2 H-Bis-1,2,3-triazolo-isoquinoline: Design, Synthesis, and Photophysical Study

Article abstract of DOI:10.1021/acs.joc.0c00263

An efficient three-step synthesis of a new heterocyclic system is described wherein the 2H-bis([1,2,3]triazolo)[5,1-a:4′,5′-c]isoquinoline ring system is elaborated using a simple synthetic strategy. The approach permits the preparation of target compounds in high yields using readily available arylhydrazines and o-alkynylbenzaldehydes as starting materials. The photophysical properties of the prepared heterocycles were studied to demonstrate that the prepared compounds are attractive blue-emitting fluorophores, exhibiting quantum yields up to 98% and Stokes shifts up to 67 nm. A strong effect of the steric hindrance on the absorption and emission spectra was revealed.

Full text of DOI:10.1021/acs.joc.0c00263

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Article
2H-bis-1,2,3-triazolo-isoquinoline. Design, synthesis and photophysical study
Biligma Tsyrenova, Victor N. Khrustalev, and Valentine Georgievich Nenajdenko
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c00263 • Publication Date (Web): 27 Apr 2020
Downloaded from pubs.acs.org on April 29, 2020
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Page 1 of 29
The Journal of Organic Chemistry
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2H-bis-1,2,3-triazolo-isoquinoline. Design, synthesis and photophysical study
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Biligma Tsyrenovaa, Victor Khrustalevb,c, Valentine Nenajdenkoa*
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aDepartment of Chemistry, Lomonosov Moscow State University, 119899 Moscow, Russia;
bPeoples’ Friendship University of Russia, 117198 Moscow, Russia.
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c N. D. Zelinsky Institute of Organic Chemistry of RAS, 47 Leninsky Prospect, 119991 Moscow, Russia
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R1
N
R1
N
H
N
N
NH2
O
N
R2
N
N
High yields
Efficient blue fluorescence
Quantum yields up to 0.98
R2
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ABSTRACT
An efficient three-step synthesis of a new heterocyclic system is described wherein the - 2H-
bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline ring system was elaborated using a simple synthetic strategy. The
approach permits the preparation of target compounds in high yields using readily available aryl hydrazines
and o-alkynylbenzaldehydes as starting materials. Photophysical properties of the prepared heterocycles were
studied to demonstrate that the prepared compounds are attractive blue emitting fluorophores exhibiting
quantum yields up to 98 % and Stokes shifts up to 67 nm. A strong effect of the steric hindrance on the
absorption and emission spectra was revealed.
INTRODUCTION
Nowadays chemical space of known compounds reached significant milestone. Currently more than 100
million of chemical compounds have been described in the literature. Among this space, much more than 99%
of known compounds are organic molecules. On the other hand, various heterocycles can be found most
frequently as a fragment creating structural diversity. For example, combining two or more heterocycles in a
molecule one can expect formation of endless structural space of molecular architectures. Both medicinal
chemistry and chemistry of materials demand novel structural types of heterocycles to make them as a most
attractive compounds for practical use. For example, nitrogen heterocycles are among the most significant
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structural components of pharmaceuticals. More than 59% of unique small-molecule drugs contain a nitrogen
heterocycle1. Another significant field of application of heterocycles and especially condensed heterocycles is
development of various fluorescent-active dyes, effective photosensors and novel OLED materials2.
Nowadays, there are a great number of papers devoted to the synthesis and investigation of various
fluorophores, but among them there are a very small number which actually managed to reach a decent level
and began to use them in industry3. Among other heterocycles, triazoles are one of the most attractive and
popular objects of research. This heterocyclic core is one of the most common pharmacophore4. For example,
triazoles exhibit insecticidal, herbicidal activities and they are known as fungicides, plant growth regulators in
agrochemistry5. Recently it was demonstrated6 that N-2-aryl-1,2,3-triazoles are unique class of effective
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UV/blue-light-emitting dyes (Fig. 1). As a result, 2-substituted 1,2,3-triazole became more and more popular
for optical study7.
R3
R2
N
R1
R1
N
N
N
N
N
N
Ar
Ar
Good conjugation and good photostability
Figure 1. Generalized structures of N-2-aryl-1,2,3-triazoles
This manuscript is devoted to the synthesis of new heterocyclic system 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-
c]isoquinoline. This unique heterocyclic system contains two triazole rings condensed to isoquinoline
fragment. Short and highly efficient route based on intramolecular [2+3] cycloaddition to form triazole
fragment was elaborated. Structural and optical properties of prepared condensed heterocycles were examined.
RESULTS AND DISCUSSION
Recently we have demonstrated efficient synthesis of 2,5-diaryl-4-azido-1,2,3-triazoles by the reaction of
1,1-dichlorodiazenes with sodium azide8. 1,1-Dichlorodiazadienes are known as an important class of
electrophiles9 and diazodyes10. Using 4,4-dichloro-1,2-diazabuta-1,3-dienes as a starting materials we have
been able to synthesize very rare 1,1-bis-azides by the reaction with sodium azide (Scheme 1). These extremely
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labile compounds have a tendency to cyclize into 4-azido-1,2,3-triazoles containing two aryl (heteroaryl)
groups at positions 2 and 5. The reaction turned out to be very common for the high-yield synthesis of diverse
4-azidotriazoles.
1
2
3
4
5
6
7
8
Scheme 1. The formation of 4-azido-1,2,3-triazoles
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Ar1
N3
Cl
Cl
Ar1
N
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H
N3
N3
Ar1
N
CCl4, CuCl (1%)
NaN3
H
N
N
Ar1
N
Ar2
N
TMEDA (2.5 eq.)
DMSO, rt.
DMSO
-N2
Ar2
N
N
N
Ar2
Ar2
up to 95%
up to 97 %
The prepared 2-arylsubstituted azidotriazoles11 demonstrated fluorescence in 347-419 nm region, however
very low quantum yields were observed (up to 0.02). Therefore, we decided to perform modification of these
derivatives to improve their optical properties. We decided to study synthesis of derivatives having additional
acetylenic fragment in ortho-position of Ar1 group (Scheme 2). Subsequent intramolecular cyclization to form
another 1,2,3-triazole ring can open direct access to new type of heterocycles - 2H-bis([1,2,3]triazolo)[5,1-
a:4',5'-c]isoquinolines. This heterocyclic system is unknown in literature; however, its flat -conjugated system
is very attractive for design of new dye compounds containing extended blue light emitting fragment.
Scheme 2. Design of new family of UV/blue-light-emitting dyes
R
R
N
N
H
H
N
intramolecular
cyclization
N3
N
N
steps
N
Ar2
blue light emitting
fragment
N
N
N
N
N
R
Ar2
Ar2
According to scheme of assembly of azidotriazoles (Scheme 2), ortho-alkynyl substituted aldehydes can
be used as a key building blocks for subsequent intramolecular cyclization. Sonogashira coupling was used to
prepare a set of acetylene derived benzaldehydes starting from 2-brombenzaldehyde12. Next, the corresponding
N-substituted hydrazones were prepared using the reaction with arylhydrazines. These starting materials were
transformed in situ into the corresponding 1,1-dichlorodiazenes using our previously elaborated approach.
Application of catalytic system CuCl (1%) - tetramethylethylenediamine CCl4 resulted in formation of the
corresponding acetylene derived diazadienes 1a-n in up to 80% yield8.
Scheme 3. The scope of 1,1-dichlorodiazenes
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TMEDA
CuCl
CCl4
R1
R1
N
1
2
3
4
5
6
7
R1
N2H3
DMSO
N
N
DMSO
one pot
O
N
H
R2
R2
R2
one pot
Cl
Cl 31-80%
O
O
8
9
Ph
Ph
O
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N
N
Ph
N
Ph
N
N
Ph
N
Ph
N
Ph
N
N
N
Cl
Cl
1e
(54%)
Cl
Cl
1a
Cl
Cl
(74%)
1c
1b
(59%)
(80%)
F
Cl
Cl
Cl
1d
Cl
Cl
(71%)
Ph
TMS
Ph
Ph
Ph
Cl
N
Ph
N
N
N
N
N
N
N
N
N
Cl
1g
(70%)
Cl
Cl 1f
(71%)
Cl
Cl
Cl
Cl
Cl
Cl
Cl
1i
(74%)
1j
(77%)
1h
(57%)
Ph
Ph
Ph
Ph
N
CN
O
N
N
N
N
N
N
N
O
Cl
Cl
Cl
Cl
Cl
Cl
1n
(31%)
1k
1m
(63%)
(68% )
Cl
Cl
1l
(64%)
Only in the case of synthesis of cyano derivative 1n decreasing yield (31%) was noticed. The proposed
approach permits variation of substituents of aryl R1 group having different acetylene fragments and R2
substituents of hydrazine moiety (Scheme 3). The reaction has broad scope and we found no limitations to
prepare target derivatives 1.
Next, the transformation of prepared diazadienes 1 into 4-azido-1,2,3-triazoles 2 was studied (Scheme 4).
To our delight, the reaction is very general in the case of alkynyl derived diazodienes 1a-n to give target
products 2a-n in up to 82% yield. Again, broad scope was demonstrated. Both substituents at the nitrogen and
at the triple bond can be varied to open access to azidotriazoles having acetylenic fragment in the structure. It
should be pointed out that due to the presence of two reactive fragments in the structure of 2a-n these
compounds have tendency to spontaneous cyclization even during storage at room temperature.
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The Journal of Organic Chemistry
Scheme 4. The scope of 4-azido-1,2,3-triazoles
1
2
3
R1
R1
4
5
6
7
N3
NaN3(5 eq.)
DMSO
N
N
N
N
R2
N
Cl
Cl
8
55-81%
9
R2
10
11
12
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O
O
Ph
O
Ph
N3
N3
N3
N3
N3
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
2a
(69%) Ph
Ph
Ph
2b
(70%)
Ph
2c
(82%)
2e
2d
(72%)
(78%)
Ph
Ph
TMS
Ph
Ph
Ph
N3
N3
N3
N3
N3
N
N
N
N
(57%)
Ph
N
N
N
N
N
N
N
N
N
N
N
2f
Cl
2g
(71%)
2h
(59%)
2i
(74%)
Cl
2j
(88%)
F
Ph
Ph
Ph
Ph
N3
N3
N3
N3
N
N
N
N
N
N
O
N
N
N
N
N
N
O
2l
(74%)
2k
(79%)
2m
(55%)
2n
(72%)
CN
We studied intramolecular cyclization to form 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline system. It
was found that reflux in toluene permits to perform such transformation very efficiently. As a result, unique
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condensed heterocycles 3a-n containing two triazole rings were prepared in up to 85% yield (Scheme 5).
Moreover, target products 3a-n can be isolated in pure form by simple filtration of the reaction mixture after
cooling to room temperature which is significant advantage of the synthetic procedure.
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Scheme 5. The scope of isoquinoline derivatives
1
2
3
4
5
6
7
8
R1
R1
N
N3
N
N
toluene
N
N
N
N
N
1. reflux, 6h
2. filtration
N
43-85%
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R2
R2
O
O
O
Ph
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Ph
Ph
Ph
3d
3a
3b
(78%) Ph
(82%)
(82%)
3c
3e
(77%)
(75 %)
Ph
H
N
Ph
Ph
Ph
Ph
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Ph
N
F
N
N
N
3f
(78%)
Cl
3g
(85%)
3i
3j
3h
(71%)
(47%)
Ph
(76%)
Cl
Ph
Ph
Ph
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
O
N
N
N
N
N
N
O
3m
(43%)
3k
(49%)
3l
(74%)
3n
(71%)
CN
All prepared compounds 3 were characterized by NMR and other methods of analysis. In addition, the
structure of compound 3c was unambiguously established by X-ray diffraction study13 (Fig. 2). The central
fragment containing the four fused rings (two triazole, tetrahydropyridine and benzene) in 3c are practically
planar (rms deviation is 0.059 Å). The two aryl substituents are twisted relative to the parent triazole rings by
11.56(9) (C11-C16, at the N5 atom) and 54.10(7) (C17-C22, at the C1 atom). Methoxy group is coplanar to
the parent phenyl ring (the C23─O1─C19─C18 torsion angle is equal to 3.1(3)). Crystal packing of 3c is
stacked along the crystallographic a axis. The molecules between the stacks are bound by the weak ⋅⋅⋅
stacking interactions (Fig. 2).
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The Journal of Organic Chemistry
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21
22
23
Figure 2. Molecular structure of 3c (50% ellipsoids) and its crystal structure along the crystallographic a axis
We decided also to study possibility to made additional cycle and to convert compounds 3 into totally
planar conjugated system. For this aim oxidative aromatization of compound 3a was studied (Scheme 6)14.
However, our attempts of oxidative cyclization using both FeCl3 and PIFA (bis(trifluoroacetoxy)iodo)benzene)
were unsuccessful.
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Scheme 6. Oxidative aromatization of 3a.
Ph
FeCl3(dry)
N
N
N
CH3NO2
N
N
N
PIFA
N
N
BF3*Et2O
N
N
N
N
Ph
CH2Cl2
Ph
We suggested also alternative approach to prepare 3a starting from bromo-substituted azidotriazole 2a’
(Scheme 7). To our surprise, model Sonogashira reaction resulted in the corresponding product 2a’’ having
additional triazole ring. That means that copper catalyzed azide-alkyne cycloaddition15 proceeded more quickly
in this particular case. Nevertheless, the target 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline system can be
synthesized using subsequent palladium catalyzed cyclization16.
Scheme 7. Extra method of isoquinoline derivative synthesis
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Ph
1
2
3
4
5
6
7
8
N
Ph
N
N
Br
PdCl2(PPh3)2
n-Bu4NOAc
N
N
CuI(1mol%)
N3
N
N
Br
NMP
Ar
N
N
NEt3, Ar
N
N
N
N
N
N
Ph
Ph
Ph
2a'
2a
3a
(33%)
'' (82%)
(78%)
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The structure of compound 2a’’ was established by X-ray diffraction study (Figure 3). The two triazole
rings in 2a’’ are twisted relative to each other by 45.16(13). Moreover, the three aryl substituents are also
twisted relative to the parent triazole rings by 23.83(15) (C3-C8, at the N2 atom), 50.44(9) (C17-C22, at the
C2 atom) and 24.24(12) (C11-C16, at the C9 atom). Interestingly, the two unsubstituted phenyl substituents
are turned out to be almost coplanar to each other (the corresponding interplane angle is 5.93(16)). In the
crystal of 2a’’, molecules are packed in stacks along the crystallographic b axis. The molecules within the
stacks are linked by the weak C10─H10⋅⋅⋅N6 hydrogen bonds (C⋅⋅⋅N 3.374(4) Å, H⋅⋅⋅N 2.44 Å, C─H⋅⋅⋅N
166°) (Fig. 3).
Figure 3. Molecular structure of 2a’’ (50% ellipsoids) and its crystal structure along the crystallographic b
axis
Having in hand new heterocyclic system of 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline, we started
study of their optical properties. UV-Vis absorption and fluorescence spectra were obtained for compounds 3
using CH2Cl2 as a solvent (c = 10−6 M) at room temperature (Table 1). Similar photophysical behavior was
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found for all set of compounds 3 having absorption maxima in 312–349 nm range (Fig. 4). No significant
effects of substituent R1 on absorption spectra were observed. Compounds 3a-e have absorption maxima in
338-340 nm region. Slight hypsochromic shift was observed for compound 3f having unsubstituted upper
triazole ring. More pronounced is the influence of the substituents in aryl group at N(2) of lower triazole.
1
2
3
4
5
6
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0.15
0.1
0.05
0
0.2
0.15
0.1
3a
3b
3c
3d
3e
3f
3h
3i
3j
3k
3l
3m
3n
3g
0.05
0
300
325
350
375
400
300
325
350
375
400
Wavelength, nm
Wavelength, nm
Figure 4. Absorption spectra of 3a-3n in dichloromethane at room temperature.
Bathochromic shifts were observed for compounds 3m,n containing MeO or CN group in para-position
of aryl at N(2). On the contrary, hypsochromic shifts were observed for compounds 3k, 3l, 3j and 3h containing
substituents in the ortho-position of aryl fragment at N(2) of lower triazole. The largest hypsochromic shift
was observed for 2,6-disubstituted derivative 3k having both ortho-positions occupied by methyl groups.
Table 1. Photophysical data for a series of isoquinoline derivatives 3a-n
№
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
R1
Ph
2-MeO-Ph
3-MeO-Ph
R2
H
H
H
H
H
H
4-F
λabs, nm λem, nm
lgε
ΦF
Stokes shift, nm
340
339
340
340
338
335
340
326
343
328
312
326
349
348
389
396
396
407
376
362
371
375
373
371
364
373
383
387
4.49
4.55
4.51
4.49
4.52
4.09
4.28
4.32
4.55
4.40
4.36
4.39
4.59
4.68
0.18
0.36
0.16
0.23
0.71
0.90
0.17
0.18
0.31
0.12
0.01
0.25
0.98
0.71
49
55
56
67
40
29
31
47
28
43
52
49
34
39
3,4-diMeC6H4
PhOCH2
H
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2,4-2Cl
4-Me
2,4-diMe
2,6-diMe
2-MeO
4-MeO
4-CN
*Fluorescence quantum yields are measured relative to 0.1 M H2SO4 solution of quinine (Φf=0.55)17.
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Fluorescence spectra of solutions 3a-3n were measured at an excitation wavelength corresponding to the
maximum in the absorption spectra (Fig. 5). To our delight, all new heterocycles demonstrated high quantum
yields (up to 98%). Looking at the spectra, one can immediately note almost complete quenching of
fluorescence was observed for compound 3k having two methyl-groups in the ortho-positions of aryl group at
N(2) of triazole (Table 1). Partial quenching can also be detected for sterically hindered compound 3j. These
data demonstrated importance of conjugation of aryl ring at N(2) of triazole.
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Wavelength, nm
Figure 5. Emission spectra of 3a-3n in dichloromethane at room temperature
Bulky ortho-substituents are not desirable in this position. On the other hand quantum yield of fluorescence
was reasonably high for compound 3h having chlorine in ortho-position. Most probably this difference can be
explained by longer C-Cl bond. The strong electron-donor MeO-group in aryl at N(2)-triazole especially in the
para-position gives powerful growth of emission (ΦF up to 0.980, compound 3m). The highest quantum yield
was observed also for compound 3n having a strong electron-withdrawing CN-group (ΦF up to 0.708). Possible
explanation for this behavior is the internal charge transfer from the electron-donating (electron-withdrawing)
group to the part of the molecule with a deficit (surplus) of electrons, so the most effective conjugation is
achieved. An interesting observation is the strong increase in fluorescence for compounds 3e, 3f having no aryl
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The Journal of Organic Chemistry
substituent in upper triazole ring (ΦF 0.708, 0.896 respectively). It makes perspective subsequent structural
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CONCLUSIONS
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Efficient approach to new type of heterocycles - differently substituted 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-
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c]isoquinolines 3 was elaborated. The corresponding dichlorodiazenes containing phenylacetylene fragment 1
acted as building blocks for their synthesis. Subsequent reaction with sodium azide gives the corresponding
1,2,3-triazoles 2 having in the structure both azido group and acetylene fragment. The final stage was thermal
cyclization of the last products which leads to unique heterocyclic compounds having in the structure two
triazole rings. Target compounds 3 were prepared in high yield. These products revealed excellent
photophysical properties and quantum yields of fluorescence.
EXPERIMENTAL SECTION
Materials and methods. All fine chemicals had a reagent purity and were used directly without purification
unless otherwise noted. 1H and 13C{1H} nuclear magnetic resonance (NMR) spectra were acquired at various
1
field strengths as indicated, and were referenced to chloroform-d (7.25 and 77.00 ppm for H and 13C,
1
respectively). H NMR coupling constants are reported in Hertz. HRMS spectra were recorded at MicroTof
Bruker Daltonics and Orbitrap Elite instrument. All IR spectra were obtained on a Nicolet iS5 (Thermo
Scientific) One FT-IR spectrometer using consoles of internal reflection iS3 with ATR element from ZnSe, dip
angle 45 °C. All UV data was obtained on a UV-Visible spectrophotometer Varian Cary 60 within 250-800
nm spectral range. The UV spectra were registered in cuvettes with an optical path length of 1 cm at room
temperature using dichloromethane as a solvent. Emission spectra were recorded with Hitachi F2700
spectrofluorometer in 1cm quartz cells. Analytical TLC: aluminium-backed plates precoated (0.25 mm) with
Merck silica sel 60 F254 and Macherey-Nagel (0.20 mm) ALUGRAM®Xtra SIL G/UV254. Macherey-Nagel
silica gel 60 (70-230 mesh) was used for flash and column chromatography. All mixed solvent eluents are
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reported as v/v solutions. Solvents were purified by standard methods. DMSO was distilled over CaH2.
Tetrachloromethane was distilled over P2O5.
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Single crystals of compounds 3c and 2a’’ were prepared using methanol as a solvent by slow evaporation
method. X-ray diffraction data for 3c and 2a’’ were collected on a three-circle Bruker D8 QUEST PHOTON-
III CCD diffractometer ((MoK)-radiation, T = 100 K, graphite monochromator,  and  scan mode) and
corrected for absorption using the SADABS program18a. The data were indexed and integrated using the
SAINT program.18b For details, see ESI. The structures were solved by direct methods and refined by full-
matrix least squares technique on F2 with anisotropic displacement parameters for non-hydrogen atoms. The
hydrogen atoms were placed in calculated positions and refined within riding model with fixed isotropic
displacement parameters [Uiso(H) = 1.5Ueq(C) for the CH3-groups and 1.2Ueq(C) for the other groups]. The
absolute structure of 1 was objectively determined by the refinement of Flack parameter which has been equal
to 0.007(8). All calculations were carried out using the SHELXTL18c program suite. Crystallographic data for
3c and 2a’’ have been deposited with the Cambridge Crystallographic Data Center, CCDC 1973844 and CCDC
1973845, respectively. Copies of this information may be obtained free of charge from the Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK(Fax: +44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk or
www.ccdc.cam.ac.uk). Crystal structure determination was performed in the Department of Structural Studies
of Zelinsky Institute of Organic Chemistry, Moscow, Russia.
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Synthesis and characterization. General procedure for preparation of dichlorodiazabutadienes 1.
Dichlorodiazabutadienes containing phenylacetylene were synthesized based on previous work8. The
corresponding 2-(phenylethynyl)benzaldehyde (1.5 mmol) and phenyl hydrazine (1.5 mmol) were stirring in
DMSO (5 ml) for 2 hours. Further tetramethylethylenediamine (TMEDA) (3.75 mmol, 2.5 eq.), CuCl (0.015
mmol, 0.01 eq.) and carbon tetrachloride (15 mmol, 10 eq.) were put into the reaction mixture during 5 min
under cooling with water bath. After TLC analysis revealed complete removal of intermediate product
(hydrazone), the reaction mixture was transferred to water (200 mL), and extracted with CH2Cl2 (3 x 20 mL).
The collected organic phase was washed with water (3 x 50 mL), brine (1 x 30 mL) and dried over anhydrous
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The Journal of Organic Chemistry
sodium sulfate. Volatiles were removed in vacuo of the rotary evaporator, the residue was purified by column
chromatography on silica gel using a mixture of n-hexane and CH2Cl2 (3/1).
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(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-phenyldiazene (1a): Yield 558 mg (74 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1): 1576, 1598,
2218. 1H NMR (400 MHz, CDCl3): δ 7.23-7.26 (m, 1H), 7.32-7.34 (m, 3H), 7.42-7.49 (m, 7H), 7.67-7.71 (m,
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1H), 7.83-7.87 (m, 2H). С{1H} NMR (100 MHz, CDСl3): δ 87.5, 92.7, 122.9, 123.2, 123.6, 128.0, 128.2,
128.3, 128.7, 128.9, 130.1, 131.4, 131.5, 131.7, 136.2, 136.3, 151.6, 153.0. HRMS (ESI) m/z: [M+H]+ Calcd.
for C22H15Cl2N2 377.0607; Found 377.0615.
(E)-1-(2,2-Dichloro-1-(2-((2-methoxyphenyl)ethynyl)phenyl)vinyl)-2-phenyldiazene (1b): Yield 651 mg
(80 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
1575, 1595, 2217. 1H NMR (400 MHz, CDCl3): δ 3.82 (s, 3H), 6.83 (d, 1H, J=8.3 Hz), 6.89 (td, 1H, J=7.5, 0.9
Hz), 7.20-7.22 (m, 1H), 7.25-7.29 (m, 1H), 7.39 (dd, 1H, J=7.6, 1.7 Hz), 7.41-7.46 (m, 5H), 7.69-7.71 (m, 1H),
7.80-7.83 (m, 2H). С{1H} NMR (100 MHz, CDСl3): δ 55.5, 89.0, 91.3, 110.5, 112.2, 120.2, 123.1, 124.0,
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127.8, 128.6, 128.8, 129.7, 129.9, 131.2, 131.7, 133.3, 136.0, 136.4, 151.6, 152.9, 160.0. HRMS (ESI) m/z:
[M+H]+ Calcd. for C23H17Cl2N2O 407.0712; Found 407.0705.
(E)-1-(2,2-Dichloro-1-(2-((3-methoxyphenyl)ethynyl)phenyl)vinyl)-2-phenyldiazene (1c): Yield 360 mg
(59 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange-red oil. IR (ν, cm-
1): 1575, 1598, 2249. 1H NMR (400 MHz, CDCl3): δ 3.77 (s, 3H), 6.88-6.91 (m, 1H), 6.95-6.96 (m, 1H), 7.05
(dt, 1H, J=7.6, 1.1 Hz), 7.22-7.26 (m, 2H), 7.43-7.48 (m, 5H), 7.67-7.71 (m, 1H), 7.83-7.88 (m, 2H). 13С{1H}
NMR (100 MHz, CDСl3): δ 55.1, 87.3, 92.6, 115.1, 116.0, 123.1, 123.5, 123.9, 124.0, 128.0, 128.7, 128.9,
129.3, 130.1, 131.4, 131.7, 136.2, 136.4, 151.6, 152.9, 159.1. HRMS (ESI) m/z: [M+H]+ Calcd. for
C23H17Cl2N2O 407.0712; Found 407.0717.
(E)-1-(2,2-Dichloro-1-(2-((3,4-dimethylphenyl)ethynyl)phenyl)vinyl)-2-phenyldiazene (1d): Yield 288 mg
(71 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
1577, 1598, 2209. 1H NMR (400 MHz, CDCl3): δ 2.21 (s, 3H), 2.25 (s, 3H), 7.06 (d, 1H, J=7.7 Hz), 7.14-7.16
(m, 2H), 7.20-7.22 (m, 1H), 7.40-7.45 (m, 5H), 7.62-7.65 (m, 1H), 7.80-7.82 (m, 2H). С{1H} NMR (100
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MHz, CDСl3): δ 19.5, 19.7, 86.6, 93.1, 120.2, 123.2, 123.9, 127.7, 128.7, 128.9, 128.9, 129.5, 130.0, 131.3,
131.6, 132.6, 136.0, 136.3, 136.5, 137.3, 151.7, 153.0. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19Cl2N2
405.0920; Found 405.0926.
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(E)-1-(2,2-Dichloro-1-(2-(3-phenoxyprop-1-yn-1-yl)phenyl)vinyl)-2-phenyldiazene (1e): Yield 440 mg
(54 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
1587, 1598, 2237. 1H NMR (400 MHz, CDCl3): δ 4.79 (s, 2H), 6.91-6.95 (m, 3H), 7.14-7.16 (m, 1H), 7.21-
7.26 (m, 2H), 7.36-7.41 (m, 2H), 7.43-7.46 (m, 3H), 7.54-7.57 (m, 1H), 7.71-7.75 (m, 2H). 13С{1H} NMR (100
MHz, CDСl3): δ 56.2, 85.0, 87.0, 114.8, 121.2, 122.7, 123.2, 128.5, 128.6, 129.3, 130.0, 131.4, 132.4, 136.3,
136.4, 151.3, 152.9, 157.5. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17Cl2N2O 407.0712; Found 407.0708.
(E)-1-(2,2-Dichloro-1-(2-((trimethylsilyl)ethynyl)phenyl)vinyl)-2-phenyldiazene (1f): Yield 264 mg (71
%), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange-red oil. IR (ν, cm-1):
1599, 1578, 2159. 1H NMR (400 MHz, CDCl3): δ 0.15 (s, 9H), 7.18-7.20 (m, 1H), 7.36-7.41 (m, 2H), 7.45-
7.47 (m, 3H), 7.57-7.59 (m, 1H), 7.79-7.82 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3): δ (-0.3), 98.1, 103.1,
123.1, 123.5, 128.2, 128.6, 128.9, 129.9, 131.3, 131.7, 136.3, 136.9, 151.5, 152.9. HRMS (ESI) m/z: [M+H]+
Calcd. for C19H19Cl2N2Si 373.0689; Found 373.0683.
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(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(4-fluorophenyl)diazene (1g): Yield 415 mg (70
%), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1): 1578,
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1592, 2217. H NMR (400 MHz, CDCl3): δ 7.11-7.17 (m, 2H), 7.21-7.25 (m, 1H), 7.31-7.34 (m, 3H), 7.41-
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7.48 (m, 4H), 7.66-7.71 (m, 1H), 7.82-7.87 (m, 2H). С{1H} NMR (100 MHz, CDСl3) (some signals are
duplicated due to the phenomenon of atropisomerism): δ 87.4, 92.7, 115.8, 116.0, 122.9, 123.6, 125.2, 125.3,
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128.0, 128.2, 128.3, 128.8, 130.0, 131.5, 131.7, 136.1, 136.3, 149.5, 149.5, 151.5, 163.3, 165.8. F (376.3
MHz, CDCl3): -109.6. HRMS (ESI) m/z: [M+H]+ Calcd. for C22H14Cl2FN2 395.0513; Found 395.0502.
(E)-1-(2,2-dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(2,4-dichlorophenyl)diazene (1h): Yield 382 mg
(57 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
1561, 1575, 1597, 2218. 1H NMR (400 MHz, CDCl3): δ 7.21-7.28 (m, 2H), 7.31-7.33 (m, 3H), 7.40-7.46 (m,
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5H), 7.61-7.66 (m, 2H). С{1H} NMR (100 MHz, CDСl3): δ 87.4, 92.7, 118.4, 123.0, 123.5, 127.6, 128.0,
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128.3, 128.3, 128.9, 130.0, 130.4, 131.5, 131.7, 135.6, 136.6, 137.5, 138.2, 147.6, 152.3. HRMS (ESI) m/z:
[M+H]+ Calcd. for C22H13Cl4N2 446.9798; Found 446.9793.
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(E)-1-(2,2-dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(p-tolyl)diazene (1i): Yield 434 mg (74 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1): 1574, 1582,
1600, 2217. 1H NMR (400 MHz, CDCl3): δ 2.41 (s, 3H), 7.21-7.26 (m, 3H), 7.30-7.33 (m, 3H), 7.41-7.46 (m,
4H), 7.65-7.69 (m, 1H), 7.74 (d, 2H, J=8.3 Hz). 13С{1H} NMR (100 MHz, CDСl3): δ 21.5, 87.5, 92.6, 123.0,
123.2, 123.6, 128.0, 128.2, 128.2, 128.6, 129.6, 130.1, 131.5, 131.7, 135.4, 136.4, 142.1, 151.1, 151.5. HRMS
(ESI) m/z: [M+H]+ Calcd. for C23H17Cl2N2 391.0763; Found 391.0757.
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(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(2,4-dimethylphenyl)diazene (1j): Yield 468 mg
(77 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange-red oil. IR (ν, cm-
1): 1575, 1599, 2217. 1H NMR (400 MHz, CDCl3): δ 2.31 (s, 3H), 2.37 (s, 3H), 7.07-7.08 (m, 2H), 7.23-7.26
(m, 1H), 7.32-7.35 (m, 3H), 7.42-7.48 (m, 4H), 7.66-7.71 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3): δ 16.9,
21.4, 87.6, 92.4, 115.2, 123.0, 123.5, 127.1, 127.8, 128.2, 128.2, 128.5, 129.9, 131.5, 131.5, 131.7, 134.5,
136.8, 139.1, 142.0, 148.9, 152.1. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19Cl2N2 405.0920; Found
405.0911.
(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(2,6-dimethylphenyl)diazene (1k): Yield 413 mg
(68 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
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1582, 1598, 2217. H NMR (400 MHz, CDCl3): δ 2.25 (s, 6H), 7.05 (d, 2H, J=7.7 Hz), 7.10 -7.14 (m, 1H),
7.20-7.23 (m, 1H), 7.31-7.33 (m, 3H), 7.41-7.44 (m, 4H), 7.62-7.67 (m, 1H). 13С{1H} NMR (100 MHz,
CDСl3): δ 19.3, 87.4, 92.5, 123.0, 123.6, 128.0, 128.3, 128.3, 128.7, 129.1, 129.7, 131.6, 131.7, 132.0, 136.1,
136.6, 150.6, 152.3. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19Cl2N2 405.0920; Found 405.0912.
(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(2-methoxyphenyl)diazene (1l): Yield 391 mg
(64 %), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1):
1574, 1592, 2216. 1H NMR (400 MHz, CDCl3): δ 3.71 (s, 3H), 6.97 (t, 2H, J=7.8 Hz), 7.23-7.25 (m, 1H), 7.30-
7.31 (m, 3H), 7.34-7.38 (m, 1H), 7.40-7.42 (m, 4H), 7.61-7.63 (m, 1H), 7.65 (d, 1H, J=8.0 Hz). 13С{1H} NMR
(100 MHz, CDСl3): δ 57.6, 87.6, 92.6, 114.9, 117.2, 120.9, 123.1, 123.5, 128.0, 128.2, 128.3, 128.6, 130.1,
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131.5, 131.7, 132.8, 135.5, 136.4, 143.1, 152.0, 157.5. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17Cl2N2O
407.0712; Found 407.0707.
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(E)-1-(2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)-2-(4-methoxyphenyl)diazene (1m): Yield 385 mg
(63 %), reaction was carried out at 700C on a heating mantle, purified by column chromatography on silica gel
(n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1): 1592, 1600, 2215. 1H NMR (400 MHz, CDCl3): δ 3.85 (s,
3H), 6.92 (d, 2H, J=9.0 Hz), 7.18-7.20 (m, 1H), 7.28-7.29 (m, 3H), 7.37-7.42 (m, 4H), 7.62-7.64 (m, 1H), 7.78
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(d, 2H, J=9.0 Hz). С{1H} NMR (100 MHz, CDСl3): δ 55.5, 87.6, 92.5, 114.1, 123.0, 123.6, 125.2, 127.9,
128.2, 128.2, 128.6, 130.1, 131.6, 131.7, 134.2, 134.6, 136.6, 147.4, 151.4, 162.4. HRMS (ESI) m/z: [M+H]+
Calcd. for C23H17Cl2N2O 407.0712; Found 407.0524.
(E)-4-((2,2-Dichloro-1-(2-(phenylethynyl)phenyl)vinyl)diazenyl)benzonitrile (1n): Yield 187 mg (31 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), orange oil. IR (ν, cm-1): 1576, 1598,
2227. 1H NMR (400 MHz, CDCl3): δ 7.18-7.20 (m, 1H), 7.29-7.36 (m, 5H), 7.40-7.47 (m, 2H), 7.63-7.65 (m,
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1H), 7.70-7.73 (m, 2H), 7.82-7.85 (m, 2H). С{1H} NMR (100 MHz, CDСl3): δ 87.2, 92.9, 114.2, 118.4,
122.7, 123.6, 128.1, 128.3, 128.5, 129.1, 130.0, 131.5, 131.9, 133.0, 135.4, 139.7, 152.1, 154.8. HRMS (ESI)
m/z: [M+H]+ Calcd. for C23H14Cl2N3 402.0559; Found 402.0547.
General procedure for preparation of 4-azido-1,2,3-triazoles 2. 4-Azido-2,5-diaryl-1,2,3-triazoles bearing
phenylacetylene were obtained according to the procedure described11. To sodium azide (5 eq.) in DMSO (10
mL) corresponding dichlorodiazene (1 mmol, 1 eq.) was added dropwise over 15 min and stirred at room
temperature for 2 h. The resulting mixture was transferred to water (100 mL) and extracted with DCM (3 x 20
mL). The combined extract was washed with water (3 x 50 mL), brine (1 x 30 ml) and dried over sodium
sulfate. Volatiles were removed in vacuum of the rotary evaporator, the residue was purified by column
chromatography on silica gel using a mixture of n-hexane and CH2Cl2 (3/1).
4-Azido-2-phenyl-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2a): Yield 250 mg (69 %), purified by
column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellowish oil. IR (ν, cm-1): 2132, 2217. 1H NMR
(400 MHz, CDCl3): δ 7.28-7.38 (m, 4H), 7.41-7.51 (m, 6H), 7.65-7.75 (m, 2H), 8.08-8.13 (m, 2H). 13С{1H}
NMR (100 MHz, CDСl3)(some signals are duplicated due to the phenomenon of atropisomerism): δ 88.3, 93.3,
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118.2, 118.5, 122.6, 123.2, 127.4, 127.8, 128.3, 128.3, 128.3, 128.9, 129.3, 129.3, 129.7, 130.1, 130.2, 131.6,
133.1, 137.7, 139.4, 144.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C22H15N6 363.1353; Found 363.1345.
4-Azido-5-(2-((2-methoxyphenyl)ethynyl)phenyl)-2-phenyl-2H-1,2,3-triazole (2b): Yield 439 mg (70 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2133, 2216.
1H NMR (400 MHz, CDCl3): δ 3.76 (s, 3H), 6.84-6.92 (m, 2H), 7.29-7.32 (m, 2H), 7.43-7.49 (m, 5H), 7.63-
7.66 (m, 1H), 7.73-7.75 (m, 1H), 8.12 (d, 2H, J=8.2 Hz). 13С{1H} NMR (100 MHz, CDСl3)(some signals are
duplicated due to the atropisomerism): δ 55.5, 89.9, 92.0, 110.4, 110.6, 112.2, 118.1, 118.4, 120.3, 120.4,
123.2, 127.2, 128.1, 128.9, 129.2, 129.2, 129.2, 129.7, 129.8, 130.2, 130.5, 132.9, 133.5, 134.3, 138.0, 139.4,
144.4, 160.0. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found 393.1457.
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4-Azido-5-(2-((3-methoxyphenyl)ethynyl)phenyl)-2-phenyl-2H-1,2,3-triazole (2c): Yield 285 mg (82 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2134, 2247.
1H NMR (400 MHz, CDCl3): δ 3.71 (s, 3H), 6.88-6.91 (m, 1H), 6.97 (m, 1H), 7.08 (dt, 1H, J=7.6, 1.1 Hz),
7.23 (t, 1H, J=8.0 Hz), 7.34-7.37 (m, 1H), 7.42-7.50 (m, 4H), 7.67-7.75 (m, 2H), 8.11-8.13 (m, 2H). 13С{1H}
NMR (100 MHz, CDСl3): δ 55.0, 88.1, 93.2, 115.3, 115.9, 118.2, 122.4, 124.1, 124.1, 127.3, 128.3, 128.8,
129.2, 129.3, 129.6, 130.2, 133.1, 137.7, 139.4, 144.2, 159.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O
393.1458; Found 393.1453.
4-Azido-5-(2-((3,4-dimethylphenyl)ethynyl)phenyl)-2-phenyl-2H-1,2,3-triazole (2d):Yield 217 mg (78
%), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2136,
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2198. H NMR (400 MHz, CDCl3): δ 2.18 (s, 3H), 2.27 (s, 3H), 7.08 (d, 1H, J=7.6 Hz), 7.21-7.23 (m, 2H),
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7.37 (t, 1H, J=7.3 Hz), 7.41-7.51 (m, 4H), 7.66-7.72 (m, 2H), 8.13 (d, 2H, J=8.1 Hz). С{1H} NMR (100
MHz, CDСl3): δ 19.5, 19.7, 87.4, 93.7, 118.2, 120.4, 122.8, 127.3, 128.0, 128.8, 129.0, 129.2, 129.6, 129.6,
130.0, 132.7, 133.0, 136.6, 137.3, 137.8, 139.4, 144.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19N6
391.1666; Found 391.1655.
4-Azido-5-(2-(3-phenoxyprop-1-yn-1-yl)phenyl)-2-phenyl-2H-1,2,3-triazole (2e): Yield 305 mg (72 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellowish oil. IR (ν, cm-1): 2134,
2230. 1H NMR (400 MHz, CDCl3): δ 4.92 (s, 2H), 6.93-7.00 (m, 3H), 7.23-7.27 (m, 2H), 7.35-7.52 (m, 5H),
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7.62-7.65 (m, 2H), 8.11 (d, 2H, J=8.2 Hz). 13С{1H} NMR (100 MHz, CDСl3): δ 56.4, 85.7, 87.8, 114.6, 118.0,
121.2, 121.6, 127.3, 128.6, 128.7, 129.2, 129.3, 129.6, 130.5, 133.3, 137.3, 139.3, 144.0, 157.6. HRMS (ESI)
m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found 393.1454.
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4-Azido-2-phenyl-5-(2-((trimethylsilyl)ethynyl)phenyl)-2H-1,2,3-triazole (2f): Yield 102 mg (57 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2132, 2159.
1H NMR (400 MHz, CDCl3): δ 0.15 (s, 9H), 7.39 (t, 1H, J=7.4 Hz), 7.43-7.46 (m, 2H), 7.49-7.53 (m, 2H),
7.47-7.60 (m, 1H), 7.64-7.67 (m, 1H). 13С{1H} NMR (100 MHz, CDСl3): δ (-0.3), 98.9, 103.0, 118.5, 123.2,
127.8, 128.5, 129.1, 129.3, 129.9, 130.6, 133.3, 137.3, 139.4, 144.7. HRMS (ESI) m/z: [M+H]+ Calcd. for
C19H19N6Si 359.1435; Found 359.1436.
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4-Azido-2-(4-fluorophenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2g): Yield 283 mg (71 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellowish oil. IR (ν, cm-1): 2133,
2217. 1H NMR (400 MHz, CDCl3): δ 7.13-7.20 (m, 2H), 7.30-7.36 (m, 3H), 7.42-7.49 (m, 4H), 7.65-7.74 (m,
2H), 8.04-8.09 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3) (some signals are duplicated due to the phenomenon
of atropisomerism): δ 88.3, 93.3, 116.0, 116.2, 119.9, 120.0, 122.5, 123.1, 128.3, 128.4, 128.9, 129.6, 130.0,
131.5, 133.1, 135.7, 137.7, 144.3, 160.4, 162.9. 19F (376.3 MHz, CDCl3): -114.5. HRMS (ESI) m/z: [M+H]+
Calcd. for C22H14FN6 381.1258; Found 381.1252.
4-Azido-2-(2,4-dichlorophenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2h): Yield 217 mg (59
%), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellowish solid, m.p. 950C. IR
(ν, cm-1): 2128, 2214. 1H NMR (400 MHz, CDCl3): δ 7.30-7.37 (m, 4H), 7.43-7.47 (m, 4H), 7.59 (d, 1H, J=2.2
13
Hz), 7.63-7.68 (m, 2H), 7.69-7.74 (m, 1H). С{1H} NMR (100 MHz, CDСl3): δ 88.0, 93.3, 122.8, 123.0,
127.6, 127.9, 128.3, 128.4, 129.1, 129.6, 129.8, 129.8, 130.9, 131.4, 133.0, 135.2, 136.2, 138.4, 144.7. HRMS
(ESI) m/z: [M+H]+ Calcd. for C22H13N6Cl2 431.0573; Found 431.0560.
4-Azido-5-(2-(phenylethynyl)phenyl)-2-(p-tolyl)-2H-1,2,3-triazole (2i): Yield 279 mg (74 %), purified by
column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2133, 2218. 1H NMR
(400 MHz, CDCl3): δ 2.42 (s, 3H), 7.28 (d, 2H, J=8.1 Hz), 7.30-7.35 (m, 4H), 7.41-7.51 (m, 4H), 7.67-7.76
(m, 2H), 7.99-8.03 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3) (some signals are duplicated due to the
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phenomenon of atropisomerism): δ 21.0, 88.0, 88.3, 93.2, 118.1, 118.3, 122.5, 123.2, 128.2, 128.2, 128.3,
128.3, 128.3, 128.7, 129.2, 129.7, 129.7, 129.8, 130.0, 130.2, 131.5, 132.9, 133.1, 136.8, 137.2, 137.3, 137.3,
137.8, 143.8. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6 377.1509; Found 377.1505.
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4-Azido-2-(2,4-dimethylphenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2j): Yield 343 mg (88 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2132, 2218.
1H NMR (400 MHz, CDCl3): δ 2.40-2.43 (m, 6H), 7.10 (d, 1H, J=8.0 Hz), 7.14 (s, 1H), 7.27-7.32 (m, 3H),
7.41-7.50 (m, 4H), 7.53 (t, 1H, J=8.6 Hz), 7.62-7.73 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3) (some signals
are duplicated due to the phenomenon of atropisomerism): δ 18.8, 19.1, 21.1, 21.1, 88.0, 88.3, 93.1, 122.7,
123.1, 123.2, 123.4, 124.7, 124.9, 127.2, 127.2, 128.2, 128.3, 128.3, 128.3, 128.8, 129.1, 129.8, 130.1, 130.4,
130.5, 131.5, 131.5, 132.1, 132.2, 132.3, 132.8, 133.0, 136.3, 137.0, 137.1, 138.7, 139.1, 143.5, 144.1. HRMS
(ESI) m/z: [M+H]+ Calcd. for C24H19N6 391.1666; Found 391.1658.
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4-Azido-2-(2,6-dimethylphenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2k): Yield 302 mg (79
%), purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2133,
2220. 1H NMR (400 MHz, CDCl3): δ 2.10-2.12 (m, 6H), 7.15-7.18 (m, 2H), 7.28-7.35 (m, 4H), 7.38-7.51 (m,
4H), 7.64-7.76 (m, 2H). 13С{1H} NMR (100 MHz, CDСl3) (some signals are duplicated due to the phenomenon
of atropisomerism): δ 17.4, 87.9, 88.2, 93.0, 122.8, 123.0, 123.2, 123.5, 128.2, 128.2, 128.2, 128.2, 128.2,
128.3, 128.3, 128.3, 128.8, 129.1, 129.8, 129.9, 130.0, 130.1, 130.4, 130.4, 131.4, 131.4, 132.8, 133.0, 135.9,
136.0, 137.0, 139.1, 143.5, 144.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19N6 391.1666; Found 391.1661.
4-Azido-2-(2-methoxyphenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2l): Yield 279 mg (74 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2132, 2217.
1H NMR (400 MHz, CDCl3): δ 3.83 (s, 3H), 7.03-7.10 (m, 2H), 7.28-7.34 (m, 3H), 7.40-7.49 (m, 5H), 7.58-
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7.61 (m, 1H), 7.63-7.73 (m, 2H). С{1H} NMR (100 MHz, CDСl3) (some signals are duplicated due to the
phenomenon of atropisomerism): δ 56.1, 88.3, 93.1, 112.6, 112.7, 120.5, 120.5, 122.8, 123.1, 123.2, 123.4,
127.0, 127.1, 128.2, 128.2, 128.8, 129.1, 129.4, 129.9, 130.1, 130.5, 130.6, 130.8, 131.5, 131.5, 132.6, 132.7,
137.5, 143.8, 153.6. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found 393.1454.
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4-Azido-2-(4-Methoxyphenyl)-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazole (2m): Yield 204 mg (55 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2131, 2217.
1H NMR (400 MHz, CDCl3): δ 3.86 (s, 3H), 6.96-7.02 (m, 2H), 7.28-7.35 (m, 3H), 7.41-7.50 (m, 4H), 7.64-
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phenomenon of atropisomerism): δ 55.5, 88.0, 88.4, 93.2, 93.2, 114.2, 114.3, 119.7, 119.9, 122.4, 123.0, 123.2,
128.2, 128.3, 128.3, 128.3, 128.7, 129.1, 129.6, 130.0, 130.3, 130.3, 131.5, 132.9, 133.1, 133.1, 133.2, 136.6,
137.1, 143.6, 144.2, 158.9, 159.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found
393.1450.
4-(4-Azido-5-(2-(phenylethynyl)phenyl)-2H-1,2,3-triazol-2-yl)benzonitrile (2n): Yield 130 mg (72 %),
purified by column chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellow oil. IR (ν, cm-1): 2132, 2230.
1H NMR (400 MHz, CDCl3): δ 7.30-7.37 (m, 3H), 7.42-7.48 (m, 4H), 7.65-7.75 (m, 4H), 8.16-8.19 (m, 2H).
13С{1H} NMR (100 MHz, CDСl3): δ 88.1, 93.5, 110.5, 118.3, 118.4, 122.5, 123.0, 128.3, 128.3, 128.5, 129.3,
129.3, 129.5, 131.4, 133.3, 133.4, 139.2, 141.8, 145.7. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H14N7
388.1305; Found 388.1297.
General procedure for preparation of 2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinolines 3. Method A:
The corresponding 1,2,3-triazole 2 (1 mmol) was refluxed for 6 h in 3 ml of toluene. Next, the mixture was
cooled to room temperature and left to stand overnight. The precipitate was filtered and dried. Method B16: To
a solution of compound 2a’’ (0.26 mmol) in NMP (5 mL) at room temperature under argon PdCl2(PPh3)2 (0.01
mmol) and n-Bu4NOAc (0.73 mmol) were successively added. The resulting mixture was stirred at 1000C on
a heating mantle for 10 h, then was quenched with a saturated aqueous solution of NH4Cl (20 ml) and extracted
with ethyl acetate (3 x 25 mL). The organic extracts were washed with an aqueous solution of NaCl (3 x 40
ml), dried over Na2SO4 and concentrated under vacuo. Purification by column chromatography was held with
n-hexane/EtOAc (3/2).
2,7-Diphenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3a): Yield 298 mg (82 %, by A), 73 mg
(78 %, by B), purified by column chromatography on silica gel (n-hexane/EtOAc= 3/2), white solid, m.p.
2500C. IR (ν, cm-1): no signals of triple bond and azido group. 1H NMR (400 MHz, CDCl3): δ 7.46-7.52 (m,
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2H), 7.57-7.63 (m, 5H), 7.67-7.71 (m, 1H), 7.76-7.80 (m, 2H), 8.17 (d, 1H, J=8.2 Hz), 8.38-8.40 (m, 2H), 8.48
(dd, 1H, J=7.9, 0.6 Hz). 13С{1H} NMR (100 MHz, CDСl3): δ 119.5, 122.5, 123.2, 123.7, 124.7, 128.7, 128.8,
128.9, 129.2, 129.5, 129.8, 129.8, 131.4, 134.8, 139.6, 143.3. HRMS (ESI) m/z: [M+H]+ Calcd. for C22H15N6
363.1353; Found 363.1355.
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For the remaining compounds, the synthesis was carried out according to method A.
7-(2-Methoxyphenyl)-2-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3b): Yield 360 mg (82
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%), yellow solid, m.p. 2490C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 3.72 (s, 3H), 7.12 (d, 1H, J=8.3 Hz), 7.19 (td, 1H, J=7.5, 0.7 Hz), 7.44-7.49 (m, 2H), 7.54-7.60 (m,
3H), 7.65-7.68 (m, 2H), 7.76 (d, 1H, J=8.1 Hz), 8.37-8.39 (m, 2H), 8.46 (d, 1H, J=7.5 Hz). 13С{1H} NMR (100
MHz, CDСl3): δ 55.4, 111.1, 119.5, 120.3, 121.1, 122.4, 123.2, 123.6, 125.4, 128.6, 129.0, 129.5, 129.5, 130.0,
131.0, 132.7, 134.9, 139.5, 139.7, 139.8, 157.6. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458;
Found 393.1454.
7-(3-Methoxyphenyl)-2-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3c): Yield 214 mg (75
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%), yellow solid, m.p. 2050C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 3.90 (s, 3H), 7.08-7.11 (m, 1H), 7.31-7.35 (m, 2H), 7.42-7.51 (m, 3H), 7.55 (t, 2H, J=7.8 Hz), 7.62
(t, 1H, J=7.6 Hz), 8.15 (d, 1H, J=8.2 Hz), 8.32 (d, 2H, J=8.4 Hz), 8.37 (d, 1H, J=8.0 Hz). 13С{1H} NMR (100
MHz, CDСl3): δ 55.4, 114.9, 115.3, 119.4, 122.1, 122.3, 123.0, 123.5, 124.7, 128.6, 128.7, 129.1, 129.5, 129.8,
129.9, 132.5, 134.6, 139.5, 143.0, 159.9. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found
393.1457.
7-(3,4-Dimethylphenyl)-2-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3d): Yield 169 mg
(78 %), white solid, m.p. 2560C. IR (ν, cm-1): no signals of triple bond and azido group. 1H NMR (400 MHz,
CDCl3): δ 2.39 (s, 3H), 2.41 (s, 3H), 7.33 (d, 1H, J=7.7 Hz), 7.43-7.49 (m, 3H), 7.54-7.58 (m, 3H), 7.61-7.66
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(m, 1H), 8.19 (d, 1H, J=8.2 Hz), 8.34 (d, 2H, J=8.4 Hz), 8.40 (d, 1H, J=7.9 Hz). С{1H} NMR (100 MHz,
CDСl3): δ 19.8, 19.8, 119.4, 122.3, 123.3, 123.5, 124.7, 127.0, 128.6, 128.6, 128.7, 129.1, 129.5, 129.6, 130.0,
130.9, 134.7, 137.3, 137.8, 139.6, 139.6, 143.4. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19N6 391.1666;
Found 391.1657.
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7-(Phenoxymethyl)-2-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3e): Yield 234 mg (77
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Hz), 7.59 (t, 2H, J=7.8 Hz), 7.75 (q, 2H, J=7.6 Hz), 8.37 (d, 2H, J=8.2 Hz), 8.46 (d, 1H, J=7.8 Hz), 8.51 (d,
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1H, J=7.6 Hz). С{1H} NMR (100 MHz, CDСl3): δ 62.3, 115.1, 119.5, 121.6, 122.7, 122.8, 123.6, 126.5,
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128.8, 129.6, 129.6, 129.9, 130.1, 131.9, 134.8, 138.3, 139.6, 157.9. HRMS (ESI) m/z: [M+H]+ Calcd. for
C23H17N6O 393.1458; Found 393.1455.
To TMS-containing compound (0,31 mmol) in THF (2 ml) TBAF (1 eq.) was added. After completion of
the reaction (about 2 h) the reaction mixture was concentrated under vacuo. The residue was purified by flash-
chromatography using mixture of n-hexane and EtOAc (6/1) as eluent.
2-Phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3f): Yield 64 mg (78 %), purified by column
chromatography on silica gel (n-hexane/EtOAc= 6/1),white solid, m.p. 830C. IR (ν, cm-1): no signals of triple
bond and azido group. 1H NMR (400 MHz, CDCl3): δ 7.57 (tt, 1H, J=7.4, 1.3 Hz), 7.68-7.73 (m, 2H), 7.83-
7.88 (m, 2H), 8.27-8.30 (m, 2H), 8.43-8.46 (m, 1H), 8.49-8.53 (m, 1H), 8.97 (s, 1H). 13С{1H} NMR (100 MHz,
CDСl3): δ 119.5, 122.3, 122.5, 123.7, 125.2, 128.1, 128.1, 128.7, 129.5, 129.6, 129.6, 130.1, 134.7, 139.6.
HRMS (ESI) m/z: [M+H]+ Calcd. for C16H11N6 287.1040; Found 287.1041.
For the remaining compounds, the synthesis was carried out according to method A (continuation).
2-(4-Fluorophenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3g): Yield 241 mg (85
1
%), yellow solid, m.p. 2550C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 7.26-7.30 (m, 2H), 7.48-7.52 (m, 1H), 7.55-7.63 (m, 3H), 7.67-7.71 (m, 1H), 7.77-7.79 (m, 2H),
8.17 (d, 1H, J=8.1 Hz), 8.35-8.38 (m, 2H), 8.46 (d, 1H, J=8.0 Hz). 13С{1H} NMR (100 MHz, CDСl3) (some
signals are duplicated due to the phenomenon of atropisomerism): δ 116.4, 116.6, 121.3, 121.4, 122.4, 123.3,
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123.7, 124.7, 128.9, 129.0, 129.3, 129.3, 129.8, 129.9, 131.3, 134.9, 135.9, 135.9, 139.7, 143.3. F (376.3
MHz, CDCl3): -113.4. HRMS (ESI) m/z: [M+H]+ Calcd. for C22H14FN6 381.1258; Found 381.1250.
2-(2,4-Dichlorophenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3h): Yield 165 mg
(76 %), white solid, m.p. 2730C. IR (ν, cm-1): no signals of triple bond and azido group. 1H NMR (400 MHz,
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CDCl3): δ 7.49-7.55 (m, 2H), 7.57-7.63 (m, 3H), 7.68-7.72 (m, 2H), 7.76-7.79 (m, 2H), 7.83 (d, 1H, J=8.6 Hz),
8.19 (d, 1H, J=8.3 Hz), 8.47 (d, 1H, J=7.8 Hz). 13С{1H} NMR (100 MHz, CDСl3): δ 122.3, 123.5, 123.9, 124.8,
128.0, 128.2, 128.7, 129.0, 129.0, 129.3, 129.6, 129.8, 130.0, 130.4, 131.1, 131.3, 135.4, 136.4, 139.9, 143.4.
HRMS (ESI) m/z: [M+H]+ Calcd. for C22H13N6Cl2 431.0573; Found 431.0560.
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7-Phenyl-2-(p-tolyl)-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3i): Yield 198 mg (71 %),
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yellowish solid, m.p. 2570C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 2.47 (s, 3H), 7.38 (d, 2H, J=8.3 Hz), 7.46-7.50 (m, 1H), 7.56-7.62 (m, 3H), 7.66-7.70 (m, 1H), 7.77-
7.80 (m, 2H), 8.16 (d, 1H, J=8.1 Hz), 8.25 (d, 2H, J=8.4 Hz), 8.46 (d, 1H, J=7.8 Hz). 13С{1H} NMR (100 MHz,
CDСl3): δ 21.2, 119.4, 122.6, 123.2, 123.6, 124.7, 128.8, 128.9, 129.1, 129.2, 129.8, 129.9, 130.1, 131.4, 134.5,
137.5, 138.9, 139.5, 143.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6 377.1509; Found 377.1500.
2-(2,4-Dimethylphenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3j): Yield 161 mg
1
(47 %), yellowish solid, m.p. 2630C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400
MHz, CDCl3): δ 2.45 (s, 3H), 2.54 (s, 3H), 7.20-7.24 (m, 2H), 7.46-7.50 (m, 1H), 7.54-7.62 (m, 3H), 7.65-7.69
(m, 1H), 7.71 (d, 1H, J=8.1 Hz), 7.79 (dd, 2H, J=7.8, 1.4 Hz), 8.17 (d, 1H, J=8.2 Hz), 8.44 (d, 1H, J=7.8 Hz).
13С{1H} NMR (100 MHz, CDСl3): δ 19.1, 21.2, 122.7, 123.1, 123.6, 124.6, 125.4, 127.4, 128.8, 128.9, 129.0,
129.2, 129.8, 129.8, 131.5, 132.5, 134.3, 137.1, 139.3, 139.7, 143.2. HRMS (ESI) m/z: [M+H]+ Calcd. for
C24H19N6 391.1666; Found 391.1665.
2-(2,6-Dimethylphenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3k): Yield 145 mg
(49 %), white solid, m.p. 2410C. IR (ν, cm-1): no signals of triple bond and azido group. 1H NMR (400 MHz,
CDCl3): δ 2.15 (s, 6H), 7.26 (d, 1H, J=7.5 Hz), 7.40 (t, 1H, J=7.6 Hz), 7.49-7.53 (m, 1H), 7.54-7.63 (m, 3H),
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7.67-7.71 (m, 1H), 7.78-7.81 (m, 2H), 8.22 (d, 1H, J=7.9 Hz), 8.46 (dd, 1H, J=7.9, 0.7 Hz). С{1H} NMR
(100 MHz, CDСl3): δ 17.5, 122.7, 123.2, 123.7, 124.6, 128.4, 128.8, 128.9, 129.1, 129.1, 129.8, 130.4, 131.5,
134.3, 134.5, 135.8, 139.3, 139.3, 143.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C24H19N6 391.1666; Found
391.1677.
2-(2-Methoxyphenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3l): Yield 206 mg (74
%), yellowish solid, m.p. 2410C. IR (ν, cm-1): no signals of triple bond and azido group. 1H NMR (400 MHz,
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CDCl3): δ 3.92 (s, 3H), 7.13-7.18 (m, 2H), 7.45-7.49 (m, 1H), 7.52-7.61 (m, 4H), 7.63-7.67 (m, 1H), 7.73 (dd,
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1H, J=7.8, 1.7 Hz), 7.76-7.79 (m, 2H), 8.16 (d, 1H, J=8.1 Hz), 8.43 (d, 1H, J=7.4 Hz). С{1H} NMR (100
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MHz, CDСl3): δ 56.2, 112.8, 120.6, 122.7, 123.1, 123.7, 124.5, 127.5, 128.7, 128.9, 129.0, 129.1, 129.4, 129.7,
129.8, 131.4, 131.5, 134.5, 139.5, 143.1, 153.8. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458;
Found 393.1464.
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2-(4-Methoxyphenyl)-7-phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinoline (3m): Yield 88 mg (43
1
%), white solid, m.p. 2680C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 3.93 (s, 3H), 7.07-7.11 (m, 2H), 7.47-7.52 (m, 1H), 7.54-7.63 (m, 3H), 7.67-7.71 (m, 1H), 7.77-7.80
(m, 2H), 8.18 (d, 1H, J=8.2 Hz), 8.29-8.33 (m, 2H), 8.48 (dd, 1H, J=7.9, 0.6 Hz). 13С{1H} NMR (100 MHz,
CDСl3): δ 55.7, 114.6, 121.0, 122.7, 123.1, 123.6, 124.7, 128.8, 128.9, 129.0, 129.8, 129.9, 131.5, 133.3, 134.4,
139.5, 143.2, 160.0. HRMS (ESI) m/z: [M+H]+ Calcd. for C23H17N6O 393.1458; Found 393.1454.
4-(7-Phenyl-2H-bis([1,2,3]triazolo)[5,1-a:4',5'-c]isoquinolin-2-yl)benzonitrile (3n): Yield 117 mg (71
1
%), white solid, m.p. 2830C. IR (ν, cm-1): no signals of triple bond and azido group. H NMR (400 MHz,
CDCl3): δ 7.53-7.64 (m, 4H), 7.73 (t, 1H, J=7.6 Hz), 7.77-7.80 (m, 2H), 7.92 (d, 2H, J=8.6 Hz), 8.19 (d, 1H,
J=8.2 Hz), 8.50 (d, 1H, J=7.8 Hz), 8.54 (d, 2H, J=8.6 Hz). 13С{1H} NMR (100 MHz, CDСl3): δ 112.1, 118.0,
119.8, 122.0, 123.7, 124.1, 124.9, 129.0, 129.4, 129.8, 130.0, 130.1, 131.1, 133.8, 136.1, 140.4, 142.2, 143.6.
HRMS (ESI) m/z: [M+H]+ Calcd. for C23H14N7 388.1305; Found 388.1303.
Procedure for preparation of 2a’. 2-brombenzaldehyde (5 mmol) and phenylhydrazine (5 mmol) were
stirring in DMSO (15 ml) for 2 hours.. Next tetramethylethylenediamine (TMEDA) (12.5 mmol, 2.5 eq.), CuCl
(0.05 mmol, 0.01 eq.) and carbon tetrachloride (50 mmol, 10 eq.) were put into the reaction mixture during 5
min under cooling with water bath. After TLC analysis showed complete removal of intermediate product
(hydrazone), sodium azide (25 mmol, 5 eq.) was slowly added over 20-30 min and stirred at room temperature.
Upon completion of the reaction, reaction mixture was transferred to water (350 mL), extracted with CH2Cl2
(50x3 mL). The collected extract was washed with water (150x3 mL), brine (100x2 ml) and dried over sodium
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sulfate. Volatiles were removed in vacuo of the rotary evaporator, the residue was purified by column
chromatography on silica gel using a mixture of n-hexane and CH2Cl2 (3/1).
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4-Azido-5-(2-bromophenyl)-2-phenyl-2H-1,2,3-triazole (2a’): Yield 561 mg (33 %), purified by column
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chromatography on silica gel (n-hexane/CH2Cl2= 3/1), yellowish solid, m.p. 1380C. IR (ν, cm-1): 2131. H
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NMR (400 MHz, CDCl3): δ 7.30-7.44 (m, 3H), 7.48-7.53 (m, 3H), 7.74 (dd, 1H, J=8.0, 1.1 Hz), 8.09-8.11 (m,
2H). 13С{1H} NMR (100 MHz, CDСl3): δ 118.2, 123.3, 127.3, 127.5, 129.3, 129.5, 130.7, 131.8, 133.4, 137.9,
139.3, 144.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C14H10BrN6 341.0145; Found 341.0153.
Synthesis of 2a’’. Phenylacetylene (0.92 mmol) and CuI (1 mol %) were added to the just synthesized 4-
azido-5-(2-bromophenyl)-2-phenyl-2H-1,2,3-triazole (0.54 mmol) in 3ml of NEt3. The reaction mixture was
heated at 800C on a heating mantle for 8 h under Ar. After completion of the reaction the solvent was removed
in vacuo and the residue subjected to column chromatography in n-hexane/CH2Cl2 (1/2) to give the desired
product.
5'-(2-Bromophenyl)-2',4-diphenyl-2'H-1,4'-bi(1,2,3-triazole) (2a’’): Yield 195 mg (82 %), purified by
column chromatography on silica gel (n-hexane/CH2Cl2= 1/2), yellowish solid, m.p. 1500C. IR (ν, cm-1): 664
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(C-Br). H NMR (400 MHz, CDCl3): δ 7.34-7.40 (M, 2H), 7.43-7.49 (m, 4H), 7.54-7.58 (m, 2H), 7.64-7.69
(m, 2H), 7.91-7.93 (m, 2H), 8.18-8.20 (m, 2H), 8.36 (s, 1H). 13С{1H} NMR (100 MHz, CDСl3): δ 118.8, 118.9,
123.9, 125.9, 127.5, 128.4, 128.6, 128.9, 129.5, 129.7, 129.8, 131.1, 132.2, 133.0, 139.1, 139.9, 141.7, 147.7.
HRMS (ESI) m/z: [M+H]+ Calcd. for C22H16BrN6 443.0614; Found 443.0607.
Compounds 1e’ and 1d’ were prepared according to the methodology presented in this article12.
2-((3,4-Dimethylphenyl)ethynyl)benzaldehyde (1e’): Yield 421 mg (36 %), purified by column
chromatography on silica gel (n-hexane/methyl t-butyl ether= 3/1), yellow solid, m.p. 840C. IR (ν, cm-1): 1693,
1
2205. H NMR (400 MHz, CDCl3): δ 2.29(s, 3H), 2.31 (s, 3H), 7.16 (d, 1H, J=7.7 Hz), 7.31-7.36 (m, 2H),
7.43-7.46 (m, 1H), 7.57-7.65 (m, 2H), 7.95 (d, 1H, J=7.7 Hz), 10.7 (s, 1H). 13С{1H} NMR (100 MHz, CDСl3):
δ 19.6, 19.9, 84.0, 96.9, 119.5, 127.1, 127.3, 128.3, 129.1, 129.8, 132.7, 133.1, 133.8, 135.7, 136.9, 138.2,
191.9. HRMS (ESI) m/z: [M+H]+ Calcd. for C17H15O 235.1117; Found 235.1126.
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2-(3-Phenoxyprop-1-yn-1-yl)benzaldehyde (1d’): Yield 566 mg (48 %), purified by column
chromatography on silica gel (n-hexane/methyl t-butyl ether= 3/1), yellowish oil. IR (ν, cm-1): 1699, 2232. 1H
NMR (400 MHz, CDCl3): δ 4.99 (s, 2H), 7.02-7.07 (m, 3H), 7.33-7.38 (m, 2H), 7.42-7.46 (m, 1H), 7.51-7.56
(m, 2H), 7.90-7.92 (m, 1H), 10.43 (s, 1H). 13С{1H} NMR (100 MHz, CDСl3): δ 56.2, 82.7, 91.0, 114.8, 121.6,
125.5, 127.1, 128.9, 129.5, 133.4, 133.6, 136.0, 157.4, 191.2. HRMS (ESI) m/z: [M+H]+ Calcd. for C16H13O2
237.0910; Found 237.0913.
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ASSOCIATED CONTENT
Supporting Information
The supporting Information is available free of charge
AUTHOR INFORMATION
Correspondending Author
*E-mail: nenajdenko@org.chem.msu.ru
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This work was supported by the RFBR (grant No. 18-53-05007). The authors acknowledge partial support in
measuring of NMR spectra from the M. V. Lomonosov Moscow State University Program of Development
and the support of the “RUDN University Program 5-100”.
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