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ORGANIC CHEMISTRY | RESEARCH ARTICLE

Cesium nitrate: As an efficient catalyst for synthesis of gem-dihydroperoxides from aldehydes and ketones using aqueous 30% H2O2Kaveh Khosravi

Cogent Chemistry (2015), 1: 1002339

O

R1 R2

H2O2 (30%)Cesium nitrate (cat)

MeCN, rtR1 R2

HOO OOH

Khosravi, Cogent Chemistry (2015), 1: 1002339http://dx.doi.org/10.1080/23312009.2014.1002339

ORGANIC CHEMISTRY | RESEARCH ARTICLE

Cesium nitrate: As an efficient catalyst for synthesis of gem-dihydroperoxides from aldehydes and ketones using aqueous 30% H2O2Kaveh Khosravi1*

Abstract: Gem-dihydroperoxides (DHPs), as key intermediates of aldehydes and ketones, are important precursors in synthesis of anti-malaria drugs and have been used as a solid and powerful oxidant in many oxidation organic reactions. For the importance of gem-DHPs, in this work, cesium nitrate has been used as an efficient and commercially available solid catalyst for catalysis peroxidation of aldehydes and ketones to corresponding gem-DHPs by 30% aqueous hydrogen peroxide at room temperature. The reactions carry on with short time and the products were obtained in excellent yields and high purity. In all reaction, no by-product was observed. This methodology is new, easy, effective, and usable.

Subjects: Clinical Chemistry; Drug Design & Development; Organic Chemistry

Keywords: gem-dihydroperoxide; aldehyde; ketones; cesium nitrate; hydrogen peroxide

1. IntroductionGem-dihydroperoxides (DHPs) which have been known as nearly steady derivatives of ketones and aldehydes have been considered because of their roles in the synthesis of peroxide anti-malarial drugs (Iskra, Bonnet-Delpon, & Bégué, 2003; Tang, Dong, & Vennerstrom, 2004; Žmitek, Zupan, & Iskra, 2007). Additionally, these compounds are key intermediates in the synthesis of some peroxides such as tetraoxanes (Amewu et al., 2006; Franco et al., 2012; Terent’ev et al., 2004), silateraoxans (Terent’ev, Platonov, Tursina, Chernyshev, & Nikishin, 2008), spirobisperoxyketals (Ghorai, Dussault, & Hu, 2008; Hang, Li, & Wu, 2007), bisperoxyketals (Hamada et al., 2002), and 1,2,4,5- tetraoxacycloalkanes (Kim et al., 2001; Masuyama, Wu, Nojima, Kim, & Wataya, 2005). Also, gem-DHPs have been employed as the initiators for radical polymerization reactions (Hansma & Schroeder, 1978) and as the precursors for synthesis of dicarboxylic acid esters (Terent’ev, Platonov, & Kutkin, 2006). As well as, this category of peroxide have been utilized as the powerful solid oxidant for

*Corresponding author: Kaveh Khosravi, Faculty of Science, Department of Chemistry, Arak University, Arak 38156-8-8349, IranE-mail: khosravi.kaveh@gmail.com; k-khosravi@araku.ac.ir

Reviewing editor:George Weaver, University of Loughborough, UK

Additional information is available at the end of the article

ABOUT THE AUTHORKaveh Khosravi obtained his Phd in organic chemistry in 2011 from Bu Ali Sina University, Hamedan, Iran. His doctoral thesis was on gem-dihydroperoxides and their application in organic chemistry. He worked as an assistant professor at Arak University from 2012 until now. His current research interest focuses on synthesis and characterization of gem-dihydroperoxides and their application in the synthesis of organic compounds. In this work, cesium nitrate has been used for efficient synthesis of gem-dihydroperoxides that can be used in several organic reactions.

PUBLIC INTEREST STATEMENTGem-dihydroperoxides (DHPs) as organic compounds are key intermediates for synthesis of anti-malaria drugs. Classical methods for preparation of these compounds have serious drawbacks. Therefore, for the importance of these compounds in the synthesis of gem-DHPs, in high yield and shorter time, the ease and effective method was been needed. The current work reports a new method that has some advantages.

Received: 11 November 2014Accepted: 19 December 2014Published: 23 January 2015

© 2015 The Author(s). This open access article is distributed under a Creative Commons Attribution (CC-BY) 4.0 license.

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Kaveh Khosravi

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several oxidation reactions including epoxidation of α,β-unsaturated ketones (Azarifar & Khosravi, 2010a; Jakka, Liu, & Zhao, 2007), enantioselective oxidation of 2-substituted 1,4-naphtoquinones (Bunge, Hamann, McCalmont, & Liebscher, 2009), oxidation of sulfides (Azarifar & Khosravi, 2010b; Jon Paul Selvam et al., 2008), and in some other oxidative organic reactions (Adam, 2000; Ando, 1992; Khosravi, Mobinikhaledi, Kazemi, Azarifar, & Rahmani, 2014). Generally, for synthesis of gem-DHPs, three conventional methods including (i) ozonolysis of ketone enol ethers or α-olefines in the presence of aqueous H2O2 (Ito, Tokuyasu, Masuyama, Nojima, & McCullough, 2003; Kim et al., 2001; (Kim et al., 1999), (ii) reaction of ketals with H2O2 in the presence of tungstic acid (Jefford, Li, Jaber, Jaber, & Boukouvalas, 1990), or BF3.Et2O (Terent’ev, Kutkin, Troizky, Ogibin, & Nikishin, 2005), and (iii) peroxidation of ketones using an acidic solvent have been reported (Ledaal & Solbjör, 1967). However, unfortunately, these methods suffer from certain drawbacks such as needing of concentrated H2O2 and extra acid, generation of mixes of peroxide products, low yield, and limited substrate range (Kharasch & Sosnovsky, 1958). Furthermore, one of the limitations in ozonolysis reaction is the presence of ozone-sensitive groups in the substrates and poor selectivity. Therefore, to modify these defects, reactions of ketones and aldehydes with H2O2 in the presence of I2 (Žmitek, Zupan, Stavber, & Iskra, 2006; Žmitek, Zupan, Stavber, & Iskra, 2007) in acetonitrile as the solvent have been reported. Several Lewis or Bronsted acids including Ceric ammonium nitrate (CAN) (Das, Krishnaiah, Veeranjaneyulu, & Ravikanth, 2007), CSA (Bunge, Hamann, & Liebscher, 2009), NaHSO4.SiO2 (Das, Veeranjaneyulu, Krishnaiah, & Balasubramanyam, 2008), Re2O7 (Ghorai & Dussault, 2008), and PMA (Li, Hao, Zhang, & Wu, 2009) have been employed as the catalyst in the synthesis of gem-DHPs by aqueous H2O2. As the importance of gem-DHPs and in continuation of our attempts to analyze new catalysts for synthesis of these compounds (Azarifar, Khosravi, & Soleimanei, 2009; Azarifar, Najminejad, & Khosravi, 2013), herein, we like to present the cesium nitrate as a nearly cheap and efficient solid catalyst in the synthesis of gem-DHPs from aldehydes and ketones with 30% aqueous H2O2 at room temperature (Scheme 1).

Cesium nitrate is commercially available solid that is nearly solvable in water and has been used widely as an effective catalyst in different reactions (Ovsienko, 2012; Jacobsen, 2000).

2. Experimental

2.1. CautionAlthough we did not encounter any problem with gem-DHPs, peroxides are potentially explosive and should be handled with precautions; all reactions should be carried out behind a safety shield inside a fume hood, and transition metal salts or heating should be avoided.

Nuclear magnetic resonance spectra were recorded on a JEOL FX 90Q spectrometer using tetramethylsilane (TMS) as an internal standard. IR spectra were recorded on a Perkin Elmer GX FT IR spectrometer (KBr pellets).

2.2. General procedure for synthesis of gem-dihyroperoxidesTo a mixture of carbonyl compound (1 mmol) and cesium nitrate (0.1 mmol, 0.0194 g) in MeCN (4 ml), 30% aqueous H2O2 (1 ml) was added, and the mixture was stirred at room temperature for an appropriate time (Table 2). After completion of the reaction as monitored by thin-layer chromatography (TLC), the mixture was diluted with water (5  ml) and extracted with ethyl acetate (3 × 5 ml). Organic layer that contains products was separated, dried over Mg2SO4, and evaporated under reduced pressure. The residue was purified by silica-packed column chromatography (hexane–EtOAc) to afford pure gem-DHPs if it was needed (Table 2). The

Scheme 1. Conversion of ketones and aldehydes to corresponding gem-DHPs.

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products were characterized on the basis of their melting points, elemental analysis and IR, 1H NMR, and 13C NMR spectral analysis. Also the amount of peroxide in products has been determined by iodometry or manganometry titration.

2.3. Spectroscopic data of unknown products are given below4-(dihydroperoxymethyl)-N,N-dimethylaniline (Table 2, entry x): Sticky brown oil. IR (Nujol mull): 3400, 3092, 1592, 1425, 1363, 1221, 1111, 979 cm−1; 1H NMR (90 MHz, CDCl3) δ: 3.00 (s, 6H), 6.28 (s, 1H), 7.32–7.42 (m, 2 H), 7.97–8.17 (m, 2 H), 9.37 (br, s, 2 H); 13C NMR (22.5 MHz, DMSO-d6) δ: 38.50, 101.00, 127.75, 130.56, 138.06, 143.42; Anal. Calcd for C9H13NO4: C, 54.26; H, 6.58; N, 7.03. Found: C, 54.44; H, 6.83; N, 7.30.

2-(dihydroperoxymethyl)thiophene (Table 2, entry y): White solid, m.p: 200–202 °C. IR (KBr pel-let): 3420, 2922, 2829, 1635, 1558, 1458, 1363, 1271, 987, 721, 599, 435, 353 cm−1; 1H NMR (90 MHz, CDCl3) δ: 6.49 (s, 1 H), 6.60 (s, 1 H), 7.06 (s, 1 H), 7.28 (s, 1 H), 9.17 (br, s, 2 H). 13C NMR (22.5 MHz, DMSO-d6): δC: 100.42, 126.75, 138.01, 139.00, 146.15; Anal. Calcd for C6H8O4S: C, 37.03; H, 3.73; S, 19.77. Found: C, 37.15; H, 3.80, S, 20.02.

3. Results and discussionIn an attempt to arrange the reaction conditions, all reaction parameters for synthesis of 1,1-dihydroperoxycyclohexane as the model reaction were studied and the results are summarized in Table 1. As we have seen, the best result in terms of yield and reaction time was provided using MeCN as solvent at room temperature with 10 mol% of catalyst loading (entry 6, Table 1).

In optimized conditions (aq 30% H2O2 (2 ml), 0.1 mmol of catalyst, MeCN (4 ml), r.t), we started to analyze the potential of the reaction using a different aliphatic and aromatic aldehydes and ketones (Table 2). According to the obtained results summarized in Table 2, generally, aliphatic ketones g-l react faster than aromatic ketones a-e to generate the corresponding gem-DHPs in higher yields. Surprisingly, the aromatic aldehydes and ketones substituted by power electron-withdrawing substituent were not reacting at all or reacted in a very long time with nearly low yields. Also, it was interesting that in cases of aliphatic aldehydes such as z and z’ entries (Table 2), addition of only one molecule of hydrogen peroxide to carbonyl group occurs and generates 1,1- hydroxyhydroperoxide derivatives instead of their expected DHPs (Scheme 2).

Table 1. Screening of reaction parameters for formation of dihydroperoxycyclohexane

H2O2 (30%)Cesium nitrate (cat)

rt

HOO OOHO

Entrya Solvent Cesium nitrate (mmol) Time (min) Yield (%)b

1 n-hex 0.1 120 5

2 EtOAc 0.1 30 82

3 CH2Cl2 0.1 100 50

4 CHCl3 0.1 120 45

5 CCl4 0.1 120 40

6 CH3CN 0.1 20 97

7 CH3CN 0.05 35 91

8 CH3CN 0.15 15 91

9 CH3CN 0.2 15 75ammol cyclohexanone, amount of H2O2 in all entries is1 ml.bIsolated yields.

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Table 2. Synthesis of gem-DHPs catalyzed by cesium nitratea

Entry Ketone or aldehyde Productb Time (min) Yield (%)c Mp (°C) Refa 200 67 75–77 36

b 200 72 Oil 36

c 205 75 Oil 36

d 190 74 Oil 36

e 90 85 Oil 36

f – 300 – – –

g 20 97 Oil 36

h 25 92 Oil 30

i 30 93 Oil 30

j 28 96 Oil 33

k 29 93 64–66 36

l 18 95 Oil 36

m 20 93 Oil 36

(Continued)

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Furthermore, we have successfully converted 2-thiophenecarbaldehyde as a heterocyclic aldehyde to corresponding gem-dihydroperoxide without any by-product (Table 2, entry y) for the first time. Again, similar to other reports, benzophenone was recovered intact after 200 min (Table 2, entry f).

It seems that cesium cation as an efficient Lewis acid activates carbonyl group to electrophilic attack by hydrogen peroxide.

aConditions: ketone and aldehyde (1 mmol), CH3CN (4 ml), Cesium nitrate (0.1 mmol), 30% aq. H2O2 (1 ml), reactions are carried out at r.t.b The structures of the products were established from their physical properties and spectral (1H NMR, 13C NMR, and IR) analysis and compared with the data reported in the literature and amount the peroxide is determined by iodometry or manganometry titration.

cIsolated yield.

Entry Ketone or aldehyde Productb Time (min) Yield (%)c Mp (°C) Refn 22 94 Oil 36

o 23 96 Oil 28

p 19 93 31–33 28

q 21 96 Oil 36

r 20 93 Oil 30

s 80 81 Oil 36

t 80 82 54–56 36

u 90 81 72–74 36

v 240 60 105–107 36

w 80 88 Oil 36

x 100 75 Sticky brown oil

New

y 120 81 98–101 New

z 110 90 Oil 36

z’ 90 92 Oil 36

Table 2. (Continued)

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Moreover, this method for peroxidation of cyclohexanone as a model method (entry a, Table 2) is compared with other reported methodologies in Table 3. From the given results, it is shown that this methodology evidently improved time reaction, yields, and reaction conditions.

4. ConclusionIn conclusion, cesium nitrate has been utilized as a highly efficient, commercially available and nontoxic catalyst for conversion of ketones and aldehydes to corresponding gem-DHPs. These reactions go on smoothly with short reaction times at room temperature to produce products from high to excellent yields. Cesium nitrate as a nearly cheap and nontoxic catalyst makes the process less contaminant, cost-effective, and environmentally friendly.

Table 3. Comparing reported results for peroxidation of cyclohexanoneEntry Catalyst Condition Concentration

of H2O2 (%)Time (min) Yield (%) Ref

1 This method (cesium nitrate) r. t 30 20 97 –

2 Silica sulfuric acid r. t 30 20 98 36

3 Bi(OTf)3 r. t 30 18 78 38

4 phosphomolybdic acid r. t 50 150 95 34

5 Re2O7 r. t 50 30 79 33

6 CAN reagent r. t 50 120 87 30

7 NaHSO4·SiO2 r. t 50 20 98 32

Scheme 2. Aliphatic aldehydes have been converted to 1,1- hydroxyhydroperoxide.

FundingThe financial support provided by the Research Council of Arak University under research project No. 15333/93/d is highly acknowledged.

Author detailsKaveh Khosravi1

E-mail: khosravi.kaveh@gmail.com1 Faculty of Science, Department of Chemistry, Arak University,

Arak 38156-8-8349, Iran.

Citation informationCite this article as: Cesium nitrate: As an efficient catalyst for synthesis of gem-dihydroperoxides from aldehydes and ketones using aqueous 30% H2O2, Kaveh Khosravi, Cogent Chemistry (2015), 1: 1002339.

Cover imageConversion of ketones and aldehydes to corresponding gem-dihydroperoxides.Source: Author.

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