 under solvent free and microwave conditions Touheeth Fatima, Govardhan Duguta, Venkanna Purugula, Hemanth Sriram Yelike, and Chinna Rajanna Kamatala Department of Chemistry, Osmania University, Hyderabad, Telangana, India ABSTRACT ARTICLE HISTORY Cornforth and Corey-Suggs reagents Pyridinium Dichromate (PDC) and Pyridinium Chlorochromate Received 19 October 2019 (PCC) were explored as efficient catalysts for sulfonation of aromatic and heteroaromatic com- Accepted 10 June 2020 pounds using NaHSO in aqueous acetonitrile medium at room temperature within 1–4 h, while 3 KEYWORDS microwave assisted reactions took place within 1–4 min under solvent-free conditions. These Cornforth and Corey-Suggs observations indicate significant rate accelerations in microwave assisted reactions. which were reagents; PDC and PCC; explained due to the bulk activation of molecules induced by insitu generated high temperatures sulfonation of aromatic and and pressures when microwaves are transmitted through reaction medium. heteroaromatic compounds; microwave assisted GRAPHICAL ABSTRACT reactions; rate enhancements Introduction compounds at room temperature.[23] The Katrizky research group took up an extensive sulfonation study The sulfonation of aromatic and heteroaromatic com- with a series of polycyclic aromatic and heteroaromatic pounds is one the foremost electrophilic aromatic substi- [24] compounds using SO3 in nitrobenzene medium. In tution reactions, which involves the introduction of addition to the above certain recent reports revealed that electrophilic SO3 or sulfonic acid (-SO3H) group onto an organo sulfur and phosphorus derivatives exhibited a [1–10] aromatic entity. Several reagents like sulfuric [25–29] – broad spectrum of biological activities. acid,[11,12] sulfur trioxide,[13 18] chlorosulfonic acid,[19] [30] – On the other hand, over the years, Cornforth and [20 22] [31,32] and silica supported sulfuric acid (Si-H2SO4) have Corey-Suggs reagents (Pyridinium dichromate or PDC, been explored for the sulfonation of aromatic compounds. and Pyridinium chlorochromate or PCC) have been used as Recently we have explored Vilsmeier-Haack adducts oxidizing agents and/or catalysts in a number of organic (DMF/POCl3,andDMF/SOCl2)togetherwithNaHSO3 as transformations to facilitate high product yields in reduced efficient reagents for the sulfonation of aromatic reaction times under acid free conditions, but have not been CONTACT Chinna Rajanna Kamatala [email protected] Department of Chemistry, Osmania University, Hyderabad, Telangana 500 007, India. Supplemental data for this article is available online at https://doi.org/10.1080/10426507.2020.1782909. ß 2020 Taylor & Francis Group, LLC 2 T. FATIMA ET AL. Y (i) Stirring at Room temperature Y PCC/ NaHSO3, Time:1 - 4 h PDC/ NaHSO , Time:1 - 4 h R 3 R 5 % (v/v) Acetonitrile in Water SO3H (ii) MWAS (Solvent -free) SO H R PCC/ NaHSO3,Time:1-4min R 3 PDC/ NaHSO ,Time:1-4min X 3 X Where Y = H, OH, NH2 and other functional group; R = EWG or EDG X = N-H, O, S for Pyrrole, Furan and thiophene respectively O O O OHPy Cr O Cr OHPy Cl Cr OHPy O O O N Pyridinium Dichromate Pyridinium Chlorochromate Pyridine Cornforth reagent (PDC) Corey-Suggs reagent (PCC) (Py) Scheme 1. Sulfonation of aromatic and heteroaromatic compounds using PCC/NaHSO3 and PDC/NaHSO3. Table 1. Optimization of catalyst quantity. extent. Therefore, all the other reactions were performed PCC/NaHSO3 PDC/NaHSO3 using (28 mmol) PCC/(16 mmol) PDC. The results are com- (Yield %) (Yield %) piled in Table 2, which show that the Cr (VI) reagent (PCC PCC PDC SN (mmol) Phenol Aniline Indole(mmol) Phenol Aniline Indole and PDC) almost exhibited the same catalytic efficiency, 1 9.28 60 62 62 5.28 62 70 63 with very good product yields, under conventional condi- 2 18.6 70 78 68 10.6 70 78 68 tions. Reactivity- selectivity principle was observed in the 3 27.9 75 80 71 15.9 73 86 70 present study even though reaction times did not appear to 4 37.2 75 82 74 21.2 75 86 73 5 46.5 75 82 74 26.5 75 86 72 follow strictly. Ortho substituted substrates afforded para- 6 55.8 75 82 74 31.8 75 86 73 substituted products, while para-substituted compounds resulted in ortho-substituted products. explored for sulfonation reactions. These features, together Under the optimized conditions, an array of aromatic with an aim of improving the conditions of sulfonation hydrocarbons, phenolic compounds, aromatic amines and het- eroaromatic compounds were used in the present study. A per- reactions, led us to explore these reagents (PDC and PCC) usal of the data compiled in Tables 2 and 3 reveal that PDC/ as eco-friendly catalysts for sulfonation of aromatic and het- NaHSO and PCC/NaHSO triggered sulfonation with aro- eroaromatic compounds using NaHSO under conventional 3 3 3 matic hydrocarbons, polycyclic aromatic compounds, phenolic and microwave assisted conditions. compounds, aromatic amines and heteroaromatic compounds, even though benzene did not undergo sulfonation with these Results and discussion reagents. All the compounds afforded the corresponding sul- fonic acid derivatives, which were identified by IR, NMR spec- Aromatic and heteroaromatic compounds when treated with troscopy and mass spectrometry methods. The IR spectra of NaHSO3 and Cornforth reagent (PDC) or Corey-Suggs the isolated compounds indicated a band in the frequency À reagent (PCC) in acetonitrile (MeCN) with continuous stir- range 1350–1342 cm 1,correspondingtoS¼Ostretching ring at room temperature for about 3 to 4 h, underwent sul- vibration, which revealed the presence of the sulfonic acid moi- fonation and afforded aryl sulfonic acids (Scheme 1). ety. The 1HNMR,13CNMR,andMSdataalongwithafew Initially we have tried to optimize the Cr (VI) quantity sample NMR spectra are also presented in the Supplemental before taking up the sulfonation reactions with hydroxyben- Materials (Figures S1–S6). Sulfonation of toluene afforded zene (phenol), phenylamine (aniline), and 1H-Indole 4-methyl benzene sulfonic acid (entry 1 in Tables 2 and 3)as (0.01 mol) as model substrates, with excess of NaHSO3 major component, while other aromatic compounds (entries 2 (0.02 mol). The reactions were performed for about 1–4h in to 9 in Tables 2 and 3) also gave corresponding sulfonic acid 5% (v/v) aqueous acetonitrile medium until the reactions were derivatives with very good yields. Phenols, substituted phenols, completed, as indicated by thin layer chromatography (TLC). and naphthol also afforded corresponding sulfonic acids in The observed results are compiled in Table 1.Excessof good yields within 1 to 4 h as shown in Tables 2 and 3 (entries NaHSO3 (0.02 mol) is used to facilitate the smooth reaction. 10–18). Heterocyclic compounds such indole and furan (entries Data presented in Table 1 shows that beyond 150 mg, the 19–22 in Tables 2 and 3), also underwent smooth sulfonation. catalyst (150 mg, 28 mmol PCC/150 mg, 16 mmol PDC) did Reaction times and product yields did not differ much when not further increase the product yield to any significant PCC/NaHSO3 is used in place of PDC/NaHSO3. PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS 3 Table 2. PDC/NaHSO3 mediated sulfonation of organic compounds under acid-free conditions. Conventional MWAS Entry Substrate Product R.T (h) Yield (%) R.T (min) Yield (%) 1 Methylbenzene 4-methylbenzene sulfonic acid 4.0 90 4.0 87 2 1,2-dimethylbenzene 3,4-dimethylbenzenesulfonic acid 3.0 82 2.5 93 3 1,3-dimethylbenzene 2,4-dimethylbenzenesulfonic acid 3.0 85 3.0 89 4 1,4-dimethylbenzene 2,5-dimethylbenzenesulfonic acid 2.0 88 2.0 81 5 Naphthalene Naphthalene-1-sulfonic acid 4.0 70 5.5 92 6 Chlorobenzene 4-chlorobenzenesulfonic acid 3.0 85 3.0 85 7 Bromobenzene 4-bromobenzenesulfonic acid 3.0 82 3.5 90 8 1,3,5-trimethylbenzene 2,4,6-trimethylbenzenesulfonic acid 2.0 80 4.0 93 9 9H-Carbazole Carbazole-3-sulfonic acid 5.0 65 4.0 72 10 Hydroxybenzene 4-hydroxybenzenesulfonic acid 2.0 75:20 1.0 80:17 11 Phenylamine 4-aminobenzenesulfonic acid 3.0 82 1.5 92 12 Methoxybenzene 4-methoxybenzenesulfonic acid 1.5 71:20 2.5 80:15 13 benzene-1,4-diol 2,5-dihydroxybenzenesulfonic acid 3.0 73:18 2.0 80:15 14 4-Nitrophenol 5-hydroxy-2-nitrobenzenesulfonic acid 2.0 81 1.0 89 15 4-Aminophenol 2-amino-5-hydroxybenzenesulfonic acid 2.5 77 1.5 86 16 1-Hydroxy-3-methylbenzene 5-hydroxy-2-methylbenzenesulfonic acid 3.0 66:18 2.0 77:16 17 benzene-1,2-diol 3,4-dihydroxybenzenesulfonic acid 2.5 81 1.5 90 18 3-hydroxychlorobenzene 2-chloro-4-hydroxybenzenesulfonic acid 2.0 69:14 2.0 70:20 19 1H-indole 1H-indole-4-sulfonic acid 3.0 74 2.5 83 20 1H-pyrrole 1H-pyrrole-4-sulfonic acid 2.0 73 2.0 82 21 Furan Furan-2-sulfonic acid 3.0 76 2.0 83 22 Dibenzothiophene Dibenzothiophene-2- sulfonic acid 4.0 75 2.5 70 Table 3.
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