Regioselective Synthesis of N 2-Alkylated-1,2,3 Triazoles and N 1-Alkylated Benzotriazoles: Cu2S as a Recyclable Nanocatalyst for Oxidative Amination of N, N -Dimethylbenzylamines

Article abstract of DOI:10.1021/acs.joc.8b00107

Copper chalcogenide nanoparticles (Cu₂S) synthesized for the first time from a single-source precursor, CuSPh, act as highly efficient and reusable heterogeneous catalyst for regioselective amination of N,N-dimethylbenzylamines with various azo

Full text of DOI:10.1021/acs.joc.8b00107

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Article
Regioselective synthesis of N2-alkylated-1,2,3 triazoles and N1-
alkylated benzotriazoles: Cu2S as a recyclable nanocatalyst
for oxidative amination of N,N-dimethylbenzylamines
Sonu Gupta, Nisha Chandna, Ajai Kumar Singh, and Nidhi Jain
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00107 • Publication Date (Web): 21 Feb 2018
Downloaded from http://pubs.acs.org on February 21, 2018
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Regioselective synthesis of N2-alkylated-1,2,3 triazoles and N1-alkylated benzotriazoles:
Cu2S as a recyclable nanocatalyst for oxidative amination of N,N-dimethylbenzylamines
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Sonu Gupta, Nisha Chandna, Ajai K. Singh, and Nidhi Jain*
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Department of Chemistry, Indian Institute of Technology, New Delhiꢀ110016
*Eꢀmail: njain@chemistry.iitd.ac.in; Fax: +91 11 26581102; Tel: +91 11 26591562
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Table of Contents
Abstract
Copper chalcogenide nanoparticles (Cu2S) synthesized for the first time from a single source
precursor, CuSPh act as highly efficient and reusable heterogeneous catalyst for
regioselective amination of N,Nꢀdimethylbenzylamines with various azoles. The reaction
involves N−H/C−H crossꢀdehydrogenative coupling (CDC) and demonstrates wide
functional group tolerance. It provides a highly selective access to N1ꢀalkylated
benzotriazoles, N2ꢀalkylated 1,2,3ꢀtriazoles & 4ꢀphenylꢀ1,2,3ꢀtriazoles, and Nꢀalkylated
carbazoles in 70ꢀ89% yields under solvent free conditions. The Cu2S nanocatalyst has been
characterized by PXRD, XPS, SEMꢀEDX and HRꢀTEM analysis. Mechanistic studies
suggest the reaction to follow a radical pathway and involve an iminium ion intermediate.
Keywords: Regioselective alkylation• Nanocatalysis • Cu2S NPs • CN coupling • N2ꢀ
alkylatedꢀ1,2,3ꢀtriazoles
Introduction
Selective conversion of C–H bonds into C–N bonds has gained tremendous importance as it
streamlines the synthesis of important Nꢀheterocycles with potential pharmaceutical and
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material applications. Aliphatic C–H amination reactions are particularly soughtꢀafter as they
provide an atomꢀefficient route to Nꢀalkylamine derivatives by avoiding the typical functional
group inter conversions requiring preꢀfunctionalized starting materials. Azoles are important
Nꢀheterocycles and form an integral part of many natural products, biologically active
molecules, and scaffolds for new pharmaceuticals.1 NꢀSubstituted 1,2,3ꢀtriazoles are
particularly important, and find widespread applications in material science and medicinal
chemistry.2 The general route to access 1,2,3ꢀtriazoles involves the reaction of organic azides
with activated alkenes,3 alkynes4 and carbonyl compounds.5 While these methods are useful
for preparing N1ꢀ or N1′ꢀalkylatedꢀ1,2,3ꢀtriazoles, they deny access to the N2ꢀsubstitutedꢀ
derivatives. For this, a postꢀNꢀfunctionalization is required; which can be accomplished with
the help of alkyl halides,6 alcohols,7 alkynes,8 and alkenes.9 In this context, methods that
allow an N2ꢀalkylation of NHꢀ1,2,3ꢀtriazoles directly with alkanes can be highly useful.
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The oxidative functionalization of tertiary amines to corresponding αꢀsubstituted tertiary
amines with good nucleophiles such as malonates, nitroalkanes, cyanide anion, silyl enolates,
ketene acetals and amides is reported.10 Most of these functionalizations involve either cyclic
tertiary amines such as 1,2,3,4ꢀtetrahydroisoquinoline, pyrrolidine, and piperidine or acyclic
tertiary amine like N,Nꢀdimethylaniline as substrate. However, intermolecular
functionalization of sp3 CꢀH bond adjacent to nitrogen atom in N,Nꢀdimethylbenzylamine has
very few reports. α ꢀcyanation of N,Nꢀdimethylbenzylamines has been achieved oxidatively
with the help of iron chloride/TBHP catalysis or mediated by tropylium ion.11 In 2004, Li et
al. reported a copper catalyzed alkynylation of N,Nꢀdimethylbenzylamine using TBHP albeit
in low yield (36%).12 In 2008, Fu and coꢀworkers were successful in obtaining moderate
yields (≤ 65%) of the coupled products by replacing TBHP with NBS.13 Recently, we
demonstrated that with the help of copper selenide nanocatalyst, a notable improvement in
reaction efficiency could be achieved.14 Another report on oxidative carbonꢀcarbon crossꢀ
coupling of N,Nꢀdimethylbenzylamines came from Itami and coworkers in an iron catalyzed
reaction with electronꢀrich heteroarenes (Scheme 1).15 Later, a metalꢀfree crossꢀ
dehydrogenative coupling between tertiary aliphatic amines and 1,3ꢀdicarbonyl compounds
was shown by Wang et al. using Bu4NI but N,Nꢀdimethylbenzylamines were found to be inert
in this reaction.16 Apparently, the studies with N,Nꢀdimethylbenzylamines are limited to C−C
bondꢀforming reactions only, with no literature precedence on a direct αꢀamination at the sp3
carbon. In continuation of our interest in direct CꢀN bond formations,17 we explored a
N−H/C−H crossꢀdehydrogenative coupling between azoles and N,Nꢀdimethylbenzylamines
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using a nanoꢀcatalytic system comprising of Cu2S NPs. The methodology was explored for
triazoles (NHꢀ1,2,3ꢀtriazoles, 4ꢀphenylꢀNHꢀ1,2,3ꢀtriazoles, 1Hꢀbenzotriazoles and 5,6ꢀ
dimethylꢀ1Hꢀbenzotriazoles) and carbazoles as coupling partners (Scheme 1).
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Scheme 1. Crossꢀdehydrogenative coupling reactions of N,Nꢀdimethylbenzylamines
Results and discussion
In light of the significant advantages offered by a heterogeneous nanocatalyst in a reaction,
we initiated this work with the preparation of copper sulphide nanoparticles. The NPs
(Scheme 2) were prepared by thermolysis of CuSPh complex, synthesized by modifying the
reported procedure.18
Scheme 2. Synthesis of Cu2S NPs
They were authenticated by HRTEM (Figure S1 of SI), SEMꢀEDX (Figure S2 of SI), and
PXRD (Figure S3 of SI) data. TEM images revealed the particles to have hexagonal
morphology with a size of ~28ꢀ36 nm (see size distribution curve in SI Figure S4). The
PXRD pattern exhibited diffraction lines (hkl) at 3.73 (242), 3.59 (302), 3.27 (420), 3.18
(262), 3.05 (243), 2.94 (091), 2.72 (044), 2.52 (423), 2.47 (433), 2.40 (1111), 2.32 (174), 2.24
(205), 2.21 (225), 1.97 (2131), 1.87 (2140), 1.70 (406). These diffraction peaks were indexed
to the hexagonal phase of Cu2S NPs, as they showed good agreement with the literature data
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(JCPDS 23ꢀ0961). SEMꢀenergyꢀdispersive Xꢀray spectral data confirmed the presence of Cu
and S in these NPs in the ratio 2:1.
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Figure 1. Highꢀresolution XPS of Cu2S NPs (a) Cu 2p and (b) S 2p
The oxidation state of both Cu and S in Cu2S NPs was assigned with the help of XPS
analysis. As shown in Figure 1, the material was found to comprise of copper and sulphur
only. The Cu 2p spectrum illustrated that the peaks for binding energies for Cu 2p3/2 and 2p1/2
appearing at 932.9 and 952.7 eV, respectively were symmetric, narrow, and devoid of
satellite.19 These values of binding energies indicated the oxidation state of Cu in Cu2S NPs
to be (+1). In the S 2p XPS spectrum (Figure 1b), the binding energy peak corresponding to S
2p3/2 and S 2p1/2 appeared at 161.7 and 162.8 eV, respectively and was characteristic of Sꢀ2.20
Using the prepared Cu2S nanocatalyst, we investigated the reaction of N,Nꢀ
dimethylbenzylamine (1a) (2 equiv.) with NHꢀ1,2,3ꢀtriazole (2a) (1 equiv.) in presence of
TBHP and DMSO under nitrogen at 110 °C. After 3h of reaction time, complete conversion
of the starting materials was observed, and Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀ
phenylmethanamine (3a) was isolated in 58% yield. It was interesting to notice that the
triazole witnessed an exclusive N2 alkylation with 1a. While methods to prepare N2ꢀaryl6a, 21
and N2ꢀallylꢀ1,2,3ꢀtriazoles22 have been reported recently, there is no literature on alkylation
of 4,5ꢀunsubstitutedꢀ1,2,3ꢀtriazoles exclusively at N2 through CDC. In previous studies, N2ꢀ
selective amidoalkylation has been achieved by controlling the steric requirements of the
substrate, and tuning the substituents at 4,5ꢀposition on NHꢀ1,2,3ꢀtriazoles.23 Alternately, NIS
mediated iodofunctionalization of olefins is reported to provide access to N2ꢀalkylated 1,2,3ꢀ
triazoles.9 Despite these advances, there still exist several constraints and challenges which
tend to limit their synthetic utility. In this context, our preliminary results seemed to provide a
useful solution. To improve the yield of product 3a, optimization of reaction conditions was
carried out (Table 1). With conventional copper salts such as CuBr, CuCl and Cu(OAc)2, 3a
was isolated in lower yields (Table 1, entries 2−4). Changing to solvents like dioxane, DCE,
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chlorobenzene and acetonitrile did not give encouraging results either (Table 1, entries 5−8).
Notably, we found that under solventꢀfree condition, the reaction was much cleaner, and 3a
was isolated in 65% yield after 1 h (Table 1, entry 9). Lowering the reaction temperature to
90 °C increased the yield to 72% (Table 1, entry 10). Further, reducing the catalytic loading
to 1 mol % did not affect the reaction, full conversion and similar yield was obtained (Table
1, entry 11). A comparison with bulk Cu2O and Cu2S, and previously reported Cu6Se4.5
nanocatalyst14 was made, and lower yields were obtained in all the cases (Table 1, entry 11).
However, control reaction in absence of copper catalyst did not give any product (Table 1,
entry 12). Other oxidants such as NBS, H2O2, K2S2O8 and oxygen were screened, and all
were found to be ineffective in enabling the CꢀN bond formation (Table 1, entries 13ꢀ16). No
improvement in the yield was observed on increasing the amount of TBHP to 3 equivalents
while it dropped to 54% on reducing TBHP to 0.5 equivalents (Table 1, entry 17).
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Table 1: Optimization of reaction conditions.a
catalyst
(mol%)
oxidant
(equiv.)
temp.
(° C)
110
entry
solvent
yield (%)
Cu2S NPs (5)
1)
2)
3)
4)
5)
6)
7)
8)
9)
TBHP (1)
DMSO
DMSO
DMSO
DMSO
58
CuBr (5)
110
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
TBHP (1)
35
CuCl (5)
110
110
45
Cu(OAc)2 (5)
Cu2S NPs (5)
Cu2S NPs (5)
Cu2S NPs (5)
Cu2S NPs (5)
Cu2S NPs (5)
Cu2S NPs (5)
Cu2S NPs (1)
37
110
Dioxane
35
110
DCE
38
110
PhCl
20
110
ACN
40
65
ꢀ
ꢀ
-
110
10)
11)
100, 90
90
67, 72
74, 55b, 50c, 52d
TBHP (1)
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-
12)
13)
14)
15)
16)
17)
ꢀ
TBHP (1)
90
90
90
90
90
90
0
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Cu2S NPs (1)
Cu2S NPs (1)
Cu2S NPs (1)
Cu2S NPs (1)
Cu2S NPs (1)
NBS
H2O2
ꢀ
18
K2S2O8
ꢀ
ꢀ
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O2 Balloon
TBHP (3, 0.5)
73, 54
aReaction conditions. 1a (2 mmol), 2a (1 mmol), copper catalyst, TBHP (5.5 M in decane, 1
o
b
c
d
equiv, 0.2 mL), N2, 90 C, Cu2S bulk as catalyst, Cu2O bulk as catalyst, Cu6Se4.5
nanoparticles as catalyst.
Scheme 3: N2ꢀselective alkylation of 4,5ꢀunsubstituted and 4ꢀphenyl substituted 1,2,3ꢀ
triazoles.a
aReaction conditions. 1 (2 mmol), 2 (1 mmol), Cu2S NPs (1 mol%), TBHP (5.5M in decane,
1equiv, 0.2 mL), N2, 90 oC for 1h.
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The best conditions for the reaction required 1 mol% Cu2S and 1 equiv. of TBHP in neat
conditions at 90 °C under nitrogen (Table 1, entry 11). Further, the addition of bases such as
Na2CO3, K2CO3, NaOAc and DBU to the optimized conditions did not facilitate the reaction.
The scope of the reaction was examined by taking different substituents on phenyl ring of 1
and reacting them with 2. As shown in Scheme 3, all the substrates provided moderate to
good yield of products (3a-g). However, 1 bearing electron donating groups like pꢀCH3 and
pꢀOCH3 afforded the corresponding products 3b and 3c in slightly higher yields (80ꢀ82%)
than those (3dꢀ3g, 70ꢀ78%) with moderately electronꢀwithdrawing groups (Cl, Br). Further,
with very strong electron withdrawing groups like NO2 and CN, no product formation was
seen. The position of chloro substituent at orthoꢀ, metaꢀ or paraꢀ position of 1 had little
effect, and the corresponding products 3dꢀ3f were formed in similar yields. The reaction also
worked with NꢀmethylꢀNꢀethylꢀbenzylamine, and N2ꢀmethylatedꢀ1,2,3ꢀtriazole (3h) was
obtained in 68% yield. Next, we tried the reaction with 4ꢀphenyl substituted 1,2,3ꢀtriazole
(2b). 4ꢀArylꢀNHꢀ1,2,3ꢀtriazoles have recently been identified as potent inhibitors of cobalt
activated human methionine amino peptidase type 2 (hMetAP2)24 and indole amine 2,3ꢀ
dioxygenase (IDO);25 showing promise as anticancer drugs. Gratifyingly, the coupling
reaction between 1 and 2b was equally facile and furnished the expected N2ꢀalkylated
products 3iꢀ3n in good yields (77ꢀ84%). The structure of Nꢀ(4ꢀbromobenzyl)ꢀNꢀmethylꢀ1ꢀ(4ꢀ
phenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methanamine (3n) was also confirmed by Xꢀray crystallography
(see Supporting Information).
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The scope of the strategy was further extended to benzotriazoles (4) as they constitute an
essential structural motif in medicinal chemistry, corrosion inhibitors and supramolecular
ligands.26 N1ꢀSubstituted benzotriazoles (Btꢀ1) are usually prepared as a mixture with their
N2ꢀsubstituted isomers (Btꢀ2) by reaction of benzotriazole with the corresponding alkylating
reagents or halogen derivatives in the presence of a base. In these methods, the
regioselectivity of 1ꢀalkylated benzotriazoles is poor, and the ratio of N1/N2 varies from 1/1 to
3/1.27 Thus, advances for synthesis of diverse N1ꢀalkylated benzotriazoles are desirable. A
CDC of unsubstituted benzotriazole 4a with 1a was carried out under the optimized
conditions (Scheme 4). The reaction completed in 1 h, and afforded a single product in 81%
yield. The product, characterized as N1ꢀalkylated benzotriazole (5a) is a useful intermediate
in the synthesis of kinase inhibitor.28 Other N1ꢀalkylated benzotriazole derivatives (5bꢀ5f)
with substitutions on phenyl ring of 1 were also obtained in good yields (77ꢀ85%). With 5,6ꢀ
dimethyl substituted benzotriazoles, the corresponding N1ꢀalkylated derivatives 5g-5h formed
in 83ꢀ89% yields. These molecules are known to be powerful corrosion inhibitors in chemical
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mechanical planarization (CMP),29 and were synthesized easily by this method. N1ꢀ and N2ꢀ
alkylated benzotriazoles equilibrate to different extents when dissolved in organic solvents
such as DMSO, chloroform or others.30 Thus, the observed and highlighted N1ꢀselectivity
may degrade when the compounds 5 are dissolved in organic solvents.
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Scheme 4: Scope with benzotriazoles.a
aReaction conditions. 1 (2 mmol), 4 (1 mmol), Cu2S NPs (1 mol %), TBHP (5.5M in decane,
1equiv, 0.2 mL), N2, 90 oC.
Recently, McKnight and coꢀworkers reported aminopropyl carbazole (P7C3) to be a potent
proneurogenic and neuroprotective compound.31 This instigated us to explore our Nꢀ
alkylation strategy with carbazoles as substrates; since they are useful motifs in treatment of
chronic diseases like Alzheimer’s and Parkinson’s.32 As shown in Scheme 5, the coupling
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reaction worked well, and gave the desired products 7aꢀ7g in good yields (72ꢀ82%). To
ascertain the synthetic utility of the developed protocol for practical purposes, this reaction
was also carried out on a gram scale. 1g of carbazole 6 was treated with 11.96 mmol of 4ꢀ
chloroꢀN,Nꢀdimethylbenzyl amine under the standard reaction conditions, and the coupled
product 7f was isolated in 76% yield (1.52 g).
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Scheme 5: Nꢀalkylation of cabazoles with N, Nꢀdimethylbenzylamines.a
aReaction conditions. 1 (2 mmol), 6 (1 mmol), Cu2S NPs (1 mol%), TBHP (5.5M in decane,
1 equiv, 0.2 mL), N2, 90 oC, breaction was carried out on a gram scale.
Further, the CꢀN bond formation was investigated with N,Nꢀdimethylaniline (8) as the
coupling partner (Scheme 6). The reactions of 2, 4 and 6 with 8 tolerated the reaction
conditions well, and gave the desired Nꢀalkylated products 9a-9f in 65ꢀ88% yields. Our
results are in contrast to a recent study by Li and Chen where they reported that N,Nꢀ
dimethylanilines were inert for Cu(OAc)2 catalyzed CꢀN bond formation with NHꢀ1,2,3ꢀ
triazoles.23 These findings are thus significant as there is no literature precedence on the
synthesis of such molecules.
Scheme 6: Nꢀalkylation of azoles (2/4/6) with N,Nꢀdimethylanilines (8).a
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aReaction conditions. 8 (2 mmol), 2/4/6 (1 mmol), Cu2S NPs (1 mol%), TBHP (5.5 M in
decane, 1 equiv, 0.2 mL), N2, 90 oC.
To understand the mechanism, several control experiments were carried out as shown in
Scheme 7. The involvement of freeꢀradical species in the reaction was ascertained by
performing quenching studies with a radical scavenger (2,2,6,6ꢀtetramethylpiperidinꢀ1ꢀ
yl)oxidanyl (TEMPO). It was found that the reaction of 1a with 2 in presence of TEMPO
34gave the corresponding products 3a or 3i in lower yields; and the yields were found to
decrease in a dose dependent manner (Scheme 7(1)). The inhibitory effect of TEMPO
suggested the reaction to proceed via radical intermediate(s). Notably, formation of small
amounts (3%) of 4ꢀmethoxybenzaldehyde (10) was observed when the reaction of 1ꢀ(4ꢀ
methoxyphenyl)ꢀN,Nꢀdimethylmethanamine and 2a was carried out under optimized
conditions. To understand its formation, a control experiment was carried out in aqueous
TBHP; wherein 3c and 10 were obtained in 65 and 15% yields respectively (Scheme 7(2)).
This is consistent with the earlier observations by Smith et al. who reported the formation of
10 during the oxidation of 1 with FeIIITPPClꢀPhIO, and suggested its formation via benzylic
iminium ion intermediate (B).33a Similarly in another report, Wu and coꢀworkers
demonstrated oxidative cleavage of benzylic C–N bonds through iminium ion B.33b Further,
changes in the oxidation state of copper during the reaction were analyzed through time
dependent EPR studies of the reaction mixture. The data indicated generation of Cu (II)
during the catalytic cycle ((Scheme 7(3) and see SI). Appearance of peak at 134.0956 in the
HRMS of reaction mixture supported the formation of iminium ions A/B. Control
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in the HRMS.
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Scheme 7: Preliminary Mechanistic Studies
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Figure 2 Proposed Mechanism
Based on the results of the control experiments and literature reports, a mechanism for the
reaction has been proposed in Figure 2. It is believed that the reaction is initiated by copper
catalyzed decomposition of TBHP to generate a tertꢀbutoxyl radical, and a single electron
transfer (SET) from amine 1 generates a radical cation. This is followed by abstraction of the
sp3 hydrogen of the radical cation to generate an iminium type intermediate A or B. The
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reaction of A with triazole/carbazole results in the formation of complex C; which furnishes
the CꢀN coupled product via nucleophilic attack of the azole on iminium ion with a
concurrent regeneration of Cu2S for the next catalytic cycle. We believe that the amine (2
equiv.)13,34 might be involved in trapping the proton released in this step. The generation of
iminium type B in reaction mixture results in the formation of benzaldehyde as a side product
on hydrolysis as is observed with 1ꢀ(4ꢀmethoxyphenyl)ꢀN,Nꢀdimethylmethanamine. The
formation of B might be favored with the ΠꢀDonor (+ M) substituents such as 4ꢀOMe, which
can stabilize it by direct conjugation.
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To check the reusability of the catalyst for the next catalytic cycle, it was recovered from the
reaction mixture by centrifugation, washed with ethanol and dried in vacuum. The activity of
the recovered Cu2S catalyst was examined up to five cycles, and was found to decrease
slightly after every reaction (Figure S6 of SI). After the fourth cycle, the reaction mixture
containing the catalyst was centrifuged, and its surface morphology was compared to the
fresh catalyst using PXRD and TEM (Figure S5 and S1 of SI respectively), which showed
agglomeration of the catalyst during the course of the reaction.
Conclusions
In conclusion, we demonstrate an unprecedented synthesis of Cu2S NPs via single source precursor
route from CuSPh. The prepared NPs are highly active and catalyze an efficient and versatile
C−H/NꢀH cross dehydrogenative coupling between sp3 αꢀC−H of N,Nꢀdimethylbenzylamines
and azoles under solventꢀfree conditions. This method enables a highly N1ꢀselective and N2ꢀ
selective alkylation of benzotriazoles and 4,5ꢀunsubstituted 1,2,3ꢀtriazoles, respectively. It
also allows access to N2ꢀalkylated 4ꢀphenylꢀ1,2,3ꢀtriazoles and Nꢀalkylated carbazoles in
good yields. The catalyst is reusable up to five reaction cycles with slight loss in activity. The
reaction is believed to follow a radical pathway involving an iminium ion intermediate.
EXPERIMENTAL SECTION
General Remarks
All reactions were carried out in ovenꢀdried round bottom flasks. Reagents were purchased at
the highest commercial quality and used without further purification, unless otherwise stated.
Reactions were monitored by thin layer chromatography (TLC) carried out on a 0.25 mm
silica gel plates (60F−254) and visualized under UV illumination at 254 nm and iodine
chamber. Further visualization was achieved by iodine vapour adsorbed on silica gel
depending on the product type. Organic extracts were dried over anhydrous sodium sulphate.
Solvents were removed in a rotary evaporator under reduced pressure. Column
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chromatography was performed on silica gel 100−200 mesh using a mixture of hexane and
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ethyl acetate as eluent, an isolated compounds were characterized by H NMR, 13C NMR,
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and HRMS data. NMR spectra for all the samples were taken in deuterochloroform (CDCl3)
1
and dimethylsulfoxideꢀd6 (DMSOꢀd6) as the solvents. H and 13CꢀNMR spectra were
9
recorded at ambient temperature on 300 MHz and 75 MHz spectrometer using
tetramethylsilane (TMS) as internal reference. The chemical shifts are quoted in δ units, parts
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per million (ppm) up field from the signal of internal TMS. H NMR data is represented as
follows: Chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, dd = double doublet), integration and coupling constant(s) J in Hertz (Hz). High
resolution mass spectra (HRMS) were recorded on a Mass spectrometer using electrospray
ionizationꢀtime of flight (ESIꢀTOF) reflectron experiments.
For EDX studies, instrument was used Model QuanTax 200, based on the SDD technology
and giving an energy resolution of 127 eV at MnKα to estimate elemental compositions.
Sample was mounted on a circular metallic sample holder with a sticky carbon tape. Powder
Xꢀray diffraction (PXRD) studies were carried out on a Bruker D8 Advance diffractometer
using Niꢀfiltered CuKα radiation, scan speed of 1 s and scan step of 0.05o. Transmission
electron microscopic (TEM) studies were carried out using a JEOL JEM200CX TEM
instrument operated at 200 kV. The specimens for these studies were prepared by dispersing
the powdered sample in ethanol by ultrasonic treatment. Few drops of resulting solution were
put on a porous carbon film supported on a copper grid and dried in air. Xꢀray photoelectron
spectroscopy (XPS) measurements were carried out using an EA 125 electron spectrometer
manufactured by OMICRON Nanotechnology GmbH (Germany), with AlꢀKα radiation
(1486.7ꢁeV). Xꢀband EPR measurements were performed on a JEOL JESꢀFA 200 instrument.
The Electron Paramagnetic Resonance (EPR) spectra were measured in a frozen DMF
solution at 77 K (Xꢀband, Frequency = 1.103 GHz, Power = 1.15 mW).
Reagent Information
Trioctylphosphine (TOP), CuSO4.5H2O, Thiophenol, were procured from Sigmaꢀ
Aldrich (USA). Hydroxylamine hydrochloride (NH2OH.HCl), N,Nꢀdimethylbenzylamine
(Acros organics), were used as received. All the solvents of AR grade i.e. acetone,
diethylether, ethanol were dried and distilled before use by known standard procedures. The
synthesis of CuSPh complex is detailed below.
Procedure for the synthesis of CuSPh complex17
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To an ice cold mixture of conc. aqueous NH3 (25 mL) and water (100 mL), CuSO4.5H2O
(6.26 g, 25.1 mmol) was added resulting in a blue coloured solution. Then, a solid form of
o
NH2OH.HCl (3.89 g, 56.0 mmol) was added and the contents were stirred overnight at 25 C
under a nitrogen purge to produce a colourless solution of [Cu(NH3)2]+. A solution of PhSH
(2.84 g, 25.8 mmol) in 125 mL of ethanol was added dropwise, resulting in formation of a
pale yellow solid. The solid product was collected via filtration, washed several times with
water, ethanol and ether respectively. The solid was finally dried in vacuum. Yellowish solid;
yield: 82%
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Procedure for the synthesis of Cu2S Nanoparticles
A slurry containing 0.5 mmol CuSPh in 2 mL trioctylphosphine (TOP) in a three neck 50 mL
round bottom flask was heated under N2 atmosphere to 100 ºC to remove water and oxygen.
The resulting homogeneous solution was heated to 320 ºC for 1.5 h with continuous stirring
affording brownish black colloidal solution. The mixture was cooled to room temperature and
20 mL of acetone was added into the flask to obtain a brown precipitate which was separated
by centrifugation. The precipitate was washed three times with acetone (20 mL) and dried in
vacuum.
General procedure for the synthesis of compounds (3a-3n, 5a-5k, 7a-7g and 9a-9f):
To the mixture of N,Nꢀdimethylbenzylamine/N,Nꢀdimethylaniline (1/8) (1.0 mmol), triazole
(2)/benzotriazole (4) or carbazole (6) (0.5 mmol), tertꢀbutyl hydroperoxide (0.2 mL, 1.2
mmol decane solution) and Cu2S NP catalyst (1 mol%, 0.8 mg) were added under nitrogen at
room temperature. The reaction temperature was raised to 90 °C and the contents were stirred
at the same temperature for 1 h. The reaction mixture was then cooled to room temperature.
The resulting suspension was diluted with ethylacetate and the organic layer was washed off
with 5% sodium bicarbonate aq. solution (3 × 10 mL) and dried over anhydrous Na2SO4.
Solvent was evaporated and the residue was purified by column chromatography on silica gel
(eluting with hexane/ethyl acetate = 95:5).
Characterization Data:
Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀphenylmethanamine (3a):
Yellow liquid (0.15 g, 74%). 1H NMR (300 MHz, CDCl3): 7.66 (s, 2H), 7.39ꢀ7.26 (m, 5H),
5.30 (s, 2H), 3.71 (s, 2H), 2.34 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3) : δ 138.2(C),
134.0(CH), 129.0(CH), 128.4(CH), 127.3(CH), 74.0(CH2), 58.2(CH2), 39.6(CH3). HRMS
(ESIꢀTOF) m/z: [M]+ Calcd for C11H14N4 202.1213; Found 202.1214.
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Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀ(pꢀtolyl)methanamine (3b):
White solid (0.173 g, 80%), m.p. 42ꢀ44 ºC . 1H NMR (300 MHz, CDCl3): 7.69 (s, 2H), 7.29
(d, J = 8.1 Hz, 2H), 7.17 (d, J = 7.8 Hz, 2H), 5.32 (s, 2H), 3.70 (s, 2H), 2.36 (s, 6H).
13C{1H}NMR (75 MHz, CDCl3): δ 136.8(C), 135.2(C), 134.0(CH), 129.0(CH), 128.9(CH),
73.9(CH2), 57.9(CH2), 39.6(CH3), 21.1(CH3). HRMS (ESIꢀTOF) m/z: [M]+ Calcd for
C12H16N4 216.1369; Found 216.1361.
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Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀNꢀmethylmethanamine (3c):
1
Yellow liquid (0.19 g, 82%). H NMR (300 MHz, CDCl3): 7.66 (s, 2H), 7.30 (dd, J1 = 6.6
Hz, J2 = 2.1 Hz, 2H), 6.88 (dd, J1 = 6.5 Hz, J2 = 2.1 Hz, 2H), 5.28 (s, 2H), 3.81 (s, 3H),
3.65 (s, 2H), 2.34 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 158.9(C), 134.0(CH),
130.3(C), 130.2(CH), 113.7(CH), 73.7(CH2), 57.6(CH2), 55.3(CH3), 39.6(CH3). HRMS
(ESIꢀTOF) m/z: [M]+ Calcd for C12H16N4O 232.1319; Found 232.1332.
Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀ1ꢀ(4ꢀchlorophenyl)ꢀNꢀmethylmethanamine (3d):
Yellow liquid (0.18 g, 76%). 1H NMR (300 MHz, CDCl3): 7.66 (s, 2H), 7.32 (m, 4H), 5.28
(s, 2H), 3.67 (s, 2H), 2.34 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 136.8(C),
134.1(CH), 133.0(C), 130.3(CH), 128.5(CH), 73.8(CH2), 57.5(CH2), 39.7(CH3). HRMS
(ESIꢀTOF) m/z: [M + Na]+ Calcd for C11H13ClN4Na 259.0721; Found 259.0722.
Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀ1ꢀ(2ꢀchlorophenyl)ꢀNꢀmethylmethanamine (3e):
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Yellow liquid (0.165 g, 70%). H NMR (300 MHz, CDCl3): 7.68 (s, 2H), 7.52ꢀ7.49 (m,
1H), 7.39ꢀ7.36 (m, 1H), 7.26ꢀ7.22 (m, 2H), 5.34 (s, 2H), 3.82 (s, 2H), 2.40 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 135.8(C), 134.7(C), 134.1(CH), 130.9(CH), 129.7(CH),
128.6(CH), 126.6(CH), 74.3(CH2), 55.4(CH2), 39.6(CH3). HRMS (ESIꢀTOF) m/z: [M +
Na]+ Calcd for C11H13ClN4Na 259.0721; Found 259.0722.
Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀ1ꢀ(3ꢀchlorophenyl)ꢀNꢀmethylmethanamine (3f):
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Yellow liquid (0.18 g, 73%). H NMR (300 MHz, CDCl3): 7.67 (s, 2H), 7.40 (s, 1H), 7.25
(s, 3H), 5.30 (s, 2H), 3.70 (s, 2H), 2.34 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ
140.5(C), 134.1(CH), 129.6(CH), 128.9(CH), 127.9(C), 127.5(CH), 127.0(CH), 74.0(CH2),
57.7(CH2), 39.6(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C11H13ClN4Na
259.0721; Found 259.0703.
N ꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀ1ꢀ(4ꢀbromophenyl)ꢀNꢀmethylmethanamine (3g):
º
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White solid (0.219 g, 78%), m.p. 46ꢀ48 C. H NMR (300 MHz, CDCl3): 7.66 (s, 2H),
7.48ꢀ7.45 (m, 2H), 7.27 (d, J = 8.4 Hz, 2H), 5.27 (s, 2H), 3.66 (s, 2H), 2.34 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 137.3(C), 134.0(CH), 131.5(CH), 130.6(CH), 121.1(C),
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73.8(CH2), 57.5(CH2), 39.7(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for
C11H13BrN4Na 303.0216; Found 303.0187.
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Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀNꢀbenzylethanamine (3h):
Colourless liquid (0.147 g, 68%). 1H NMR (300 MHz, CDCl3): 7.65 (s, 2H), 7.43ꢀ7.40 (m,
2H), 7.38ꢀ7.32 (m, 2H), 7.29ꢀ7.26 (m, 1H) 5.31 (s, 2H), 3.78 (s, 2H), 2.59 (q, J = 7.2 Hz,
2H), 1.16 (t, J = 7.2 Hz, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 138.8(C), 133.9(CH),
128.9(CH), 128.3(CH), 127.1(CH), 70.3(CH2), 56.0(CH2), 45.5(CH2), 12.8(CH3). HRMS
(ESIꢀTOF) m/z: [M + H]+ Calcd for C12H17N4 217.1448; Found 217.1440.
NꢀbenzylꢀNꢀmethylꢀ1ꢀ(4ꢀphenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methanamine (3i):
White solid (0.223 g, 80%), m.p. 76ꢀ78 ºC. 1H NMR (300 MHz, CDCl3): 7.90 (s, 1H), 7.84
(d, J = 7.5 Hz, 2H), 7.47ꢀ7.27 (m, 8H), 5.31 (s, 2H), 3.77 (s, 2H), 2.40 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 147.6(C), 138.3(C), 130.9(CH), 130.6(C), 129.1(CH),
128.9(CH), 128.4(CH), 128.3(CH), 127.3(CH), 126.0(CH), 74.2(CH2), 58.3(CH2),
39.8(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C17H18N4Na 301.1424; Found
301.1412.
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NꢀmethylꢀNꢀ(4ꢀmethylbenzyl)ꢀ1ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)methanamine (3j):
White solid (0.240 g, 82%), m.p. 78ꢀ80 ºC. 1H NMR (300 MHz, CDCl3): 7.89 (s, 1H), 7.84
(d, J = 1.2 Hz, 1H), 7.82 (t, J = 1.2 Hz, 1H), 7.48ꢀ7.42 (m, 2H), 7.39ꢀ7.35 (m, 1H), 7.29 (d,
J = 8.1 Hz, 2H), 7.16 (d, J = 8.1 Hz, 2H), 5.30 (s, 2H), 3.73 (s, 2H), 2.40 (s, 3H), 2.35 (s,
3H). 13C{1H}NMR (75 MHz, CDCl3): δ 147.5(C), 136.9(C), 135.2(C), 130.8(CH),
130.7(C), 129.1(CH), 129.0(CH), 128.9(CH), 128.4(CH), 126.0(CH), 74.1(CH2),
58.0(CH2), 39.7(CH3), 21.1(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C18H21N4
293.1761; Found 293.1757.
Nꢀ(2ꢀchlorobenzyl)ꢀNꢀmethylꢀ1ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)methanamine (3k):
Colourless liquid (0.241 g, 77%). 1H NMR (300 MHz, CDCl3): 7.91 (s, 1H), 7.86ꢀ7.83 (m,
2H), 7.54ꢀ7.33 (m, 5H), 7.28ꢀ7.21 (m, 2H), 5.34 (s, 2H), 3.88 (s, 2H), 2.45 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 147.6(C), 135.8(C), 134.7(C), 130.9(CH), 130.5(C),
129.7(CH), 128.8(CH), 128.5(CH), 128.4(CH), 126.5(CH), 125.9(CH), 74.3(CH2),
55.4(CH2), 39.7(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C17H17ClN4Na
335.1034; Found 335.1018.
Nꢀ(3ꢀchlorobenzyl)ꢀNꢀmethylꢀ1ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)methanamine (3l):
Colourless liquid (0.247 g, 79%). 1H NMR (300 MHz, CDCl3): 7.90 (s, 1H), 7.85ꢀ7.82 (m,
2H), 7.49ꢀ7.43 (m, 3H), 7.39ꢀ7.33 (m, 1H), 7.29ꢀ7.26 (m, 3H), 5.30 (s, 2H), 3.74 (s, 2H),
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2.40 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 147.7(C), 140.5(C), 134.3(C), 130.9(CH),
130.5(C), 129.6(CH), 129.0(CH), 128.9(CH), 128.5(CH), 127.5(CH), 127.1(CH),
126.0(CH), 74.1(CH2), 57.7(CH2), 39.8(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for
C17H18ClN4 313.1215; Found 313.1187.
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White solid (0.253 g, 81%), m.p. 80ꢀ82 C. H NMR (300 MHz, CDCl3): 7.89 (s, 1H),
7.84ꢀ7.82 (m, 2H), 7.48ꢀ7.43 (m, 2H), 7.39ꢀ7.30 (m, 5H), 5.28 (s, 2H), 3.72 (s, 2H), 2.39
(s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 147.6(C), 136.8(C), 133.0(C), 130.9(CH),
130.5(C), 130.4(CH), 128.9(CH), 128.5(CH), 128.4(CH), 125.9(CH), 73.9(CH2),
57.5(CH2), 39.8(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C17H18ClN4 313.1215;
Found 313.1210.
Nꢀ(4ꢀbromobenzyl)ꢀNꢀmethylꢀ1ꢀ(4ꢀphenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methanamine (3n):
White solid (0.300 g, 84%), m.p. 84ꢀ86 C.1H NMR (300 MHz, CDCl3): 7.89 (s, 1H), 7.82
º
(d, J = 7.8 Hz, 2H) 7.48ꢀ7.36 (m, 5H), 7.28 (d, J = 8.4 Hz, 2H), 5.28 (s, 2H), 3.70 (s, 2H),
2.39 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 147.6(C), 137.3(CH), 131.5(CH),
131.0(CH), 130.8(CH), 130.5(C), 128.9(CH), 128.5(CH), 126.0(CH), 121.1(C), 73.9(CH2),
57.6(CH2), 39.8(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C17H17BrN4Na
379.0529; Found 379.0524.
Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀphenylmethanamine (5a)30:
White solid (0.204 g, 81%), m.p. 114ꢀ116 ºC. 1H NMR (300 MHz, DMSOꢀd6): 8.06 (d, J =
8.1 Hz, 1H), 7.94 (d, J = 8.7 Hz, 1H), 7.56 (t, J = 7.2 Hz, 1H), 7.44ꢀ7.39 (m, 1H), 7.36ꢀ
7.26 (m, 5H), 5.64 (s, 2H), 3.67 (s, 2H), 2.19 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6):
δ 145.3(C), 138.6(C), 134.4(C), 129.1(CH), 128.7(CH), 127.8(CH), 127.6(CH),
124.4(CH), 119.4(CH), 111.5(CH), 68.5(CH2), 58.4(CH2), 39.5(CH3). HRMS (ESIꢀTOF)
m/z: [M + H]+ Calcd for C15H17N4 253.1448; Found 253.1448.
Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀ(pꢀtolyl)methanamine (5b):
Colourless liquid (0.210 g, 79%), H NMR (300 MHz, DMSOꢀd6): 8.07 (d, J = 8.4 Hz,
1
1H), 7.96 (d, J = 8.7 Hz, 1H), 7.57 (t, J = 7.2 Hz, 1H), 7.42 (t, J = 8.1 Hz, 1H), 7.21 (d, J =
8.1 Hz, 2H), 7.15 (d, J = 7.2 Hz, 2H), 5.64 (s, 2H), 3.64 (s, 2H), 2.29 (s, 3H), 2.19 (s, 3H).
13C{1H}NMR (75 MHz, DMSOꢀd6): δ 145.4(C), 136.7(C), 135.5(CH), 134.4(C),
129.3(CH), 129.1(CH), 127.8(CH), 124.3(CH), 119.5(CH), 111.6(CH), 68.5(CH2),
58.2(CH2), 39.4(CH3), 21.2(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C16H19N4
267.1604; Found 267.1595.
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Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀNꢀmethylmethanamine
(5c):
Colourless liquid (0.24 g, 85%). 1H NMR (300 MHz, DMSOꢀd6): 8.07 (d, J = 8.4 Hz, 1H),
7.97 (d, J = 7.8 Hz, 1H), 7.60ꢀ7.55 (m, 1H), 7.44ꢀ7.39 (m, 1H), 7.24 (d, J = 8.4 Hz, 2H),
6.91ꢀ6.88 (d, J = 8.7 Hz, 2H), 5.63 (s, 2H), 3.71 (s, 3H), 3.60 (s, 2H), 2.17 (s, 3H).
13C{1H}NMR (75 MHz, DMSOꢀd6): δ 158.9(C), 145.3(C), 134.4(C), 130.4(C), 130.4(CH),
127.8(CH), 124.4(CH), 119.5(CH), 114.1(CH), 111.6(CH), 68.3(CH2), 57.8(CH2),
55.5(CH3), 39.3((CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C16H18N4ONa
305.1373; Found 305.1369.
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Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀ1ꢀ(2ꢀchlorophenyl)ꢀNꢀmethylmethanamine
(5d):
1
Colourless liquid (0.221 g, 77%). H NMR (300 MHz, DMSOꢀd6): 8.07 (d, J = 9.0 Hz,
1H), 7.97 (d, J = 9.0 Hz, 1H), 7.60ꢀ7.50 (m, 2H), 7.46ꢀ7.40 (m, 2H), 7.37ꢀ7.31 (m, 2H),
5.69 (s, 2H), 3.80 (s, 2H), 2.24 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 145.4(C),
135.9(C), 134.4(C), 133.9(C), 131.3(CH), 129.9(CH), 129.4(CH), 127.9(CH), 127.6(CH),
124.4(CH), 119.5(CH), 111.5(CH), 68.7(CH2), 55.6(CH2), 39.5(CH3). HRMS (ESIꢀTOF)
m/z: [M + Na]+ Calcd for C15H15ClN4Na 309.0877; Found 309.0887.
Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀ1ꢀ(3ꢀchlorophenyl)ꢀNꢀmethylmethanamine
(5e):
Colourless liquid (0.227 g, 79%).1H NMR (300 MHz, DMSOꢀd6): 8.07 (d, J = 8.1 Hz, 1H),
7.98 (d, J = 8.4 Hz, 1H), 7.61ꢀ7.55 (m, 1H), 7.45ꢀ7.30 (m, 5H), 5.66 (s, 2H), 3.71 (s, 2H),
2.22 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 145.4(C), 141.5(C), 134.4(C),
133.5(C), 130.6(CH), 128.8(CH), 127.9(CH), 127.7(CH), 127.6(CH), 124.4(CH),
119.5(CH), 111.5(CH), 68.5(CH2), 57.7(CH2), 39.5(CH3). HRMS (ESIꢀTOF) m/z: [M +
Na]+ Calcd for C15H15ClN4Na 309.0877; Found 309.0887.
Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀ1ꢀ(4ꢀchlorophenyl)ꢀNꢀmethylmethanamine
(5f)30:
1
Colourless liquid (0.232 g, 81%). H NMR (300 MHz, DMSOꢀd6): 8.06 (d, J = 8.4 Hz,
1H), 7.97 (d, J = 8.4 Hz, 1H), 7.59ꢀ7.54 (m, 1H), 7.44ꢀ7.33 (m, 5H), 5.65 (s, 2H), 3.67 (s,
2H), 2.20 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 145.4(C), 137.7(C), 134.4(C),
132.2(C), 130.9(CH), 128.7(CH), 127.9(CH), 124.4(CH), 119.5(CH), 111.5(CH),
68.4(CH2), 57.6(CH2), 39.5(CH3). HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for
C15H15ClN4Na 309.0877; Found 309.0887.
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Nꢀbenzylꢀ1ꢀ(5,6ꢀdimethylꢀ1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)ꢀNꢀmethylmethanamine (5g):
White solid (0.236 g, 84%), m.p. 116ꢀ118 ºC.1H NMR (300 MHz, DMSOꢀd6): 7.80 (s, 1H),
7.67 (s, 1H), 7.35ꢀ7.30 (m, 5H), 5.55 (s, 2H), 3.66 (s, 2H), 2.38 (s, 3H), 2.37 (s, 3H), 2.20
(s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 144.6(C), 138.7(C), 137.7(C), 133.7(C),
133.4(C), 129.2(CH), 128.7(CH), 127.6(CH), 118.4(CH), 110.6(CH), 68.2(CH2),
58.4(CH2), 39.6(CH3) 20.9(CH3), 20.3(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for
C17H21N4 281.1761; Found 281.1761.
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1ꢀ(5,6ꢀdimethylꢀ1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)ꢀNꢀmethylꢀNꢀ(4ꢀ
methylbenzyl)methanamine (5h):
º
1
White solid (0.262 g, 89%), m.p. 120ꢀ122 C. H NMR (300 MHz, DMSOꢀd6): 7.80 (s,
1H), 7.65 (s, 1H), 7.25ꢀ7.13 (m, 4H), 5.53 (s, 2H), 3.60 (s, 2H), 2.38 (s, 3H), 2.37 (s, 3H),
2.29 (s, 2H), 2.18 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 144.6(C), 137.7(C),
136.7(C), 135.6(C), 133.7(C), 133.4(C), 129.3(CH), 129.2(CH), 118.4(CH), 110.7(CH),
68.1(CH2), 58.2(CH2), 39.6(CH3) 21.2(CH3), 20.9(CH3), 20.3(CH3). HRMS (ESIꢀTOF)
m/z: [M + H]+ Calcd for C18H23N4 295.1917; Found 295.1904.
Nꢀ(2ꢀchlorobenzyl)ꢀ1ꢀ(5,6ꢀdimethylꢀ1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)ꢀNꢀmethylmethanamine
(5i):
1
Colourless liquid (0.261 g, 83%). H NMR (300 MHz, DMSOꢀd6): 7.80 (s, 1H), 7.66 (s,
1H), 7.52 (d, J = 7.5 Hz, 1H), 7.45ꢀ7.42 (m, 1H), 7.38ꢀ7.29 (m, 2H), 5.58 (s, 2H), 3.77 (s,
2H), 2.37 (s, 3H), 2.36 (s, 3H), 2.23 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ
144.6(C), 137.8(C), 136.0(C), 133.9(C), 133.8(C), 133.4(C), 131.3(CH), 129.9(CH),
129.4(CH), 127.5(CH), 118.4(CH), 110.6(CH), 68.4(CH2), 55.6(CH2), 39.6(CH3),
20.8(CH3), 20.3(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C17H20ClN4 315.1371;
Found 315.1367.
Nꢀ(3ꢀchlorobenzyl)ꢀ1ꢀ(5,6ꢀdimethylꢀ1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)ꢀNꢀmethylmethanamine
(5j):
º
1
White solid (0.268 g, 85%), m.p. 118ꢀ120 C. H NMR (300 MHz, DMSOꢀd6): 7.80 (s,
1H), 7.66 (s, 1H), 7.39ꢀ7.30 (m, 4H), 5.54 (s, 2H), 3.67 (s, 2H), 2.39 (s, 3H), 2.37 (s, 3H),
2.22 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 144.6(C), 141.5(C), 137.8(C),
133.8(C), 133.5(C), 133.4(C), 130.6(CH), 128.8(CH), 127.7(CH), 127.6(CH), 118.4(CH),
110.6(CH), 68.1(CH2), 57.7(CH2), 39.7(CH3), 20.9(CH3), 20.3(CH3). HRMS (ESIꢀTOF)
m/z: [M + H]+ Calcd for C17H20ClN4 315.1371; Found 315.1375.
Nꢀ(4ꢀchlorobenzyl)ꢀ1ꢀ(5,6ꢀdimethylꢀ1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)ꢀNꢀmethylmethanamine
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º
1
White Solid (0.274 g, 87%), m.p. 122ꢀ124 C. H NMR (300 MHz, DMSOꢀd6): 7.80 (s,
1H), 7.68 (s, 1H), 7.41ꢀ7.33 (m, 4H), 5.55 (s, 2H), 3.65 (s, 2H), 2.38 (s, 3H), 2.36 (s, 3H),
2.19 (s, 3H). 13C{1H}NMR (75 MHz, DMSOꢀd6): δ 144.6(C), 137.8(C), 133.8(CH),
133.4(C), 132.1(C), 131.0(CH), 129.0(C), 128.7(CH), 118.4(CH), 110.6(CH), 68.1(CH2),
57.6(CH2), 39.6(CH3) 20.9(CH3), 20.3(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for
C17H20ClN4 315.1371; Found 315.1382.
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Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀphenylmethanamine (7a):
º
1
White solid (0.216 g, 72%), m.p. 58ꢀ60 C. H NMR (300 MHz, CDCl3): 8.08 (d, J = 7.5
Hz, 2H), 7.52ꢀ7.40 (m, 5H), 7.32ꢀ7.31 (m, 3H), 7.28ꢀ7.21 (m, 3H), 4.97 (s, 2H), 3.68 (s,
2H), 2.25 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 141.2(C), 138.5(C), 128.9(CH),
128.3(CH), 127.2(CH), 125.7(CH), 123.2(C), 120.2(CH), 119.4(CH), 109.7(CH),
64.9(CH2), 59.7(CH2), 40.2(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C21H21N2
301.1699; Found 301.1703.
Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀNꢀmethylꢀ1ꢀ(pꢀtolyl)methanamine (7b):
º
1
White solid (0.252 g, 80%), m.p. 54ꢀ56 C. H NMR (300 MHz, CDCl3): 8.13 (d, J = 7.8
Hz, 2H), 7.57ꢀ7.44 (m, 5H), 7.32ꢀ7.25 (m, 4H), 7.18 (d, J = 7.8 Hz, 1H), 5.0 (s, 2H), 3.70
(s, 2H), 2.39 (s, 3H) 2.28 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 141.2(C), 136.8(C),
135.3(C), 129.0(CH), 128.9(CH), 125.7(CH), 123.2(C), 120.1(CH), 119.3(CH),
109.7(CH), 64.8(CH2), 59.4(CH2), 40.1(CH3), 21.1(CH3). HRMS (ESIꢀTOF) m/z: [M +
H]+ Calcd for C22H23N2 315.1856; Found 315.1865.
Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀNꢀmethylmethanamine (7c):
º
1
White solid (0.270 g, 82%), m.p. 55ꢀ57 C. H NMR (300 MHz, CDCl3): 8.12 (d, J = 7.8
Hz, 2H), 7.55ꢀ7.44 (m, 4H), 7.30ꢀ7.26 (m, 4H), 6.89 (d, J = 8.7 Hz, 2H), 4.99 (s, 2H), 3.83
(s, 3H), 3.66 (s, 2H), 2.28 (s, 3H). C{1H}NMR (75 MHz, CDCl3): δ 158.8(C), 141.1(C),
13
130.1(CH), 125.7(CH), 123.1(C), 120.1(CH), 119.3(CH), 113.7(CH), 110.5(C),
109.7(CH), 64.7(CH2), 59.0(CH2), 55.3(CH3), 40.1(CH3). HRMS (ESIꢀTOF) m/z: [M +
H]+ Calcd for C22H23N2O 331.1805; Found 331.1820.
Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀ1ꢀ(2ꢀchlorophenyl)ꢀNꢀmethylmethanamine (7d):
º
1
White solid (0.251 g, 75%) , m.p. 52ꢀ54 C. H NMR (300 MHz, CDCl3): 8.12 (d, J = 7.8
Hz, 2H), 7.57 (d, J = 8.1 Hz, 2H), 7.52ꢀ7.45 (m, 3H), 7.41ꢀ7.22 (m, 5H), 5.06 (s, 2H), 3.87
(s, 2H), 2.32 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 141.1(C), 135.9(C), 134.3(C),
130.9(CH), 129.5(CH), 128.4(CH), 126.7(CH), 125.7(CH), 123.2(C), 120.2(CH),
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119.4(CH), 109.6(CH), 65.0(CH2), 56.2(CH2), 40.1(CH3). HRMS (ESIꢀTOF) m/z: [M +
H]+ Calcd for C21H20ClN2 335.1310; Found 335.1297.
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º
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White solid (0.258 g, 77%), m.p. 53ꢀ55 C. H NMR (300 MHz, CDCl3): 8.08 (d, J = 7.8
Hz, 2H), 7.53ꢀ7.41 (m, 5H), 7.31ꢀ7.14 (m, 5H), 4.97 (s, 2H), 3.63 (s, 2H), 2.26 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 141.1(C), 140.7(C), 134.2(C), 129.5(CH), 128.8(CH),
127.4(CH), 126.8(CH), 125.8(CH), 123.2(C), 120.2(CH), 119.4(CH), 109.6(CH),
64.9(CH2), 58.9(CH2), 40.2(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C21H20ClN2
335.1310; Found 335.1298.
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º
1
White solid (0.264 g, 79%), m.p. 58ꢀ60 C. H NMR (300 MHz, CDCl3): 8.07 (d, J = 7.8
Hz, 2H), 7.51ꢀ7.38 (m, 5H), 7.26ꢀ7.18 (m, 5H), 4.95 (s, 2H), 3.60 (s, 2H), 2.22 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 141.1(C), 137.0(C), 132.8(C), 130.1(CH), 128.4(CH),
125.7(CH), 123.2(C), 120.2(CH), 119.4(CH), 109.6(CH), 64.9(CH2), 58.7(CH2),
40.0(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C21H20ClN2 335.1310; Found
335.1328.
Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀ1ꢀ(4ꢀbromophenyl)ꢀNꢀmethylmethanamine (7g):
º
1
White solid (0.281 g, 74%), m.p. 56ꢀ58 C. H NMR (300 MHz, CDCl3): 8.07 (d, J = 8.1
Hz, 2H), 7.55ꢀ7.38 (m, 6H), 7.27ꢀ7.19 (m, 3H), 7.14 (d, J = 8.1 Hz, 1H), 4.95 (s, 2H), 3.58
(s, 2H), 2.23 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 141.1(C), 137.6(C), 131.4(CH),
130.4(CH), 125.7(CH), 123.2(C), 121.0(C), 120.2(CH), 119.4(CH), 109.6(CH), 64.9(CH2),
58.7(CH2), 40.0(CH3). HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd for C21H20BrN2 379.0804;
Found 379.0791.
Nꢀ((2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)ꢀNꢀmethylaniline (9a):
Colourless liquid (0.16 g, 85%).1H NMR (300 MHz, CDCl3): 7.61 (s, 2H), 7.31ꢀ7.25 (m,
2H), 7.04 (d, J = 8.7 Hz, 2H), 6.84 (t, J = 7.8 Hz, 1H), 5.90 (s, 2H), 3.21 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3): δ 147.3, 134.3, 129.2, 119.0, 113.7, 70.8, 38.4. HRMS
(ESIꢀTOF) m/z: [M + Na]+ Calcd for C10H12N4Na 211.0954; Found 211.0953.
NꢀmethylꢀNꢀ((4ꢀphenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)aniline (9b):
White solid (0.196 g, 74%), m.p. 62ꢀ64 ºC.1H NMR (300 MHz, CDCl3): 7.82 (s 1H), 7.78ꢀ
7.75 (m, 1H), 7.44ꢀ7.39 (m, 3H), 7.35ꢀ7.25 (m, 3H), 7.07 (d, J = 8.1 Hz, 2H), 6.84 (t, J =
7.8 Hz, 1H), 5.90 (s, 2H), 3.24 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 148.0, 147.5,
131.2, 129.2, 128.8, 128.4, 126.1, 126.0, 119.0, 113.9, 71.1, 38.5. HRMS (ESIꢀTOF) m/z:
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[M + Na]+ Calcd for C16H16N4Na 287.1267; Found 287.1261.
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N,4ꢀdimethylꢀNꢀ((4ꢀphenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)aniline (9c):
º
White solid (0.214 g, 77%), m.p. 64ꢀ66 C.1H NMR (300 MHz, CDCl3): 7.82 (s, 1H), 7.66
(d, J = 8.4 Hz, 2H), 7.44ꢀ7.33 (m, 3H), 7.08 (d, J = 8.1 Hz, 2H), 6.98ꢀ6.95 (m, 2H), 5.88 (s,
2H), 3.20 (s, 3H), 2.25 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3), δ 147.7, 147.2, 131.2,
130.5, 129.7, 128.8, 128.4, 128.3, 126.0, 114.2, 71.4, 38.6, 20.3. HRMS (ESIꢀTOF) m/z:
[M + H]+ Calcd for C17H19N4 279.1604; Found 279.1604.
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4ꢀchloroꢀNꢀmethylꢀNꢀ((4ꢀphenylꢀ2Hꢀ1,2,3ꢀtriazolꢀ2ꢀyl)methyl)aniline (9d):
º
1
White solid (0.194 g, 65%), m.p. 66ꢀ68 C. H NMR (300 MHz, CDCl3): 7.85 (s, 1H),
7.80ꢀ7.77 (m, 2H), 7.47ꢀ7.34 (m, 3H), 7.28 (m, 2H), 7.25ꢀ7.22 (m, 1H), 7.01 (d, J = 8.7
Hz, 1H), 5.86 (s, 2H), 3.24 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3): δ 147.9, 145.9, 131.3,
130.2, 129.0, 128.8, 128.5, 125.9, 124.1, 115.1, 70.9, 38.7. HRMS (ESIꢀTOF) m/z: [M +
Na]+ Calcd for C16H15ClN4Na 321.0877; Found 321.0861.
Nꢀ((1Hꢀbenzo[d][1,2,3]triazolꢀ1ꢀyl)methyl)ꢀNꢀmethylaniline (9e):
1
Colourless liquid (0.209 g, 88%). H NMR (300 MHz, DMSOꢀd6): 8.02 (d, J = 8.4 Hz,
1H), 7.78 (d, J = 8.4 Hz), 7.51 (t, J = 7.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.22 (t, J = 7.8
Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H), 6.78 (t, J = 7.8 Hz, 1H), 6.37 (s, 2H), 3.08 (s, 3H).
13C{1H}NMR (75 MHz, CDCl3), δ 147.8, 145.5, 133.2, 129.5, 127.9, 124.4, 119.5, 119.2,
114.7, 111.4, 65.4, 38.5. HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C14H14N4Na
261.1111; Found 261.1111.
Nꢀ((9Hꢀcarbazolꢀ9ꢀyl)methyl)ꢀNꢀmethylaniline (9f):
º
1
White solid (0.215 g, 75%) , m.p. 46ꢀ48 C. H NMR (300 MHz, CDCl3): 8.11 (d, J = 7.8
Hz, 4H), 7.46ꢀ7.44 (m, 3H), 7.42ꢀ7.36 (m, 3H), 7.28ꢀ7.24 (m, 2H), 7.05 (d, J = 8.7 Hz,
1H), 5.79 (s, 2H), 2.78 (s, 3H). 13C{1H}NMR (75 MHz, CDCl3), δ 140.6, 139.5, 129.5,
125.8, 123.4, 120.3, 119.6, 115.5, 110.5, 109.5, 61.6, 35.7. HRMS (ESIꢀTOF) m/z: [M +
Na]+ Calcd for C20H18N2Na 309.1362; Found 309.1353.
Acknowledgments
S. G. thanks UGC for his graduate fellowship. Dr. N. C. thanks DST for SERBꢀ
National PostꢀDoctoral Fellowship. The authors thank Council of Scientific and Industrial
Research (CSIR), India (02(180)/14/EMRꢀII) for financially supporting this work. DSTꢀFIST
for funding the ESIꢀHRMS, SCXRD facility at IIT Delhi and MNIT Jaipur for XPS
measurement are gratefully acknowledged. The authors thank Dr. Sayantan Paria, IITD for
useful discussions on EPR and Dr. Anil Kumar, BITS Pilani for HRMS measurement.
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Supporting Information
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1H and 13CNMR spectra for all the synthesized compounds, ORTEPs and associated Xꢀray
crystallographic data for 3n and 5a (CIF), nanoparticle characterization data (TEM, SEM,
PXRD). This material is available free of charge via the Internet at http://pubs.acs.org.
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