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One-pot tandem reactions for directconversion of thiols and disulfidesto sulfonic esters, and Paal–Knorrsynthesis of pyrrole derivativescatalyzed by TCCASaba Hemmati a b , Mohammad Majid Mojtahedi c , MohammadSaeed Abaee c , Zahra Vafajoo d , Shokufe Ghahri Saremi a ,Mohammad Noroozi e , Alireza Sedrpoushan b & Meral Ataee ba Department of Chemistry , Payame Noor University ,19395-4697 , Tehran , Iranb Department of Chemistry , Islamic Azad University-SavehBranch , PO 39187-366, Saveh , Iranc Chemistry and Chemical Engineering Research Center of Iran , POBox 14335–186, Tehran , Irand Department of Chemistry , The University of Sistan andBaluchestan , PO Box 98135-674, Zahedan , Irane Research Institute of Petroleum Industry (RIPI) , Kermanshah ,IranPublished online: 03 Dec 2012.

To cite this article: Saba Hemmati , Mohammad Majid Mojtahedi , Mohammad Saeed Abaee , ZahraVafajoo , Shokufe Ghahri Saremi , Mohammad Noroozi , Alireza Sedrpoushan & Meral Ataee (2013)One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, andPaal–Knorr synthesis of pyrrole derivatives catalyzed by TCCA, Journal of Sulfur Chemistry, 34:4,347-357, DOI: 10.1080/17415993.2012.744410

To link to this article: http://dx.doi.org/10.1080/17415993.2012.744410

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Journal of Sulfur Chemistry, 2013Vol. 34, No. 4, 347–357, http://dx.doi.org/10.1080/17415993.2012.744410

SHORT COMMUNICATION

One-pot tandem reactions for direct conversion of thiols anddisulfides to sulfonic esters, and Paal–Knorr synthesis of pyrrolederivatives catalyzed by TCCA

Saba Hemmatia,b*, Mohammad Majid Mojtahedic*, Mohammad Saeed Abaeec, Zahra Vafajood,Shokufe Ghahri Saremia, Mohammad Noroozie, Alireza Sedrpoushanb and Meral Ataeeb

aDepartment of Chemistry, Payame Noor University, 19395-4697 Tehran, Iran; bDepartment of Chemistry,Islamic Azad University-Saveh Branch, PO 39187-366, Saveh, Iran; cChemistry and Chemical EngineeringResearch Center of Iran, PO Box 14335-186, Tehran, Iran; dDepartment of Chemistry, The Universityof Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran; eResearch Institute of Petroleum Industry(RIPI), Kermanshah, Iran

(Received 23 October 2012; final version received 23 October 2012 )

A convenient synthesis of sulfonic esters from thiols and disulfides is described. In situ preparation ofsulfonyl chlorides from thiols is accomplished by oxidation with trichloroisocyanuric acid (TCCA), tetra-butylammonium chloride (t-Bu4NCl), and water. The sulfonyl chlorides are then further allowed to reactwith phenol derivatives in the same reaction vessel. Also, a facile synthesis of N-substituted pyrroles bythe reaction of hexane-2,5-dione with primary amines has been accomplished using TCCA as a catalystunder mild condition with excellent yields.

R SEt3N, r.t.

RNH2

O

O

N

R

+

R: alkyl and aryl

CH3CN, r.t.

TCCA

TCCA

N

N

N

O

OO

Cl

Cl

Cl

R SHR S

O

O

Cl R S

O

O

OArArOH

t-Bu4NClCH3CN, H2O

TCCA

S R

Keywords: thiols; disulfides; sulfonic esters; pyrroles; TCCA

*Corresponding authors. Emails: s_organo2007@yahoo.com; m_mojtahedi@yahoo.comThis article was originally published with errors. This version has been corrected. Please see corrigendum(http://dx.doi.org/10.1080/17415993.2012.757440).

© 2013 Taylor & Francis

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1. Introduction

Sulfonic esters are a class of sulfonic acid derivatives that have drawn much attention because theyare valuable intermediates in organic synthesis and are suitable precursors for sulfonamides (1). Inaddition, various sulfonic esters exhibit interesting biological and pharmacological properties (2).Therefore, it is not surprising that the synthesis of sulfonic esters has always been of great interestto organic chemists. The most typical method for the preparation of sulfonic esters is the reactionof sulfonyl chlorides with alcohols or phenols in the presence of a base (3–9). However, thepreparation of sulfonic esters from phenols has been much less investigated when compared withthe preparation of sulfonic esters from alcohols.

The pyrrole ring system is a useful structural element in medicinal chemistry (10) and hasfound broad application in drug development for antibacterial, antiviral, anti-inflammatory, anti-tumoral, and antioxidant (11) activity and is widely used in materials science (12). Therefore,the preparation of pyrroles is an important reaction for which a wide variety of methods havebeen developed (13). One of the general routes for the synthesis of pyrroles is the Paal–Knorrreaction which convert γ -diketone to pyrroles by the interaction of primary amines in the pres-ence of various promoting agents such as montmorillonite KSF (14), microwave irradiation (15),Bi(NO3)3 · 5H2O (16), Sc(OTf)3 (17), layered zirconium phosphate and zirconium sulfophenylphosphonate (18), titanium (19), TiCl4/Et3N (20), p-TSA (21), and I2 (14). Some other methodsfor the synthesis of pyrroles included conjugate addition reactions (22), annulation reactions (23),and aza-Wittig reactions (24, 25). However, some of these reactions involving the use of excessamounts of acids, hazardous organic solvents, tedious workup, or large amounts of solid cata-lysts (26) may not be the preferred choices in view of green chemistry. Hence, an efficient andmild Paal–Knorr condensation is needed for contemporary chemical synthesis. Also, N-Halocompounds are versatile reagents and have been employed as potentially reactive intermediatesthat are widely used in organic synthesis (27).

2. Results and discussion

We would like to present a direct convenient one-pot synthesis of sulfonic esters from thiolsand disulfides, and phenols using trichloroisocyanuric acid (TCCA)/t-Bu4NCl/H2O under mildconditions (Scheme 1).

R SEt3N, r.t.

R SHR S

O

O

Cl R S

O

O

OArArOH

t-Bu4NClCH3CN, H2O

TCCA

S R

Scheme 1. Convenient one-pot synthesis of sulfonic esters from thiols and disulfides.

In order to find optimized conditions for the reaction, 4-methyl-thiophenol and phenol wereselected as model substrates in acetonitrile at room temperature (rt). After many optimizationexperiments with respect to the molar ratio of the reactants, reaction time, and possible solvents,the best result was achieved by using the reaction of 4-methyl-thiophenol (1 equiv.), with t-Bu4NCl(3 equiv.), H2O (2.5 equiv.), and TCCA (0.70 equiv.) in CH3CN (10 min, rt) with continuous addi-tion of phenol (1.1 equiv., 30 min) and triethylamine (Et3N, 1.1 equiv.) to give the correspondingsulfonic ester in 92% yield (Table 1, Entry 1). Et3N was used as base and HCl trapper in thereaction medium.

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Journal of Sulfur Chemistry 349

To extend the scope of the reaction and to generalize the procedure, we then investigatedthe generality and versatility of this procedure using a series of structurally different thiols andphenols (commercially available) under these optimized conditions. A combinatorial library (par-allel format) of sulfonic esters was smoothly prepared in good to high yields and the results aresummarized in Table 1.

An investigation into the mechanistic aspects of oxidative chlorination of thiols showed that thecorresponding disulfide is the main intermediate in this transformation. In order to further verifythe mediation of the disulfides in the oxidative chlorination of thiols, reactions were repeated witha range of symmetrical disulfides for the synthesis of sulfonic esters (Schemes 1 and 2). Afteroptimizing the reaction in order to identify conditions that consistently produced excellent yieldsof sulfonic esters, we found that the best reaction conditions required the presence of TCCA(0.4 equiv.), t-Bu4NCl (1.5 equiv.), H2O (1.5 equiv.), and disulfide (1 mmol) in acetonitrile at rt.The generality and the scope of the reaction were investigated and the results of the study aresummarized in Table 2. As shown, all reactions resulted in the formation of the correspondingsulfonic esters in excellent yields with high purity. This shows that successive oxidation of the

Table 1. Preparation of sulfonic esters from thiols.

Entry Sulfonic estera Yield (%) Mp (◦C) Ref.

1 92 92–94 28S

O

O

OH3C

2 90 70–71 28S

O

O

O OMeH3C

3 85 94–95 8S

O

O

O NO2H3C

4 90 Oil 28S

O

O

OF

5 95 90–92 28OS

O

O

6 90 110 7S

O

O

OO2N

7 88 Oil 28S

O

O

O OMe

8 95 99–100 7S

O

O

OO2N Me

9 90 73–75 28S

O

O

O

10 87 Oil 29S

O

O

OH3C

Note: aProducts were characterized from their physical properties, comparison with authenticsamples and by spectroscopic methods.

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350 S. Hemmati et al.

sulfur atom, followed by S–S bond cleavage and subsequent chlorination, occurs during the directconversion of thiols into the corresponding sulfonyl chlorides and subsequently to sulfonic esters.

PhOH

t-Bu4NClCH3CN, H2O

TCCAS

O

O

OH3CS SH3C CH3

Scheme 2. Synthesis of sulfonic esters from disulfides.

A possible mechanism for this transformation is shown in Scheme 3 (27i). Molecular chlorinegenerated from TCCA and t-Bu4NCl effects the oxidative chlorination. It is reasonable to assumethat the thiol will chlorinate in the presence of chlorine. Therefore, the mechanism that proceedsthrough hydroxylation of thiol leads to the formation of sulfenic acid (I), which gives the cor-responding symmetric disulfide (II). Then, the successive oxidation of both sulfur atoms of thedisulfide molecule by chlorine produces the intermediate (III) that undergoes rapid isomerizationto the a (IV) (27l, 30), which can easily furnish sulfonyl chloride (V). Then, the sulfonyl chloride(V) reacts with phenol to form the corresponding sulfonic esters (VI).

In continuation of our works, we wish to report our preliminary results on the synthesis ofpyrroles from a γ -diketone and primary amines with TCCA as a catalyst under mild conditionwith excellent yields (Scheme 4).

Table 2. Preparation of sulfonic esters from disulfides.

Entry Sulfonic estera Sulfonic ester Yield (%)

1 90

2

S

Me

S

O

O

OH3C

2 95

2

S

Me

S

O

O

O OMeH3C

3 92

2

S

Me

S

O

O

O NO2H3C

4 80

2

S

F

S

O

O

OF

5 92S

2

OS

O

O

6 90

2

S

O2NS

O

O

OO2N

7 95S

2

S

O

O

O OMe

Note: aProducts were characterized from their physical properties, comparison with authenticsamples and by spectroscopic methods.

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Journal of Sulfur Chemistry 351

t-Bu4NCl Cl2RSH RS Cl

H2ORS OH

-H2O -HCl

HCl-Cl

RS OH2RSH-H2O-HCl

RS SRCl2

-OHS SRR

Cl

S SRR

Cl

OH

-HCl Cl2

S Cl

O

O

-RSH HCl

R

S SR

O

O

RS

O

R S

O

RS

O

R SR

H2O

PheOH

I

IV

V

II

III

CH3CN

R S

O

O

OPhVI

N

N

N

O

OO

Cl

Cl

Cl

HN

NH

NH

O

OO

Et3N

Scheme 3. Possible mechanism for synthesis of sulfonic esters.

RNH2

O

O

N

R

+

R: alkyl and aryl

CH3CN, r.t.

TCCA

Scheme 4. Synthesis of pyrroles from a γ -diketone and primary amines.

Accordingly, treatment of 1,4-diketone with aniline in the presence of a catalytic amountof TCCA afforded 2,5-dimethyl-N-phenylpyrrole in 80% yield under solvent-free condition(Scheme 4). In continuation, we investigated the effect of solvents on this reaction. Several sol-vents including acetonitrile, dichloromethane, chloroform, water, and ethanol were also examinedduring the course of this study. These experiments show that CH3CN is a better solvent than theother solvents tested (97% yield).

These results prompted us to investigate the scope and the generality of these new protocols forvarious amines (aliphatic and aromatic) under optimized conditions. In the same manner, a varietyof amines were coupled with a 1,4-diketone in the presence of a catalytic amount of TCCA at rtto give the corresponding pyrroles in good to excellent yields (Table 3). The less basic aromaticamines require only slightly more time than the more basic amino compounds and both lead tohigh yields of the pyrrole products.

As shown in Table 3, aromatic amines with electron-donating groups (Table 3, Entries 6, 7, and10) or electron-withdrawing group (Table 3, Entries 8 and 9) are both effective in the Paal–Knorrreaction. Due to the good results obtained, we found that the present protocol was also applied toless nucleophilic aromatic amines.

Having these results in hand, several amines including monocyclic, bicyclic aromatic, aliphatic,benzylic, diamines, and triamine have been subjected to the above-mentioned optimized condi-tions, and the results are also presented in Table 3. It is evident that our methodology is reasonably

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Table 3. Pyrroles derivatives produced from Paal–Knorr condensation with TCCA at rt.

Entry Amine (1) Producta Time Yield (%) Ref

1 2 h 90 27cNH2

N

2 5 min 98 27cNH2

N

3 10 min 96 27cNH2

MeO

N

MeO

4 10 min 92 27c

NH2

H2N

NN

5 2.5 h 80 27c

NH2

Cl

N

Cl

6 3 h 85 27cNH2

OMe

N

OMe

7 2 h 90 27cNH2

Me

N

Me

8 3 h 85 27c

NH2

CF3

N

CF3

9 4 h 70 27c

NH2

COOH

N

COOH

10 45 h 85 27c

NH2

NH2

N

N

(Continued)

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Table 3. Continued.

Entry Amine (1) Producta Time Yield (%) Ref

11 5.5 h 80 27c

NH2

NH2

N

N

12 3.5 h 82 27cNH2

N

13 5 h 75 27c

NH2

NH2

N

N

14 15 min 96 27cNH2 N

15 20 min 96 27c

H2NNH2

NN

16 25 min 92 27c

H2N

HN

NH2

N

HN

N

17 1.5 min 96 27c

H2NN

NH2

NH2

NN

N

N

Note: aProducts were characterized from their physical properties, comparison with authentic samples and byspectroscopic methods.

general and can be applied to several amines. The other starting material hexane-2,5-dione wascommercially available (Scheme 4). The yields of products are also shown in Table 3.

As shown in Table 3, a series of aromatic amines bearing either electron-withdrawing or electronreleasing groups on the aromatic ring was investigated. The substituent group on the phenyl ringdid not make any difference in the Paal–Knorr reaction. Moreover, we also examined the Paal–Knorr reaction of aliphatic amines with hexane-2,5-dione (Table 3, Entries 14–17). Similarly, thecorresponding products were obtained in excellent yield.

We found that this method is selective for the preparation of pyrrole containing aromatic ringswith functional groups such as chlorine (Table 3, Entry 5) and carboxylic acids (Table 3, Entry 9).

Our experiments also indicated that TCCA is a reusable catalyst and after three runs, the catalyticactivity of the catalyst was almost the same as that of fresh catalyst. Also, to compare this methodwith previously published methods for the synthesis of N-substituted pyrroles with benzylamine,

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Table 4. Reaction times and yield for previously published methods.

Substrate Conditions Reaction time Yield (%)

Benzylamine Montmorillonite, KSF 10 h 95 (14)Benzylamine I2 0.5 h 92 (14)Benzylamine Bi(NO3)3· 5H2O 10 h 95 (16)Benzylamine Microwave 0.5 min 90 (15)Benzylamine α-Zr(KPO4)2 2 h 78 (18)1-Naphthylamine Sc(OTf)3 40 min 90 (17)1-Naphthylamine Montmorillonite, KSF 11 h 83 (14)1-Naphthylamine I2 1 h 85 (14)1-Naphthylamine Bi(NO3)3· 5H2O 11 h 83 (16)2-Aminopyridine Bi(NO3)3· 5H2O 25 h 70 (16)2-Aminopyridine Montmorillonite, KSF 25 h 70 (14)2-Aminopyridine I2 1 h 78 (14)

naphthylamine, and 2-aminopyridine, we carried out the following studies, as shown in Table 4.These results clearly demonstrates that this procedure is a good system for the preparation ofN-alkyl and N-aryl-2,5-dimethylpyrroles.

Since TCCA contains a halogen atom that is attached to the nitrogen atoms, it is very possiblethat Cl+ released in situ can act as a catalyst in the reaction medium. In Scheme 5, the suggestedmechanism for the synthesis of pyrroles with TCCA is shown (27c,e).

N

N

N

O

OO

Cl

Cl

Cl

TCCA

RNH2

R: alkyl and aryl

OO

OO

Cl Cl

N

R

OClClO

N

R

HOCl6+

HH

+

2

3

N

N

N

O

OO2

HN

NH

NH

O

OO2

3

33

Scheme 5. Suggested mechanism for synthesis of pyrroles with TCCA.

3. Conclusion

In conclusion, we have developed a facile and efficient methodology using one-pot tandemreactions for the direct conversion of thiols and disulfides to sulfonic esters, and synthesis ofN-substituted pyrroles using TCCA. The advantages of the method include (i) short reactiontimes, (ii) high yields, and (iii) easy work-up.

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4. Experimental section

4.1. General procedure for the synthesis of pyrroles with TCCA

To a solution of amine 1 (1 mmol) and 2,5-hexanedione 2 (1 mmol) in CH3CN (3 ml), TCCA(0.02 mmol) was added at rt. The mixture was allowed to stir at this temperature for the periodtime specified in Table 1. The reaction was monitored by thin layer chromatography (TLC)(3:1 n-hexane/acetone). After completion of the reaction, the solvent was evaporated. Then,CH2Cl2 (10 ml) was added, and the catalyst was removed by filtration. Evaporation of the sol-vent under reduced pressure gave the products. Further purification was achieved by TLC usingn-hexane/acetone (70:30) as the solvent system to afford the pyrroles.

4.2. General procedures for the conversion of thiols to sulfonic esters

To a stirred mixture of thiol (1 mmol), t-Bu4NCl (3 equiv.), and water (2.5 mmol) in CH3CN(5 ml) at 0◦C, TCCA (0.75 equiv.) was added in portions as a solid for over 1–2 min. After 30 min,a solution of phenol (1.1 mmol) in triethylamine (1.1 mmol) was added to the reaction mixturefor over 1–2 min. The resulting mixture was stirred at rt for 90 min until TLC showed completedisappearance of starting material (Table 2). The reaction mixture was then diluted with water(10 ml) and extracted with EtOAc (3 × 10 ml). The combined ethyl acetate extracts were driedwith MgSO4 and concentrated under reduced pressure to give the corresponding sulfonic ester asthe only product.

4.3. General procedures for the conversion of disulfides to sulfonic esters

To a stirred mixture of thiol (1 mmol), t-Bu4NCl (3 equiv.), and water (2.5 mmol) in CH3CN(10 ml) at 0◦C, TCCA (0.4 equiv.) was added in portions as a solid for over 1–2 min. After 30 min,a solution of phenol (1.1 mmol) in triethylamine (1.1 mmol) was added to the reaction mixturefor over 1–2 min. The resulting mixture was stirred at rt for 60 min until TLC showed completedisappearance of starting material (Table 2). The reaction mixture was then diluted with water(10 ml) and extracted with EtOAc (3 × 10 ml). The combined ethyl acetate extracts were driedwith MgSO4 and concentrated under reduced pressure to give the corresponding sulfonic ester asthe only product.

4.4. Analytical data for selected compounds

Table 1, Product 1: Mp 92–94◦C, 1H NMR (200 MHz, CDCl3): δ 2.45 (s, 3H), 6.98 (d, 2H,J = 8 Hz), 7.21–7.33 (m, 5H), 7.71 (d, 2H, J = 8 Hz); 13C NMR (50 MHz, CDCl3): δ 21.3,122.0, 126.7, 128.1, 129.2, 129.3, 131.9, 145.0, 149.2; CHNS: Anal. Calcd for C13H12O3S: C,62.89; H, 4.87; S, 12.91. Found: C, 62.78; H, 4.74; S, 12.75.

Table 1, Product 2: Mp 69–72◦C, 1H NMR (200 MHz, CDCl3): δ 2.46 (s, 3H), 3.77 (s, 3H),6.83 (d, 2H, J = 8 Hz), 6.89 (d, 2H, J = 8 Hz), 7.31 (d, 2H, J = 8 Hz), 7.69 (d, 2H, J = 8 Hz);13C NMR (50 MHz, CDCl3): δ 21.3, 55.1, 114.0, 122.9, 128.2, 129.3, 130.4, 142.2, 144.8, 157.7;CHNS: Anal. Calcd for C14H14O4S: C, 60.42; H, 5.07; S, 11.52. Found: C, 60.23; H, 4.92; S,11.35.

Table 3, Product 4: (Cream solid, mp 197–198◦C): IR (KBr): 1515, 1462, 1410, 1377, 1303,1019 cm−1; 1HNMR (CDCl3, FT-250 MHz): δ 2.13 (s, CH3, 12H), 4.97 (s, CH2, 4H), 5.84(s, pyrrolics, 4H), 6.82 (s, PhH, 4H). (Found: M+ 292.1939. C20H24N2 requires M, 292.1946.)

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Table 3, Product 11: (Brown solid, mp 99–100◦C); IR (Nujol): 1600, 1521, 1499, 1459, 1377,1321, 1006 cm−1; 1HNMR (CDCl3, FT-250 MHz): δ 2.1 (s, CH3, 12H), 5.94 (s, pyrrolics, 4H),7.12–7.68 (m, PhH, 4H). (Found: M+ 264.1626. C18H20N2 requires M, 264.1637.)

Table 3, Product 16: (Yellow solid, mp 74–75◦C); IR (Nujol): νmax 3312, 2915, 2854, 1663,1571, 1517, 1463, 1404, 1377, 1298, 1121, 1108 cm−1; 1HNMR (CDCl3, FT-250 MHz): δ 2.30(s, CH3, 12H), 2.70 (t, J = 18.5 Hz, CH2, 4H), 3.75 (t, J = 18.5 Hz, CH2, 4H), 5.70 (s, pyrrolics,4H) (Found: M+ 259.2048. C16H25N3 requires M, 259.2055).Anal. Calcd for C16H25N3: C, 74.13;H, 9.65; N, 16.21. Found: C, 73.48; H, 9.88; N, 16.07.

Table 3, Product 17: (Pale yellow solid, mp 110–111◦C); IR (Nujol): νmax 3100, 2854, 2739,1571, 1518, 1464, 1407, 1378, 1298, 1166, 1061, 1016, 745 cm−1, 1H NMR (CDCl3, FT-90 MHz):2.25 (s, CH3, 18H), 2.74 (t, J = 19.7 Hz, CH2, 6H), 3.75 (t, J = 19.7 Hz, CH2, 6H), 5.78(s, pyrrolics, 6H) Anal. Calcd for C24H36N4 · 0.5H2O: C, 74.04; H, 9.51; N, 14.39. Found: C,74.11; H, 9.67; N, 14.79.

Acknowledgement

We are thankful to Department of Chemistry, Islamic Azad University-Saveh Branch and Payame Noor University (PNU)for partial support of this work.

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