A simple and effective synthesis of aryl azides via arenediazonium tosylates

Article abstract of DOI:10.1055/s-0033-1339648

Aromatic azides are formed in high yield from arenediazonium tosylates and sodium azide in water at room temperature or from aromatic amines via diazotization in the presence of p-TsOH Besides being experimentally simple, these methods do not require any metal catalysis and provide clean products without purification. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1339648

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PAPER
paper
A Simple and Effective Synthesis of Aryl Azides via Arenediazonium Tosylates
Aryl Azides via Arenediazonium Tosylates
Ksenia V. Kutonova,a Marina E. Trusova,a Pavel S. Postnikov,a Victor D. Filimonov,*a Joseph Parello*b
a
Department of Biotechnology and Organic Chemistry, National Research Tomsk Polytechnic University, 634050 Tomsk, Russian Federation
Fax +7(3822)563637; E-mail: filimonov@tpu.ru
b
Department of Pharmacology, Vanderbilt University, Nashville, TN 37232, USA
E-mail: joseph.parello@vanderbilt.edu
Received: 22.05.2013; Accepted after revision: 30.07.2013
azide sources,1,12 including continuous-flow synthesis.13
Abstract: Aromatic azides are formed in high yield from arenedia-
However, it is well known that traditional diazonium salts
zonium tosylates and sodium azide in water at room temperature or
have certain disadvantages – poor thermal stability and
from aromatic amines via diazotization in the presence of p-TsOH.
Besides being experimentally simple, these methods do not require
explosive properties (including the more commonly used
any metal catalysis and provide clean products without purification. tetrafluoroborates14). It should be noted that the diazoni-
um tetrafluoroborates display a poor solubility in water
thus requiring use of mixtures of water and an organic sol-
vent.15
Key words: diazotization, sodium azide, aromatic amines, p-TsOH,
aqueous medium
A few years ago we reported the synthesis of aryldiazoni-
+
um tosylates ArN2 TsO– (ADT) (1), which possess high
Organic azides are valuable compounds for many fields in
organic and bioorganic chemistry.1 They are used as
equivalents of primary amines in the Staudinger reaction
and the Staudinger ligation (using phosphine, phosphite,
and phosphonite intermediates).2 In spite of the complex-
ity of their photolytic properties3 aromatic azides (as
sources of intermediate nitrenes) are of particular interest
as photoaffinity labeling reagents in structural proteomics
when combined with mass spectrometry analyses.4
diazonium reactivity but in contrast to usual diazonium
salts have good thermal and storage stabilities and are sol-
uble in water and many organic solvents.16 The aim of this
work was to assess the scope (and limitations) of ADTs as
precursors for the synthesis of aromatic azides.
Selected ADTs (up to ten; see Table 1) in aqueous solu-
tion and at room temperature instantly reacted with an
equivalent quantity of sodium azide (click reaction) re-
sulting in emission of nitrogen and insolubilization of the
corresponding aryl azides 2b,c,e,i–l,n–q, which were ob-
tained in quantitative yields (method А) (Scheme 1, Table 1).
Dipolar cycloaddition reactions of organic azides with al-
kynes and nitriles in the presence of copper salts that lead
to 1,4- or 1,5-disubstituted 1,2,3-triazoles and tetrazoles,
appear of the highest relevance in organic synthesis5 and
in the labeling of biomolecules2 (including the efficient
detection of DNA synthesis in vivo by click chemistry us-
ing 5-ethynyl-2′-deoxyuridine6), as well as to surface
modification and in polymer science.7,8
NaN3
ArN2+TsO–
ArN3 + N2 + p-TsONa
H2O, r.t.
2
1
Scheme 1 Click reaction of arenediazonium tosylates with sodium
azide (method A)
These properties have elicited various methods for prepar-
ing aromatic azides.1 Typically, these compounds are pre-
pared through nucleophilic substitution of halides in
activated arenes by the azide anion, or by azido-demetala-
tion of arylmagnesium halides and aryllithium reagents
(alkali azides, trimethylsilyl azide, or p-toluenesulfonyl
azide are the most frequent azide sources); through diazo-
tization of hydrazines; or using reactions of aromatic and
heteroaromatic amines with TfN3 or 2-azido-1,3-dimeth-
ylimidazolinium hexafluorophosphate (the diazo-transfer
reactions9) and of nitrosoarenes with hydrogen azide; as
well as through base-induced cleavage of triazenes and
copper-catalyzed reactions of boronic acids with TfN3 or
NaN3.10 More recently a method has been reported for the
direct azidation of arenes by NaICl2 and NaN3.11 The most
general method for the preparation of aromatic azides is
based on the reaction of diazonium salts with suitable
Table 1 Preparation of Aryl Azides 2 from Arenediazonium Tosyl-
ates 1 and NaN3 by Methods A and B
Entry Product
Method A, Method Bc
yield (%)a,b Time (min) Yield (%)
1
2
3
4
5
6
7
8
9
PhN3 (2a)
quant
quant
quant
40d
20
20
20
70
20
30
40
20
67
99
94
93
95
72
61
89
98
4-O2NC6H4N3 (2b)
2-O2NC6H4N3 (2c)
3-O2NC6H4N3 (2d)
4-MeOC6H4N3 (2e)
4-MeC6H4N3 (2f)
4-C6H13C6H4N3 (2g)
4-C10H21C6H4N3 (2h)
4-HO2CC6H4N3 (2i)
quant
SYNTHESIS 2013, 45, 2706–2710
Advanced online publication: 14.08.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0033-1339648; Art ID: SS-2013-T0364-OP
© Georg Thieme Verlag Stuttgart · New York
quant

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Aryl Azides via Arenediazonium Tosylates
2707
Table 1 Preparation of Aryl Azides 2 from Arenediazonium Tosyl-
ates 1 and NaN3 by Methods A and B (continued)
Importantly, method A exclusively yields the targeted aryl
azides besides p-TsONa. No side-products were detected
including phenols and triazenes (as monitored by GC-MS
and HPLC), which are often formed in the reactions with
diazonium salts. An important advantage of method A is
the use of ADT 1 and NaN3 in equimolar ratios in most
cases, thus reducing the risk of toxic hydrazoic acid. The
aryl azides 2b–d,i–r,t,u were isolated as solid compounds
through simple filtration and water washing without any
use of organic solvents, while the aryl azides 2a,e–h,s
were isolated as oily products through ethyl acetate ex-
traction and solvent evaporation. One exception is azide
2p, which was only obtained in 69% yield with the forma-
tion of side-products, among them p-nitroaniline. In addi-
tion, in this case the complete conversion of the starting
ADT (p-NH2C6H4N2+ TsO–) required three equivalents of
sodium azide.
Entry Product
Method A, Method Bc
yield (%)a,b Time (min) Yield (%)
10
11
12
13
14
2-HO2CC6H4N3 (2j)
quant
quant
quant
20
20
20
60
20
92
87
85
80e
97
3-HO2CC6H4N3 (2k)
4-PhC6H4N3 (2l)
4-IC6H4N3 (2m)
4-NCC6H4N3 (2n)
quant
quant
N3
N
15
16
17
25
98
Ph
N
(2o)
4-H2NC6H4N3
(2p)
69f
We also found that a variety of aromatic amines can be di-
rectly converted into the corresponding aromatic azides 2
in high yields by a one-pot mode via diazotization with so-
dium nitrite in water in the presence of p-TsOH followed
by the reaction with sodium azide without isolation of the
intermediate ADT (method B; Scheme 2, Table 1).
N3
N3
quant
40
45
96
98
(2q)
N3
O
NaNO2
NaN3
Ph
ArNH2 + p-TsOH
ArN2+TsO–
ArN3
+ N2 + p-TsONa
H2O, r.t.
H2O, r.t.
18
2
1
Cl
Scheme 2 One-pot preparation of aryl azides 2 from aromatic
amines (method B)
(2r)
4-BrC6H4N3
(2s)
19
20
60
60
97
93
Both reactions shown in Scheme 2 proceed smoothly at
room temperature. Only aniline diazotization is an excep-
tion. In this case the temperature was lowered to 5 °C to
afford azide 2a without the formation of side-products.
The resulting solid azides 2b–d,i–r,t–v were readily iso-
lated from water by filtration while the oily azides 2a,e–h,s
were isolated after extraction with ethyl acetate and sol-
vent evaporation. In all cases, products 2 are of sufficient-
ly high purity (NMR, GC) and can be further used without
any additional purification. Avoiding recrystallization
and distillation of the targeted products 2 enhances the
safety of the synthetic procedure considering that azides
are potentially hazardous substances and explosophores.
These points are of crucial relevance to any large-scale
azide production.
Br
N3
Br
Br
(2t)
N3
21
22
60
40
97
83
(2u)
O
N3
NH
N
O
H
In contrast to many conventional methods our proposed
synthesis of aryl azides 2 displays a general applicability
thus including aromatic azides with electron-withdrawing
or electron-donating substituents, as well as groups with a
marked lipophilic character (compounds 2 g,h). Similarly,
polycyclic and heterocyclic azides with different degrees
of steric hindrance (2t–v) are formed in high yields.
(2v)
a GC data.
b Reaction conditions: ADT (1 mmol), NaN3 (1 mmol).
c Reaction conditions: ArNH2 (1 mmol), NaNO2 (9 mmol), p-TsOH
(9 mmol), NaN3 (1.6 mmol). Time refers to the diazotization step.
Yields are for isolated pure products.
d At 5 °C.
e Reaction conditions: ArNH2 (1 mmol), NaNO2 (27 mmol), p-TsOH
(27 mmol), NaN3 (9 mmol).
One exception is the reaction with 4-iodoaniline, in which
an 80% yield of 1-azido-4-iodobenzene (2m) was only
achieved with a relatively large excess of sodium azide
(an optimal ratio of the reactants was found to be 4-iodo-
aniline/NaNO2/p-TsOH/NaN3 = 1:27:27:9).
f Reaction conditions: ADT (1 mmol), NaN3 (3 mmol).
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2706–2710

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K. V. Kutonova et al.
PAPER
id aryl azides 2b–d,i–r,t–v were filtered, washed with H2O (50 mL)
and dried. Oily azides 2a,e–h,s were extracted with EtOAc (3 × 10
mL), dried (Na2SO4), filtered, and the solvent was removed in a ro-
tary evaporator under reduced pressure (Table 1).
At the same time, method B has its limitations. It appears
unusable for the preparation of 4-azidobenzenamine (2p),
since diazotization of benzene-1,4-diamine leads to sig-
nificant amounts of by-products including PhN3, PhOH,
PhNO2, 4-HOC6H4NH2, 1,4-(O2N)2C6H4, 4-H2NC6H4NO2, Azidobenzene (2a)10a
Yield: 79.7 mg (67%, 0.67 mmol); pale yellow oil.
1H NMR (300 MHz, DMSO-d6): δ = 7.39 (m, 2 H), 7.17 (m, 1 H),
7.07 (d, J = 7.8 Hz, 2 H).
and 4-PhC6H4NH2 (GC-MS data). Finally, method B is
improper to the synthesis of azidopyridines since diazo-
tization of aminopyridines in the presence of p-TsOH
results in the formation of pyridinyl tosylates instead of
pyridinediazonium tosylates.17
1-Azido-4-nitrobenzene (2b)10c
Yield: 164 mg (quant, 1 mmol); pale yellow solid; 66 °C.
1H NMR (300 MHz, DMSO-d6): δ = 8.25 (d, J = 9.0 Hz, 2 H), 7.35
(d, J = 9.0 Hz, 2 H).
In summary, we have developed a reliable and efficient
approach for the synthesis of aryl azides through the reac-
tion of arenediazonium tosylates with sodium azide in
water at room temperature. This procedure offers several
advantages over the methods reported so far that include
an increased safety and a large chemical applicability (al-
though with some limitations) under metal-free condi-
tions with minimal purification stages.
1-Azido-2-nitrobenzene (2c)19
Yield: 154 mg (94%, 0.94 mmol); orange solid; 52 °C.
1H NMR (300 MHz, DMSO-d6): δ = 8.01 (d, J = 9.6 Hz, 1 H), 7.74
(m, 1 H), 7.59 (m, 1 H), 7.36 (d, J = 9.6 Hz, 1 H).
1-Azido-3-nitrobenzene (2d)10b
Yield: 152.5 mg (93%, 0.93 mmol); orange solid; 52°C.
1H NMR (300 MHz, DMSO-d6): δ = 7.99 (d, J = 6.9 Hz, 1 H), 7.82
(s, 1 H), 7.68 (m, 1 H), 7.59 (d, J = 6.9 Hz, 1 H).
All starting materials were ACS grade and were used without fur-
ther purification. Arenediazonium tosylates 1 were prepared by a
previously described method.16 HPLC analyses were conducted
with an Agilent 1200 instrument fitted with an Eclipse Plus C18 col-
umn (5 μm, 4.6 × 150 mm) and UV detector; 0.1% TFA–H2O and
0.1% TFA–MeCN were used as eluents. GC-MS measurements
1-Azido-4-methoxybenzene (2e)20
Yield: 141.5 mg (95%, 0.95 mmol); yellow oil.
IR (film): 2106 cm–1.
1H NMR (300 MHz, DMSO-d6): δ = 7.05 (d, J = 9.3 Hz, 2 H), 6.98
(d, J = 9.0 Hz, 2 H), 3.39 (s, 3 H, OCH3).
13C NMR (75 MHz, DMSO-d6): δ = 156.8, 131.4, 120.9, 115.3,
55.4.
MS (EI): m/z = 149 ([M]+), 121, 106, 91, 78, 64, 52, 45, 39.
1
were obtained with an Agilent 7890/5975C instrument. H, 13C
NMR, and IR spectra were recorded on a Bruker Avance 300 and
PerkinElmer BXII instruments. Melting points (uncorrected) were
obtained with a Melting point system MP50, Mettler, Toledo. Ele-
mental analyses were performed with a Vario MACRO cube CHNS
instrument (Elementar Analysensysteme GmbH, Germany). Ther-
mal analyses of some of the starting ADT were performed on an in-
tegrated DSC-TGA-DTA instrument STD Q600 in open cells.
1-Azido-4-methylbenzene (2f)9c
Yield: 96 mg (72%, 0.72 mmol); brown oil.
1H NMR (300 MHz, DMSO-d6): δ = 7.22 (d, J = 8.4 Hz, 2 H), 7.00
(d, J = 8.4 Hz, 2 H), 2.28 (s, 3 H).
Thermal stability for some ADT salts (as assessed by DSC between
0–600 °C under a N2 atmosphere). Decomposition temperature (°C)
and decomposition energy (J/g): Ar = 4-NO2C6H4 137, –339.9; 2-
NO2C6H4: 144, –323.0; 3-NO2C6H4: 141, –389.8; 4-C6H13C6H4:
128, –785.0; 4-CO2HC6H4: 97, –412.4; 2-CO2HC6H4: 121, –840.3;
4-IC6H4: 115, –245.5; 4-CNC6H4: 113, –332.4; 4-NH2C6H4: 148,
–298.0; 2,4,6-Br3C6H2: 139, –184.7.
1-Azido-4-hexylbenzene (2g)21
Yield: 124 mg (61%, 0.61 mmol); brown oil.
1H NMR (300 MHz, DMSO-d6): δ = 7.23 (d, J = 8.4 Hz, 2 H), 7.02
(d, J = 8.1 Hz, 2 H), 2.57 (m, 2 H), 1.55 (m, 2 H), 1.25 (m, 6 H),
0.87 (m, 3 H).
Reaction of ADT 1 with NaN3 (Method A); General Procedure
To a solution of ADT (1.0 mmol) in H2O (10 mL) at r.t. was added
NaN3 (65 mg, 1.0 mmol) under stirring. An immediate emission of
N2 was observed. Solid compounds 2b–d,i–r,t,u were filtered and
washed with H2O (50 mL) (Table 1).
1-Azido-4-decylbenzene (2h)
Yield: 231 mg (89%, 0.89 mmol); brown oil.
IR (film): 2109 cm–1.
1H NMR (300 MHz, DMSO-d6): δ = 7.23 (d, J = 8.1 Hz, 2 H), 7.02
(d, J = 8.1 Hz, 2 H), 2.56 (m, 2 H), 1.52 (m, 3 H), 1.22 (m, 7 H),
1.03 (m, 5 H), 0.84 (m, 4 H).
13C NMR (75 MHz, DMSO-d6): δ = 139.3, 136.5, 129.8, 118.8,
34.4, 31.2, 30.9, 28.9, 28.6, 28.4, 22.0, 13.9.
4-Azidobenzenamine (2p)18
Yield: 92.5 mg (69%, 0.69 mmol); brown solid; mp 60 °C.
1H NMR (300 MHz, DMSO): δ = 6.77 (d, J = 6.0 Hz, 2 H), 6.59 (d,
J = 6.0 Hz, 2 H), 5.14 (s, 2 H).
Anal. Calcd for C16H25N3: C, 74.09; H, 9.71; N, 16.20. Found: C,
74.22; H, 9.78; N, 16.24.
Aryl Azides 2 from Aromatic Amines (Method B); General Pro-
cedure
Caution! Volatile, highly toxic, and explosive HN3 can occasionally
evolve and this operation needs to be conducted in a well-ventilated
exhaust hood.
4-Azidobenzoic Acid (2i)10c
Yield: 160 mg (98%, 0.98 mmol); white solid, 113 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.95 (d, J = 8.4 Hz, 2 H), 7.20
(d, J = 8.4 Hz, 2 H).
To a solution of p-TsOH·H2O (1.62 g, 9 mmol) in H2O (9 mL) was
added ArNH2 (1 mmol). After stirring for 1 min, andhydrous
NaNO2 (0.621 g, 9 mmol) was added gradually during 5 min. The
resulting solution was then stirred for 2–60 min until the starting
ArNH2 disappeared as monitored by TLC (eluent: benzene–EtOH,
9:1). To the resulting solution, andhydrous NaN3 (0.104 g, 1.6
mmol) was added. An immediate emission of N2 was observed. Sol-
2-Azidobenzoic Acid (2j)22
Yield: 150 mg (92%, 0.92 mmol); beige solid; 136 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.78 (d, J = 7.5 Hz, 1 H), 7.62
(m, 1 H), 7.37 (d, J = 7.5 Hz, 1 H), 7.29 (m, 1 H).
Synthesis 2013, 45, 2706–2710
© Georg Thieme Verlag Stuttgart · New York

PAPER
Aryl Azides via Arenediazonium Tosylates
2709
3-Azidobenzoic Acid (2k)23
Supporting Information for this article is available online at
Yield: 150 mg (92%, 0.92 mmol); white solid; 164 °C.
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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1H NMR (300 MHz, DMSO-d6): δ = 7.72 (d, J = 7.5 Hz, 1 H), 7.58
(s, 1 H), 7.39 (m, 1 H), 7.14 (d, J = 7.5 Hz, 1 H).
References
4-Azidobiphenyl (2l)10c
Yield: 122.8 mg (63%, 0.63 mmol); pale brown solid; 62 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.69 (d, J = 8.4 Hz, 2 H), 7.63
(d, J = 7.2 Hz, 2 H), 7.47–7.42 (m, 2 H), 7.37–7.32 (m, 1 H), 7.19
(d, J = 8.4 Hz, 2 H).
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1-Azido-4-iodobenzene (2m)10c
Yield: 196 mg (80%, 0.8 mmol); beige solid; 31 °C.
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4-Azidobenzonitrile (2n)10c
Yield: 139.6 mg (97%, 0.97 mmol); white solid; 60 °C.
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7.29 (d, J = 8.4 Hz, 2 H, ArH).
(E)-1-(4-azidophenyl)-2-phenyldiazene (2o)24
Yield: 218.5 mg (98%, 0.98 mmol); dark orange solid; 63 °C.
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7.89–7.87 (m, 2 H, ArH), 7.62–7.58 (m, 1 H, ArH), 7.50 (d, J = 7.8
Hz, 2 H, ArH), 7.13 (d, J = 7.8 Hz, 2 H, ArH).
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Bis(4-azidophenyl)methane (2q)25
Yield: 240 mg (96%, 0.96 mmol); dark red solid; 110–113 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.25 (d, J = 5.7 Hz, 4 H), 7.03
(d, J = 6.0 Hz, 4 H), 3.90 (s, 2 H).
(2-Azido-5-chlorophenyl)phenylmethanone (2r)26
Yield: 251.8 mg (98%, 0.98 mmol); beige solid; 82 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.74–7.67 (m, 4 H), 7.57–7.48
(m, 4 H).
1-Azido-4-bromobenzene (2s)10c
Yield: 191 mg (97%, 0.97 mmol); yellow oil.
1H NMR (300 MHz, DMSO-d6): δ = 7.58 (d, J = 8.7 Hz, 2 H), 7.09
(d, J = 8.7 Hz, 2 H).
2-Azido-1,3,5-tribromobenzene (2t)27
Yield: 331 mg (93%, 0.93 mmol); beige solid; 74 °C.
1H NMR (300 MHz, DMSO-d6): δ = 7.97 (s, 2 H).
2-Azidoanthracene (2u)9a
Yield: 212.4 mg (97%, 0.97 mmol); dark gray solid; 170–172 °C.
1H NMR (300 MHz, DMSO-d6): δ = 8.58 (s, 1 H), 8.52 (s, 1 H), 8.17
(d, J = 8.7 Hz, 3 H), 7.79 (s, 1 H), 7.52 (d, J = 6.9 Hz, 1 H), 7.28 (d,
J = 9.0 Hz, 1 H), 7.13 (d, J = 7.2 Hz, 1 H).
5-Azidouracil (2v)
Yield: 127 mg (83%, 0.83 mmol); beige solid; 98 °C (dec.).
IR (KBr): 2158, 2116 cm–1.
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Borger, E. D.; Stick, R. V. Org. Lett. 2007, 9, 3797.
(c) Kitamura, M.; Yano, M.; Tashiro, N.; Miyagawa, S.;
Sando, M.; Okauchi, T. Eur. J. Org. Chem. 2011, 458.
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Han, F.-S. Chem. Eur. J. 2010, 16, 7969. (c) Grimes, K. D.;
Gupte, A.; Aldrich, C. C. Synthesis 2010, 1441.
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1085.
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1H NMR (300 MHz, DMSO-d6): δ = 7.28 (s).
13C NMR (75 MHz, DMSO-d6): δ = 160.9, 150.2, 130.2, 112.2.
Anal. Calcd for C4H3N5O2: C, 31.38; H, 1.98; N, 45.74. Found: C,
31.42; H, 1.97; N, 45.79.
Acknowledgment
This research was supported by the scientific programme ‘Nauka’
N 30060.2012 (State contract 16.512.11.2127) and a private fun-
ding to J.P. M.E.T. acknowledges the young scientific RFBR grant
N 12-03-31594.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2706–2710

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