Startseite Regio- and stereoselective synthesis of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts via electrophilic heterocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles and their antimicrobial activity
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Regio- and stereoselective synthesis of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts via electrophilic heterocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles and their antimicrobial activity

  • Mikhailo Slivka EMAIL logo , Nataliya Korol , Valerij Pantyo , Vjacheslav Baumer und Vasil Lendel
Veröffentlicht/Copyright: 30. März 2017
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Heterocyclic Communications
Aus der Zeitschrift Heterocyclic Communications Band 23 Heft 2

Abstract

A procedure for the preparation of the title salts via regioselective halocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles is reported. Stereoselectivity of electrophilic heterocyclization depends on the nature of the electrophilic reagent: bromination is better than iodobromination and iodination. The heterocyclization with tellurium tetrahalogenides leads to the formation of a mixture of geometric isomers of the salts. Their structure was confirmed by 1H NMR, 13C NMR, НМВС and single crystal X-ray diffraction analysis.

Keywords: electrophilic cyclization; halogen; regioselectivity; stereoselectivity; tellurium tetrahalogenides; [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts

Introduction

Küçükgüzel and Çıkla-Süzgün [1] recently reviewed the application of 1,2,4-triazoles in biology and medicine. The electrophilic heterocyclization has become an important tool in the synthesis of bioactive 1,2,4-triazoles, their fused derivatives and analogues [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28]. This report describes preparative methods for the synthesis of condensed 1,2,4-triazole-3-thione derivatives via electrophilic heterocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles. The regioselectivity and stereoselectivity of this electrophilic heterocyclization is also analyzed.

Results and discussion

In our previous work, we showed the possibility of the synthesis of condensed triazoles by halogenation of 3-alkenylthio-4,5-diphenyl-3H-1,2,4-triazoles [18], [19]. In order to study the regioselectivity and stereoselectivity of such electrophilic cyclization in this work, we used the propargyl derivatives of 3-mercapto-1,2,4-triazole 2 synthesized by the reaction of propargyl bromide with the corresponding triazoles 1 under basic conditions (Scheme 1). The structure of thioethers 2 was confirmed by 1H NMR and 13C NMR spectroscopy. The cyclization of thioethers 2 in the presence of a halogen in glacial acetic acid at room temperature led to regio-selective formation of condensed [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts 3 and 4. It should be noted that the use of less polar solvents including chloroform, dichloromethane and tetrachloromethane resulted in a non-selective formation of a mixture of halogenated products. The structures of the salts 3 and 4 were confirmed by analysis of 1H NMR and 13C NMR spectra. Thus, the 1H NMR spectrum of tribromide 3а lacks the signals of the propargyl fragment. On the other hand, the signal of the proton of bromomethylidene group in the aromatic region and the presence of a proton signal of the endocyclic methylene group at 5.10 ppm confirms the annulation to a thiazoline ring system. In the 13C NMR spectrum of tribromide 3а, all signals correspond to sp3- and sp2-carbons. The lack of signals for sp-carbons, which are characteristic for a propargyl fragment, is also consistent with the ring structure for tribromide 3а. The NMR spectra for triiodides 4 are similar to NMR spectra of tribromides 3. Cyclization of the starting thioether 2 was also carried out by treatment with iodine bromide. Chemical shifts in the NMR spectra of the resultant products 5 are similar to those of triiodides 4.

Scheme 1 Synthesis of compounds 3–6.
Scheme 1

Synthesis of compounds 3–6.

It should be noted that the halogenation proceeds with different stereoselectivity for different electrophilic reagents. Thus, the ratio of the peaks of methylene protons in 1H NMR spectra of crude products 3–5 shows that bromination is the most stereoselective process resulting in an almost 90% formation of E-isomer. By contrast, iodination is practically non-stereoselective, leading to the formation of almost equal amounts of E-stereoisomers and Z-stereoisomers. Stereoselective formation of the E-isomer was confirmed by heteronuclear correlation analysis for tribromide 3a. It was possible to grow a single crystal of the E-isomer of 3a for X-ray crystallographic diffraction analysis (Figure 1).

Figure 1 X-ray crystallographic diffraction analysis of bromide 3a.
Figure 1

X-ray crystallographic diffraction analysis of bromide 3a.

Cyclization of thioethers 2 by treatment with tellurium tetrachloride or tellurium tetrabromide was also studied. The analysis of the 1H NMR and 13C NMR spectra of crude cyclization products shows that the heterocyclization leads regioselectively to a single E-diastereomer of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salt 6 in each case. By contrast, a similar treatment of 2 with a selenium tetrahalide yielded amorphous selenium and several oily products that defied purification. This result can be explained in terms of low stability of the selenium-containing products, which agrees with the literature data [26].

Antimicrobial activity

Antimicrobial activity was evaluated by measuring the zone of inhibition against the test organism. Ampicillin (10 μg/mL) and fluconazole (5 μg/mL) were used as standard drugs. The antimicrobial activity (at 10 μg/mL) results are summarized in Figure 2. As can be seen, compound 2b exhibits moderate activity against Staphylococcus aureus ATCC 25923. Compounds 5a and 5b demonstrate slight activity against Escherichia coli ATCC 25922 and Candida albicans ATCC60193. Compound 6a shows considerable activity against Gram-negative bacteria Escherichia coli ATCC 25922 and Salmonella enteritidis. Importantly, compound 6c shows high inhibitory activities towards Escherichia coli ATCC 25922 and Salmonella enteritidis that are superior to the activities of the reference antibiotic ampicillin. This compound also has moderate activity against Staphylococcus aureus ATCC 25923 and Klebsiella pneumoniae. Only compounds 2b, 5a and 6a show moderate antifungal activity against Candida albicans ATCC60193.

Figure 2 Antimicrobial activity of compounds 2b, 5a,b, 6a. Relative zones of inhibition are shown.
Figure 2

Antimicrobial activity of compounds 2b, 5a,b, 6a. Relative zones of inhibition are shown.

Conclusions

Treatment of 3-propargylthio-1,2,4-triazoles with bromine, iodine, iodine bromide, and tellurium tetrahalides leads to the formation of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts. The stereoselectivity of the cyclization process was studied. Several products are antimicrobial and antifungal agents.

Experimental

1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were recorded in DMSO-d6 on a Varian VXR 400 instrument. Melting points were determined on a Stuart SMP30 instrument. Elemental analyses were performed on an Elementar Vario analyzer.

General procedure for synthesis of 3-S-prop-2-yn-1-ylsulfanyl-4Н-1,2,4-triazoles 2a–c

A substituted triazole 1 (10.0 mmol) was dissolved in ethanol (20 mL) with the addition of potassium hydroxide (10.0 mmol) under heating. Propargyl bromide (12.0 mmol) in ethanol (5 mL) was added to this solution and the mixture was heated under reflux for 1 h. After cooling, the precipitated product 2 was filtered, washed with water, dried and crystallized from ethanol.

3,4-Diphenyl-5-(prop-2-yn-1-ylsulfanyl)-4H-1,2,4-triazole (2а)

This compound was obtained from 1a; yield 93% (colorless crystals); mp 133–135°C; 1H NMR: δ 7.50–7.57 (m, 3H); 7.29–7.45 (m, 7H), 3.97 (s, 2H), 3.23 (s, 1H); 13C NMR: δ 155.3, 151.0, 134.4, 130.7, 130.6, 130.4, 129.2, 128.6, 128.3, 127.2, 80.0, 75.3, 21.6. Anal. Calcd for C17H13N3S: C, 70.08; H, 4.50; N, 14.42; S, 11.00. Found: C, 70.36; H, 4.46; N, 14.35; S, 10.97.

3-(4-Bromophenyl)-4-phenyl-5-(prop-2-yn-1-ylsulfanyl)-4H-1,2,4-triazole (2b)

This compound was obtained from 1b; yield 92% (colorless crystals); mp 127–129°C; 1H NMR: δ 7.56–7.63 (m, 5H); 7.41–7.47 (m, 2H), 7.31 (d, J=6.8 Hz, 2H), 3.99 (s, 2H), 3.26 (s, 1H). Anal. Calcd for C17H12BrN3S: C, 55.14; H, 3.27; N, 11.35; S, 8.66. Found: C, 55.21; H, 3.24; N, 11.28; S, 8.74.

3-Benzyl-4-phenyl-5-(prop-2-yn-1-ylsulfanyl)-4H-1,2,4-triazole (2c)

This compound was obtained from 1c; yield 88% (colorless crystals); mp 139–141°C; 1H NMR: δ 6.90–7.51 (m, 10H), 3.99 (s, 2H), 3.88 (s, 2H), 2.49 (s, 1H). Anal. Calcd for C18H15N3S: C, 70.79; H, 4.95; N, 13.76; S, 10.50. Found: C, 70.91; H, 4.76; N, 13.82; S, 10.54.

General procedure for the electrophilic heterocyclization of 3-S-prop-2-yn-1-ylsulfanyl-4Н-1,2,4-triazoles 2a–c

A solution of iodine (20.0 mmol), bromine (10.0 mmol), iodine bromide (10 mmol), tellurium tetrabromide (10.0 mmol) or tellurium tetraiodide (10 mmol) in glacial acetic acid was added dropwise to the solution of triazole 2 (10.0 mmol) in glacial acetic acid with constant stirring at room temperature for 24 h. The resultant solid product was filtered, washed with hot acetic acid (3×5 mL), cooled and then washed again with diethyl ether (2 mL).

(5E)-6-(bromomethylidene)-2,3-diphenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium tribromide (3а)

This compound was obtained from 2a via bromination; yield 88%; yellow crystals; mp 167–168°C; 1H NMR: δ 7.47–7.88 (m, 11H), 5.10 (s, 2H); 13C NMR: δ 162.2, 157.7, 133.6, 133.1, 132.5, 132.0, 131.4, 129.9, 129.6, 126.6, 123.3, 97.5, 42.3. Anal. Calcd for C17H13Br4N3S: C, 33.42; H, 2.14; 6.88; S, 5.25. Found: C, 33.12; H, 2.05; N, 6.82; S, 5.03.

(5E)-2-benzyl-6-(bromomethylidene)-3-phenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]-triazol-7-ium tribromide (3c)

This compound was obtained from 2c via bromination; yield 59%; mp 178–179°C; 1H NMR: δ 7.57–7.66 (m, 4H) 7.41 (s, 1H), 7.10–7.33 (m, 6H), 5.00 (s, 2H), 4.25 (s, 2H). Anal. Calcd for C18H15Br4N3S: C, 34.59; H, 2.42; N, 6.72; S, 5.13. Found: C, 34.33; H, 2.36; N, 6.63; S, 5.04.

(5E)-6-(iodomethylidene)-2,3-diphenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium triiodide (4а)

This compound was obtained from 2a via iodination; yield 82% (brown crystals); 1H NMR: δ 8.34 (s, 1H), 7.45–7.68 (m, 10H), 5.00 (s, 2H); 13C NMR: δ 161.9, 157.4, 133.0, 132.8, 132.4, 131.8, 131.4, 129.7, 129.4, 126.5, 123.1, 80.4, 35.6. A triiodide 4a: mp 147–149°C. Anal. Calcd for C17H13I4N3S: C, 25.56; H, 1.64; N, 5.26; S, 4.01. Found: C, 25.27; H, 1.59; N, 5.11; S, 3.91.

(5E)-2-(4-bromophenyl)-6-(iodomethylidene)-3-phenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium triiodide (4b)

This compound was obtained from 2b via iodination; yield 77% (brown crystals); mp 182–184°C; 1H NMR: δ 8.32 (s, 1H), 7.32–7.76 (m, 9H), 5.01 (s, 2H). 13C NMR : δ 162.0, 156.7, 136.0, 132.9, 132.7, 131.6, 131.2, 127.4, 127.1, 126.8, 121.7, 80.7, 35.6. Anal. Calcd for C17H12BrI4N3S: C, 23.26; H, 1.38; N, 4.79; S, 3.65. Found: C, 23.09; H, 1.32; N, 4.72; S, 3.58.

(5E)-2-benzyl-6-(iodomethylidene)-3-phenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]-triazol-7-ium triiodide (4c)

This compound was obtained from 2c via iodination; yield 62% (brown crystals); mp 197–199°C; 1H NMR: δ 8.34 (s, 1H), 7.70–7.68 (m, 10H), 4.94 (s, 2H), 4.22 (s, 2H). Anal. Calcd for C18H15I4N3S: C, 26.59; H, 1.86; N, 5.17; S, 3.94. Found: C, 26.43; H, 1.78; N, 5.08; S, 3.83.

(5E)-6-(iodomethylidene)-2,3-diphenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium bromide (5а)

This compound was obtained from 2a via iodo-bromination; yield 84% (pale-yellow crystals); mp 152–153°C; 1H NMR: δ 8.33 (s, 1H), 7.41–7.67 (m, 10H), 5.01 (s, 2H). 13C NMR: δ 161.7, 157.3, 133.0, 132.9, 132.3, 131.8, 131.3, 129.7, 129.3, 126.2, 123.2, 80.4, 35.6. Anal. Calcd for C17H13BrIN3S: C, 40.99; H, 2.63; N, 8.43; S, 6.44. Found: C, 41.12; H, 2.58; N, 8.35; S, 6.61.

(5E)-2-(4-bromophenyl)-6-(iodomethylidene)-3-phenyl-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium bromide (5b)

This compound was obtained from 2b via iodo-bromination; yield 63% (pale-yellow crystals); mp 185–187°C; 1H NMR: δ 8.33 (s, 1H), 7.32–7.76 (m, 9H), 5.00 (s, 2H). Anal. Calcd for C17H12Br2IN3S: C, 35.38; H, 2.10; N, 7.28; S, 5.56. Found: C, 35.43; H, 2.12; N, 7.15; S, 5.60.

(5E)-2-(4-bromophenyl)-3-phenyl-6-[(trichloro-λ4-telluranyl)methyl]-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium chloride (6a)

This compound was obtained from 2b and tellurium tetrachloride; yield 61% (white powder); mp 188–189°C; 1H NMR: δ 8.32 (s, 1H), 7.59 (m, 5H), 7.44 (m, 2H), 7.30 (d, J=8.0 Hz, 2H), 4.91 (s, 2H) 13C NMR: 154.1, 151.6, 133.6, 132.2, 130.9, 130.6, 128.2, 128.1, 128.0, 125.5, 124.4, 79.7, 21.4. Anal. Calcd for C17H12BrCl4N3STe: C, 31.92; H, 1.89; N, 6.57; S, 5.01. Found: C, 32.03; H, 1.83; N, 5.64; S, 5.12.

(5E)-2-benzyl-3-phenyl-6-[(trichloro-λ4-telluranyl)methyl]-5,6-dihydro-3H-[1,3]thiazolo-[3,2-b][1,2,4]triazol-7-ium chloride (6b)

This compound was obtained from 2c and tellurium tetrachloride; yield 58% (white powder); mp 182–183°C; 1H NMR: δ 8.30 (bs, 1H+H2O), 6.98–7.60 (m, 10H), 4.88 (s, 2H), 4.12 (s, 2H). Anal. Calcd for C18H15Cl4N3STe: C, 37.61; H, 2.63; N, 7.31; S, 5.58. Found: C, 37.54; H, 2.68; N, 7.25; S, 5.63.

(5E)-2-(4-bromophenyl)-3-phenyl-6-[(tribromo-λ4-telluranyl)methyl]-5,6-dihydro-3H-[1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium bromide (6c)

This compound was obtained from 2b and tellurium tetrabromide; yield 48% (yellow powder); mp 179–181°C; 1H NMR: δ 8.32 (s, 1H), 7.58 (m, 5H), 7.44 (m, 2H), 7.30 (d, J=8.0 Hz, 2H), 5.03 (s, 2H); 13C NMR: 154.1, 151.6, 133.7, 132.2, 130.9, 130.6, 130.5, 128.1, 125.6, 124.4, 79.7, 21.4. Anal. Calcd for C17H12Br5N3STe: C, 24.98; H, 1.48; N, 5.14; S, 3.92. Found: C, 25.11; H, 1.51; N, 5.05; S, 4.01.

(5E)-2-benzyl-3-phenyl-6-[(tribromo-λ4-telluranyl)methyl]-5,6-dihydro-3H-[1,3]thiazolo-[3,2-b][1,2,4]triazol-7-ium bromide (6d)

This compound was obtained from 2c and tellurium tetrabromide; yield 46% (yellow powder); mp 186–188°C; 1H NMR: δ 8.31 (s, 1H), 6.97–7.67 (m, 10H), 5.02 (s, 2H), 4.08 (s, 2H). Anal. Calcd for C18H15Br4N3STe: C, 28.73; H, 2.01; N, 5.58; S, 4.26. Found: C, 28.82; H, 2.04; N, 5.49; S, 4.31.

X-ray diffraction analysis of 3a

Single crystals of C17H13N3SBr43а were crystallized from ethanol. The single crystal was placed in an inert oil and then transferred to the diffractometer under a cold stream of an inert gas. The structure of salt 3a was performed on an automatic diffractometer Oxford Diffraction Xcalibur at room temperature [293(2) K], interpreted by a direct method and refined by the full-matrix least-squares technique in an anisotropic approximation for non-hydrogen atoms using the SHELX-97 program package [29]. The program WinGX [30] was used to analyze the structure and production of the illustrations. All C-H hydrogen atoms were placed in calculated positions and refined as a riding model. For all distance bonds and valence angles of expected values in cation of tribromide 3a were found.

Crystal structure determination of 3a: C17H13N3SBr4, M=611.00, monoclinic, a=12.1614(12) Å, b=7.2386(4) Å, c=24.0202(17) Å, β=102.896(8)°, U=2061.2(3) Å3, T=293.0, space group P21̅n (no. 14), Z=4, μ(Mo Kα)=7.917, 7981 reflections measured, 4369 unique (Rint=0.0621) which were used in all calculations. The final wR(F2) was 0.2376 (all data).

Acknowledgments

The authors thank the International Centre for Diffraction Data for financial support (Grant #03-02).

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Received: 2016-12-16
Accepted: 2017-2-27
Published Online: 2017-3-30
Published in Print: 2017-4-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Artikel in diesem Heft

  1. Frontmatter
  2. Preliminary Communications
  3. Synthesis of 7-cyanoindolizine derivatives via a tandem reaction
  4. A new facile way for the preparation of 3-formylcoumarins
  5. Research Articles
  6. Synthesis and spectral evaluation of 5,10,15,20-tetrakis(3,4-dibenzyloxyphenyl)porphyrin
  7. Stereoselective cascade assembling of benzylidenecyanoacetates and 1,3-dimethylbarbituric acid into (1R*,2S*)-1-cyano-5,7-dialkyl-4,6,8-trioxo-2-aryl-5,7-diazaspiro[2.5]octane-1-carboxylates
  8. Ultrasound mediated synthesis of dihydropyrano[3,2-d][1,3]dioxin-7-carbonitrile derivatives in H2O/EtOH medium
  9. Simple and efficient approach to synthesis of [1,2,4]triazolo[4,3-b][1,2,4,6]thiatriazine- 1-oxides from N-triazol-3-ylamidines
  10. Synthesis of 4H-3-aryl-2-cyano-1,4-benzothiazine 1,1-dioxides for antiviral studies
  11. Design, synthesis and antibacterial evaluation of 2-alkyl- and 2-aryl-3-(phenylamino)quinazolin-4(3H)-one derivatives
  12. Regio- and stereoselective synthesis of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts via electrophilic heterocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles and their antimicrobial activity
  13. Synthesis, spectroscopic characterization, X-ray structure and DFT calculations of Ni(II)bis(3,4 dimethoxybenzoate)bis(nicotinamide) dihydrate
  14. 13C NMR spectroscopy of heterocycles: 1-phenyl-3-aryl/t-butyl-5-arylpyrazoles
https://doi.org/10.1515/hc-2016-0233
Schlagwörter für diesen Artikel
electrophilic cyclization; halogen; regioselectivity; stereoselectivity; tellurium tetrahalogenides; [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts
Creative Commons
BY-NC-ND 3.0

Artikel in diesem Heft

  1. Frontmatter
  2. Preliminary Communications
  3. Synthesis of 7-cyanoindolizine derivatives via a tandem reaction
  4. A new facile way for the preparation of 3-formylcoumarins
  5. Research Articles
  6. Synthesis and spectral evaluation of 5,10,15,20-tetrakis(3,4-dibenzyloxyphenyl)porphyrin
  7. Stereoselective cascade assembling of benzylidenecyanoacetates and 1,3-dimethylbarbituric acid into (1R*,2S*)-1-cyano-5,7-dialkyl-4,6,8-trioxo-2-aryl-5,7-diazaspiro[2.5]octane-1-carboxylates
  8. Ultrasound mediated synthesis of dihydropyrano[3,2-d][1,3]dioxin-7-carbonitrile derivatives in H2O/EtOH medium
  9. Simple and efficient approach to synthesis of [1,2,4]triazolo[4,3-b][1,2,4,6]thiatriazine- 1-oxides from N-triazol-3-ylamidines
  10. Synthesis of 4H-3-aryl-2-cyano-1,4-benzothiazine 1,1-dioxides for antiviral studies
  11. Design, synthesis and antibacterial evaluation of 2-alkyl- and 2-aryl-3-(phenylamino)quinazolin-4(3H)-one derivatives
  12. Regio- and stereoselective synthesis of [1,3]thiazolo[3,2-b][1,2,4]triazol-7-ium salts via electrophilic heterocyclization of 3-S-propargylthio-4Н-1,2,4-triazoles and their antimicrobial activity
  13. Synthesis, spectroscopic characterization, X-ray structure and DFT calculations of Ni(II)bis(3,4 dimethoxybenzoate)bis(nicotinamide) dihydrate
  14. 13C NMR spectroscopy of heterocycles: 1-phenyl-3-aryl/t-butyl-5-arylpyrazoles
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