ARTICLE

Catalytic activity of dithioic acid copper complexes in the alkyne–azidecycloadditionBayardo E. Velasco, Gustavo López-Téllez, Nelly González-Rivas, Iván García-Orozco, and Erick Cuevas-Yañez

Abstract: Diverse dithioic acid copper complexes exhibit a high catalytic activity in the copper-catalyzed alkyne–azide cy-cloaddition using several solvents under different temperatures, showing a high efficiency with only 0.005 mmol catalyst/mmolalkyne or less. A dithioic acid copper complex derived from acetophenone was selected and used as the catalyst in the prepara-tion of a library of 1,4-disubstituted-1,2,3-triazoles. This process occurred in high yields and good functional group tolerance.

Key words: dithioic acid copper complex, alkyne–azide cycloaddition, 1,2,3-triazoles.

Résumé : Divers complexes cuivrique de l'acide dithoïque présentent une activité catalytique élevée pour la réaction decycloaddition alcyne-azoture, catalysée par le cuivre, dans divers solvants et a diverses températures; leur efficacité est déjagrande avec des quantitésmaximales de seulement 0,005mmole catalyseur/mmole alcyne. On a choisi un complexe de cuivre del'acide dithioïque dérivé de l'acétophénone et on l'a utilisé comme catalyseur dans la préparation d'une librairie de 1,2,3-triazolesdisubstitués en positions 1,4. Ce processus se produit avec des rendements élevés et avec une bonne tolérance pour la présenced'autres groupes fonctionnels. [Traduit par la Rédaction]

Mots-clés : complexes cuivrique de l'acide dithoïque, cycloaddition alcyne-azoture, 1,2,3-triazoles.

IntroductionDuring this century, copper-catalyzed alkyne–azide cycloaddition

(CuAAC) has become one of the most important methods for theassembly of diverse components through a chemical process.1 Inaddition, this reaction represents the main route to obtain1,2,3-triazoles, which have been proposed as an importantsource of potential novel compounds for the pharmaceuticalindustry.2

These elements inspired us to start an investigation about thesynthesis of triazoles from CuAAC. One important part is thechoice of the catalytic system, essentially based on a copper(I) salt.In this regard, the most extended protocols to synthesize 1,2,3-triazolesweredevelopedby thegroupsofMeldal3 and Fokin.4 Thesemethodologies are widespread in application affording the de-sired compounds in a high yield, regioselectivity, and atom econ-omy. However, we found that certain alkynes and azides do notgive 1,2,3-triazoles or the yields are low using these conditions.These unsuccessful attempts motivated us to seek alternative cat-alytic systems for CuAAC. A current trend in this area is the use ofpreformed copper(I) catalysts with phosphine or analogous li-gands, which show significant catalytic activity.5–8 In this context,we were attracted by a novel kind of stable copper(I) complexesderived from propendithioic acids that contain in their structureboth triphenylphosphine and dithioate as ligands coordinated tothe transition metal.9 In a previous short communication, wefound that a specific dithioic acid copper complex derived fromacetophenone showed high catalytic activity in CuAAC for thesynthesis of some tetrahydrofuranyl-1,2,3-triazoles.10 To explorethe scope of the process, we decided to investigate other dithioicacid copper complexes with the aim to develop better catalysts forCuAAC. Herein is described a summary of our recent successfulendeavors in this area.

Results and discussionThe first experiments were conducted to prepare the copper cata-

lysts. Compounds 1 and 2 were synthesized from an adaptationof the methodology described by García-Orozco et al.,9 whereascompounds 3 and 4 were obtained from the correspondingdithiocarbamates, which in turn were prepared from the condensa-tion of secondary amines and carbon disulfide (Scheme 1).11–13

These compounds were characterized by the conventional spec-troscopic techniques and they were analyzed by X-ray photoelec-tron spectroscopy (XPS). In our case, XPS was used to determinewhether there is evidence of an interaction between S and Cu, andP with Cu, hence giving evidence that the proposed structure ofthe catalyst is correct. For example, the wide spectra (not shown)of catalyst 1 had the characteristic signals of C1s, O1s, Cu2p3/2 andCu2p1/2, S2p3/2, and P2p3/2. All of these elements constitute thecatalyst complex. A narrow spectrum of the Cu2p3/2 region wasrecorded to further analyze the chemical state and composition ofCu. Figure 1a shows the curve fitting of the Cu2p3/2 signal. Threesignals were found to fit the original signal. According to thecomplex structure, Cu complexes with two S species, which areslightly different in terms of electronic density due to one havinga double bond with the rest of themolecule. This explains the twosignals obtained, which are in a region in agreement with that ofa Cu(I) complex with S.14 The third signal corresponds to Cu–P andfits the reported chemical shift of Cu(I) due to two chelating phos-phorous atoms.15 An interesting fact is that Cu(II) signals are notobserved. Figures 1b and 1c show the narrow spectra of S2p andP2p, respectively. The signals present are in agreement with thosereported for this species forming various complexes,15 which arein the range of 163–164.7 eV for S and 131.3–133.1 eV for P. Therewas no evidence in the spectra that suggested an interaction withO since those compounds appear at higher binding energies.

Received 20 August 2012. Accepted 3 November 2012.

B.E. Velasco, G. López-Téllez, N. González-Rivas, I. García-Orozco, and E. Cuevas-Yañez. Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM.Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México 50200, Mexico.

Corresponding author: Erick Cuevas-Yañez (e-mail: ecuevasy@uaemex.mx).

292

Can. J. Chem. 91: 292–299 (2013) dx.doi.org/10.1139/cjc-2012-0325 Published at www.nrcresearchpress.com/cjc on 21 November 2012.

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The copper complexes 1–4 were tested in the cycloaddition ofphenylacetylene (5) and benzyl azide (6) in acetonitrile at roomtemperature using 5 mol % catalyst in each case, and obtainingtriazole (7) as the only product in high yields (Scheme 2, Table 1).

From these results, copper complexes 1–4 were active catalystsin the cycloaddition between phenylacetylene (5) and benzylazide (6) at room temperature. This catalytic ability was con-firmed when butylcarbamic acid prop-2-ynyl ester (8) was reactedwith benzyl azide (6) in the presence of catalytic amounts of com-plexes 1–4 affording triazole 9. These reactions were carried outusing chloroform as the solvent at room temperature and underreflux temperature conditions obtaining similar yields in shortertimes (Scheme 3, Table 2). In contrast, the use of the classic cata-lytic system CuSO4–sodium ascorbate gave a moderate yield (63%)in this process.

Although all copper complexes showed good catalytic activi-ties, we found that complex 1 was more stable in air and gave thebest results. These properties motivated us to select complex 1 asthe catalyst in subsequent experiments.

To explore the scope of the process, several solvents were testedin the cycloaddition of azide 6 and alkyne 5 using catalyticamounts of copper complex 1, which was soluble in all evaluatedsolvents. Thus, experiments demonstrated that compound 1 is aneffective catalyst using a wide range of solvents (Table 3). Further-more, when the reaction is performed using polar solvents, thereaction times decreased, unlike solvents such as toluene, whichafforded high yields but the longest reaction times.

The effect of the catalyst concentration was also studied. Theresults, summarized in Table 4, show that catalyst 1 is efficient ina 0.5% mol concentration giving quantitative yields and shorterreaction times. Moreover, we also found that catalyst 1 was activedown to the 0.1%mol concentration affording almost quantitativeyields of product 7 after 72 h. This catalytic behavior is similar to

Scheme 1. Reagents and conditions: (a) t-BuOK, CS2, 25–30 °C; (b) NaOH, Cu(PPh3)2Cl, EtOH, reflux, 2 h; (c) CS2, NaOH, 0–5 °C; (d) Cu(PPh3)2Cl,EtOH, reflux, 2 h.

Fig. 1. XPS narrow spectra of compound 1 for (a) Cu2p3/2, (b) S2p3/2,and (c) P2p3/2 regions.

Scheme 2. Cu-catalyzed cycloaddition between azide 6 andalkyne 5.

Table 1. Synthesis of triazole 7 using catalysts.

CatalystReactiontime (h)

Conversion(%)a

Yield(%)b

None 50 0 01 8 100 84.12 10 100 91.03 8 100 86.44 8 97.5 86.4

aCrude yields determined by HPLC.bYields determined after purification.

Velasco et al. 293

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other catalysts based on copper complexes of N-heterocyclic car-benes,16–18 phosphines,5,6 phosphinites,7 or phosphoramidites.8.

Although many copper catalysts have been successfully used forCuAAC, dithioic acid copper complexes exhibit a remarkable cata-lytic activity in this process,which is in contrast to traditional coppercatalytic systems (CuI–DIPEA (N,N-diisopropylethylamine),3 CuSO4–sodium ascorbate4). This fact could be attributed to the sulfur andphosphorus ligands in complexes 1–4, which not only protect thecopper(I) ion from possible oxidation, but also activate the coppercenter and likely stabilize some intermediates such as copperacetylides19 or copper triazolides20,21 proposed in the catalyticcycle, affording milder reaction conditions, compatibility, andtolerance in a wide range of solvents, and a lower catalyst loading.Thus, a plausible reaction mechanism involves the formation of

intermediates like the copper acetylide complex 42 and the sub-sequent copper triazolide 44 (Scheme 4). In this catalytic cycle, theCH alkyne hydrogen is transferred from the alkyne carbon to oneof the sulfur atoms in the ditioic acid copper complex, which isweakly bonded to the copper ion.22 In the final step, a secondhydrogen transfer might occur between the sulfur atom and theheterocyclic ring to afford the corresponding triazole and regen-erating the catalyst. As a consequence of this catalytic cycle, theuse of dithioic acid copper complexes in CuAAC avoids the use ofadditional bases or reducing agents required in other catalyticsystems for this reaction.

Furthermore, alkynes and azides were reacted using catalyticamounts of compound 1. The results in Table 5 suggest that abroad scope of functional groups can be used on the alkyne part aswell as on the azidemoleculewithout loss of efficiency. Therefore,compound 1 is an excellent catalyst for selective cycloadditionbetween alkynes and azides to prepare 1,2,3-triazoles.

ConclusionsIn summary, dithioic acid copper complexes represent a novel

kind of effective catalysts for CuAAC, which combine a good tol-erance to solvents and functional groups, and an outstandingcatalytic ability (0.5% mol or less). As a consequence, a novel li-brary of 1,2,3-triazoles was easily obtained when azides weretreated with diverse terminal alkynes using dithiopronenoic acidcopper(I) complex 1 as the catalyst, which is a simple, stable,useful, and effective catalyst, to obtain 1,2,3-triazoles in goodyields and purity levels under a process that occurs in one step andadditional bases or reducing agents are not required. The simplic-ity of the method suggests that these catalysts and this route to1,2,3-triazoles will enjoy widespread applications.

Experimental

General remarksThe starting materials were purchased from Sigma-Aldrich

and were used without further purification. Solvents were dis-tilled before use. Silica plates of 0.20 mm thickness were usedfor thin-layer chromatography. Melting points were deter-mined with a Fisher-Johns melting point apparatus and theyare uncorrected. 1H and 13C NMR spectra were recorded using aVarian 500 spectrometer; the chemical shifts (�) are given inppm relative to tetramethylsilane (TMS) as the internal stan-dard (0.00). For analytical purposes the mass spectra were re-corded on a JEOL JMS-5X 10217 instrument in the electronionization (EI) mode, 70 eV, 200 °C via direct inlet probe. Onlythe molecular and parent ions (m/z) are reported. IR spectrawere recorded on a Nicolet Magna 55-X FT instrument.

The XPS wide and narrow spectra were acquired using a JEOLJPS-9200 instrument equipped with a Mg X-ray source (1253.6 eV)at 200 W. The area of analysis was 1 mm, and the vacuum was inthe order of 10–8 Torr (1 Torr = 133.3224 Pa) for all samples. Thespectra were analyzed using the SpecSurf software included withthe instrument. All spectra were charge corrected bymeans of theadventitious carbon signal (C1s) at 284.5 eV. The Shirley methodwas used for the background subtraction, whereas for the curvefitting, the Gauss–Lorentzmethodwas used. Samples were fixatedon carbon tape and analyzed without further treatment. Prior toanalysis, the instrument was calibrated by means of the Au 4f7/2signal using a gold standard. Propendithioic acid copper com-plexes 1 and 2 were prepared according to García-Orozco andet al.9

Preparation of copper complexes 1 and 2

Synthesis of bis(triphenylphosphine)copper(I) chlorideA solution of triphenylphosphine (32.8 g, 125 mmol) in ethanol

(650 mL) was stirred at reflux temperature until triphenylphos-phine was dissolved. The solution was cooled to room tempera-

Scheme 3. Cu-catalyzed cycloaddition between azide 6 andalkyne 8.

Table 2. Synthesis of triazole 9 using catalysts.

CatalystReactiontime (h)

Conversion(%)a

Yield(%)b

1 5 100 952 6 98 933 5 95 934 6 85 60CuSO4–sodium

ascorbate6 86 63

aCrude yields determined by HPLC.bYields determined after purification.

Table 3. The effect of solvent in the cycloaddition between alkyne 5and azide 6.

Solvent

Reactiontemperature(°C)

Reactiontime (h)

Conversion(%)a

Yield(%)b

Acetonitrile 60 3 100 88Ethyl acetate 60 5 100 83Methanol 58 5 100 88Acetone 50 5 100 85Tetrahydrofuran 60 5 100 88Chloroform 60 5 100 86Toluene 60 8 100 90

aCrude yields determined by HPLC.bYields determined after purification.

Table 4. The effect of the catalyst concentrationin the cycloaddition between alkyne 5 and azide 6.

mmol Catalyst1/mmol azide

Reactiontime (h)

Conversion(%)a

Yield(%)b

0.001 72 100 950.002 12 100 930.005 5 100 950.05 5 100 95

aCrude yields determined by HPLC.bYields determined after purification.

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ture and freshly prepared CuCl23 (6.2 g, 62.6 mmol) was added.The resulting reaction mixture was stirred at reflux temperaturefor 18 h. The mixture was cooled to room temperature over-night. The solid was filtered, washed with ethanol (50 mL), anddried under vacuum (60 °C/10 mm Hg; 1 mm Hg = 133.3224 Pa).The final product (38.4 g, 98.5% yield) was used without addi-tional purification.

Synthesis of propendithioic acidsTypical procedure: A solution of the corresponding ace-

tophenone (166.8 mmol) and carbon disulfide (6.4 g, 84 mmol) inisopropyl ether (20 mL) was dropped into a suspension of potas-sium tert-butoxide (19.7 g, 166.8 mmol) in isopropyl ether (80 mL)for 30min at 25–30 °C under a nitrogen atmosphere. The resultingreaction mixture was stirred at room temperature overnight. Wa-ter (100 mL) was added, and the organic phase was washed withwater (2 × 50 mL). The aqueous phases were joined and a 30%H2SO4 solution (28.6 mL) was added. The solid was filtered,washed with water, and dried under vacuum (60 °C/10 mm Hg).The final product was purified by crystallization.

3-Hydroxy-3-phenyl-2-propenedithioic acidRed solid (80%); mp 63 °C (lit. value9 mp 63 °C). IR (KBr, cm−1):

3430, 2512, 1591, 1550, 1486, 1452, 1244. 1H NMR (CDCl3) �: 5.42 (s,1H), 6.96 (s, 1H), 7.46 (m, 2H), 7.55 (m, 1H), 7.87 (m, 2H), 15.3 (s, 1H).13C NMR (CDCl3) �: 108.2, 127.0, 129.0, 132.7, 133.8, 172.9, 211.4.

3-Hydroxy-3-(p-methoxyphenyl)-2-propenedithioic acidRed solid (77%); mp 76–77 °C (lit. value9mp 73 °C). IR (KBr, cm−1):

3430, 1603, 1582, 1545, 1503, 1430, 1232. 1H NMR (CDCl3) �: 3.87 (s,3H), 5.33 (s, 1H), 6.95 (d, 2H, J = 8.70 Hz), 6.95 (s, 1H), 7.86 (d, 2H, J =8.70 Hz), 15.19 (s, 1H). 13C NMR (CDCl3) �: 55.6, 107.2, 114.3, 126.3,128.7, 162.9, 169.6, 215.7.

Synthesis of propendithioic acid copper complexes 1 and 2Typical procedure: A mixture of the corresponding propenedithioic

acid (10.6 mmol), ethanol (15 mL), and a 2 mol/L NaOH solution(5.3 mL) was stirred at 60 °C. The reddish solution was successivelytreated with Cu(PPh3)2Cl (6.6 g, 10.6 mmol) and CH2Cl2 (50 mL).The resulting reaction mixture was stirred at reflux temperaturefor 2 h. The mixture was cooled to room temperature overnight.Water (50 mL) was added, and the product was extracted withCH2Cl2 (2 × 25 mL). The organic phases were joined and dried over

Na2SO4. The solvent was removed under vacuum and the productwas purified by crystallization.

(3-Hydroxy-3-phenyl-2-propenedithioate-S,S=)-bis(triphenylphosphine-P) copper(I) (compound 1)

Red solid (60%); mp 166–167 °C. IR (attenuated total reflection(ATR), cm−1): 3432, 3050, 1680, 1586, 1565, 1480, 1432, 1205, 1044.1H NMR (500 MHz, CDCl3) �: 4.62 (s, 2H, H-2, keto), 6.89 (s, 1H, H-2,enol), 7.25 (m, PPh3), 7.47 (t, H-6, enol), 7.42 (m, 2H, H-6, keto), 7.53(m, 2H, H-7, keto + enol), 7.96 (m, 2H H-5, enol), 8.17 (m, 2H, H-5,keto), 13.04 (s, 1H, H-8, enol). 13C NMR (125 MHz, CDCl3) �: 66.1,113.6, 126.4, 128.2, 128.5, 128.6, 129.5, 130.4, 132.9, 133.7, 135.8,136.9, 162.9, 193.7. Fast atom bombardment (FAB) MS m/z: 845.0[M + Cu]+. HR-MS FAB (m/z) calcd. for C45H37Cu2OP2S2: 845.0353;found: 845.0369. Anal. calcd. for C45H37CuOP2S2 (%): C 68.99, H 4.76;found: C 68.79, H 4.82.

(3-Hydroxy-3-(4-methoxyphenyl)-2-propenedithioate S,S=)-bis(triphenylphosphine-P) copper(I) (compound 2)

Red solid (60%); mp 170–172 °C. IR (ATR, cm−1): 3050, 1680, 1565,1480, 1205, 987, 745, 693, 510. 1H NMR (500 MHz, CDCl3) �: 3.82 (m,3H, ceto + enol), 4.56 (s, 2H, H-2 ceto), 6.89 (m, 1H, H-2, enol), 7.25(m, PPh3), 7.48 (t, H-6, enol), 7.50 (m, 2H, H-7, ceto + enol), 7.72 (m,2H, H-5, enol), 8.12 (d, 2H, H-5, ceto), 13.06 (s, 1H, H-8, enol).13C NMR (125 MHz, CDCl3) �: 55.3, 55.4, 66.0, 113.6, 127.8, 127.9, 128.4,128.4, 128.5, 129.4, 130.0, 131.5, 131.5, 131.7, 132.2, 132.3, 133.2, 133.6,163.2, 192.2. MS [FAB+] m/z (%): 877 [M + Cu]+, 587 [Cu(PPh3)2]+, 325[Cu(PPh3)]+, 262 [(PPh3)]+. HR-MS FAB (m/z) calcd. for C46H39CuO2P2S2:875.0659; found: 875.0661. Anal. calcd. for C46H39CuOP2S2 (%):C 69.28, H 4.93; found: C 69.55; H 4.84.

Preparation of copper complexes 3 and 4

Synthesis of sodium salts of dialkyldithiocarbamic acidsTypical procedure: Carbon disulfide (25.3 g, 333 mmol) was

added to a previously cooled (0 °C) mixture of water (40 mL) andthe corresponding amine (333 mmol). The resulting reactionmixture was stirred for 15 min at 0–5 °C. A 30% NaOH aqueoussolution (43.4 mL, 333 mmol) was added and the water wasremoved under vacuum. The product was used without addi-tional purification.

Scheme 4. Plausible mechanism of 1,2,3-triazole formation.

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Synthesis of dialkyldithiocarbamic acid copper complexes 3 and 4Typical procedure: The appropriate dialkyldithiocarbamic

acid sodium salt (12.6 mmol) was added to a solution of bis(triphenylphosphine) copper(I) chloride (7.78 g, 12.5 mmol) inEtOH (100mL). The resulting reactionmixturewas stirred at refluxtemperature for 2 h. The reaction mixture was cooled to roomtemperature and water (159 mL) was added. The crystals werefiltered, washed with water (20 mL) and EtOH (20 mL), and dried

under vacuum (60 °C/10mmHg). The final product was purified bycrystallization.

(Dimethyldithiocarbamoate-S,S=)-bis(triphenylphosphine-P)copper(I) (compound 3)

White solid; mp 193 °C. IR (ATR, cm−1): 3050, 2800, 1960, 1900,1875, 1675, 1475, 1375, 1250, 980, 750, 700, 510. 1H NMR (500 MHz,CDCl3) �: 3.35 (s, 6H), 7.19–7.44 (m, 30H). 13C NMR (125MHz, CDCl3)�: 55.2, 128.1, 128.2, 129.2, 133.7, 133.9. MS [FAB+] m/z (%): 771 [M +

Table 5. Synthesis of 1,2,3-triazoles using catalyst 1.

Compound R1 R2 SolventReactiontime (h) Conversion (%)a Yield (%)b

7 Ph PhCH2 CH3CN 3 99 949 CH2OCONHC4H9 PhCH2 CHCl3 5 100 9510 CH2O(4-CH3)C6H4 PhCH2 CHCl3 12 100 9711 CH2O(4-CH3O)C6H4 PhCH2 CHCl3 12 100 9612 CH2O(4-Cl)C6H4 PhCH2 CHCl3 12 100 9513 CH2O(4-CO2CH3)C6H4 PhCH2 CHCl3 32 100 9514 CH2O(4-CHO)C6H4 PhCH2 CHCl3 26 100 9515 CH2OH PhCH2 CHCl3 7 100 9216 CH2OCONHC4H9 3,4-ClC6H3 CHCl3 10 100 9317 Ph Ph CHCl3 20 91 8718 Ph 3,4-ClC6H3 CHCl3 14 91 8919 PhCH2 CHCl3 9 100 97

20 3,4-ClC6H3 CHCl3 17 90 85

21 4-ClC6H4 CH3OH 3 90 85

22 CH2N(CH3)2C14H29Br PhCH2 CHCl3 32 54 5423 CH2N(C4H9)2 PhCH2 CHCl3 23 91 8624 CH2N(C4H9)2 4-ClC6H4 CHCl3 25 100 9625 CH2N(C4H9)2 3,4-ClC6H3 CHCl3 25 95 9226 Ph 2-NO2C6H4 CH3CN 11 93 8927 Ph 4-NO2C6H4 CH3CN 5 94 8828 CH2O(4-CO2CH3)C6H4 CH3CN 12 98 93

29 Ph CH3CN 16 90 84

30 Ph 4-ClC6H4 CH3CN 12 100 9631 Ph 4-CH3OC6H4 CH3CN 11 100 9532 Ph 4-BrC6H4 CH3CN 12 100 9533 Ph 4-CH3C6H4 CH3CN 5 100 9734 4-CF3C6H4 Ph CH3CN 5 100 9535 4-CF3C6H4 4-CH3C6H4 CH3CN 5 100 9336 4-CH3C6H4 Ph CH3CN 8 100 9637 4-CH3OC6H4 Ph CH3CN 8 100 9538 4-(C5H11)C6H4 Ph CH3CN 8 100 9439 4-(CH3)2NC6H4 Ph CH3CN 8 100 97

aCrude yields determined by HPLC.bYields determined after purification.

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Cu]+. HR-MS FAB (m/z) calcd. for C39H36Cu2NP2S2: 770.0556; found:770.0561. Anal. calcd. for C39H36CuNP2S2 (%): C 66.13; H 5.12, N 1.98;found: C 66.45; H 5.23, N 1.87.

(Dibutyldithiocarbamoate-S,S=)-bis(triphenylphosphine-P)copper(I) (compound 4)

White solid; mp 179 °C. IR (ATR, cm−1): 3100, 3050, 2880, 1960,1900, 1875, 1775, 1675, 1475, 1400, 1250, 1000, 750, 700, 500. 1H NMR(500 MHz, CDCl3) �: 0.93 (s, broad, 6H), 1.32 (s, broad, 4H), 1.67(s, broad, 4H), 3.83 (s, broad, 4H), 7.12–7.41 (m, 30H). 13C NMR(125 MHz, CDCl3) �: 14.1, 20.1, 29.369, 52.0, 128.2, 128.2, 128.5, 128.6,129.0, 129.1, 129.4, 131.6, 131.6, 132.0, 132.0, 132.0, 132.1, 132.1, 132.2,132.3, 132.6, 133.0, 133.3, 133.6, 133.8, 133.9, 134.6, 134.8. MS [FAB+]m/z (%): 854 [M + Cu]+ (1), 587 [Cu(PPh3)2]+, 325 [Cu(PPh3)]+, 262[(PPh3)]+. HR-MS FAB (m/z) calcd. for C45H48Cu2NP2S2: 854.1495;found: 854.1501. Anal. calcd. for C45H48CuNP2S2 (%): C 68.20,H 6.10, N 1.77; found: C 68.25, H 6.33, N 1.71.

Synthesis of 1,2,3-triazolesTypical procedure: The appropriate alkyne (1.05mol) was added

in one portion to a solution of the corresponding azide (1 mol) andthe catalyst 1 (0.005 mmol) in acetonitrile (30 mL). The resultingmixture was stirred at 60 °C for 2 h or at room temperature for10 h. The mixture was cooled to room temperature and thesolvent was removed in vacuo. The reaction product was ex-tracted with toluene (40 ml) and treated with activated char-coal (0.5 g). The mixture was filtered and evaporated in vacuo,and the product was crystallized from hot ethyl acetate andn-heptane (toluene and petroleum spirits were also used de-pending on product solubility).

1-Benzyl-4-phenyl-1,2,3-triazole (7)White solid;mp132 °C (lit. value24mp130–130.9 °C). IR (ATR, cm−1):

3250, 2850, 1650, 1600. 1H NMR (500 MHz, CDCl3) �: 5.59 (s,2H), 7.33–7.39 (m, 1H), 7.41–7.41 (m, 4H), 7.68–7.82 (m, 2H), 7.68 (s,1H). 13C NMR (125 MHz, CDCl3) �: 54.2, 119.5, 125.6 (2C), 127.9 (2C),128.1, 128.7, 128.8 (2C), 129.1 (2C), 130.5, 134.6, 148.2. MS [EI+]m/z (%):235 ([M]+, 21), 206 ([M – HN2]+, 74), 116 ([M – C6H5N3]+, 100), 91([C6H5CH2]+, 94).

(1-Benzyl-1,2,3-triazol-4-yl)methyl butylcarbamate (9)White solid;mp 83.6 °C (lit. value25mp 82–83 °C). IR (ATR, cm−1):

3250, 2850, 1650. 1H NMR (500 MHz, CDCl3) �: 0.91 (t, 3H), 1.29 (tq,2H), 1.44 (t, 2H), 3.15 (t, 2H), 5.15 (s, 2H), 5.51 (s, 2H), 7.25–7.27 (m,1H), 7.28–7.36 (m, 2H), 7.37–7.37 (m, 2H), 7.549 (s, 1H). 13C NMR(125 MHz, CDCl3) �: 13.6, 19.8, 31.9, 40.7, 54.1, 57.7, 123.6, 128.1,128.73, 129.1, 134.462, 143.9, 156.1. MS [EI+] m/z (%): 288 ([M]+, 1.63),189 (87), 91 (100).

1-Benzyl-4-p-tolyloxymethyl-[1,2,3]triazole (10)White solid;mp 93.5 °C (lit. value25mp 92–93 °C). IR (ATR, cm−1):

2950, 1650, 1600. 1H NMR (500 MHz, CDCl3) �: 2.29 (s, 3H), 5.16 (s,2H), 5.53 (s, 2H), 6.86–6.89 (dd, 2H, J = 2 Hz, J = 9 Hz), 7.07–7.10 (dd,2H, J = 3 Hz, J = 9 Hz), 7.26–7.30 (m, 2H), 7.36–7.40 (m, 3H), 7.54 (s,1H). 13C NMR (125 MHz, CDCl3) �: 20.5, 54.2, 62.1, 114.6, 122.6, 128.1,128.8, 129.1, 130.5, 134.4, 144.8, 156.0. MS [EI+]m/z (%): 279 ([M]+, 43),91 ([C6H5CH2]+, 100), 144 ([C10H10N]+, 92), 172 ([C10H10N3]+, 20).

1-Benzyl-4-(4-methoxy-phenoxymethyl)-1,2,3-triazole (11)White solid;mp 92.7 °C (lit. value26mp 92–93 °C). IR (ATR, cm−1):

2950, 1650, 1600. 1H NMR (500 MHz, CDCl3) �: 3.76 (s, 3H), 5.13 (s,2H), 5.52 (s, 2H), 6.80–6.82 (dd, 2H, J = 2 Hz, J = 9 Hz), 6.88–6.90 (dd,2H, J = 2 Hz, J = 9 Hz), 7.26–7.27 (m, 2H), 7.36–7.38 (m, 3H), 7.50 (s,1H). 13C NMR (125 MHz, CDCl3) �: 54.2, 55.6, 62.8, 114.6, 115.9, 122.5,128.1, 128.8, 129.1, 134.5, 144.9, 152.3, 154.2. MS [EI+] m/z (%): 295([M]+, 40), 91 ([C6H5CH2]+, 100), 144 ([C10H10N]+, 80), 124 ([C7H8O2]+,68), 172 ([C10H10N3]+, 5).

1-Benzyl-4-(4=-chlorophenoxymethyl)-1,2,3-triazole (12)White solid;mp 102.3 °C (lit. value27mp 102–103 °C). IR (ATR, cm−1):

1650, 1600. 1H NMR (500 MHz, CDCl3) �: 5.16 (s, 2H), 5.54 (s,2H), 6.89–6.92 (dd, 2H, J = 2 Hz, J = 9 Hz), 7.22–7.25 (dd, 2H, J = 3 Hz,J = 9 Hz), 7.27–7.30 (m, 2H), 7.38–7.40 (m, 3H), 7.53 (s, 1H). 13C NMR(125 MHz, CDCl3) �: 54.2, 62.2, 116.0, 122.6, 126.1, 128.154, 128.8,129.1, 129.4, 134.3, 144.1, 156.7. MS [EI+] m/z (%): 299 ([M]+, 15), 91([C6H5CH2]+, 100), 144 ([C10H10N]+, 78), 172 ([C10H10N3]+, 25).

4-(1-Benzyl-1,2,3-triazol-4-ylmethoxy)-benzoic acid methylester (13)

White solid; mp 145.7 °C. IR (ATR, cm−1): 1753, 1650, 1600.1H NMR (500 MHz, CDCl3) �: 3.87 (s, 3H), 5.22 (s, 2H), 5.53 (s, 2H),6.96–6.99 (dd, 2H, J = 3 Hz), 7.96–7.99 (dd, 2H, J = 3 Hz), 7.26–7.28(m, 2H), 7.35–7.39 (m, 3H), 7.53 (s, 1H). 13C NMR (125 MHz, CDCl3) �:51.8, 54.3, 62.1, 114.3, 122.722, 123.1, 128.1, 128.8, 128.8, 129.0, 129.1,131.6, 131.8, 143.9, 161.8, 166.7. MS [EI+] m/z (%): 323 ([M]+, 15), 91([C6H5CH2]+, 100), 144 ([C10H10N]+, 95), 172 ([C10H10N3]+, 45). HR-MS(EI+) calcd. for C18H17N3O3: 323.1270; found: 323.1273. Anal. calcd.for C18H17N3O3 (%): C 66.86, H 5.30, N 13.00; found: C 66.65, H 5.23,N 13.21.

4-(1-Benzyl-1,2,3-triazol-4-ylmethoxy)-benzaldehyde (14)White solid;mp 79.3 °C (lit. value28mp 79–80 °C). IR (ATR, cm−1):

1660, 1600. 1H NMR (500 MHz, CDCl3) �: 5.26 (s, 2H), 5.54 (s, 2H),7.07–7.09 (dd, 2H, J = 3 Hz, J = 9 Hz), 7.82–7.83 (dd, 2H, J = 3 Hz, J =9 Hz), 7.26–7.29 (m, 2H), 7.36–7.38 (m, 3H), 7.54 (s, 1H), 9.88 (s, 1H).13C NMR (125 MHz, CDCl3) �: 54.3, 62.2, 115.0, 122.7, 128.1, 128.9,129.2, 130.3, 134.3, 143.6, 163.3, 190.7. MS [EI+] m/z (%): 293 ([M]+, 5),91 ([C6H5CH2]+, 100), 144 ([C10H10N]+, 65), 172 ([C10H10N3]+, 35).

(1-Benzyl-1,2,3-triazol-4-yl)-methanol (15)White solid; mp 77.8 °C (lit. value29mp 76–77 °C). IR (ATR, cm−1):

3330, 2850, 1600. 1H NMR (500 MHz, CDCl3) �: 3.36 (s, 1H), 4.51 (s,2H), 5.57 (s, 2H), 7.30–7.37 (m, 5H), 8.00 (s, 1H). 13C NMR (125 MHz,CDCl3) �: 53.1, 55.4, 123.2, 128.3, 128.5, 129.1, 136.6, 148.7. MS [EI+]m/z (%): 189 ([M]+, 4), 91 ([C6H5CH2]+, 100).

Butyl-carbamic acid 1-(3,4-dichlorophenyl)-1,2,3-triazol-4-ylmethylester (16)

White solid; mp 150.4 °C. IR (ATR, cm−1): 3250, 2850, 1600.1HNMR (500MHz, CDCl3) �: 0.91 (t, 3H), 1.35 (m, 2H), 1.46 (m, 2H), 3.15(m, 2H), 5.25 (s, 2H), 5.70 (s, 1H, NH), 7.60–7.68 (m, 2H), 7.95–7.96(m, 1H), 8.21 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 18.4, 24.5, 36.6,44.7, 62.1, 124.1, 126.8, 136.1, 137.4, 138.537, 140.6, 149.6, 160.9. MS[EI+] m/z (%): 342 ([M]+, 5), 198 ([M – C6H3Cl2]+, 100). HR-MS (EI+)calcd. for C14H16Cl2N4O2: 342.0605; found: 342.0609. Anal. calcd.for C14H16Cl2N4O2 (%): C 48.99, H 4.70, N 16.32; found: C 48.95, H4.73, N 16.30.

1,4-Diphenyl-1,2,3-triazole (17)White solid;mp 96.2 °C (lit. value30mp 97–98 °C). IR (ATR, cm−1):

3050, 1600. 1H NMR (500 MHz, CDCl3) �: 7.25–7.92 (m, 10H), 8.20 (s,1H). 13C NMR (125 MHz, CDCl3) �: 120.5, 121.5, 125.8, 128.2, 128.4,128.5, 128.7, 128.9, 128.9, 129.7, 130.7, 130.8, 134.9, 147.6. MS [EI+]m/z (%): 222 ([M + 1]+, 5), 193 ([M – N2]+, 95), 165 (100).

1-(3,4-Dichlorophenyl)-4-phenyl-1,2,3-triazole (18)White solid; mp 210.3 °C (lit. value31 mp 79 °C). IR (ATR, cm−1):

3050, 1600. 1HNMR (500MHz, CDCl3) �: 7.27–7.51 (m, 5H), 7.63–7.70(m, 3H), 7.90–7.98 (m, 2H), 8.20 (s, 1H). 13C NMR (125MHz, CDCl3) �:120.5, 121.5, 125.8, 127.7, 128.2, 128.5, 128.9, 129.7, 130.2, 130.803,134.9, 147.6, 128.5, 128.4. MS [EI+]m/z (%): 289 ([M]+, 5), 261 ([M –N2]+,100), 226 ([M – N2 – Cl]+, 60).

1-Benzyl-4-[5-chloro-2-(2,4-dichlorophenoxy)-phenoxymethyl]-1,2,3-triazole (19)

Whitesolid;mp101.7 °C. IR (ATR,cm−1): 3050, 1600. 1HNMR(500MHz,CDCl3) �: 5.17 (s, 2H), 5.56 (s, 2H), 6.69 (d, 1H, J = 9 Hz), 7.02 (s,

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2H), 7.20–7.25 (m, 3H), 7.33–7.35 (m, 3H), 7.47–7.47 (m, 1H), 7.54–7.55 (m, 1H), 7.95 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 53.3, 62.7,116.1, 119.138, 121.9, 122.4, 123.8, 124.9, 127.5, 128.3, 128.6, 128.7,129.2, 129.9, 130.1, 136.2, 142.8, 143.1, 150.3, 152.1. MS [EI+] m/z (%):459 ([M]+ 6), 290 (15), 91 ([C6H5CH2]+, 100). HR-MS (EI+) calcd.for C22H16Cl3N3O2: 459.0308; found: 459.0310. Anal. calcd. forC22H16Cl3N3O2 (%): C 59.41, H 3.63, N 9.45; found: C 59.55, H 3.69,N 9.37.

4-[5-Chloro-2-(2,4-dichlorophenoxy)-phenoxymethyl]-1-(3,4-dichloro-phenyl)-1,2,3-triazole (20)

White solid; mp 163 °C. IR (ATR, cm−1): 3100, 1550, 1500, 1250,1000. 1H NMR (500 MHz, CDCl3) �: 5.17 (s, 2H), 5.56 (s, 2H), 6.69 (d,1H, J = 9 Hz), 7.023 (s, 2H), 7.20–7.25 (m, 3H), 7.33–7.35 (m, 3H),7.47–7.47 (m, 1H), 7.54–7.55 (m, 1H), 7.95 (s, 1H). 13C NMR (125 MHz,CDCl3) �: 53.3, 62.7, 116.1, 119.1, 121.9, 122.4, 123.8, 124.9, 127.5,128.3, 128.6, 128.7, 129.2, 129.9, 130.1, 136.2, 142.8, 143.1, 150.3, 152.1.MS [EI+] m/z (%): 513 ([M]+, 15), 145 (100). HR-MS (EI+) calcd.for C21H12Cl5N3O2: 512.9372; found: 512.9375. Anal. calcd. forC21H12Cl5N3O2 (%): C 48.92, H 2.35, N 8.15; found: C 48.86, H 2.39, N8.19.

4-[5-Chloro-2-(2,4-dichlorophenoxy)-phenoxymethyl]-1-(4-chloro-phenyl)-1H-[1,2,3]triazole (21)

White solid; mp 160.0 °C. IR (ATR, cm−1): 3100, 1550, 1500, 1250.1H NMR (500 MHz, CDCl3) �: 5.27 (s, 2H), 6.67 (d, 1H, J = 9 Hz),6.95–6.99 (m, 1H), 7.09–7.11 (d, 1H, J = 3 Hz), 7.18–7.19 (d, 1H, J = 3 Hz),7.26 (s, 1H), 7.41–7.442 (d, 1H, J = 3 Hz), 7.51–7.52 (d, 1H, J =3 Hz), 7.63–765 (m, 1H), 7.67 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 63.6,115.966, 118.2, 120.4, 121.5, 122.1, 122.3, 124.4, 127.8, 128.1, 130.0,130.1, 130.7, 134.7, 135.3, 143.3, 144.5, 149.8, 152.3. MS [EI+] m/z (%):479 ([M]+, 5), 318 (8), 290 (17), 164 (100), 128 (27), 111 (41). HR-MS (EI+)calcd. for C21H13Cl4N3O2: 478.9762; found: 478.9764. Anal. calcd.for C21H13Cl4N3O (%): C 54.22, H 2.82, N 9.03; found: C 54.87, H 2.89,N 9.12.

(1-Benzyl-1,2,3-triazol-4-ylmethyl)-dimethyl-tetradecyl-ammoniumbromide (22)

Colorless oil. IR (ATR, cm−1): 3400, 2290, 1450, 1100. 1HNMR (500MHz,CDCl3) �: 0.81 (t, 3H), 1.21 (s, 22), 1.65 (q, 2H), 2.99 (s, 6H), 3.04(t, 2H), 4.64 (s, 2H), 5.68 (s, 2H), 7.31–7.36 (m, 5H), 8.51 (s, 1H).13C NMR (125 MHz, CDCl3) �: 14.3, 21.9, 22.2, 22.5, 26.0, 26.1, 26.2, 28.8,28.9, 29.1, 29.2, 29.2, 29.3, 29.3, 29.4, 29.5, 31.4, 31.7, 49.2, 50.1, 53.4,53.6, 63.7, 128.4, 128.6, 128.7, 128.8, 129.1, 129.2, 136.0. MS [EI+] m/z(%): 226 ([M]+, 5), 91 ([C6H5CH2]+, 100). HR-MS (EI+) calcd.for C26H45BrN4: 492.2828; found: 492.2831. Anal. calcd. forC26H45BrN4 (%): C 63.27, H 9.19, N 11.35; found: C 63.22, H 9.21, N11.32.

(1-Benzyl-1,2,3-triazol-4-ylmethyl)-dibutyl-amine (23)White solid; mp 66 °C (lit. value28 mp 66–67 °C). IR (ATR, cm−1):

3400, 2875, 2850, 1450, 1350, 1275, 1050. 1H NMR (500 MHz, CDCl3)�: 0.84 (t, 6H), 1.21–1.23 (m, 4H), 1.40–1.46 (m, 4H), 2.41 (t, 4H), 3.75(s, 2H), 5.51 (s, 2H), 7.23–7.26 (m, 3H), 7.33–7.38 (m, 3H), 7.35 (s, 1H).13C NMR (125 MHz, CDCl3) �: 14.0, 20.5, 29.1, 49.0, 53.5, 54.0, 127.9,128.6, 129.0, 134.9. MS [EI+] m/z (%): 300 ([M]+, 84), 257 ([M – HN3]+,100), 173 ([M – N(C4H9)2]+, 92), 128 ([N(C4H9)2]+, 88), 91 ([C6H5CH2]+,80).

Dibutyl-[1-(4-chlorophenyl)-1,2,3-triazol-4-ylmethyl]-amine (24)Colorless oil. IR (ATR, cm−1): 3400, 2875, 2850, 1450, 1350, 1275,

1050. 1H NMR (500 MHz, CDCl3) �: 0.82 (t, 6H), 1.21–1.28 (m, 4H),1.40–1.46 (m, 4H), 2.42 (t, 4H), 3.73 (s, 2H), 7.61–7.62 (d, 2H), 7.89 (s,1H), 7.90–7.91 (d, 2H). 13C NMR (125 MHz, CDCl3) �: 14.0, 20.6, 29.2,48.9, 53.6, 119.3, 120.3, 122.1, 131.4, 132.6, 133.9, 136.2. MS [EI+] m/z(%): 320 ([M]+, 6), 277 ([M – HN3]+, 92), 193 ([M – N(C4H9)2]+, 92), 165([C9H7N]+, 98), 128 ([N(C4H9)2]+, 88). HR-MS (EI+) calcd. forC17H25ClN4: 320.1768; found: 320.1767. Anal. calcd. for C17H25ClN4(%): C 63.64, H 7.85, N 17.46; found: C 63.62, H 7.91, N 17.45.

Dibutyl-[1-(3,4-dichlorophenyl)-1,2,3-triazol-4-ylmethyl]-amine (25)Colorless oil. IR (ATR, cm−1): 3400, 2875, 2850, 1450, 1350, 1275,

1050. 1H NMR (500 MHz, CDCl3) �: 0.89 (t, 6H), 1.28–1.35 (m, 4H),1.47–1.53 (m, 4H), 2.47 (t, 4H), 3.84 (s, 2H), 7.60 (s, 1H), 7.61(d, 1H),7.89 (s, 1H), 7.90 (d, 2H). 13C NMR (125 MHz, CDCl3) �: 14.0, 20.6,29.2, 48.9, 53.6, 119.3, 120.3, 122.1, 131.4, 133.1, 133.9, 136.2. MS [EI+]m/z (%): 354 ([M]+, 14), 311 ([M – HN3]+, 100), 227 ([M – N(C4H9)2]+, 50),198 ([C9H6Cl2N]+, 73), 128 ([N(C4H9)2]+, 73). HR-MS (EI+) calcd.for C17H24Cl2N4: 354.1378; found: 354.1379. Anal. calcd. forC17H24Cl2N4 (%): C 57.47, H 6.81, N 15.77; found: C 57.52, H 6.89,N 15.35.

1-(2-Nitrophenyl)-4-phenyl-1,2,3-triazole (26)Orange solid; mp 142.7 °C (lit. value32 mp 144–145 °C). IR (ATR, cm−1):

3050, 1600, 1550, 1350. 1H NMR (500 MHz, CDCl3) �: 7.38 (m,J = 7.5 Hz, 1H), 7.47–7.48 (m, J = 7.5 Hz, 1H), 7.68–7.73 (m, 2H),7.80–7.81 (m, 1H), 7.89–7.91 (d, J = 9 Hz, 2H), 8.06–8.11 (m, 2H).13C NMR (125 MHz, CDCl3) �: 120.9, 125.6, 126.0, 127.9, 128.6, 128.9,129.7, 130.3, 130.7, 133.850, 144.3, 148.4. MS [EI+] m/z (%): 266 ([M]+,5), 88 (100).

1-(4-Nitrophenyl)-4-phenyl-1,2,3-triazole (27)Orange solid; lit. value33 mp 254 °C (dec.). IR (ATR, cm−1): 3050,

1600, 1550, 1350. 1H NMR (500MHz, CDCl3) �: 7.40 (t, J = 7.5 Hz, 1H),7.51 (t, J = 8.0 Hz, 2H), 7.95 (m, 2H), 8.25 (m, 2H), 8.48 (m, 2H), 9.51(s, 1H). 13C NMR (125 MHz, CDCl3) �: 120.4, 120.9, 125.9, 126.1, 128.4,129.0, 129.5, 130.2, 141.3, 147.1, 148.3. MS [EI+]m/z (%): 266 ([M]+, 15),138 (75), 88 (100), 57 (90).

4-(1-(5-Chloro-2-(2,4-dichloro-phenoxy)-phenyl)-1,2,3-triazol-4-ylmethoxy)-benzoic acid methyl ester (28)

White solid; mp 157 °C. IR (ATR, cm−1): 1700, 1600, 1350, 1260.1H NMR (500 MHz, CDCl3) �: 3.78 (s, 3H), 5.30 (s, 2H), 7.02 (d, 1H, J =9Hz), 7.13 (m, 2H), 7.22 (d, 1H, J = 9 Hz), 7.41 (d, 1H, J = 2.5 Hz), 7.56 (d,1H, J = 2.5 Hz), 7.70 (d, 1H, J = 2.5 Hz), 7.86 (m, 2H), 7.94 (d, 1H, J =2.5Hz), 8.68 (s, 1H). 13CNMR (125MHz, CDCl3) �: 52.2, 61.3, 115.2, 120.1,122.673, 123.0, 126.1, 126.7, 127.0, 128.3, 128.5, 129.4, 130.2, 130.7,131.3, 131.6, 142.9, 147.8, 149.7, 162.1, 166.2. MS [EI+]m/z (%): 418 (23),324 (64), 288 (100), 290 (80), 254 (70), 161 (54). HR-MS (EI+) calcd.for C23H16Cl3N3O4: 503.0206; found: 503.0209. Anal. calcd. forC23H16Cl3N3O4 (%): C 54.73, H 3.20, N 8.32; found: C 54.62, H 3.29,N 8.37.

4-Phenyl-1-(2-(2-(4-phenyl-1,2,3-triazol-1-yl)-ethoxy)-ethyl)-1,2,3-triazole (29)

White solid; mp 177.5 °C. IR (ATR, cm−1): 3150, 1600, 1350, 1260.1H NMR (500 MHz, CDCl3) �: 3.31 (s, 4H), 3.93 (s, 4H), 4.60 (s, 4H),7.82 (m, 8H), 7.77 (m, 2H), 8.25 (s, 2H). 13C NMR (125 MHz, CDCl3) �:47.9, 67.0, 119.5, 123.4, 125.8, 126.8, 128.9, 144.8.MS [EI+]m/z (%): 360([M]+, 45), 302 (70), 245 (90), 216 (85), 116 (100). HR-MS (EI+) calcd. forC20H20N6O: 360.1699; found: 360.1698. Anal. calcd. for C20H20N6O(%): C 66.65, H 5.59, N 23.32; found: C 66.67, H 5.61, N 23.28.

1-(4-Chlorophenyl)-4-phenyl-1,2,3-triazole (30)White solid; lit. value34 mp 228.5 °C. IR (ATR, cm−1): 3050, 1500,

1250, 825. 1H NMR (500 MHz, CDCl3) �: 7.45 (m, 5H), 7.88 (d, 4H, J =8.5 Hz), 8.67 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 122.1, 124.1, 126.0,126.4, 128.2, 128.9, 131.3, 133.2, 137.4, 151.0. MS [EI+] m/z (%): 255([M]+, 1), 227 ([M – N2]+, 100), 192 ([M – N2 – Cl]+, 62), 116 ([C8H6N]+,61), 89 ([C7H5]+, 64).

1-(4-Methoxyphenyl)-4-phenyl-1,2,3-triazole (31)White solid; lit. value34 mp 167 °C. IR (ATR, cm−1): 3050, 1450,

1350, 1250. 1H NMR (500 MHz, CDCl3) �: 8.11 (s, 1H), 7.90 (m, 2H),7.69 (m, 2H), 7.46 (m, 2H), 7.36 (m, 1H), 7.04 (m, 2H), 3.88 (s, 3H).13C NMR (125 MHz, CDCl3) �: 160.2, 148.6, 130.9, 130.8, 129.3, 128.7,126.2, 122.6, 118.2, 115.2, 56.0. MS [EI+] m/z (%): 251 ([M]+, 2), 223([M – N2]+, 100), 208 ([M – N2 – CH3]+, 80), 180 ([M – N2 – CH3CO]+, 56),116 ([C8H6N]+, 23).

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1-(4-Bromophenyl)-4-phenyl-1,2,3-triazole (32)White solid; lit. value8 mp 232.4 °C. IR (ATR, cm−1): 3050, 1450,

1350, 1250. 1H NMR (500 MHz, CDCl3) �: 7.39 (m, 2H), 7.51 (m, 4H),7.86 (m, 1H), 7.93 (m, 1H), 9.33 (s, 1H). 13C NMR (125 MHz, CDCl3) �:120.1, 121.7, 122.3, 125.8, 128.8, 129.4, 130.5, 133.3, 136.3, 147.9. MS[EI+]m/z (%): 192 ([M –N2Br]+, 100), 116 ([C8H6N]+, 45), 89 ([C7H5]+, 44).

4-Phenyl-1-p-tolyl-1,2,3-triazole (33)White solid; lit. value34 mp 174 °C. IR (ATR, cm−1): 3050, 1550,

1250. 1H NMR (500 MHz, CDCl3) �: 2.42 (s, 3H), 7.32 (m, 3H), 7.44 (t,2H), 7.65 (d, 2H), 7.90 (m, 2H), 8.14 (s, 1H). 13C NMR (125MHz, CDCl3)�: 21.0, 117.6, 120.4, 125.8, 128.3, 128.8, 130.2, 130.3, 134.7, 138.8,148.2. MS [EI+] m/z (%): 235 ([M]+, 2), 207 ([M – N2]+, 100).

1-Phenyl-4-(4-trifluoromethylphenyl)-1,2,3-triazole (34)White solid; mp 231 °C (lit. value35 mp 224–228 °C). IR (ATR, cm−1):

3050, 1450, 1350, 1250. 1H NMR (500 MHz, CDCl3) �: 7.54 (m,1H), 7.65 (d, J = 8 Hz, 2H), 7.88 (d, J = 8 Hz, 2H), 7.96 (d, J = 8 Hz, 2H),8.17 (d, J = 8 Hz, 2H), 9.48 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 120.5,121.4, 126.3, 126.4, 129.3, 130.4, 134.7, 136.9, 146.3. MS [EI+] m/z (%):289 ([M]+, 2), 261 ([M – N2]+, 35), 77 ([C6H5], 100).

1-p-Tolyl-4-(4-trifluoromethylphenyl)-1,2,3-triazole (35)Slight yellow solid; mp 257.7 °C. IR (ATR, cm−1): 3050, 1550, 1250.

1H NMR (500 MHz, CDCl3) �: 2.44 (s, 3H), 7.36 (d, J = 8 Hz, 2H), 7.68(d, J = 8 Hz, 2H), 7.72 (d, J = 8 Hz, 2H), 8.04 (d, J = 8 Hz, 2H), 8.22 (s,1H). 13C NMR (125 MHz, CDCl3) �: 115.8, 117.9, 123.2, 123.3, 123.3,123.3, 127.5, 127.7, 131.2, 132.0, 136.6, 144.3. MS [EI+] m/z (%): 303([M]+, 2), 275 ([M – N2]+, (100), 207 ([M – N2CF3]+, 55), 91 ([C7H7]+, 85).HR-MS (EI+) calcd. for C16H12F3N3: 303.0983; found: 303.0986.Anal. calcd. for C16H12F3N3 (%): C 63.36, H 3.99, N 18.79; found:C 63.39, H 3.95, N 18.78.

1-Phenyl-4-p-tolyl-1,2,3-triazole (36)White solid;mp 156.2 °C (lit. value36mp 155–156 °C). IR (ATR, cm−1):

3050, 1450, 1350, 1250. 1H NMR (500 MHz, CDCl3) �: 2.39 (s,3H), 7.25 (d, J = 8 Hz, 2H), 7.45 (t, J = 8 Hz, 1H), 7.55 (m, 2H), 7.79 (m,4H), 8.14 (s, 1H). 13CNMR (125MHz, CDCl3) �: 21.3, 117.2, 120.4, 125.7,127.434, 128.6, 129.5, 129.7, 137.1, 138.3, 148.4. MS [EI+] m/z (%): 235([M]+, 4), 207 ([M – N2]+, 100), 77 ([C6H5]+, 58).

4-(4-Methoxyphenyl)-1-phenyl-1,2,3-triazole (37)White solid;mp152.6 °C (lit. value 36mp153–154 °C). IR (ATR, cm−1):

3050, 1450, 1350, 1250. 1H NMR (500 MHz, CDCl3) �: 3.85 (s,3H), 6.98 (m, 2H), 7.44 (m, 1H), 7.53 (m, 2H), 7.77 (m, 2H), 7.84 (m,2H), 8.10 (s, 1H). 13C NMR (125 MHz, CDCl3) �: 55.3, 114.3, 116.7,120.467, 122.9, 127.1, 128.6, 129.7, 137.1, 148.2, 159.8. MS [EI+]m/z (%):251 ([M]+, 10), 223 ([M – N2]+, 58), 208 ([M – N2 – CH3]+, 100), 180([M – C2H3N2O]+, 21), 77 ([C6H5]+, 39).

4-(4-Pentylphenyl)-1-phenyl-1,2,3-triazole (38)White solid; mp 127.0 °C. IR (ATR, cm−1): 3050, 2850, 1600, 1550,

1250. 1H NMR (500 MHz, CDCl3) �: 0.90 (t, 3H), 1.33 (m, 4H), 1.64 (m,2H), 2.63 (t, 2H), 7.24–7.26 (m, 2H), 7.41–7.43 (m, 1H), 7.49–7.52 (m,2H), 7.76–7.78 (m, 2H), 7.80–7.81 (m, 2H), 8.15 (s, 1H). 13C NMR(125MHz, CDCl3) �: 14.0, 22.5, 31.0, 31.4, 35.7, 120.4, 125.7, 127.6, 128.6,128.9, 129.7, 137.1, 143.3, 148.5. MS [EI+] m/z (%): 291 ([M]+, 4), 263([M–N2]+, 16), 206 ([M–C4H9N2]+, 100), 77 ([C6H5]+, 39).HR-MS (EI+) calcd.for C19H21N3: 291.1735; found: 764.1738. Anal. calcd. for C19H21N3 (%):C 78.32, H 7.26, N 14.42; found: C 78.35, H 7.25, N 14.39.

Dimethyl-(4-(1-phenyl-1,2,3-triazol-4-yl)-phenyl)-amine (39)White solid; mp 178.0 °C. IR (ATR, cm−1): 3050, 2850, 1600, 1550.

1H NMR (500 MHz, CDCl3) �: 2.97 (s, 6H), 6.77 (m, 2H), 7.41 (m, 1H),7.48 (m, 2H), 7.76 (m, 4H), 8.039 (s, 1H). 13C NMR (125 MHz, CDCl3)�: 40.3, 112.4, 115.9, 118.3, 120.3, 126.7, 128.4, 129.6, 137.2, 148.9,150.5. MS [EI+] m/z (%): 264 ([M]+, 22), 236 ([M – N2]+, 100), 221 ([M –CH3N2]+, 32), 207 ([M – C2H6N3]+, 48), 159 ([M – C6H5N2]+, 33), 77

([C6H5]+, 33). HR-MS (EI+) calcd. for C16H16N4: 264.1375; found:764.1377. Anal. calcd. for C16H16N4 (%): C 72.70, H 6.10, N 21.20;found: C 72.64, H 6.13, N 21.21.

AcknowledgementsFinancial support from the Consejo Nacional de Ciencia y Tech-

nología (CONACYT; project No. 135053) is gratefully acknowl-edged. The authors would like to thank Organo Síntesis, S.A. deC.V. (OSSA) for some graciously donated solvents and reagents andto N. Zavala, A. Nuñez, and L. Triana for the technical support.

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