Facile method for the synthesis of vicinal azidoiodides by the reaction of the NaN3-I2 system with unsaturated compounds

Article abstract of DOI:10.1080/00397910802226572

A facile and efficient method was developed for the synthesis of vicinal azidoiodides in 62-77% yields by the reaction of sodium azide and iodine with unsaturated compounds in methanol, aqueous methanol, or the water-methanol- tetrahydrofuran solvent system. The reaction in Et2O or CHCl3 produced only vicinal diiodides. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802226572

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Facile Method for the Synthesis
of Vicinal Azidoiodides by the
Reaction of the NaN3–I2 System
with Unsaturated Compounds
Alexander O. Terent'ev a , Igor B. Krylov a , Vladimir
A. Kokorekin a & Gennady I. Nikishin a
a N. D. Zelinsky Institute of Organic Chemistry,
Russian Academy of Sciences , Moscow, Russian
Federation
Published online: 14 Oct 2008.
To cite this article: Alexander O. Terent'ev , Igor B. Krylov , Vladimir A. Kokorekin
& Gennady I. Nikishin (2008) Facile Method for the Synthesis of Vicinal Azidoiodides
by the Reaction of the NaN3–I2 System with Unsaturated Compounds, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 38:21, 3797-3809, DOI: 10.1080/00397910802226572
To link to this article: http://dx.doi.org/10.1080/00397910802226572
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Synthetic Communications1, 38: 3797–3809, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802226572
Facile Method for the Synthesis of Vicinal
Azidoiodides by the Reaction of the NaN3–I2
System with Unsaturated Compounds
Alexander O. Terent’ev, Igor B. Krylov, Vladimir A. Kokorekin,
and Gennady I. Nikishin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy
of Sciences, Moscow, Russian Federation
Abstract: A facile and efficient method was developed for the synthesis of vicinal
azidoiodides in 62–77% yields by the reaction of sodium azide and iodine with
unsaturated compounds in methanol, aqueous methanol, or the water–methanol–
tetrahydrofuran solvent system. The reaction in Et2O or CHCl3 produced only
vicinal diiodides.
Keywords: Alkenes, azides, azidoiodination, iodine, sodium azide
INTRODUCTION
The azidoiodination of unsaturated compounds has long attracted atten-
tion as an efficient tool for C-N bond formation. Organic azides have
found use in the synthesis of vinyl azides,[1] amines,[2] aziridines,[3] and
lactams.[4] In recent years, interest in these compounds has quickened
because of the development of a facile method for the synthesis of
1,2,3-triazoles by the reaction of azides with terminal acetylenes catalyzed
by copper salts.[5] Compounds containing the 1,2,3-triazole ring are read-
ily available, which has stimulated extensive research into their practical
application. These compounds were found to have a wide spectrum of
Received April 11, 2008.
Address correspondence to Alexander O. Terent’ev, N. D. Zelinsky Institute
of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.,
119991 Moscow, Russian Federation. E-mail: terentev@ioc.ac.ru
3797

3798
A. O. Terent’ev et al.
biological activities,[6] for example, antituberculosis,[7] antibiotic,[8] antic-
ancer,[9] immunostimulating,[10] and anti-HIV[11] activities. New types of
monomers have been synthesized starting from these compounds.[12]
Triazoles can be used for improvement of the proton transport in fuel
cells,[13] and so on. Because of their high reliability and efficiency of
the assembly of the triazole ring by reactions in the presence of copper
salts, these heterocycles serve as convenient linkers for joining fragments
with different useful properties in a single molecule.[6a,6b,14]
The first attempt to synthesize azidoiodoalkanes by the reaction of
alkenes with IN3, which was prepared by the reaction of AgN3 with I2,
was made as early as in 1900 by Hantsch.[15] Since that time, several pro-
cedures and techniques have been developed for the synthesis of various
representatives of this class of compounds. The practical interest in
azidoiodoalkanes has stimulated a search for new methods for their
synthesis. Azidoiodoalkanes were prepared by the reaction of alkenes
with IN3, which was synthesized in situ from ICl and NaN3,[16] and by
the reaction of alkenes with I2 and NaN3 immobilized on aluminum
oxide.[17] The binary tetramethylene sulfone–chloroform (exemplified
by the synthesis of azidoiodocyclohexane)[18] and CHCl3–H2O mixtures
in the presence of the phase-transfer catalysts Adogen 464 and
18-Crown-6 were used as solvents.[19] Azidoiodoalkenes were synthesized
with the use of iodosofluorosulfate instead of iodine combined with
NaN3.[20] In the past decade, extensive research into the azidoiodination
reaction was continued. Methods were developed for the synthesis of
azidoiodoalkanes based on the reactions of alkenes with the following
azidoiodine-containing systems more complex than I2–NaN3: NaN3–
[22]
NaI–cerium ammonium nitrate,[21] NaN3–KI–oxone–wet Al2O3
,
bis(pyridine)iodonium(I) tetrafluoroborate–TMSN3–BF3-Et2O,[23] and
(diacetoxyiodo)benzene–TMSN3–tetraethylammonium
iodide.[24rsqb;
Polymer-bound iodine azide can serve as the azidoiodination reagent.[25]
RESULTS AND DISCUSSION
When searching for facile and efficient methods for the synthesis of vic-
inal azidoiodides (2a–l), we found that these compounds can be prepared
at room temperature during a rather short period of time (2–4 h) in good
yields in the absence of catalysts, expensive solvents, and considerable
excess of the reagents by the reactions of alkenes (1a–l) with sodium azide
and iodine in methanol, aqueous methanol, or the water–methanol–
tetrahydrofuran (THF) system (Scheme 1, Tables 1 and 2).
Under particular conditions, the reactions afford azidoiodides 2
along with the corresponding vicinal diiodides.

Synthesis of Vicinal Azidoiodides
3799
Scheme 1. Synthesis of azidoiodides 2a–l from alkenes 1a–l.
The nature of the solvent has a decisive influence on the composition
and the yields of the reaction products as exemplified by the azidoiodina-
tion of hex-1-ene 1a (Table 1).
Depending on the nature of the solvent, azidoiodide 2a or diiodide 3a
can be synthesized as the only reaction product. Polar protic solvents
(MeOH, MeOH–H2O, or MeOH–H2O–THF), in which the diiodide is
virtually not formed and the target azidoiodide is produced in 71–73%
yield, are most favorable for the azidoiodination. The reactions in MeOH
require vigorous stirring to obtain reproducible results. The yield of azi-
doiodide 2a in MeOH–H2O is reproduced better than in MeOH. The
addition of water to methanol results in the dissolution of the major por-
tion of sodium azide, which makes the reaction weakly sensitive to the
intensity of stirring. The reaction mixture can be easily homogenized with
the use of the three-component MeOH–H2O–THF solvent system,
because it dissolves both organic and inorganic components of the
mixture, but the presence of the third cosolvent somewhat complicates
Table 1. Yields of the azidoiodination products of hex-1-ene 1aa
MeOH=
THF
H2O= H2O=MeOH=
THF
MeOH
Product Et2O CHCl3 CH3CN THF (1=1)b MeOH (1=5)b
(2=3=5)b
2a
3a
Traces 0%
42%
62% 55% Traces 26%
31%
36%
7%
71%
Traces
73%
0%
72%
0%
aReaction conditions: sodium azide (0.618 g, 9.5 mmol, 2 mol=1 mol 1a) was added to a
solution of 1a (0.4 g, 4.75 mmol) in the solvent (10 ml), and then I2 (1.81 g, 7.13 mmol,
1.5 mol=1 mol 1a) was added with stirring at 20–25ꢀC. The reaction mixture was stirred
for 1.5 h.
bThe v=v ratio.

3800
A. O. Terent’ev et al.
Table 2. Synthesis of azidoiodoalkanes 2a–l
Reaction
time (h)
Yield
(%)a
Run
1
Alkene
Azidoiodoalkane
3
74
2
3
74b
3
3
72b
4
3
2d0 þ 2d00, 77
5
2
75b
(Continued )

Synthesis of Vicinal Azidoiodides
3801
Table 2. Continued
Reaction
time (h)
Yield
(%)a
Run
6
Alkene
Azidoiodoalkane
2
76b
7
8
2
48
2 g, 72
2 g, 55;
4 g, 15
0.5
71
9
0.5
73
10
5
24
63
2j, 35;
4j, 29
(Continued )

3802
A. O. Terent’ev et al.
Table 2. Continued
Reaction
time (h)
Yield
(%)a
Run
11
Alkene
Azidoiodoalkane
5
65
12
5
62
aThe yield based on the isolated product.
bExperiments on the synthesis of 2b, c, e, and f were scaled with an increase in the
amounts of the reagents by a factor of 10.
the experimental technique. In aprotic solvents (CHCl3 or Et2O), the
azidoiodination is almost completely absent; in THF, 2a and 3a are
produced in approximately equal yields (30%).
Taking into account the results of optimization of the synthesis of 2-
azido-1-iodohexane (Table 1), we performed the azidoiodination of a series
of unsaturated hydrocarbons, ethers, and esters with the NaN3–I2 system
in MeOH–H2O with the aim of preparing the corresponding azidoiodine-
containing compounds required for further investigations (Table 2).
Vicinal azidoiodides are produced in higher yields (71–77%) from
alkenes, styrenes, and enol ethers (runs 1–9) and in somewhat lower
yields (62–69%) from esters (runs 10–13). A mixture of cis and trans iso-
mers 2d0 and 2d00 is formed in a total yield of 77% from cyclooctene 1d
(run 4). In runs 7 and 10, the azidoiodination of indene and methylacry-
late over a longer period of time (48 and 24 h) affords vicinal diazides 4g
and 4j, apparently as a result of the nucleophilic displacement of the
iodine atom with the azido group in azidoiodine adducts 2g and 2j.
Among the unsaturated compounds listed in Table 2, cyclic enol ethers
exhibit the highest reactivity in the reaction with NaN3–I2 (0.5 h, runs 8
and 9). The reactions with unsaturated compounds conjugated with
electron-withdrawing groups proceed more slowly (5 h, runs 10–12).

Synthesis of Vicinal Azidoiodides
CONCLUSIONS
3803
A facile and efficient procedure was developed for the synthesis of vicinal
azidoiodides in yields up to 77% from linear and cyclic alkenes, styrene,
its analogs, cyclic enol ethers, and unsaturated compounds containing an
electron-withdrawing group. This method is based on the reaction of sodium
azide with iodine (used in a small excess) with an unsaturated compound in
methanol, aqueous methanol, or the water–methanol–THF solvent system.
EXPERIMENTAL
NMR spectra were recorded on Bruker AC-200 (200.13 MHz for 1H and
1
50.32 MHz for 13C) and Bruker Avance 300 (300.13 MHz for H and
75.48 MHz for 13C) spectrometers in CDCl3. Analytical thin-layer
chromatography(TLC): Silufol UV-254, Silpearl as the sorbent, starch
as the binder. Flash chromatography was performed on silica gel (63–
200 mesh, Merk). Alkenes, NaN3, and Na2S2O5 were purchased from
Acros. Methanol, ethanol, THF, hexane, CHCl3, CH3CN, Et2O, and
iodine (all of reagent grade) were used without additional purification.
Azidoiodination of Hex-1-ene (1a), Table 1
Hex-1-ene 1a (0.4 g, 4.75 mmol) was dissolved in 10 ml of the solvent
(Et2O, CHCl3, CH3CN, THF, MeOH, MeOH–THF (5 ml þ 5 ml), H2O–
MeOH (2 ml þ 8 ml), or H2O–MeOH–THF (2 ml þ 3 ml þ 5 ml). Sodium
azide (0.618 g, 9.5 mmol, 2 mol=1 mol 1a) was added at 20–25ꢀC, and then
I2 (1.81 g, 7.13 mmol, 1.5 mol=1 mol 1a) was added with stirring. The
reaction mixture was stirred for 90 min, CH2Cl2 (50 ml) and H2O
(30 ml) were added, and the CH2Cl2 layer was separated, washed with
5% Na2S2O5 until it became colorless (with caution, extensive elimination
of N2) and again with H2O (2 ꢁ 20 ml), and dried over MgSO4. The
product was isolated by column chromatography.
Azidoiodination of Alkenes (1a–g, j–l) (General Procedure), Table 2
Alkene 1a–g, j–l (0.4 g) was dissolved in a mixture of MeOH (or EtOH in
run 11; 15 ml) and H2O (2 ml; if required, THF was added for homoge-
nization). At 20–25ꢀC, NaN3 (4 mol=1 mol 1a–g, j–l) was added. Then
I2 (2 mol=1 mol 1a–g, j–l) was added with stirring. The reaction mixture
was stirred during a period from 2 to 48 h and worked as described
for 1a.

3804
A. O. Terent’ev et al.
Azidoiodination of Dihydrofuran (1 h) and Dihydropyran (1i), Table 2
Sodium azide (3 mol=mol 1h, i; 1.1 or 0.93 g; 17.1 or 14.3 mmol) and dihy-
drofuran 1 h or dihydropyran 1i (0.4 g; 5.71 or 4.76 mmol) were succes-
sively dissolved in methanol (10 ml) and water (4 ml). Then iodine
(1 mol=mol 1h, i; 1.45 or 1.21 g; 5.71 or 4.76 mmol) was added with stir-
ring. The reaction mixture was stirred at 20–25ꢀC for 0.5 h and worked
up as described for 1a.
Data
2-Azido-1-iodohexane (2a)[16a]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 0.90 (t, 3H, CH3,
J ¼ 6.9 Hz), 1.26–1.82 (m, 6H, CH2), 3.18–3.30 (m, 2H, CH2I), 3.32–
3.44 (m, 1H, CH). 13C NMR (75.48 MHz, CDCl): d ¼ 8.6 (CH2I), 13.8
(CH3CH2), 22.2, 27.9 (CH2), 34.1 (CH2), 62.6 (CN3).
1-Azido-2-iodocyclopentane (2b)[26]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 1.61–2.42 (m, 6H,
CH2), 4.03–4.27 (m, 2H, CHI, CHN3). 13C NMR (75.48 MHz, CDCl):
d ¼ 22.3, 28.5, 29.1 (CH2), 36.5 (CHI), 71.5 (CHN3). Anal. Calcd. for
C5H8IN3: C, 25.33; H, 3.40; I, 53.54; N, 17.73. Found: C, 25.15; H,
3.41; I, 53.22; N, 18.01.
1-Azido-2-iodocyclohexane (2c)[18]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 1.19–1.63 (m, 4H,
CH2), 1.75–2.50 (m, 4H, CH2), 3.42–3.59 (m, 1H, CHN3), 3.87–4.01
(m, 1H, CHI). 13C NMR (75.48 MHz, CDCl): d ¼ 23.7, 26.9, 31.8, 33.2
(CH2), 38.3 (CHI), 67.1 (CHN3). Anal. calcd. for C6H10IN3: C, 28.70;
H, 4.01; I, 50.55; N, 16.74. Found: C, 29.11; H, 4.06; I, 50.26; N, 17.05.
1-Azido-2-iodocyclooctane (the Mixture of Isomers, Ratio 1=2)
(2d0 þ 2d00):
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 1.28–2.44 (m, 12H,
CH2), the first isomer 3.38–3.49 (m, 1H, CHN3), 4.53–4.65 (m, 1H, CHI),
C
the second isomer 3.83–3.95 (m, 1H, CHN3), 4.18–4.30 (m, 1H, CHI). 13
NMR (75.48 MHz, CDCl): d ¼ 24.0–27.2 (8 CH2), 31.5, 31.7, 34.2, 36.9
(CH2), 38.9, 39.4 (CHI), 64.1, 71.1 (CHN3). Anal. calcd. for C8H14IN3:

Synthesis of Vicinal Azidoiodides
3805
C, 34.42; H, 5.06; I, 45.47; N, 15.05. Found: C, 34.37; H, 5.08; I, 45.43; N,
15.21.
2-Iodo-1-phenylethyl Azide (2e)[17]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 3.39 (d, 2H, CH2,
J ¼ 7.3 Hz), 4.72 (t, 1H, CH, J ¼ 7.3 Hz), 7.28–7.47 (m, 5H, Ph). 13C
NMR (75.48 MHz, CDCl3): d ¼ 8.1 (CI), 67.1 (CN3), 126.6, 129.0 (CH,
Ar), 137.8 (C, Ar).
1-(1-Azido-2-iodoethyl)-4-methylbenzene (2f)
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 2.39 (s, 3H, CH3),
3.40 (d, 2H, CH2, J ¼ 7.3 Hz), 4.71 (t, 1H, CH, J ¼ 7.3 Hz), 7.20–7.27
(m, 4H, Ph). 13C NMR (75.48 MHz, CDCl): d ¼ 8.1 (CI), 21.2 (CH3),
66.9 (CN3), 126.5, 129.7 (CH, Ar), 134.8, 139.0 (C, Ar). Anal. calcd.
for C9H10IN3: C, 37.65; H, 3.51; I, 44.20; N, 14.64. Found: C, 37.42;
H, 3.39; I, 44.47; N, 14.61.
1-Azido-2-iodo-2,3-dihydro-1H-indene (2g)[24]
1
Mp 55–57ꢀC. Mp cis-isomer 53ꢀC[24]. H NMR (300.13 MHz, CDCl3):
d ¼ 3.31–3.42 (m, 1H, CH2), 3.59–3.71 (m, 1H, CH2), 4.34–4.43 (m,
1H, CHN3), 5.09–5.18 (m, 3H, CHI), 7.27–7.48 (m, 4H, Ph). 13C NMR
(75.48 MHz, CDCl): d ¼ 25.2, 43.6 (CI, CH2), 75.0 (CN3), 124.5, 124.8,
127.7, 129.5 (CH, Ar), 138.6, 141.3 (C, Ar).
2-Azido-3-iodotetrahydrofuran (2h)
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 2.18–2.28 (m, 1H,
CH2), 2.47–2.60 (m, 1H, CH2), 4.08–4.26 (m, 3H, CH2O, CHI), 5.68–
5.71 (m, 1H, CHO). 13C NMR (75.48MHz, CDCl): d ¼ 23.6, 35.4 (CH2,
CI), 68.5 (CH2O), 98.8 (CHO). Anal. calcd for C4H6IN3O: C, 20.10; H,
2.53; I, 53.09; N, 17.58. Found: C, 20.01; H, 2.28; I, 53.45; N, 17.51.
2-Azido-3-iodotetrahydro-2H-pyran (2i)
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 1.59–1.72 (m, 2H,
CH2), 1.90–2.11 (m, 1H, CH2), 2.25–2.45 (m, 1H, CH2), 3.57–3.70
(m, 1H), 3.85–3.96 (m, 1H), 4.01–4.14 (m, 1H), 4.85–4.94 (m, 1H,
CHO). 13C NMR (75.48 MHz, CDCl): d ¼ 26.2, 27.3, 33.8 (CH2, CI),

3806
A. O. Terent’ev et al.
66.0 (CH2O), 92.2 (CHO). Anal. calcd. for C5H8IN3O: C, 23.73; H, 3.19;
I, 50.15; N, 16.61. Found: C, 23.54; H, 3.02; I, 50.46; N, 16.57.
Methyl 3-Azido-2-iodopropanoate (2j)[16c]
Pale yellow oil. Rf ¼ 0.43 (TLC, hexane=EA ¼ 5=1). 1H NMR
(300.13 MHz, CDCl3): d ¼ 3.62 (dd, 1H, CH2, J ¼ 12.5; 5.1 Hz), 3.79 (s,
3H, CH3), 3.89 (dd, 1H, CH2, J ¼ 12.5; 9.5 Hz), 4.37 (dd, 1H, CH,
J ¼ 9.5; 5.1 Hz). 13C NMR (75.48 MHz, CDCl3): d ¼ 14.6 (CI), 53.2,
54.7 (CH2, CH3), 170.2 (CO). Anal. calcd. for C4H6IN3O2: C, 18.84;
H, 2.37; I, 49.76; N, 16.48. Found: C, 18.80; H, 2.37; I, 49.38; N, 16.91.
Ethyl 3-Azido-2-iodobutanoate (2k)
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 1.28 (t, 3H, CH3,
J ¼ 7.2 Hz), 1.50 (d, 3H, CH3, J ¼ 6.6 Hz), 3.87 (m, 1H, CH), 4.15–4.27
(m, 3H, CH, CH2). 13C NMR (75.48 MHz, CDCl): d ¼ 13.7, 19.2
(CH3), 24.6 (CI), 59.3, 62.2 (CH, CH2), 169.6 (CO). Anal. Calcd. for
C6H10IN3O2: C, 25.46; H, 3.56; I, 44.83; N, 14.84. Found: C, 25.31; H,
3.42; I, 45.11; N, 14.74.
Methyl 3-Azido-2-iodo-2-methylpropanoate (2l)[16c]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 2.07 (s, 3H, CCH3),
3.65 (d, 1H, CH2, J ¼ 12.5 Hz), 3.79 (s, 3H, OCH3), 4.10 (d, 1H, CH2,
J ¼ 12.5 Hz). 13C NMR (75.48 MHz, CDCl3): d ¼ 28.0 (CH3), 34.6 (CI),
53.3 (OCH3), 61.7 (CH2), 171.8 (CO).
1,2-Diazido-2,3-dihydro-1H-indene (4g)[27]
1
Pale yellow oil. H NMR (300.13 MHz, CDCl3): d ¼ 3.38–3.44 (m, 3H,
CH, CH2), 4.71–4.81 (m, 1H, CH), 7.31–7.50 (m, 4H, Ph). 13C NMR
(75.48 MHz, CDCl): d ¼ 36.1 (CH2), 67.6, 70.2 (CN3), 124.5, 125.1,
127.7, 129.4 (CH, Ar), 137.7, 139.0 (C, Ar).
Methyl 2,3-Diazidopropanoate (4j)
Pale yellow oil. Rf ¼ 0.29 (TLC, hexane=EA ¼ 5=1). 1H NMR
(200.13 MHz, CDCl3): d ¼ 3.61 (d, 2H, CH2, J ¼ 5.3 Hz), 3.82 (s, 3H,
CH3), 4.09 (t, 1H, CH, J ¼ 5.3 Hz). 13C NMR (50.32 MHz, CDCl3):
d ¼ 51.8 (CH2), 53.1 (CH), 61.4 (CH3), 168.2 (CO). Anal. calcd. for

Synthesis of Vicinal Azidoiodides
3807
C4H6N6O2: C, 28.24; H, 3.55; N, 49.40. Found: C, 28.63; H, 3.55;
N, 49.40.
ACKNOWLEDGMENT
This work is supported by the Program for Support of Leading Scientific
Schools of the Russian Federation (Grant NSh 2942.2008.3), the Grant
of President of Russian Federation (No. MK-3515.2007.3), and the
Russian Science Support Foundation.
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