Next Article in Journal
A Series of Asymmetrical Phthalocyanines: Synthesis and Near Infrared Properties
Previous Article in Journal
Functionalization of Multi-Walled Carbon Nanotubes with Thermo-Responsive Azide-Terminated Poly(N-isopropylacrylamide) via Click Reactions
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 18
Issue 4
10.3390/molecules18044613
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Synthesis of New 1,2,3-Triazole Derivatives of Uracil and Thymine with Potential Inhibitory Activity against Acidic Corrosion of Steels

by
Guillermo E. Negrón-Silva
1,*,
Rodrigo González-Olvera
1,
Deyanira Angeles-Beltrán
1,
Nidia Maldonado-Carmona
1,
Araceli Espinoza-Vázquez
1,2,
Manuel E. Palomar-Pardavé
2,
Mario A. Romero-Romo
2 and
Rosa Santillan
3
1
Departamento de Ciencias Básicas, Universidad Autónoma Metropolitana, Av. San Pablo No. 180, México D.F., C.P. 02200, Mexico
2
Departamento de Materiales, Universidad Autónoma Metropolitana, Av. San Pablo No. 180, México D.F., C.P. 02200, Mexico
3
Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Apartado Postal 14-740, 07000 México D.F., Mexico
*
Author to whom correspondence should be addressed.
Molecules 2013, 18(4), 4613-4627; https://doi.org/10.3390/molecules18044613
Submission received: 26 January 2013 / Revised: 11 April 2013 / Accepted: 16 April 2013 / Published: 18 April 2013
(This article belongs to the Section Organic Chemistry)
Browse Figures
Versions Notes

Abstract

:
Ten 1,4-disubstituted 1,2,3-triazoles were synthesized from one of 1-(azido-methyl)benzene, 1-(azidomethyl)-4-fluorobenzene, 1-(azidomethyl)-4-chlorobenzene, 1-(azidomethyl)-4-bromobenzene or 1-(azidomethyl)-4-iodobenzene, generated in situ from sodium azide and the corresponding benzyl halide, and dipropargyl uracil or dipropargyl thymine. Optimal experimental conditions were established for the conventional click chemistry. The corrosion inhibiting properties of some of these compounds, which were determined by means of an electrochemical technique, are also presented.

Graphical Abstract

1. Introduction

Corrosion problems have received considerable attention due to their detrimental effects on materials that contribute to substantial economic losses and environmental pollution. The use of organic inhibitors is one of the most practical and environmentally-friendly methods to protect metals and alloys against corrosion, particularly at acid pHs that certainly damage the steel industrial infrastructure, relevant to overall economic behaviour as one determinant factor of the GNP. A number of heterocyclic organic compounds having either a delocalized set of electrons or just an electron pair on nitrogen, oxygen or sulfur heteroatoms, through which they adsorb on metallic surfaces, can block the active sites to decrease the rate of corrosion of steel, for example. Pyrimidines have various pharmaceutical applications as analgesic, antipyretic, antihypertensive and anti-inflammatory drugs, in pesticides, herbicides, plant growth regulators, and as organic calcium channel modulators [1,2,3,4]. A perusal of the literature revealed that pyrimidine derivatives and the uracil and thymine nitrogen bases [5,6,7,8,9,10,11,12,13,14,15,16] are efficient inhibitors to protect steel in acidic solutions [15,17]. 1,2,3-Triazoles have been the subject of considerable research, mainly due to their usefulness in synthetic organic chemistry and also due to their variety of interesting biological activities, forming part of the scaffolds of antibacterial and antituberculosis agents [18,19], neuraminidase inhibitors [20], anticancer compounds [21,22,23,24], antiviral agents [25,26,27], analgesic compounds [28], fungicidal activity [29,30,31], protein tyrosine phosphatase inhibitors [32,33], and assorted biomolecules (nucleosides and nucleotides) [34,35]. On the other hand, 1,2,3-triazoles have other applications, like in chemosensors [36] and organocatalysts [37]. Just as relevant to applications of 1,2,3-triazoles in the biological and pharmaceutical fields, these molecules belong to the heterocyclic compounds class, constituting an important category of organic inhibitors for corrosion protection of industrial alloys in different acidic solutions. Many substituted triazole compounds continue to be of scientific and engineering interest, and thus they have been studied in considerable detail as effective corrosion inhibitors for steel in acidic media [38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57]. In this context, we decided to explore the synthesis of some new 1,2,3-triazoleuracils and 1,2,3-triazolethymines and their anti-corrosion properties.

2. Results and Discussion

2.1. Synthesis

The dipropargyl uracil 3 was prepared from uracil (1) and propargyl bromide in the presence of DBU by refluxing the mixture in acetonitrile for 18 h. The TLC (CH2Cl2/MeOH 95:5 v/v) for the crude reaction mixture showed the formation of 3 (major product) and N-1-propargyluracil (minor product).
Molecules 18 04613 g002 550
Scheme 1. Dialkylation of pyrimidine nucleobases 1–2 with propargyl bromide.
Scheme 1. Dialkylation of pyrimidine nucleobases 1–2 with propargyl bromide.
Molecules 18 04613 g002
The desired product 3 was obtained in 79% yield before purification by column chromatography (Scheme 1). These same conditions were used for the preparation of 4, which was obtained in 70% yield from thymine (Scheme 1). The second step of the synthesis was the preparation of 1,2,3-triazole nucleobases 5–14 through a Huisgen cycloaddition reaction between azides and the terminal alkynes. Based on the Fokin and Van der Eychen methodology [58], it was decided to carry out a multicomponent Cu(I)-catalyzed click reaction for the preparation of the compounds [59,60,61,62,63,64,65,66]. Initially, the reaction was tested by mixing dipropargyl uracil 3, benzyl chloride and sodium azide in the presence of triethylamine and a catalytic amount of Cu(I) iodide [67,68,69,70,71], and stirring at room temperature for 36 h, whereby compound 5 was obtained in 44% yield (Table 1, entry 1). When the reaction was repeated using Cu(OAc)2•H2O as precatalyst [72,73,74], sodium ascorbate as reducing agent, and 1,10-phenanthroline•H2O as ligand [67,75] in EtOH-H2O at room temperature, compound 5 was obtained in 74% yield (Table 1, entry 2). With these reaction conditions established, the remaining compounds 6–14 were prepared and obtained in good yields (Table 1, entries 3-11).
Table
Table 1. Multicomponent click reaction catalyzed by Cu(OAc)2•H2O.Molecules 18 04613 i001
Table 1. Multicomponent click reaction catalyzed by Cu(OAc)2•H2O.Molecules 18 04613 i001
EntryCompoundR1R2XYield a (%)
1 b5HHCl44
25HHCl74
36HFCl78
47HClCl71
58HBrBr87
69HIBr84
710CH3HCl64
811CH3FCl87
912CH3ClCl74
1013CH3BrBr73
1114CH3IBr86
a Isolated yields after purification; b The reaction was carried out employing 0.53 mmol of 3, Cu(I) iodide (5 mol%), and NEt3 (3 eq.), stirring at room temperature for 36 h.
The structure of all compounds was confirmed by examination of their 1H- and 13C-NMR spectra, IR and mass spectra. The presence of the 1,4-disubstituted 1,2,3-triazole nucleobases was unequivocally established by means of the characteristic chemical shift values of the triazolyl hydrogens at 7.49–8.14 ppm and the chemical shift values for the carbon atoms of the triazole ring at 123.4–124.5 ppm for CH and 142.3–143.7 ppm for the quaternary carbon (Table 2). These chemical shift values are completely consistent with those reported by Creary for 1,4-disubstituted 1,2,3-triazoles [76].
Table
Table 2. 1H- and 13C-NMR chemical shifts (ppm) of the triazole ring in compounds 5–14.Molecules 18 04613 i002
Table 2. 1H- and 13C-NMR chemical shifts (ppm) of the triazole ring in compounds 5–14.Molecules 18 04613 i002
CompoundR1R2H-5C-5C-4
5HH7.49/7.62123.4/123.7142.3/143.4
6HF7.96/8.12124.0/124.3143.0/143.4
7HCl7.98/8.14124.2/124.5143.0/143.4
8HBr7.98/8.13124.2/124.5143.0/143.4
9HI7.95/8.12124.1/124.5143.0/143.4
10CH3H7.49/7.62123.5/123.7142.6/143.5
11CH3F7.96/8.12124.0/124.3143.1/143.5
12CH3Cl7.50/7.64123.5/123.7142.8/143.7
13CH3Br7.50/7.65123.5/123.7142.8/143.7
14CH3I7.95/8.11124.1/124.4143.1/143.5

2.2. Corrosion Inhibition Efficiencies

We evaluated, using electrochemical means, the corrosion inhibition efficiencies of the first four compounds considered in this work. Figure 1 depicts, as an example, the impedance measurements for both bare steel surfaces immersed in 1 M HCl (see Figure 1a), and the same system after adding 25 ppm of compound 3 to the acid media (see Figure 1b). The results of the analysis of the impedance data are shown in Table 3. It is important to remark that all these compounds have corrosion inhibition efficiencies, IE, close to 90% at a rather low concentration value.
Molecules 18 04613 g001 550
Figure 1. Experimental impedance data, Nyquist plots, recorded in the systems a) API 5L X52/1 M HCl and b) API 5L X52/1 M HCl + 25 ppm of compound 3.
Figure 1. Experimental impedance data, Nyquist plots, recorded in the systems a) API 5L X52/1 M HCl and b) API 5L X52/1 M HCl + 25 ppm of compound 3.
Molecules 18 04613 g001
Table
Table 3. Electrochemical parameters obtained from experimental impedance data, see Figure 1, including the corrosion inhibition efficiencies, IE.
Table 3. Electrochemical parameters obtained from experimental impedance data, see Figure 1, including the corrosion inhibition efficiencies, IE.
CompoundRs/Ω cm2Rp/Ω cm2C/µFIE/%
Blank2.430310-
12.52429488
27.13049790
32.016316782
41.823310087

3. Experimental

3.1. General

Commercially available reagents and solvents were used as received. Flash column chromatography was performed on Kieselgel silica gel 60 (230–400 mesh). Melting points were determined on a Fisher-Johns apparatus and are uncorrected. IR spectra were recorded on a Bruker Alpha FT-IR/ATR spectrometer (Leipzig, Germany). NMR spectra (1H at 500 MHz, 13C at 125.76 MHz) were obtained with a JEOL ECA-500 (500 MHz) spectrometer (Tokyo, Japan). Chemical shifts (δ) are given in ppm downfield from Me4Si used as an internal reference; coupling constants are given in J (Hertz). High-resolution mass spectra (HRMS) were recorded on a JEOL JMS-SX 102a and Agilent-MSD-TOF-1069A spectrometers (Tokyo, Japan). The electrochemical impedance study was performed at room temperature using the IM6-ZAHNER electrochemical workstation (ZAHNER-Elektrik GmbH & Co.KG, Kronach, Germany), applying a sinusoidal ± 10 mV perturbation, within the frequency range of 100 KHz to 0.1 Hz to an electrochemical cell with three-electrode setup. A saturated Ag/AgCl mini-electrode was used as reference, with a graphite bar as counter electrode, while the working electrode was a steel sample of API 5L X52 with an exposed area of approximately 1 cm2, which was prepared using standard metallographic procedures. The corrosion inhibition efficiency (IE) was evaluated by means of Electrochemical Impedance Spectroscopy (EIS) in the API 5L X52/1 M HCl system containing 0 (blank) or 25 ppm of the inhibitor molecule. Simulation of the impedance data recorded was conducted by means of electrical equivalent circuits [17] and the electrical parameters: Rs, solution resistance, Rtc, charge transfer resistance and C, the capacitance, were obtained in this way.

3.2. Product Synthesis and Characterization

1,3-Di(prop-2-ynyl)pyrimidine-2,4(1H,3H)-dione (3). In a 100 mL round-bottom flask containing a magnetic stirrer and equipped with a reflux condenser, uracil (1, 1.12 g, 10 mmol) was suspended in dry acetonitrile (15 mL), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 3.3 mL, 3.35 g, 22 mmol) was added and the mixture stirred for a few minutes until a clear solution was obtained. Subsequently, propargyl bromide (80 wt. % in toluene, 2.22 mL, 2.97 g, 25 mmol) was added and the whole reaction mixture was heated at reflux for 18 h. The acetonitrile was evaporated under vacuum and CH2Cl2 (20 mL) was added. The organic phase was washed with aqueous NH4Cl solution (5%, 20 mL), dried with anhydrous Na2SO4 and concentrated under vacuum. The residue was purified by column chromatography (CH2Cl2) and recrystallized from CH2Cl2/hexane (1:1 v/v) to obtain 1.48 g (79% yield) of 3 as a white solid, m.p. 102–104 °C [Lit. [77] m.p. 105 °C]. 1H-NMR (CDCl3): δ = 2.17 (t, J = 2.5 Hz, 1H, ≡C-H), 2.50 (t, J = 2.6 Hz, 1H, ≡C-H), 4.59 (d, J = 2.6 Hz, 2H, CH2), 4.68 (d, J = 2.5 Hz, 2H, CH2), 5.83 (d, J = 8.0 Hz, 1H, CH), 7.46 (d, J = 8.0 Hz, 1H, NCH). 13C-NMR (CDCl3): δ = 30.5 (CH2), 38.0 (CH2), 70.9 (≡C-H), 75.9 (C), 76.0 (≡C-H), 77.9 (C), 102.4 (CH), 140.8 (NCH), 150.5 (N2C=O), 161.7 (NC=O). FT-IR/ATR νmax cm−1: 3,289, 3,259 (≡C-H), 3,117, 3,090, 3,006, 2,983, 2,949, 2,124 (C≡C), 1,708 (C=C), 1,648 (NC=O, N2C=O), 1,540, 1,432. HRMS (ESI-TOF) calculated for C10H8N2O2+H+: 189.0658; Found: 189.0661.
5-Methyl-1,3-di(prop-2-ynyl)pyrimidine-2,4-(1H,3H)-dione (4). The procedure described above was followed to obtain compound 4, employing thymine (2, 1.26 g, 10 mmol), DBU (3.3 mL, 22 mmol) and propargyl bromide (80 wt. % in toluene, 2.22 mL, 25 mmol). The crude product was purified by column chromatography (CH2Cl2) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 1.41 g (70% yield) of 4 as a white solid, m.p. 96–100 °C [Lit. [77] m.p. 101 °C]. 1H-NMR (CDCl3): δ = 1.97 (d, J = 1.3 Hz, 3H, CH3), 2.17 (t, J = 2.5 Hz, 1H, ≡C-H), 2.47 (t, J = 2.6 Hz, 1H, ≡C-H), 4.57 (d, J = 2.6 Hz, 2H, CH2), 4.72 (d, J = 2.5 Hz, 2H, CH2), 7.26 (q, J = 1.2 Hz, 1H, NCH). 13C-NMR (CDCl3): δ = 13.2 (CH3), 30.7 (CH2), 37.6 (CH2), 70.8 (≡C-H), 75.4 (≡C-H), 76.4 (C), 78.1 (C), 110.9 (CCH3), 136.8 (NCH), 150.4 (N2C=O), 162.6 (NC=O). FT-IR/ATR νmax cm−1: 3,274, 3,260 (≡C-H), 3,072, 2,985, 2,931, 2,128 (C≡C), 1,700 (C=C), 1,657 (NC=O), 1,628 (N2C=O), 1,463. HRMS (ESI-TOF) calculated for C11H10N2O2+H+: 203.0815; Found: 203.0817.
1,3-Bis((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4-(1H,3H)-dione (5). In a 50 mL round-bottomed flask equipped with a magnetic stirrer, were added Cu(OAc)2•H2O (5 mg, 0.027 mmol, 5 mol%), 1,10-phenanthroline monohydrate (5 mg, 0.027 mmol, 5 mol%) and sodium L-ascorbate (107 mg, 0.54 mmol) in EtOH-H2O (6:4 v/v, 5 mL), followed by stirring for five minutes at room temperature. Subsequently, 3 (100 mg, 0.53 mmol), sodium azide (76 mg, 1.17 mmol) and benzyl chloride (0.13 mL, 1.17 mmol) were added to the reaction mixture, which was stirred during 36 h at room temperature (the product starts to precipitate after a few hours). Afterwards, H2O (15 mL) was added to the reaction mixture to complete precipitation of the product, which was filtered off, washed with H2O, then with hexane and dried under vacuum. The crude product was purified by column chromatography (CH2Cl2/EtOH 98:2 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 180 mg (74% yield) of 5 as a white solid, m.p. 171–172 °C. 1H-NMR (CDCl3): δ = 4.93 (s, 2H, CH2NC=O), 5.15 (s, 2H, CH2NC=O), 5.43 (s, 2H, NCH2Ph), 5.47 (s, 2H, NCH2Ph), 5.69 (d, J = 7.9 Hz, 1H, CH), 7.20–7.28 (m, 4H, ArH), 7.32–7.42 (m, 6H, ArH), 7.44 (d, J = 8.0 Hz, 1H, NCH), 7.49 (s, 1H, ArH, triazole), 7.62 (s, 1H, ArH, triazole). 13C-NMR (CDCl3): δ = 36.2 (CH2NC=O), 44.2 (CH2NC=O), 54.2 (NCH2Ph), 54.4 (NCH2Ph), 102.0 (CH), 123.4 (ArCH, triazole), 123.7 (ArCH, triazole), 128.2 (2×ArCH), 128.4 (2×ArCH), 128.8 (ArCH), 129.0 (ArCH), 129.1 (2×ArCH), 129.3 (2×ArCH), 134.2 (Cipso), 134.6 (Cipso), 142.3 (Cipso, triazole), 142.6 (NCH), 143.4 (Cipso, triazole), 151.2 (N2C=O), 162.6 (NC=O). FT-IR/ATR νmax cm−1: 3,133, 3,067, 3,012, 2,954, 1,700 (C=C), 1,650 (NC=O, N2C=O), 1,555, 1,496, 1,452, 1,434. HRMS (ESI-TOF) calculated for C24H22N8O2+H+: 455.1938; Found: 455.1939.
1,3-Bis((1-(4-fluorobenzyl)-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4(1H,3H)-dione (6). The procedure described above (using the same quantities of Cu(OAc)2•H2O, 1,10-phenanthroline monohydrate, and sodium L-ascorbate) was followed to obtain the compound 6, employing 3 (100 mg, 0.53 mmol), sodium azide (76 mg, 1.17 mmol) and 4-fluorobenzyl chloride (0.14 mL, 1.17 mmol). The crude product was purified by column chromatography (CH2Cl2/MeOH 90:10 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 203 mg (78% yield) of 6 as a white solid, m.p. 186–188 °C. 1H-NMR (DMSO-d6): δ = 4.95 (s, 2H, CH2NC=O), 4.97 (s, 2H, CH2NC=O), 5.48 (s, 2H, NCH2Ph), 5.53 (s, 2H, NCH2Ph), 5.73 (d, J = 7.9 Hz, 1H, CH), 7.13–7.19 (m, 4H, ArH), 7.31–7.37 (m, 4H, ArH), 7.80 (d, J = 7.9 Hz, 1H, NCH), 7.96 (s, 1H, ArH, triazole), 8.12 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 36.3 (CH2NC=O), 44.1 (CH2NC=O), 52.4 (NCH2Ph), 52.5 (NCH2Ph), 101.0 (CH), 116.0 (d, J2CF = 21.4 Hz, 2×ArCH), 116.2 (d, J2CF = 21.4 Hz, 2×ArCH), 124.0 (ArCH, triazole), 124.3 (ArCH, triazole), 130.8 (d, J3CF = 8.8 Hz, 2×ArCH), 130.9 (d, J3CF = 8.8 Hz, 2×ArCH), 132.6 (d, J4CF = 2.5 Hz, Cipso), 132.8 (d, J4CF = 2.5 Hz, Cipso), 143.0 (Cipso, triazole), 143.4 (Cipso, triazole), 144.9 (NCH), 151.3 (N2C=O), 161.4 (d, JCF = 243.8 Hz, Cipso), 162.5 (NC=O), 163.4 (d, JCF = 243.8 Hz, Cipso). FT-IR/ATR νmax cm−1: 3,126, 3,066, 3,012, 2,969, 1,705 (C=C), 1,657 (NC=O, N2C=O), 1,604, 1,544, 1,508, 1,453. HRMS (ESI-TOF) calculated for C24H20F2N8O2+H+: 491.1750; Found: 491.1751.
1,3-Bis((1-(4-chlorobenzyl)-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4(1H,3H)-dione (7). The procedure described above (using the same quantities of Cu(OAc)2•H2O, 1,10-phenanthroline monohydrate, and sodium L-ascorbate) was followed to obtain compound 7, employing 3 (100 mg, 0.53 mmol), NaN3 (76 mg, 1.17 mmol) and 4-chlorobenzyl chloride (198 mg, 1.23 mmol). The crude product was purified by column chromatography (CH2Cl2/EtOH 97:3 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 197 mg (71% yield) of the desired product 7 as a white solid, m.p. 185–187 °C. 1H-NMR (DMSO-d6): δ = 4.96 (s, 2H, CH2NC=O), 4.98 (s, 2H, CH2NC=O), 5.51 (s, 2H, NCH2Ph), 5.55 (s, 2H, NCH2Ph), 5.73 (d, J = 7.9 Hz, 1H, CH), 7.28 (d, J = 8.4 Hz, 2H, ArH), 7.30 (d, J = 8.3 Hz, 2H, ArH), 7.39 (d, J = 8.4 Hz, 2H, ArH), 7.40 (d, J = 8.4 Hz, 2H, ArH), 7.80 (d, J = 7.9 Hz, 1H, NCH), 7.98 (s, 1H, ArH, triazole), 8.14 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 36.3 (CH2NC=O), 44.1 (CH2NC=O), 52.4 (NCH2Ph), 52.6 (NCH2Ph), 101.0 (CH), 124.2 (ArCH, triazole), 124.5 (ArCH, triazole), 129.27 (2×ArCH), 129.30 (2×ArCH), 130.46 (2×ArCH), 130.49 (2×ArCH), 133.38 (Cipso), 133.44 (Cipso), 135.4 (Cipso), 135.5 (Cipso), 143.0 (Cipso, triazole), 143.4 (Cipso, triazole), 144.9 (NCH), 151.3 (N2C=O), 162.6 (NC=O). FT-IR/ATR νmax cm−1: 3,128, 3,064, 3,013, 2,970, 2,951, 1,702 (C=C), 1,655 (NC=O, N2C=O), 1,542, 1,491, 1,453. HRMS (ESI-TOF) calculated for C24H20Cl2N8O2+H+: 523.1159; Found: 523.1158.
1,3-Bis((1-(4-bromobenzyl)-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4(1H,3H)-dione (8). The procedure described above (using the same quantities of Cu(OAc)2•H2O, 1,10-phenanthroline monohydrate, sodium L-ascorbate) was followed to obtain compound 8, employing 3 (100 mg, 0.53 mmol), NaN3 (76 mg, 1.17 mmol) and 4-bromobenzyl bromide (292 mg, 1.17 mmol). The crude product was purified by column chromatography (CH2Cl2/EtOH 97:3 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 288 mg (87% yield) of the desired product 8 as a white solid, m.p. 196–198 °C. 1H-NMR (DMSO-d6): δ = 4.96 (s, 2H, CH2NC=O), 4.98 (s, 2H, CH2NC=O), 5.49 (s, 2H, NCH2Ph), 5.53 (s, 2H, NCH2Ph), 5.73 (d, J = 7.9 Hz, 1H, CH), 7.21 (d, J = 8.4 Hz, 2H, ArH), 7.23 (d, J = 8.3 Hz, 2H, ArH), 7.53 (d, J = 8.3 Hz, 2H, ArH), 7.54 (d, J = 8.4 Hz, 2H, ArH), 7.80 (d, J = 7.9 Hz, 1H, NCH), 7.98 (s, 1H, ArH, triazole), 8.13 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 36.3 (CH2NC=O), 44.1 (CH2NC=O), 52.5 (NCH2Ph), 52.6 (NCH2Ph), 101.0 (CH), 121.9 (Cipso), 122.0 (Cipso), 124.2 (ArCH, triazole), 124.5 (ArCH, triazole), 130.76 (2×ArCH), 130.79 (2×ArCH), 132.21 (2×ArCH), 132.23 (2×ArCH), 135.8 (Cipso), 135.9 (Cipso), 143.0 (Cipso, triazole), 143.4 (Cipso, triazole), 144.9 (NCH), 151.2 (N2C=O), 162.5 (NC=O). FT-IR/ATR νmax cm−1: 3,141, 3,128, 3,073, 1,703 (C=C), 1,656 (NC=O, N2C=O), 1,593, 1,543, 1,488, 1,455. HRMS (ESI-TOF) calculated for C24H20Br2N8O2+H+: 611.0148; Found: 611.0150.
1,3-Bis((1-(4-iodobenzyl)-1H-1,2,3-triazol-4-yl)methyl)pyrimidine-2,4(1H,3H)-dione (9). The procedure described above (using the same quantities of Cu(OAc)2•H2O, 1,10-phenanthroline mono-hydrate, sodium L-ascorbate) was followed to obtain compound 9, employing 3 (100 mg, 0.53 mmol), NaN3 (76 mg, 1.17 mmol) and 4-iodobenzyl bromide (365 mg, 1.23 mmol). The crude product was purified by column chromatography (CH2Cl2/MeOH 90:10 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 315 mg (84% yield) of the desired product 9 as a white solid, m.p. 202–204 °C. 1H-NMR (DMSO-d6): δ = 4.95 (s, 2H, CH2NC=O), 4.97 (s, 2H, CH2NC=O), 5.46 (s, 2H, NCH2Ph), 5.50 (s, 2H, NCH2Ph), 5.73 (d, J = 7.9 Hz, 1H, CH), 7.06 (d, J = 8.2 Hz, 2H, ArH), 7.07 (d, J = 8.2 Hz, 2H, ArH), 7.69 (d, J = 8.2 Hz, 2H, ArH), 7.70 (d, J = 8.3 Hz, 2H, ArH), 7.79 (d, J = 7.9 Hz, 1H, NCH), 7.95 (s, 1H, ArH, triazole), 8.12 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 36.3 (CH2NC=O), 44.1 (CH2NC=O), 52.6 (NCH2Ph), 52.8 (NCH2Ph), 95.02 (Cipso), 95.08 (Cipso), 101.0 (CH), 124.1 (ArCH, triazole), 124.5 (ArCH, triazole), 130.81 (2×ArCH), 130.83 (2×ArCH), 136.2 (Cipso), 136.3 (Cipso), 138.06 (2×ArCH), 138.08 (2×ArCH), 143.0 (Cipso, triazole), 143.4 (Cipso, triazole), 144.9 (NCH), 151.2 (N2C=O), 162.5 (NC=O). FT-IR/ATR νmax cm−1: 3,127, 3,074, 3,011, 2,944, 1,703 (C=C), 1,654 (NC=O, N2C=O), 1,588, 1,544, 1,484, 1,453. HRMS (ESI-TOF) calculated for C24H20I2N8O2+H+: 706.9871; Found: 706.9851.
1,3-Bis((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-5-methylpyrimidine-2,4(1H,3H)-dione (10). The procedure described above was followed to obtain compound 10, employing Cu(OAc)2•H2O (4.5 mg, 0.025 mmol), 1,10-phenanthroline monohydrate (5 mg, 0.025 mmol), sodium L-ascorbate (99 mg, 0.5 mmol), 4 (100 mg, 0.49 mmol), NaN3 (70 mg, 1.08 mmol) and benzyl chloride (0.12 mL, 1.08 mmol). The crude product was purified by column chromatography (CH2Cl2/EtOH 98:2 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 148 mg (64% yield) of the desired product 10 as a white solid, m.p. 187–189 °C. 1H-NMR (CDCl3): δ = 1.86 (d, J = 1.0 Hz, 3H, CH3), 4.91 (s, 2H, CH2NC=O), 5.16 (s, 2H, CH2NC=O), 5.43 (s, 2H, NCH2Ph), 5.46 (s, 2H, NCH2Ph), 7.21–7.28 (m, 4H, ArH), 7.29 (d, J = 1.1 Hz, 1H, NCH), 7.30–7.37 (m, 6H, ArH), 7.49 (s, 1H, ArH, triazole), 7.62 (s, 1H, ArH, triazole). 13C-NMR (CDCl3): δ = 13.0 (CH3), 36.4 (CH2NC=O), 43.9 (CH2NC=O), 54.2 (NCH2Ph), 54.4 (NCH2Ph), 110.3 (CCH3), 123.5 (ArCH, triazole), 123.7 (ArCH, triazole), 128.2 (2×ArCH), 128.4 (2×ArCH), 128.8 (ArCH), 129.0 (ArCH), 129.1 (2×ArCH), 129.3 (2×ArCH), 134.3 (Cipso), 134.7 (Cipso), 138.7 (NCH), 142.6 (Cipso, triazole), 143.5 (Cipso, triazole), 151.2 (N2C=O), 163.5 (NC=O). FT-IR/ATR νmax cm−1: 3,133, 3,115, 3,068, 2,956, 1,697 (C=C), 1,672 (NC=O), 1,646 (N2C=O), 1,550, 1,496, 1,453, 1,432. HRMS (ESI-TOF) calculated for C25H24N8O2+H+: 469.2094; Found: 469.2096.
1,3-Bis((1-(4-fluorobenzyl)-1H-1,2,3-triazol-4-yl)methyl)-5-methylpyrimidine-2,4(1H,3H)-dione (11). The procedure described above was followed to obtain compound 11, employing Cu(OAc)2•H2O (4.5 mg, 0.025 mmol), 1,10-phenanthroline monohydrate (5 mg, 0.025 mmol), sodium L-ascorbate (99 mg, 0.5 mmol), 4 (100 mg, 0.49 mmol), NaN3 (70 mg, 1.08 mmol) and 4-fluorobenzyl chloride (0.13 mL, 1.08 mmol). The crude product was purified by column chromatography (CH2Cl2/MeOH 90:10 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 216 mg (87% yield) of the desired product 11 as a white solid, m.p. 170–172 °C. 1H-NMR (DMSO-d6): δ = 1.77 (d, J = 1.0 Hz, 3H, CH3), 4.92 (s, 2H, CH2NC=O), 4.99 (s, 2H, CH2NC=O), 5.49 (s, 2H, NCH2Ph), 5.53 (s, 2H, NCH2Ph), 7.13–7.19 (m, 4H, ArH), 7.31–7.37 (m, 4H, ArH), 7.69 (d, J = 1.1 Hz, 1H, NCH), 7.96 (s, 1H, ArH, triazole), 8.12 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 13.1 (CH3), 36.6 (CH2NC=O), 44.0 (CH2NC=O), 52.4 (NCH2Ph), 52.5 (NCH2Ph), 108.6 (CCH3), 116.0 (d, J2CF = 21.4 Hz, 2×ArCH), 116.2 (d, J2CF = 21.4 Hz, 2×ArCH), 124.0 (ArCH, triazole), 124.3 (ArCH, triazole), 130.8 (d, J3CF = 8.8 Hz, 2×ArCH), 130.9 (d, J3CF = 8.8 Hz, 2×ArCH), 132.7 (d, J4CF = 2.5 Hz, Cipso), 132.8 (d, J4CF = 2.5 Hz, Cipso), 140.7 (NCH), 143.1 (Cipso, triazole), 143.5 (Cipso, triazole), 151.1 (N2C=O), 161.4 (d, JCF = 245.1 Hz, Cipso), 163.3 (NC=O), 163.4 (d, JCF = 245.1 Hz, Cipso). FT-IR/ATR νmax cm−1: 3,133, 3,073, 3,012, 2,954, 1,694, 1,664, 1,641, 1,605, 1,510, 1,463, 1,435. HRMS (ESI-TOF) calculated for C25H22F2N8O2+H+: 505.1906; Found: 505.1916.
1,3-Bis((1-(4-chlorobenzyl)-1H-1,2,3-triazol-4-yl)methyl)-5-methylpyrimidine-2,4-(1H,3H)-dione (12). The procedure described above was followed to obtain compound 12, employing 4.5 mg (0.025 mmol) of Cu(OAc)2•H2O, 1,10-phenanthroline monohydrate (5 mg, 0.025 mmol), sodium L-ascorbate (99 mg, 0.5 mmol), 4 (100 mg, 0.49 mmol), NaN3, (70 mg, 1.08 mmol) and 4-chlorobenzyl chloride (184 mg, 1.14 mmol). The crude product was purified by column chromatography (CH2Cl2/EtOH 97:3 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 198 mg (74% yield) of the desired product 12 as a white solid, m.p. 154–156 °C. 1H-NMR (CDCl3): δ = 1.87 (d, J = 1.1 Hz, 3H, CH3), 4.91 (s, 2H, CH2NC=O), 5.17 (s, 2H, CH2NC=O), 5.41 (s, 2H, NCH2Ph), 5.44 (s, 2H, NCH2Ph), 7.17 (d, J = 8.5 Hz, 2H, ArH), 7.21 (d, J = 8.5 Hz, 2H, ArH), 7.29 (d, J = 1.1 Hz, 1H, NCH), 7.30 (d, J = 8.5 Hz, 2H, ArH), 7.33 (d, J = 8.5 Hz, 2H, ArH), 7.50 (s, 1H, ArH, triazole), 7.64 (s, 1H, ArH, triazole). 13C-NMR (CDCl3): δ = 13.0 (CH3), 36.3 (CH2NC=O), 44.1 (CH2NC=O), 53.4 (NCH2Ph), 53.6 (NCH2Ph), 110.3 (CCH3), 123.5 (ArCH, triazole), 123.7 (ArCH, triazole), 129.3 (2×ArCH), 129.5 (2×ArCH), 129.6 (2×ArCH), 129.7 (2×ArCH), 132.8 (Cipso), 133.1 (Cipso), 134.8 (Cipso), 135.1 (Cipso), 138.7 (NCH), 142.8 (Cipso, triazole), 143.7 (Cipso, triazole), 151.2 (N2C=O), 163.5 (NC=O). FT-IR/ATR νmax cm−1: 3,142, 3,121, 3,068, 3,012, 2,955, 2,925, 1,693 (C=C), 1,662 (NC=O), 1,637 (N2C=O), 1,491, 1,462, 1,433. HRMS (ESI-TOF) calculated for C25H22Cl2N8O2+H+: 537.1315; Found: 537.1323.
1,3-Bis((1-(4-bromobenzyl)-1H-1,2,3-triazol-4-yl)methyl)-5-methylpyrimidine-2,4-(1H,3H)-dione (13). The procedure described above was followed to obtain compound 13, employing Cu(OAc)2•H2O (4.5 mg, 0.025 mmol), 1,10-phenanthroline monohydrate (5 mg, 0.025 mmol), sodium L-ascorbate (99 mg, 0.5 mmol), 4 (100 mg, 0.49 mmol), NaN3 (70 mg, 1.08 mmol) and 4-bromobenzyl bromide (270 mg, 1.08 mmol). The crude product was purified by column chromatography (CH2Cl2/EtOH 97:3 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 225 mg (73% yield) of the desired product 13 as a white solid, m.p. 148–150 °C. 1H-NMR (CDCl3): δ = 1.87 (d, J = 1.2 Hz, 3H, CH3), 4.91 (s, 2H, CH2NC=O), 5.16 (s, 2H, CH2NC=O), 5.39 (s, 2H, NCH2Ph), 5.42 (s, 2H, NCH2Ph), 7.10 (d, J = 8.6 Hz, 2H, ArH), 7.15 (d, J = 8.6 Hz, 2H, ArH), 7.29 (d, J = 1.2 Hz, 1H, NCH), 7.46 (d, J = 8.5 Hz, 2H, ArH), 7.49 (d, J = 8.5 Hz, 2H, ArH), 7.50 (s, 1H, ArH, triazole), 7.65 (s, 1H, ArH, triazole). 13C-NMR (CDCl3): δ = 13.0 (CH3), 36.3 (CH2NC=O), 44.1 (CH2NC=O), 53.5 (NCH2Ph), 53.7 (NCH2Ph), 110.3 (CCH3), 122.9 (Cipso), 123.2 (Cipso), 123.5 (ArCH, triazole), 123.7 (ArCH, triazole), 129.9 (2×ArCH), 130.0 (2×ArCH), 132.3 (2×ArCH), 132.4 (2×ArCH), 133.3 (Cipso), 133.7 (Cipso), 138.7 (NCH), 142.8 (Cipso, triazole), 143.7 (Cipso, triazole), 151.2 (N2C=O), 163.4 (NC=O). FT-IR/ATR νmax cm−1: 3,139, 3,101, 3,069, 2,998, 2,953, 2,922, 1,693 (C=C), 1,661 (NC=O), 1,637 (N2C=O), 1,488, 1,462, 1,432. HRMS (ESI-TOF) calculated for C25H22Br2N8O2+H+: 625.0305; Found: 625.0311.
1,3-Bis((1-(4-iodobenzyl)-1H-1,2,3-triazol-4-yl)methyl)-5-methylpyrimidine-2,4-(1H,3H)-dione (14). The procedure described above was followed to obtain compound 14, employing Cu(OAc)2•H2O (4.5 mg, 0.025 mmol), 1,10-phenanthroline monohydrate (5 mg (0.025 mmol), sodium L-ascorbate (99 mg, 0.5 mmol), 4 (100 mg, 0.49 mmol), NaN3 (70 mg, 1.08 mmol) and 4-iodobenzyl bromide (339 mg, 1.14 mmol). The crude product was purified by column chromatography (CH2Cl2/MeOH 90:10 v/v) and recrystallized from CH2Cl2/hexane (1:1 v/v) to afford 305 mg (86% yield) of the desired product 14 as a white solid, m.p. 229–231 °C. 1H-NMR (DMSO-d6): δ = 1.77 (s, 3H, CH3), 4.92 (s, 2H, CH2NC=O), 4.99 (s, 2H, CH2NC=O), 5.46 (s, 2H, NCH2Ph), 5.50 (s, 2H, NCH2Ph), 7.06 (d, J = 7.7 Hz, 2H, ArH), 7.07 (d, J = 7.7 Hz, 2H, ArH), 7.68–7.71 (m, 5H, NCH, ArH), 7.95 (s, 1H, ArH, triazole), 8.11 (s, 1H, ArH, triazole). 13C-NMR (DMSO-d6): δ = 13.1 (CH3), 36.6 (CH2NC=O), 44.0 (CH2NC=O), 52.6 (NCH2Ph), 52.8 (NCH2Ph), 95.01 (Cipso), 95.07 (Cipso), 108.6 (CCH3), 124.1(ArCH, triazole), 124.4 (ArCH, triazole), 130.81 (2×ArCH), 130.82 (2×ArCH), 136.2 (Cipso), 136.3 (Cipso), 138.05 (2×ArCH), 138.08 (2×ArCH), 140.7 (NCH), 143.1 (Cipso, triazole), 143.5 (Cipso, triazole), 151.1 (N2C=O), 163.3 (NC=O). FT-IR/ATR νmax cm−1: 3,138, 3,119, 3,072, 2,957, 1,696, 1,640, 1,590, 1,555, 1,464. HRMS (ESI-TOF) calculated for C25H22I2N8O2+H+: 721.0028; Found: 721.0019.

4. Conclusions

Ten new triazole derivatives of the pyrimidine bases uracil and thymine which are potential corrosion inhibitors of steel in acidic media were synthesized in good yields, employing a “click” multicomponent reaction.

Acknowledgments

The authors would like to thank Consejo Nacional de Ciencia y Tecnología, CONACyT (project 181448) for financial support. GENS, MEPP, MARR, and RS wish to acknowledge the SNI for the distinction of their membership and the stipend received. We also wish to thank Rebeca Yépez for technical assistance and Teresa Cortes for her help with NMR experiments.

References

  1. Dinakaran, V.S.; Bhargavi, B.; Srinivasan, K.K. Fused pyrimidines: The heterocycle of diverse biological and pharmacological significance. Der Pharma Chem. 2012, 4, 255–265. [Google Scholar]
  2. Sugimachi, K.; Maehara, Y.; Ogawa, M.; Kakegawa, T.; Tomita, M. Dose intensity of uracil and tegafur in postoperative chemotherapy for patients with poorly differentiated gastric cancer. Cancer Chemother. Pharmacol. 1997, 40, 233–238. [Google Scholar] [CrossRef]
  3. Kurebayashi, J.; Nukatsuka, M.; Fujoka, A.; Saito, H.; Takeda, S.; Unemi, N.; Fukumori, H.; Kurosumi, M.; Sonoo, H.; Dickson, R.B. Postsurgical oral adminitratios of uracil and tegafur inhibts progession of micrometastasis of human breast cancer cells in nude mice. Clin. Cancer Res. 1997, 3, 653–659. [Google Scholar]
  4. Mani, S.; Sciortino, D.; Samuels, B.; Arrietta, R.; Schilsky, R.L.; Vokes, E.E.; Benner, S. Phase II trial of uracil/tegafur (UFT) plus leucovorin in patients with advanced biliary carcinoma. Invest. New Drugs 1999, 17, 97–101. [Google Scholar]
  5. Yadav, D.K.; Quraishi, M.A. Application of Some Condensed Uracils as Corrosion Inhibitors for Mild Steel: Gravimetric, Electrochemical, Surface Morphological, UV-Visible, and Theoretical Investigations. Ind. Eng. Chem. Res. 2012, 51, 14966–14979. [Google Scholar] [CrossRef]
  6. Loto, R.T.; Loto, C.A.; Popoola, A.P.I.; Ranyaoa, M. Pyrimidine derivatives as environmentally-friendly corrosion inhibitors: A review. Int. J. Phys. Sci. 2012, 7, 2697–2705. [Google Scholar]
  7. Udhayakala, P.; Rajendiran, T.V.; Gunasekaran, S. Theoretical approach to the corrosion inhibition efficiency of some pyrimidine derivatives using DFT method. J. Comput. Meth. Mol. Des. 2012, 2, 1–15. [Google Scholar]
  8. Bosch, L.; Delelis, O.; Subra, F.; Deprez, E.; Witvrow, M.; Vilarrasa, J. Thymidine- and AZT-linked 5-(1,3-dioxoalkyl)tetrazoles and 4-(1,3-dioxoalkyl)-1,2,3-triazoles. Tetrahedron Lett. 2012, 53, 514–518. [Google Scholar] [CrossRef]
  9. Abiola, O.K.; John, M.O.; Asekunowo, P.O.; Okafor, P.C.; James, O.O. 3-[(4-amino-2-methyl-5-pyrimidinyl)methyl]-5-(2-hydroxyethyl)-4-methyl thiazolium chloride hydrochloride as green corrosion inhibitor of copper in HNO3 solution and its adsorption characteristics. Green Chem. Lett. Rev. 2011, 4, 273–279. [Google Scholar] [CrossRef]
  10. Khaled, K.F.; Hamed, M.N.H.; Abdel-Azim, K.M.; Abdelshafi, N.S. Inhibition of copper corrosion in 3.5% NaCl solutions by a new pyrimidine derivative: Electrochemical and computer simulation techniques. J. Solid State Electrochem. 2011, 15, 663–673. [Google Scholar] [CrossRef]
  11. Caliskan, N.; Akbas, E. The inhibition effect of some pyrimidine derivatives on austenitic stainless steel in acidic media. Mater. Chem. Phys. 2011, 126, 983–988. [Google Scholar] [CrossRef]
  12. Masoud, M.S.; Awad, M.K.; Shaker, M.A.; El-Tahawy, M.M.T. The role of structural chemistry in the inhibitive performance of some aminopyrimidines on the corrosion of steel. Corros. Sci. 2010, 52, 2387–2396. [Google Scholar] [CrossRef]
  13. Sathya, P.; Parameswari, K.; Chitra, S.; Selvaraj, A. A comparative study of the corrosion inhibitive properties of pyrimidine derivatives for mild steel. E-J. Chem. 2009, 6, S65–S74. [Google Scholar] [CrossRef]
  14. Elewady, G.Y. Pyrimidine Derivatives as Corrosion Inhibitors for Carbon-Steel in 2M Hydrochloric Acid Solution. Int. J. Electrochem. Sci. 2008, 3, 1149–1161. [Google Scholar]
  15. Issa, R.M.; Awad, M.K.; Atlam, F.M. Quantum chemical studies on the inhibition of corrosion of copper surface by substituted uracils. Appl. Surf. Sci. 2008, 255, 2433–2441. [Google Scholar] [CrossRef]
  16. Fouda, A.S.; El-Dafrawy, H. Inhibitive effect of some pyrimidine derivatives on the cyclic stressed specimens of stainless steel type 304 in acidic media. Int. J. Electrochem. Sci. 2007, 2, 721–733. [Google Scholar]
  17. Espinoza-Vázquez, A.; Negrón-Silva, G.E.; Angeles-Beltrán, D.; Palomar-Pardavé, M.E.; Romero-Romo, M.A.; Herrera-Hernández, H. Electrochemical impedance evaluation of uracil and thymine pyrimidine derivatives and its nucleosides compounds as a non-toxic corrosion inhibitors of steels in 1M HCl. ECS Trans. 2011, 36, 217–228. [Google Scholar]
  18. Dabak, K.; Sezer, O.; Akar, A.; Anac, O. Synthesis and investigation of tuberculosis inhibition activities of some 1,2,3-triazole derivatives. Eur. J. Med. Chem. 2003, 38, 215–218. [Google Scholar] [CrossRef]
  19. Shanmugavelan, P.; Nagarajan, S.; Sathishkumar, M.; Ponnuswamy, A.; Yogeeswari, P.; Sriram, D. Efficient synthesis and in vitro antitubercular activity of 1,2,3-triazoles as inhibitors of Mycobacterium tuberculosis. Bioorg. Med. Chem. Lett. 2011, 21, 7273–7276. [Google Scholar] [CrossRef]
  20. Kai, H.; Hinou, H.; Nishimura, S.-I. Aglycone-focused randomization of 2-difluoromethylphenyltypesialoside suicide substrates for neuraminidases. Bioorg. Med. Chem. 2012, 20, 2739–2746. [Google Scholar] [CrossRef]
  21. Singh, P.; Sharma, P.; Anand, A.; Bedi, P.M.S.; Kaur, T.; Saxena, A.K.; Kumar, V. Azide-alkyne cycloaddition en route to novel 1H-1,2,3-triazole tethered isatin conjugates with in vitro cytotoxic evaluation. Eur. J. Med. Chem. 2012, 55, 455–461. [Google Scholar] [CrossRef]
  22. Lakshman, M.K.; Kumar, A.; Balachandran, R.; Day, B.W.; Andrei, G.; Snoeck, R.; Balzarini, J. synthesis and biological properties of C-2 triazolylinosine derivatives. J. Org. Chem. 2012, 77, 5870–5883. [Google Scholar] [CrossRef]
  23. Zou, Y.; Zhao, Q.; Hu, H.; Hu, L.; Yu, S.; Xu, M.; Wu, Q. Synthesis and in vitro antitumor activities of xanthone derivatives containing 1,4-disubstituted-1,2,3-triazole moiety. Arch. Pharm. Res. 2012, 35, 2093–2104. [Google Scholar] [CrossRef]
  24. Singh, P.; Raj, R.; Kumar, V.; Mahajan, M.P.; Bedi, P.M.S.; Kaur, T.; Saxena, A.K. 1,2,3-Triazole tethered β-lactam-Chalcone bifunctional hybrids: Synthesis and anticancer evaluation. Eur. J. Med. Chem. 2012, 47, 594–600. [Google Scholar] [CrossRef]
  25. Al-Masoudi, N.A.; Pfleiderer, W.; Pannecouque, C. Nitroimidazoles part 7. Synthesis and anti-HIV activity of new 4-nitroimidazole derivative. J. Chem. Sci. 2012, 67, 835–842. [Google Scholar]
  26. Kanishchev, O.S.; Gudz, G.P.; Shermolovich, Y.G.; Nesterova, N.V.; Zagorodnya, S.D.; Golovan, A.V. Synthesis and biological activity of the nucleoside analogs based on polyfluoroalkyl-substituted 1,2,3-triazoles. Nucleo. Nucleot. Nucleic Acids 2011, 30, 768–783. [Google Scholar] [CrossRef]
  27. Cheng, H.; Wan, J.; Lin, M.I.; Liu, Y.; Lu, X.; Liu, J.; Xu, Y.; Chen, J.; Tu, Z.; Cheng, Y.S.E.; Ding, K. Design, synthesis, and in vitro biological evaluation of 1H-1,2,3-Triazole-4-carboxamide derivatives as new anti-influenza A agents targeting virus nucleoprotein. J. Med. Chem. 2012, 55, 2144–2153. [Google Scholar] [CrossRef]
  28. Turan-Zitouni, G.; Kaplancikli, Z.A.; Erol, K.; Kilic, F.S. Synthesis and analgesic activity of some triazoles and triazolo-thiadiazines. Farmaco 1999, 54, 218–223. [Google Scholar] [CrossRef]
  29. He, J.; Feng, L.; Li, J.; Tao, R.; Wang, F.; Liao, X.; Sun, Q.; Long, Q.; Ren, Y.; Wan, J.; He, H. Design, synthesis and biological evaluation of novel 2-methylpyrimidine-4-ylamine derivatives as inhibitors of Escherichia coli pyruvate dehydrogenase complex E1. Bioorg. Med. Chem. 2012, 20, 1665–1670. [Google Scholar] [CrossRef]
  30. Lima-Neto, R.G.; Cavalcante, N.N.M.; Srivastava, R.M.; Mendonca, F.J.B., Jr.; Wanderley, A.G.; Neves, R.P.; dos Anjos, J.V. Synthesis of 1,2,3-triazole derivatives and in vitro antifungal evaluation on Candida strains. Molecules 2012, 17, 5882–5892. [Google Scholar] [CrossRef]
  31. Zhao, X.; Lu, B.W.; Lu, J.R.; Xin, C.W.; Li, J.F.; Liu, Y. Design, synthesis and antimicrobial activities of 1,2,3-triazole derivatives. Chin. Chem. Lett. 2012, 23, 933–935. [Google Scholar] [CrossRef]
  32. He, X.-P.; Xie, J.; Tang, Y.; Li, J.; Chen, G.-R. CuAAC Click chemistry accelerates the discovery of novel chemical scaffolds as promising protein tyrosine phosphatases inhibitors. Curr. Med. Chem. 2012, 19, 2399–2405. [Google Scholar] [CrossRef]
  33. Luo, L.; He, X.-P.; Shen, Q.; Li, J.-Y.; Shi, X.-X.; Xie, J.; Li, J.; Chen, G.-R. Synthesis of (Glycopyrasonyl-tryazolyl-purines and their inhibitory Activities against Protein Tyrosine Phosphatase 1B (PTP1B). Chem. Biodivers. 2011, 8, 2035–2044. [Google Scholar] [CrossRef]
  34. Gramlich, P.M.E.; Wirges, C.T.; Manetto, A.; Carell, T. Postsynthetic DNA Modification through the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction. Angew. Chem. Int. Ed. 2008, 47, 8350–8358. [Google Scholar] [CrossRef]
  35. Amblard, F.; Cho, J.-H.; Schinazi, R.F. Cu(I)-Catalyzed Huisgen Azide-Alkyne 1,3-Dipolar Cycloaddition Reaction in Nucleoside, Nucleotide, and Oligonucleotide Chemistry. Chem. Rev. 2009, 109, 4207–4220. [Google Scholar] [CrossRef]
  36. Tang, Y.-H.; Qu, Y.; Song, Z.; He, X.-P.; Xie, J.; Hua, J.; Chen, G.-R. Discovery of a sensitive Cu(II)-cyanide “off-on” sensor based on new C-glycosyl triazolyl bis-amino acid scaffold. Org. Biomol. Chem. 2012, 10, 555–560. [Google Scholar] [CrossRef]
  37. Beckendorf, S.; Asmus, S.; Mück-Lichtenfeld, C.; García Mancheño, O. "Click” Bis-Triazoles as Neutral C-H⋅Anion-Acceptor Organocatalysts. Chem. Eur. J. 2013, 19, 1581–1585. [Google Scholar] [CrossRef]
  38. Hamdy, H.H.; Essam, A.; Mohammed, A.A. Inhibition of mild steel corrosion in hydrochloric acid solution by triazole derivatives Part I. Polarization and EIS studies. Electrochim. Acta 2007, 52, 6359–6366. [Google Scholar] [CrossRef]
  39. Li, W.; He, Q.; Pei, C.; Hou, B. Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media. Electrochim. Acta 2007, 52, 6386–6394. [Google Scholar] [CrossRef]
  40. Sherif, E.-S.M.; Erasmus, R.M.; Comins, J.D. Effects of 3-amino-1,2,4-triazole on the inhibition of copper corrosion in acidic chloride solutions. J. Colloid Interface Sci. 2007, 311, 144–151. [Google Scholar] [CrossRef]
  41. Bentiss, F.; Bouanis, M.; Mernari, B.; Traisnel, M.; Vezin, H.; Lagrenée, M. Understanding the adsorption of 4H-1,2,4-triazole derivatives on mild steel surface in molar hydrochloric acid. Appl. Surf. Sci. 2007, 253, 3696–3704. [Google Scholar] [CrossRef]
  42. Allam, N.K. Thermodynamic and quantum chemistry characterization of the adsorption of triazole derivatives during Muntz corrosion in acidic and neutral solutions. Appl. Surf. Sci. 2007, 253, 4570–4577. [Google Scholar] [CrossRef]
  43. Lebrini, M.; Traisnel, M.; Lagrenée, M.; Mernari, B.; Bentiss, F. Inhibitive properties, adsorption and a theoretical study of 3,5-bis(n-pyridyl)-4-amino-1,2,4-triazoles as corrosion inhibitors for mild steel in perchloric acid. Corros. Sci. 2008, 50, 473–479. [Google Scholar] [CrossRef]
  44. Xu, F.; Duan, J.; Zhang, S.; Hou, B. The inhibition of mild steel corrosion in 1 M hydrochloric acid solutions by triazole derivative. Mater. Lett. 2008, 62, 4072–4074. [Google Scholar] [CrossRef]
  45. Khaled, K.F. Molecular simulation, quantum chemical calculations and electrochemical studies for inhibition of mild steel by triazoles. Electrochim. Acta 2008, 53, 3484–3492. [Google Scholar] [CrossRef]
  46. Qiao, W.L.; Zhang, H.S.; Pei, C.; Hou, B. Some new triazole derivatives as inhibitors for mild steel corrosion in acidic medium. J. Appl. Electrochem. 2008, 38, 289–295. [Google Scholar] [CrossRef]
  47. Tang, Y.M.; Chen, Y.; Yang, W.Z.; Liu, Y.; Yin, X.S.; Wang, J.T. Electrochemical and theoretical studies of thienyl-substituted amino triazoles on corrosion inhibition of copper in 0.5 M H2SO4. J. Appl. Electrochem. 2008, 38, 1553–1559. [Google Scholar] [CrossRef]
  48. Bentiss, F.; Jama, C.; Mernari, B.; Attari, H.E.; Kadi, L.E.; Lebrini, M.; Traisnel, M.; Lagrenée, M. Corrosion control of mild steel using 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4- triazole in normal hydrochloric acid medium. Corros. Sci. 2009, 51, 1628–1635. [Google Scholar] [CrossRef]
  49. Tao, Z.; Zhang, S.; Li, W.; Hou, B. Corrosion inhibition of mild steel in acidic solution by some oxo-triazole derivatives. Corros. Sci. 2009, 51, 2588–2595. [Google Scholar] [CrossRef]
  50. Khadom, A.A.; Musa, A.Y.; Kadhum, A.A.H.; Mohamad, A.B.; Takriff, M.S. Adsorption kinetics of 4-amino-5-phenyl-4h-1,2,4-triazole-3-thiol on mild steel surface. Portugaliae Electrochim. Acta 2010, 28, 221–230. [Google Scholar] [CrossRef]
  51. Musa, A.Y.; Kadhum, A.A.H.; Mohamad, A.B.; Takriff, M.S.; Daud, A.R. Siti kartom kamarudin on the inhibition of mild steel corrosion by 4-amino-5-phenyl-4h-1,2,4-trizole-3-thiol. Corros. Sci. 2010, 52, 526–533. [Google Scholar] [CrossRef]
  52. Song, S.-X.; Zhang, H.-L.; Kim, C.-G.; Sheng, L.; He, X.-P.; Long, Y.-T.; Li, J.; Chen, G.-R. Expeditious preparation of triazole-linked glycolipids via microwave accelerated click chemistry and their electrochemical and biological assessments. Tetrahedron 2010, 66, 9974–9980. [Google Scholar] [CrossRef]
  53. Mert, B.D.; Mert, M.E.; Kardas, G.; Yazici, B. Experimental and theoretical investigation of 3-amino-1,2,4-triazole-5-thiol as a corrosion inhibitor for carbon steel in HCl medium. Corros. Sci. 2011, 53, 4265–4272. [Google Scholar] [CrossRef]
  54. John, S.; Joseph, A. Electro analytical, surface morphological and theoretical studies on the corrosion inhibition behavior of different 1,2,4-triazole precursors on mild steel in 1 M hydrochloric acid. Mater. Chem. Phys. 2012, 133, 1083–1091. [Google Scholar] [CrossRef]
  55. Deng, Q.; He, X.-P.; Shi, H.-W.; Chen, B.-Q.; Liu, G.; Tang, Y.; Long, Y.-T.; Chen, G.-R.; Chen, K. Concise Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition reaction ligation remarkably enhances the corrosion inhibitive potency of natural amino acids for mild steel in HCl. Ind. Eng. Chem. Res. 2012, 51, 7160–7169. [Google Scholar]
  56. Deng, Q.; Ding, N.-N.; Wei, X.-L.; Cai, L.; He, X.-P.; Long, Y.-T.; Chen, G.-R.; Chen, K. Identification of diverse 1,2,3-triazole-connected benzyl glycoside-serine/threonine conjugates as potent corrosion inhibitors for mild steel in HCl. Corros. Sci. 2012, 64, 64–73. [Google Scholar] [CrossRef]
  57. Deng, Q.; Shi, H.-W.; Ding, N.-N.; Chen, B.-Q.; He, X.-P.; Liu, G.; Tang, Y.; Long, Y.-T.; Chen, G.-R. Novel triazolyl bis-amino acid derivatives readily synthesized via click chemistry as potential corrosion inhibitors for mild steel in HCl. Corros. Sci. 2012, 57, 220–227. [Google Scholar] [CrossRef]
  58. Appkkuttan, P.; Dehaen, W.; Fokin, V.V.; van der Eycken, E. A Microwave-assisted click chemistry synthesis of 1,4-disubstituted 1,2,3-triazoles via a copper(I)-catalyzed three-component reaction. Org. Lett. 2004, 6, 4223–4225. [Google Scholar] [CrossRef]
  59. Albadi, J.; Keshavarz, M.; Shirini, F.; Vafaie-nezhad, M. Copper iodide nanoparticles on poly(4-vinylpyridine): A new and efficient catalyst for multicomponent click synthesis of 1,4-disubstituted-1,2,3-triazoles in water. Catal. Commun. 2012, 27, 17–20. [Google Scholar]
  60. Jin, G.; Zhang, J.; Fu, D.; Wu, J.; Cao, S. One-Pot, Three-component synthesis of 1,4,5-trisubstituted 1,2,3-triazoles starting from primary alcohols. Eur. J. Org. Chem. 2012, 5446–5449. [Google Scholar]
  61. Hosseinzadeh, R.; Sepehrian, H.; Shahrokhi, F. Preparation of Cu(OAc)2/MCM-41 catalyst and its application in the one-pot synthesis of 1,2,3-triazoles in water. Heteroatom Chem. 2012, 23, 415–421. [Google Scholar] [CrossRef]
  62. Kumar, B.S.P.A.; Reddy, K.H.V.; Madhav, B.; Ramesh, K.; Nageswar, Y.V.D. Magnetically separable CuFe2O4 nano particles catalyzed multicomponent synthesis of 1,4-disubstituted 1,2,3-triazoles in tap water using 'click chemistry'. Tetrahedron Lett. 2012, 53, 4595–4599. [Google Scholar] [CrossRef]
  63. Alonso, F.; Moglie, Y.; Radivoy, G.; Yus, M. Multicomponent click synthesis of 1,2,3-triazoles from epoxides in water catalyzed by copper nanoparticles on activated carbon. J. Org. Chem. 2011, 76, 8394–8405. [Google Scholar] [CrossRef] [Green Version]
  64. Yadav, J.S.; Reddy, B.V.S.; Reddy, G.M.; Anjum, S.R. Cu(OTf)2/Cu-catalyzed four-component reaction: a facile synthesis of α-alkoxytriazoles via click chemistry. Tetrahedron Lett. 2009, 50, 6029–6031. [Google Scholar] [CrossRef]
  65. Kalisiak, J.; Sharpless, K.B.; Fokin, V.V. Efficient synthesis of 2-substituted-1,2,3-triazoles. Org. Lett. 2008, 10, 3171–3174. [Google Scholar] [CrossRef]
  66. Sreedhar, B.; Reddy, P.S.; Krishna, V.R. Regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles via three-component coupling of secondary alcohols, TMSN3 and alkynes. Tetrahedron Lett. 2007, 48, 5831–5834. [Google Scholar] [CrossRef]
  67. Hwang, S.; Bae, H.; Kim, S.; Kim, S. An efficient and high-yielding one-pot synthesis of 4-acyl-1,2,3-triazoles via triisopropylsilyl-protected ynones. Tetrahedron 2012, 68, 1460–1465. [Google Scholar] [CrossRef]
  68. Krim, J.; Taourirte, M.; Engels, J.W. Synthesis of 1,4-disubstituted mono and bis-triazolocarbo-acyclonucleoside analogues of 9-(4-hydroxybutyl)guanine by Cu(I)-catalyzed click azide-alkyne cycloaddition. Molecules 2012, 17, 179–190. [Google Scholar]
  69. Brotherton, W.S.; Clark, R.J.; Zhu, L. Synthesis of 5-iodo-1,4-disubstituted-1,2,3-triazoles mediated by in situ generated copper(I) catalyst and electrophilic triiodide ion. J. Org. Chem. 2012, 77, 6443–6455. [Google Scholar] [CrossRef]
  70. Stefani, H.A.; Amaral, M.F.Z.J.; Manarin, F.; Ando, R.A.; Silva, N.C.S.; Juaristi, E. Functionalization of 2-(S)-isopropyl-5-iodo-pyrimidin-4-ones through Cu(I)-mediated 1,3-dipolar azide-alkyne cycloadditions. Tetrahedron Lett. 2011, 52, 6883–6886. [Google Scholar] [CrossRef]
  71. Wang, F.; Fu, H.; Jiang, Y.; Zhao, Y. Quick and highly efficient copper-catalyzed cycloaddition of aliphatic and aryl azides with terminal alkynes “on water”. Green Chem. 2008, 10, 452–456. [Google Scholar] [CrossRef]
  72. Saraiva, M.T.; Seus, N.; de Souza, S.; Rodrigues, O.E.D.; Paixão, M.W.; Jacob, R.G.; Lenardão, E.J.; Perin, G.; Alves, D. Synthesis of [(arylselanyl)alkyl]-1,2,3-triazoles by copper-catalyzed 1,3-dipolar cycloaddition of (arylselanyl)alkynes with benzyl azides. Synthesis 2012, 44, 1997–2004. [Google Scholar] [CrossRef]
  73. Kuang, G.-C.; Michaels, H.A.; Simmons, J.T.; Clark, R.J.; Zhu, L. Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition. J. Org. Chem. 2010, 75, 6540–6548. [Google Scholar] [CrossRef]
  74. Brotherton, W.S.; Michaels, H.A.; Simmons, J.T.; Clark, R.J.; Dalal, N.S.; Zhu, L. Apparent copper(ii)-accelerated azide-alkyne cycloaddition. Org. Lett. 2009, 11, 4954–4057. [Google Scholar] [CrossRef]
  75. Lewis, W.G.; Magallon, F.G.; Fokin, V.V.; Finn, M.G. Discovery and characterization of catalysts for azide-alkyne cycloaddition by fluorescence quenching. J. Am. Chem. Soc. 2004, 126, 9152–9153. [Google Scholar] [CrossRef]
  76. Creary, X.; Anderson, A.; Brophy, C.; Crowell, F.; Funk, Z. Method for assigning structure of 1,2,3-triazoles. J. Org. Chem. 2012, 77, 8756–8761. [Google Scholar] [CrossRef]
  77. Krim, J.; Sillahi, B.; Taourirte, M.; Rakib, E.M.; Engels, J.W. Microwave-assisted click chemistry: Synthesis of mono and bis-1,2,3-triazole acyclonucleoside analogues of ACV via copper(I)-catalyzed cycloaddition. Arkivoc 2009, xiii, 142–152. [Google Scholar]
  • Sample Availability: Samples of the compounds 3–14 are available from the authors.

Share and Cite

MDPI and ACS Style

Negrón-Silva, G.E.; González-Olvera, R.; Angeles-Beltrán, D.; Maldonado-Carmona, N.; Espinoza-Vázquez, A.; Palomar-Pardavé, M.E.; Romero-Romo, M.A.; Santillan, R. Synthesis of New 1,2,3-Triazole Derivatives of Uracil and Thymine with Potential Inhibitory Activity against Acidic Corrosion of Steels. Molecules 2013, 18, 4613-4627. https://doi.org/10.3390/molecules18044613

AMA Style

Negrón-Silva GE, González-Olvera R, Angeles-Beltrán D, Maldonado-Carmona N, Espinoza-Vázquez A, Palomar-Pardavé ME, Romero-Romo MA, Santillan R. Synthesis of New 1,2,3-Triazole Derivatives of Uracil and Thymine with Potential Inhibitory Activity against Acidic Corrosion of Steels. Molecules. 2013; 18(4):4613-4627. https://doi.org/10.3390/molecules18044613

Chicago/Turabian Style

Negrón-Silva, Guillermo E., Rodrigo González-Olvera, Deyanira Angeles-Beltrán, Nidia Maldonado-Carmona, Araceli Espinoza-Vázquez, Manuel E. Palomar-Pardavé, Mario A. Romero-Romo, and Rosa Santillan. 2013. "Synthesis of New 1,2,3-Triazole Derivatives of Uracil and Thymine with Potential Inhibitory Activity against Acidic Corrosion of Steels" Molecules 18, no. 4: 4613-4627. https://doi.org/10.3390/molecules18044613

APA Style

Negrón-Silva, G. E., González-Olvera, R., Angeles-Beltrán, D., Maldonado-Carmona, N., Espinoza-Vázquez, A., Palomar-Pardavé, M. E., Romero-Romo, M. A., & Santillan, R. (2013). Synthesis of New 1,2,3-Triazole Derivatives of Uracil and Thymine with Potential Inhibitory Activity against Acidic Corrosion of Steels. Molecules, 18(4), 4613-4627. https://doi.org/10.3390/molecules18044613

Article Metrics

Back to TopTop