Umpolung strategy for the electrochemical synthesis of novel anthraquinone-based sulfonamide derivatives: a facile and sustainable strategy

Abstract

A facile and sustainable galvanostatic strategy was developed for the synthesis of novel sulfonamide derivatives containing anthraquinone moieties. These syntheses were successfully carried out in a divided cell (divided by glass frit) using a graphite anode and a stainless steel cathode in water/acetonitrile solutions at room temperature. The Umpolung strategy employed in these syntheses is straightforward. It is based on the oxidative conversion of 1,4-diaminoanthraquinone from a nucleophile to an electrophile, followed by its reaction with arylsulfinic acid derivatives. The synthesis strategy, as well as the mechanism governing it, has been determined based on the differences in data obtained from electrochemical studies on the oxidation of 1,4-diaminoanthraquinone in the absence and presence of arylsulfinic acid derivatives. This process exhibits high atom economy, does not require a catalyst, is carried out in one pot, is easily scalable, and can be used for a wide range of arylsulfinic acid derivatives.

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Introduction

Anthraquinones are a group of compounds classified as quinones and are found in natural materials. These compounds are natural pigments, and approximately 700 of their compounds have been identified.¹ In addition to their well-known use as natural dyes, anthraquinones are of interest to researchers due to their remarkable biological activities, including anti-inflammatory, anticancer, antibacterial, antifungal, antimalarial, diuretic, and antiarthritic properties.^1,2 1,4-Diaminoanthraquinone (DAA) (Fig. 1) is a member of this family that is used as a precursor for dyes and has applications in optical sensors.³ DAA and its derivatives have also been used in the fixation of lactate dehydrogenase.⁴

Fig. 1 Structures of 1,4-diaminoanthraquinone (DAA), benzenesulfonanilide, and synthesized compounds.

On the other hand, the benzenesulfonanilide skeleton (Fig. 1) has been identified as a remarkable scaffold in drug discovery. For example, in 1998, a benzenesulfonamide derivative (a hydroxyphenoxybenzenesulfonanilide derivative) was reported by Merck researchers as one of the first selective human β3-AR agonists.^5,6 In 2009, Maruyama et al. selected this derivative as their lead compound.⁷ In 2007, Zheng et al. designed and synthesized simple benzenesulfonanilide-type cyclooxygenase-1-selective inhibitors as analgesic agents without causing gastric damage.⁸ In 2012, Rew et al. introduced a series of benzenesulfonanilide derivatives as 11b-HSD1 inhibitors.⁹ In 2016, Yamada et al. introduced N-(4-phenoxyphenyl) benzenesulfonamide derivatives as a new class of nonsteroidal progesterone receptor (PR) antagonists.¹⁰ In 2023, Ouellette et al. reported that 4-(3-alkyl-2-oxoimidazolidin-1-yl)-N-phenylbenzenesulfonamides are prodrugs that are bioactivated by cytochrome P450 1A1 in breast cancer cells to form the potent metabolite 4-(2-oxoimidazolidin-1-yl)-N-phenylbenzenesulfonamide.¹¹

The interesting and sometimes unique properties of 1,4-diaminoanthraquinone (DAA) and benzenesulfonanilide prompted us to synthesize molecules containing both moieties and hope that, like other anthraquinone-based sulfonamide derivatives,¹² they will exhibit significant pharmacological properties. For this purpose, we converted DAA into an electron acceptor (Michael) by taking two electrons from it and then reacting it with arylsulfinic acids (SUL) as nucleophiles. In this study, we developed a simple and practical one-pot electrochemical method to obtain novel anthraquinone-based sulfonamide derivatives (ANS). In this green strategy (Umpolung strategy), the nature of DAA is changed from a nucleophile to an electrophile, simply by capturing its electrons through an electrode. With this strategy, we succeeded in synthesizing unique sulfonamides (ANS) via a simple method in a divided cell, with both controlled potential and constant current methods, on the surface of a graphite electrode in a water/acetonitrile mixture at room temperature and without using a catalyst, in good yield.

Results and discussion

General studies

The DAA has an interesting structure. While its central ring is a reducible quinone ring, its diamine ring can be independently oxidized. Fig. 2 shows the cyclic voltammogram of DAA in water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) mixture, which confirms what was previously reported. When the potential is scanned from −0.1 to −1.0 V, the voltammogram shows a well-defined cathodic peak (C₀) at −0.73 V vs. SCE. This peak is related to the two-electron reduction of the quinone ring to its diol form (DAA_R) (Scheme 1). In such a situation, the peak's counterpart (A₀) appears in the reverse scan at −0.65 V. The peak-to-peak separation of the A₀/C₀ redox peaks is 80 mV at 100 mV s⁻¹, indicating a quasi-reversible electrochemical process. When the potential scan is initially performed in the anodic direction, the voltammogram shows an independent anodic peak (A₁) at a potential of 0.56 V, which corresponds to the two-electron oxidation of the para-diaminobenzene ring to the corresponding quinonediimine (DAA_O).

Fig. 2 Cyclic voltammogram of DAA (1 mM) in water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) mixture at 100 mV s⁻¹ at room temperature. Working electrode: glassy carbon.

Scheme 1 The reduction and oxidation pathways of DAA.

Under these conditions, by reversing the direction of the potential sweep, the cathode peak (C₁) associated with peak A₁ appears at a potential of 0.49 V. The peak-to-peak separation for the A₁/C₁ redox peaks is 70 mV at 100 mV s⁻¹, indicating a quasi-reversible electrochemical process. Notably, the peak current ratio of C₁ to A₁ (I_pC1/I_pA1) is smaller than one and decreases as the scan rate decreases. This fact indicates the high reactivity of DAA_O and its participation in reactions such as dimerization/polymerization,^3,13 hydrolysis,¹⁴ or ring opening.¹⁵ Moreover, the peak current ratio of C₀ to A₀ (I_pC0/I_pA0) remains constant with increasing scan rate, indicating the stability of the anthraquinone structure on the voltammetric time scale.¹⁶

Electrochemical oxidation of DAA in the presence of arylsulfinic acids

The results showed that electrochemically produced DAA_O is a reactive intermediate and, even in the absence of conventional nucleophiles, can react with the parent DAA molecule to form dimers or react with water and be hydrolyzed. In this section, we examine the oxidation mechanism of DAA in the presence of a strong nucleophile such as benzenesulfinic acid. Fig. 3, part I, shows the cyclic voltammograms of DAA in the absence and presence of benzenesulfinic acid (SUL1) to investigate the reactivity of DAA_O with benzenesulfinic acid. In the presence of SUL1, the C₁ peak current decreases, and the extent of this decrease increases with increasing SUL1 concentration; thus, when the SUL1 concentration reaches 2 mM, no trace of peak C₁ is observed. Notably, the shift of the A₁ peak potential toward more positive potentials is due to fouling of the electrode surface by the product resulting from the reaction of DAA_O with SUL1, which reduces the efficiency of the electrode.

Fig. 3 Part I. Cyclic voltammograms of DAA (1.0 mM): (a) in the absence of SUL1. (b) In the presence of 1.0 mM SUL1. (c) In the presence of 2.0 mM SUL1. (d) Cyclic voltammogram of SUL1 (1.0 mM) in the absence of DAA and (e) background electrolyte at a scan rate of 25 mV s⁻¹. Part II. Normalized cyclic voltammograms of DAA (1.0 mM) in the presence of 1.0 mM SUL1 at different scan rates: (a) 100, (b) 50, and (c) 10 mV s⁻¹. Part III. Cyclic voltammograms of DAA (1.0 mM). (a) In the absence of SUL1. (b) In the presence of 1.0 mM SUL1 at a scan rate of 25 mV s⁻¹. Solvent: a mixture of water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) at room temperature. Working electrode: glassy carbon.

Increasing the potential scan rate has the opposite effect as increasing the SUL1 concentration, such that the peak current ratio I_pC1/I_pA1 increases with the potential scan rate. Fig. 3, part II, which shows normalized voltammograms of DAA in the presence of SUL1, clearly shows the effect of increasing the scan rate on the voltammogram shape. Notably, normalization is achieved by dividing the current (µA) by the square root of the scan rate (mV s⁻¹).

Fig. 3, part III, CVb, shows the cyclic voltammogram of DAA in the presence of SUL1, in which the anodic switching potential has been extended to 1.1 V, and compares it with the cyclic voltammogram of DAA in the absence of SUL1. In this case, a new pair of peaks (A_p and C_p) appears at more positive potentials, which could be related to the redox reaction of the product formed at the electrode surface. These results confirm the reaction between DAA_O and SUL1 and indicate that the reaction of DAA_O with SUL1 is faster than other possible reactions, such as hydrolysis, dimerization, and ring opening. Based on the voltammetric data as well as the spectroscopic results of the synthesized product, the following mechanism (Scheme 2) is proposed for the oxidation of DAA in the presence of SUL. Further oxidation of the product (ANS) does not occur under the conditions used because the oxidation of the product is more difficult than that of the starting material (DAA), due to the presence of the electron-withdrawing benzenesulfinyl group and the insolubility of the product in the electrolysis solution.

Scheme 2 Electrochemical oxidation pathway of DAA in the presence of SUL.

As shown in Fig. 3, part III, the redox reaction associated with peaks A_p and C_p is shown in Scheme 3. The presence of the electron-withdrawing benzenesulfinyl group in the ANS1 structure causes its oxidation to occur at more positive potentials than DAA does.

Scheme 3 Redox reactions associated with the A_p and C_p peaks.

Controlled-potential synthesis

Controlled potential coulometry was performed to determine the number of electrons exchanged during DAA oxidation in the presence of SUL1, and the coulometric progress was followed via linear sweep voltammetry (Fig. 4, part I). The experiment was conducted in a two-compartment cell with a water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) mixture.

Fig. 4 Part I: linear sweep voltammograms of DAA (0.25 mmol) in the presence of SUL1 (0.25 mmol) during controlled-potential coulometry at 0.70 V vs. SCE. (a): 0 C, (b) 12 C, (c) 23 C, (d) 34 C, (e) 34 C and (f) 48 C. (inset): Variations in the A₁ peak current (I_pA1) versus the charge consumption. Part II: (a) cyclic voltammogram of DAA and (b) cyclic voltammogram of a saturated solution of the product (ANS1). The current of CVa decreases by approximately 80% compared with that of CVb. Scan rate of 25 mV s⁻¹. Solvent: a mixture of water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) at room temperature. Working electrode: glassy carbon.

According to the coulometric results and the line equation obtained via coulometry (Fig. 4, part I, inset), the number of electrons consumed per DAA molecule is 2.3, which is consistent with what was reported in Scheme 2 (n = 2) for the oxidation of DAA in the presence of SUL1.

After isolation and purification of the product (ANS1), the cyclic voltammogram of its saturated solution was recorded (Fig. 4, part II, CVb) and compared with the cyclic voltammogram of DAA (Fig. 4, part II, CVa). Notably, the CVa currents were reduced by approximately 80% for better comparison. Two important points can be drawn from this comparison: (1) the oxidation of the product (ANS1) has become more difficult than that of the starting material (DAA). This change can be explained by the addition of the electron-withdrawing benzenesulfinyl group to the amine group. (2) The peak current ratio of ANS1 (I_pCp/I_pAp) is greater than that of the starting material (I_pC1/I_pA1). This indicates that the participation of the oxidized form of the product (ANS1_O) in side reactions, such as dimerization, is less than that of DAA_O due to the addition of the benzenesulfinyl group to the amine group. The addition of a benzenesulfinyl group to the nitrogen atom eliminates (or greatly reduces) the nucleophilicity of the amine group and therefore slows down the rate of dimerization resulting from the reaction of ANS1 with ANS1_O.

Galvanostatic synthesis

In this section, the efficiency of the constant current method in the synthesis of ANS compounds was investigated due to its greater simplicity. However, it should be noted that the efficiency of this method is strongly affected by parameters such as the applied current density and the amount of electricity consumed. Based on the results obtained in the previous section, the amount of electricity consumed in the experiments is considered to be 60 coulombs (1.24 F mol⁻¹). To optimize the current density, current densities of 0.13, 0.26, 0.52, 0.78, 1.05, and 1.31 mA cm⁻² were applied to the cell, and the ANS1 synthesis yield was investigated by keeping the other parameters constant. The results of these experiments are shown in Fig. 5, part I. The results show that the optimal current density for ANS1 synthesis is 0.52 mA cm⁻². At lower current densities, owing to the lower overvoltage, DAA oxidation and, consequently, DAA_O formation occur at a slower rate, which causes the DAA to DAA_O concentration ratio at the electrode surface to be high. Under such conditions, the competition between the dimerization reaction and the sulfonylation reaction is high, and therefore, the yield of ANS1 decreases. On the other hand, since in this optimization, the amount of electricity is kept constant (60 coulombs), at current densities higher than 0.52 mA cm⁻², the possibility of selective oxidation of DAA decreases. In other words, as the current density increases, the current efficiency decreases and, consequently, the yield also decreases. Here, side reactions that can occur and reduce the current efficiency include: over-oxidation of ANS1, oxidation of the nucleophile, solvent, or supporting electrolyte.

Fig. 5 Part I: effect of current density on the yield of ANS1. DAA: 0.5 mmol. SUL1: 1.0 mmol. Charge: 60 coulombs. Solvent: a mixture of water (acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) at room temperature. Part II: effect of pH on the yield of ANS1 at 0.52 mA cm⁻². The other conditions are the same as those in part I. Values represent means ± SD of three experiments.

For pH optimization, electrolysis was performed at 0.52 mA cm⁻² at different pH values (1.0, 3.0, 5.0, 7.0, and 9.0), and the results are shown in Fig. 5, part II. The results show that the optimal pH value for ANS1 synthesis is 5.0. The decrease in yield at more acidic pH values could be due to protonation of the nucleophile, leading to its inactivation as a nucleophile. On the other hand, an acidic environment causes the protonation of DAA, making it more difficult to oxidize. This condition allows other side oxidation processes to participate in the oxidation process. At pH values higher than 5.0, the occurrence of side reactions such as dimerization reactions, hydroxylation, or overoxidation of ANS1 causes a decrease in yield. DAA dimerization can be reduced by oxidation in more dilute solutions.

Conclusions

The idea of synthesizing ANS derivatives arose when researchers discovered that anthraquinone-based benzenesulfonamide derivatives had significant pharmacological properties. Therefore, we decided to synthesize new sulfonamides containing an anthraquinone moiety. We developed a simple and practical one-pot electrochemical method to achieve this goal. In this method, we took advantage of the change in the nature of DAA from a nucleophile to an electrophile, by capturing its electrons via an electrode (Umpolung strategy). Detailed voltammetric studies revealed that when DAA is oxidized, a reactive intermediate (DAA_O) is formed that can participate in various reactions. However, if strong nucleophiles, such as arylsulfinic acids, are present in the presence of DAA_O, DAA_O will undergo a chemical reaction with them and be converted to the desired product. This result was exactly what we needed, and on the basis of our data, we performed electrolysis on a preparative scale and succeeded in synthesizing the desired products. In this work, to simplify and generalize the method, in addition to the controlled-potential synthesis method, the constant current method was also used, and the parameters affecting it were optimized. The results show that the highest yield at pH 5.0 (aqueous acetate buffer, pH = 5.0, c = 0.2 M)/acetonitrile (40/60 v/v) is achieved by applying a current density of 0.52 mA cm⁻² in a divided cell equipped with graphite anodes and stainless steel cathodes.

Experimental section

Reagents and apparatus

1,4-Diaminoanthraquinone (DAA) (catalogue number 842128, for synthesis-grade), benzenesulfinic acid sodium salt (98%) (SUL1) (catalogue number 123579), 4-toluenesulfinic acid sodium salt (95%) (SUL2) (catalogue number 455652), acetonitrile (catalogue number 100030, gradient grade), ethyl acetate (catalogue number 109623, for analysis-grade), n-hexane (98.50%) (catalogue number 104374), sodium acetate (catalogue number 106264, ACS reagent), and hydrochloric acid (catalogue number 109060, c(HCl) = 0.1 mol l⁻¹ (0.1 N)) were purchased from Merck and Sigma-Aldrich and were used without purification.

The cyclic voltammetry and linear sweep voltammetry experiments were performed using an Autolab PGSTAT 20 potentiostat/galvanostat. Cyclic voltammograms were recorded at 25 °C via a three-electrode system with a 1.8 mm-diameter (2.5 mm² area) glassy carbon disc as the working electrode, a stainless-steel wire as the counter electrode, and an Ag/AgCl reference electrode (3 M KCl). All electrodes were manufactured by Azar Electrode Company (Iran). The glassy carbon electrode was polished with alumina slurry.

To record linear sweep voltammograms during coulometry, first, the coulometry was stopped after consuming a certain amount of electricity, and voltammetry was performed after placing the electrodes introduced for voltammetry.

For electrosynthesis under constant current conditions, a Dazheng PS-303D power supply was used, and for electrosynthesis under controlled potential, a BEHPAJOOH-C2056 potentiostat was used. The syntheses were carried out in a divided cell (100 mL) equipped with a magnetic stirrer, containing four graphite rods (each 4 cm long and 1 cm in diameter) (total anode surface area: 53.4 cm²) as anodes and a stainless-steel rod as the cathode. The cathode is placed in the cathodic compartment. The cathodic compartment consists of a glass tube (10 mm diameter), closed at one end by a medium-porosity glass frit and containing a mixture of acetate buffer (pH = 5.0, c = 0.2 M)/acetonitrile (40/60, v/v). The cathodic compartment is placed in the center, and the graphite electrodes are placed at equal distances at the four corners of a square to distribute the potential evenly across all the anodes. Acetonitrile was used as a cosolvent to increase its solubility because of the low solubility of DAA in water. The ohmic resistance between the anode and the cathode in this configuration was about 400 Ohm.

Synthesis of 2-chlorobenzenesulfinic acid (SUL3)

2-Chlorobenzenesulfinic acid (SUL3) was synthesized in our laboratory according to the literature¹⁷ as described in the patent.¹⁸ Sodium sulfite (8.96 g, 71.1 mmol) and 2-chlorobenzenesulfonyl chloride (5 g, 23.7 mmol) were dissolved in 50 mL of water. The mixture was then heated at 80 °C for 5 h, and the completion of the reaction was checked by TLC. After the reaction mixture was cooled to room temperature, it was extracted with dichloromethane (2 × 50 mL). Then, the pH of the aqueous layer was adjusted to 2–3 by adding 6 M HCl, which resulted in the formation of a white precipitate. The precipitate was filtered and washed with water 2–3 times to give a white, needle-shaped product (3.68 g, 87.9% yield).

General approach for the synthesis of ANS1–ANS3

A mixture of acetate buffer (pH = 5.0, c = 0.2 M)/acetonitrile (40/60, v/v) (70 mL) containing DAA (0.5 mmol, 0.119 g) and SUL (1.0 mmol) was electrolyzed in a divided cell equipped with a graphite anode and a stainless-steel rod cathode at 0.60 V vs. SCE at room temperature. Electrolysis was terminated when the current decreased by more than 95% (after about 2.5 h). At the end of electrolysis, the solution was concentrated using a rotary evaporator and placed in the refrigerator overnight. The precipitated solid was collected by filtration and washed several times with water. After drying at room temperature for 24 h under ambient pressure, the yield was determined and the product was further purified by thin-layer chromatography on silica gel (50 : 50 ethyl acetate/n-hexane). The products (ANSs) were characterized by IR, ¹H NMR, ¹³C NMR, and mass spectrometry. In the synthesis of products by the constant current method, a current density of 0.52 mA cm⁻² is applied to the working electrode (anode), and electrolysis is performed until 60 coulombs of electricity pass through. It should be noted that other conditions are similar to the synthesis by the controlled potential method.

Characteristics of the products

N-(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl) benzenesulfon amide (ANS1) (C₂₀H₁₄N₂O₄S).
Crimson precipitate (0.165 g, yield 87%), Mp. 293–295 °C (dec), ¹H NMR δ ppm (500 MHz, CDCl₃): 4.35 (broad, 2H, NH), 6.61 (t, 3H, aromatic), 6.73 (d, J = 10 Hz, 2H, aromatic), 7.16–7.20 (m, 6H, aromatic), 7.28 (broad, ∼1H, NH). ¹³C NMR: δ ppm (125 MHz, CDCl₃): 109.7, 117.6, 126.4, 127.0, 127.3, 128.0, 129.8, 129.9, 133.6, 134.1, 182.9, 185.8. IR (KBr) (cm¹): 3441, 3301, 2823, 1731, 1633, 1579, 1542, 1457, 1366, 1269, 1158, 1089, 971, 727, 571. MS (m/z) (EI, 70 EV) (relative intensity): 77 (70), 127 (50), 182 (60), 209 (62), 237 (100), 378 (M, 70).

N-(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)-4-methylbenzenesulfonamide (ANS2) (C₂₁H₁₆N₂O₄S).
Crimson precipitate (0.161 g, yield 82%), Mp. 285–288 °C (dec), ¹H NMR δ ppm (500 MHz, CDCl₃): 2.24 (s, 3H, CH₃), 7.26–7.31 (m, 3H, aromatic), 7.69 (d, J = 10 Hz, 2H, aromatic), 7.78–7.92 (m, 3H, aromatic), 8.11 (d, J = 10 Hz, 2H, aromatic), 12.25 (s, 1H, NH). ¹³C NMR: δ ppm (125 MHz, CDCl₃): 21.4, 109.6, 117.5, 126.5, 127.0, 127.3, 128.1, 130.1, 132.1, 132.9, 133.8, 135.2, 136.3, 144.6, 149.8, 182.9, 186.9. IR (KBr) (cm¹): 3447, 3307, 3070, 2919, 2953, 2853, 1685, 1636, 1592, 1542, 1470, 1370, 1268, 1158, 1088, 971, 914, 881, 814, 714, 656, 547. MS (m/z) (EI, 70 EV) (relative intensity): 65 (40), 91 (100), 155 (20), 237 (80), 391 (M–1, 30).

N-(4-Amino-9,10-dioxo-9,10-dihydroanthracen-1-yl)-2-chlorobenzene sulfonamide (ANS3) (C₂₀H₁₃ClN₂O₄S).
Crimson color (0.157 g, yield 76%), Mp. 310–312 °C (dec), ¹H NMR δ ppm (500 MHz, DMSO-d₆): 7.30 (d, J = 10 Hz, 1H, aromatic), 7.58 (d, J = 10 Hz, 2H, aromatic), 7.72 (d, J = 10 Hz, 1H, aromatic), 7.80–7.90 (m, 4H, aromatic), 8.11–8.15 (m (2d), 2H, aromatic), 12.2 (broad, 1H, NH). ¹³C NMR: δ ppm (125 MHz, DMSO-d₆): 109.8, 126.6, 127.0, 128.1, 129.3, 130.1, 133.8, 134.1, 182.8, 196.2. IR (KBr) (cm¹): 3482, 3317, 2920, 2850, 1636, 1591, 1574, 1538, 1435, 1434, 1361, 1343, 1278, 1157, 1092, 970, 915, 829, 728, 609, 588. MS (m/z) (EI, 70 EV) (relative intensity): 75 (30), 111 (40), 182 (50), 209 (62), 237 (100), 412 (M, 50).

Ethical statement

This article does not contain any studies with animals per formed by any of the authors.

Author contributions

Davood Nematollahi: supervision, project administration, resources, writing – review & editing, conceptualization. Niloofar Mohamadighader: investigation, project administration, data curation. Faezeh Zivari-Moshfegh: investigation, project administration, writing – original draft.

Conflicts of interest

There are no conflicts to declare.

Data availability

The data that supports the findings of this study are available in the supplementary information (SI) of this article. Supplementary information: FT-IR, ¹H NMR, ¹³C NMR and MS spectra of SUL1–SUL3. See DOI: https://doi.org/10.1039/d6ra00036c.

Acknowledgements

We acknowledge the Bu-Ali Sina University Research Council and the Center of Excellence in Development of environmentally Friendly Methods for Chemical Synthesis (CEDEFMCS) for their support of this work.

Notes and references

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