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Novel and Improved Method for the Synthesis of 2-Mercaptobenzimidazole Derivatives

Volume 32, Number 4

A. El Kihel1*, H. Ait Sir1, S. Jebbari1, M. Ahbala1, S. Guesmi2 and P. Bauchat3  

1Laboratoire de chimie bioorganique, Faculté des Sciences, BP20, 24000, El Jadida, Maroc.

2Laboratoire de Chimie de Coordination et d’Analytique, Faculté des Sciences, BP20, 24000, El Jadida, Maroc.

3Université de Rennes1, Sciences Chimiques de Rennes U.M.R.6226, ICMV, Campus de Beaulieu, Avenue Général Leclerc, 35042, Rennes, France.

Corresponding Author  E-mail: abdellatifelkihel@gmail.com

DOI : http://dx.doi.org/10.13005/ojc/320405

Article Publishing History
Article Received on :
Article Accepted on :
Article Published : 06 Aug 2016
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ABSTRACT:

2-mercaptobenzimidazole derivatives were synthesized by reaction of o-phenylenediamines with N-aminorhodanine. This reaction represent a new synthesis of 2-mercaptobenzazole. The structure of the obtained products was established by spectroscopic data.

KEYWORDS:

2-mercaptobenzimidazole; o-phenylenediamines; N-aminorhodanine

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Kihel A. E, Ait Sir H, Jebbari S, Ahbala M, Guesmi S, Bauchat P. Novel and Improved Method for the Synthesis of 2-Mercaptobenzimidazole Derivatives. Orient J Chem 2016;32(4).

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Kihel A. E, Ait Sir H, Jebbari S, Ahbala M, Guesmi S, Bauchat P. Novel and Improved Method for the Synthesis of 2-Mercaptobenzimidazole Derivatives. Orient J Chem 2016;32(4). Available from: http://www.orientjchem.org/?p=20229

Introduction

Thiols are very useful building blocks for the synthesis of various organosulfur compounds: they have several applications in organic synthesis, in bioorganic, medicinal and heterocyclic chemistry [1]. Also, in addition to that, thiols can act as safety-catch linker in peptide chemistry [2]. Morever, thiols have been employed as sulfur-based ligands in transition metal complexes[3, 4]. In this respect, a number of synthetic methods for the preparation of thiol derivatives by the reaction of o-phenylendiamine with carbon disulphide [5, 9], thiourea [10, 11], O-isopropylxanthic acid potassium salt [12], 5-phenyl-1,3,4-oxadiazole-2(3H)-thione derivatives and N-phenylisothiocyanate [13], thiocyanic acid ammoniac salt [14]. In continuation of our research concerning benzimidazoles[15, 19]. The condensation of o-phenylenediamine with N-aminorhodanine was carried out.

Experimental Section

General Procedure

O-phenylenediamines (0.065 mol) was heated with N-aminorhodanine (0.065 mol) in xylem (50 ml) for 5 hours. The obtained residue was filtered and was crystallized from aqueous alcohol (charcoal). The obtained solid was recrystallized in ethanol.

2-mercaptobenzimidazole 3a

Yield = 87 %; mp>250°C.1HNMR (DMSO-d6): 7.10 (m, 2Har); 7.27 (m, 2Har); 12.42 (s,

NH).13CNMR (DMSO-d6): 119.43 (CH); 126.36 (CH); 138.82 (C); 167.12 (C=S). HRMS, m/z: 150(M), calcd for C7H6N2S: 150.02517, found: 150.0251.

2-mercapto-5-nitrobenzimidazole 3b

Yield = 81 %; mp>250°C.1HNMR (DMSO-d6): 7.12 (d, JAB= 8.3Hz, 1Har); 7.29 (q, JBX=2.1Hz, JAB= 8.3Hz, 1Har); 7.46 (d, JBX= 2.1Hz, 1Har); 12.03 (s, NH).13CNMR (DMSO-d6):108.24 (CH); 113.46 (CH); 125.70 (CH); 137.45 (C); 141.94 (C); 148.01 (C); 167.54 (C=S).HRMS, m/z: 195(M), calcd for C7H5N3O2S: 195.01025, found: 195.0102.

2-mercapto-5-methylbenzimidazole 3c

Yield = 83 %; mp>250°C. 1HNMR (DMSO-d6): 2.21(s, CH3); 6.43 (d, JAB= 8.3Hz, 1Har); 6.83 (q, JBX=1.7Hz, JAB= 8.3Hz, 1Har); 7.05 (d, JBX= 1.7Hz, 1Har);  12.03 (s, NH). 13CNMR (DMSO-d6): 21.31 (CH3); 109.50 (CH); 109.99 (CH); 123.49 (CH); 130.69 (C); 131.92 (C); 132.95 (C); 168.12 (C=S). HRMS, m/z: 164(M), calcd for C9H8N2S: 164.04082, found: 164.0408.

5-chloro-2-mercaptobenzimidazole 3d

Yield = 79 %; mp>250°C. 1HNMR (DMSO-d6): 6.81 (d, JAB= 7.9Hz, 1Har); 7.03 (q, JBX=

1.9Hz, JAB= 7.9Hz, 1Har); 7.25 (d, JBX= 1.9Hz, 1Har); 11.83 (s, NH).13CNMR (DMSO-d6):101.34 (CH); 109.64 (CH); 123.71 (CH); 135.54 (C); 140.84 (C); 146.14 (C); 165.24 (C=S). HRMS, m/z: 183(M), calcd for C7H5ClN2S: 183.9962, found: 183.996.

5,6-dichloro-2-mercaptobenzimidazole 3e

Yield = 75 %; mp>250°C. 1HNMR (DMSO-d6): 7.79 (s, 1Har); 11.82 (s, NH). 13CNMR (DMSO-d6): 128.60 (CH); 127.25 (C); 135.49 (C); 168.30 (C=S). HRMS, m/z: 217(M), calcd for C7H4N2S: 217.94722, found: 217.9472.

5,6-dimethyl-2-mercaptobenzimidazole 3f

Yield = 80 %; mp>250°C. 1HNMR (DMSO-d6): 2.32(s, CH3); 7.02 (s, 1Har); 12.63 (s, NH). 13CNMR (DMSO-d6): 20.43 (CH3); 111.00 (CH); 131.25 (C); 131.59 (C); 168.00 (C=S). HRMS, m/z: 178(M), calcd for C9H10N3S: 178.05647, found: 178.0564.

Result and Discussion

In this work, we report a novel method for synthesis of 2-mercaptobenzimidazole derivatives. 2- Mercptobenzimidazoles are interesting starting compounds because of their chemical reactivity and biological activities. A mixture of o-phenylenediamines 1(a-g) and N-aminorhodanine in xylene was heated during 8 hours. (Scheme 1). The structure of the products 2(a-g) has been determined by NMR and mass data.  1HNMR spectra showed the presence of the signal of NH and the signal of the C=S was observed in 13CNMR spectra which confirms the structure of the products 2(a-g).

Scheme 1: The reaction of 2-mercaptobenzimidazoles synthesis

Scheme 1: The reaction of 2-mercaptobenzimidazoles synthesis



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A possible mechanism for the formation of the 2-mercaptobenzimidazole (2a-g) is shown in scheme 2. The key step is at the intermediate A, in which the cyclization goes to the C=S group not to C=O group in order to lead to the benzotriazepine product. In the reaction, the only 2-mercaptobenzimidazole product was obtained (Scheme 2)

Scheme 2: Proposed formation mechanism of the product

Scheme 2: Proposed formation mechanism of the product



Click here to View Scheme

 

Conclusion

In this work, we developed a novel and improved method for 2-mercaptobenzimidazole derivatives by the condensation of o-phenylenediamines with N-aminorhodanine

Aknowledgements

This work has been supported by the Chouaib Doukkali University

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