Simple and practical method for preparation of [(diacetoxy)iodo]arenes with iodoarenes and m-chloroperoxybenzoic acid

Article abstract of DOI:10.1055/s-0032-1317345

Various [(diacetoxy)iodo]arenes bearing 4-methylphenyl, phenyl, 4-nitrophenyl, 3-nitrophenyl, 4-cyanophenyl, 4-bromophenyl, 4- methoxycarbonyphenyl, 3,5-bis(trifluoromethyl)phenyl, and 4-(N,N,N- trimethylammonium)methylphenyl groups were efficiently prepared by the treatment of iodoarenes with m-chloroperoxybenzoic acid in acetic acid. The great advantage of the present method is the easy preparation and isolation of [(diacetoxy)-iodo]arenes bearing electron-withdrawing groups, such as 4-nitro, 4-cyano, 4-methoxycarbonyl, and 3,5-bis(trifluoromethyl) groups, on the aromatic ring.

Full text of DOI:10.1055/s-0032-1317345

LETTER
▌2663
lSetitemr ple and Practical Method for Preparation of [(Diacetoxy)iodo]arenes with
Iodoarenes and m-Chloroperoxybenzoic Acid
Preparation of [(Diacetoxy)iodo]arenes
Masataka Iinuma, Katsuhiko Moriyama, Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
Fax +81(43)2902792; E-mail: togo@faculty.chiba-u.jp
Received: 23.08.2012; Accepted after revision: 11.09.2012
acid,3a or potassium peroxodisulfate3c is very difficult and
Abstract: Various [(diacetoxy)iodo]arenes bearing 4-methylphe-
generally, the yields of [(diacetoxy)iodo]arenes bearing
nyl, phenyl, 4-nitrophenyl, 3-nitrophenyl, 4-cyanophenyl, 4-bromo-
those electron-withdrawing groups are extremely low
even if the reactions are carried out under heating condi-
phenyl, 4-methoxycarbonyphenyl, 3,5-bis(trifluoromethyl)phenyl,
and 4-(N,N,N-trimethylammonium)methylphenyl groups were effi-
ciently prepared by the treatment of iodoarenes with m-chloroper- tions for a long reaction time. Recently, the preparation of
oxybenzoic acid in acetic acid. The great advantage of the present
method is the easy preparation and isolation of [(diacetoxy)-
iodo]arenes bearing electron-withdrawing groups, such as 4-nitro,
methyl groups on the aromatic ring, with iodoarenes and
4-cyano, 4-methoxycarbonyl, and 3,5-bis(trifluoromethyl) groups,
on the aromatic ring.
[bis(trifluoroacetoxy)iodo]arenes bearing electron-with-
drawing groups, such as 4-nitro, 3-nitro, and 4-trifluoro-
Oxone® in trifluoroacetic acid was reported.4
On the other hand, recently, in situ formation of hyper-
valent iodines from the reaction of iodobenzene and
m-chloroperoxybenzoic acid (MCPBA) for use in organic
synthesis has become very popular.5 We previously re-
ported the direct preparation of [(hydroxy)(tosyloxy)-
iodo]arenes from the reaction of iodoarene and
PTSA·H2O with MCPBA,6a the α-tosyloxylation of ke-
tones with iodobenzene, PTSA·H2O, and MCPBA,6b–d the
preparation of oxazoles from ketones with nitriles, iodo-
benzene, MCPBA, and TfOH,6e,f and the formation of
benzosultams from 2-arylethanesulfonamides, iodoben-
zene, and MCPBA.6g,h During this study, we found that
[(diacetoxy)iodo]arenes can be isolated by the reaction of
iodoarenes with MCPBA in acetic acid, and the products
can be obtained by simple precipitation and subsequent
filtration, after chloroform extraction of the reaction mix-
ture. The great advantage of the present method is that
[(diacetoxy)iodo]arenes bearing electron-withdrawing
groups on the aromatic ring, such as 4-nitro, 3-nitro,
4-cyano, 4-methoxycarbonyl, 3,5-bis(trifluoromethyl),
and 4-(N,N,N-trimethylammonium)methyl group, can be
prepared in good yields by the simple experimental proce-
dure. It is well known that MCPBA is a stronger oxidant
than peracetic acid, because the 3-chlorophenyl group is
an electron-withdrawing group connected to the peracid
group in MCPBA.
Key words: [(diacetoxy)iodo]arene, m-chloroperoxybenzoic acid,
iodoarene, oxidation, acetic acid, electron-deficient aromatic ring
Hypervalent iodine reagents have received considerable
attention for use in organic synthesis due to their nonme-
tallic and less toxic nature, making them environmentally
benign as well as their excellent oxidation ability with
high chemoselectivity.1 Especially [(diacetoxy)iodo]-
benzene (DIB) is one of the most typical and well-used
hypervalent iodine reagents and can be used for various
oxidative reactions.2 As typical and practical methods for
the preparation of [(diacetoxy)iodo]arenes, they are gen-
erally prepared by the reaction of iodoarenes with perace-
tic acid,2a which is generated from the reaction of acetic
anhydride and hydrogen peroxide, and with sodium
peroxoborate tetrahydrate (NaBO3·4H2O),3a as less toxic
and direct methods. Another method for the preparation of
[(diacetoxy)iodo]arenes involves the two-step conversion
of iodoarenes with CrO3 in a mixture of sulfuric acid and
acetic anhydride, followed by the treatment with ammoni-
um acetate.3b This method has a strong oxidation ability
furnishing [(diacetoxy)iodo]arenes bearing electron-with-
drawing groups, such as 4-nitro and 4-cyano groups, in
good yields. However, it requires two steps and CrO3 is
highly toxic. Recently, the preparation of [(diacetoxy)-
iodo]arenes from the reaction of iodoarenes with potassi-
um peroxodisulfate (K2S2O8) in a mixture of sulfuric acid
and acetic acid was reported as another less toxic meth-
od.3c However, the preparation of [(diacetoxy)iodo]arenes
bearing electron-deficient aromatic groups, such as
4-nitro[(diacetoxy)iodo]benzene, 4-cyano[(diacetoxy)iodo]-
Thus, to a solution of 4-iodonitrobenzene (1c) in acetic
acid was added MCPBA, and the mixture was stirred at
55 °C for 48 hours. After the reaction, water was added to
the mixture, and 4-nitro[(diacetoxy)iodo]benzene (2c)
was extracted with chloroform. After being dried over
Na2SO4, filtration, and removal of the solvent, diethyl
ether and hexane were added to the residue to provide 4-
nitro[(diacetoxy)iodo]benzene (2c) in 81% yield as a pure
isolated product.7 4-Nitro[(diacetoxy)iodo]benzene could
not be obtained by the peracetic acid method and the
peroxoborate tetrahydrate method, respectively, in our
study, due to the lower oxidation ability of those oxidants
compared to MCPBA. The reaction progress was easily
benzene,
4-methoxycarbonyl[(diacetoxy)iodo]benzene,
and 3,5-bis(trifluoromethyl)-1-[(diacetoxy)iodo]benzene,
with peracetic acid,2a sodium peroxoborate in acetic
SYNLETT 2012, 23, 2663–2666
Advanced online publication: 09.10.2012
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DOI: 10.1055/s-0032-1317345; Art ID: ST-2012-U0705-L
© Georg Thieme Verlag Stuttgart · New York

2664
M. Iinuma et al.
LETTER
Table 1 Preparation of [(Diacetoxy)iodo]arenes with Iodoarenes
and MCPBA (continued)
monitored by TLC. When 4-iodotoluene (1a) and iodo-
benzene (1b), which are much more reactive than 4-iodo-
nitrobenzene (1c), were used, each mixture of 4-
iodotoluene or iodobenzene with MCPBA in acetic acid
was stirred at room temperature to provide 4-[(diace-
toxy)iodo]toluene (2a) in 71% yield or [(diacetoxy)io-
do]benzene (2b) in 83% yield, as a pure isolated product
(Table 1, entries 1–3). Other [(diacetoxy)iodo]arenes
could be obtained in good yields by the same procedure
(Table 1, entries 4–9). Thus, using this method, both [(di-
acetoxy)iodo]arenes bearing an electron-deficient aro-
matic group, such as 4-nitrophenyl, 3-nitrophenyl, 4-
cyanophenyl, 4-methoxycarbonylphenyl, 3,5-bis(trifluo-
romethyl)phenyl, and 4-(N,N,N-trimethylammonium)-
methylphenyl, and [(diacetoxy)iodo]benzene bearing an
electron-rich aromatic group, such as 4-methylphenyl,
could be obtained in good yields by the same procedure,
although the reaction temperature and the reaction time
would depend on the reactivity of the substrates.
MCPBA ( 1.1 equiv)
AcOH, temp, time
I(OAc)2
2
Ar
Ar
I
1
Entry
Ar
Temp
(°C)
Time Product 2 Yield
(h)
(%)a
7
r.t.
24
2g
2h
70
MeO2C
1g
F3C
8
55
24
66
CF3
1h
Table 1 Preparation of [(Diacetoxy)iodo]arenes with Iodoarenes
N
and MCPBA
9
55
55
24
24
2i
2j
82
TsO
MCPBA ( 1.1 equiv)
I(OAc)2
2
Ar
Ar
I
1i
1j
AcOH, temp, time
1
Entry
Ar
Temp
Time Product 2 Yield
(h)
80b
(°C)
(%)a
10
CO2H
a Isolated yield.
1
r.t.
24
2a
71
b Product was compound 2j.
Me
OAc
1a
I
O
2
3
4
5
r.t.
55
55
55
15
48
24
9
2b
2c
2d
2e
83
81
78
80
2j
O
1b
1-Acetoxy-1,2-benziodoxole-3(1H)-one, a cyclic triva-
lent iodine, could also be obtained from 2-iodobenzoic
acid with MCPBA in good yield (Table 1, entry 10).
When the present reaction was carried out with 20 mmol
of 4-iodonitrobenzene with MCPBA at 55 °C, 4-nitro[(di-
acetoxy)iodo]benzene was obtained in over 80% yield.
Thus, the scale-up preparation of these [(diacetoxy)-
iodo]arenes can be carried out easily.
O2N
1c
O2N
1d
The chemistry of 4-nitro[(diacetoxy)iodo]benzene (2c),
which may has a stronger oxidation ability than DIB (2b),
has not been studied well. Recently, the oxidative deami-
nation of (N,N-diisopropylamino)methylarenes with DIB
at 60 °C to produce aromatic aldehydes was reported.8
Thus, we compared the reactivity of 4-nitro[(diacet-
oxy)iodo]benzene (2c) and DIB (2b) for the oxidative de-
amination of (N,N-diisopropylamino)methylarenes to
produce aromatic aldehydes at room temperature, as
shown in Table 2. The results indicate that 4-nitro[(diacet-
oxy)iodo]benzene (2c) is a more effective reagent than
DIB (2b) for the oxidative deamination of (N,N-diiso-
NC
1e
6
r.t.
24
2f
76
Br
1f
Synlett 2012, 23, 2663–2666
© Georg Thieme Verlag Stuttgart · New York

LETTER
Preparation of [(Diacetoxy)iodo]arenes
2665
Commun. 2009, 2073. (m) Uyanik, M.; Ishihara, K. Chem.
Commun. 2009, 2086. (n) Pouységu, L.; Deffieux, D.;
Quideau, S. Tetrahedron 2010, 66, 2235. (o) Zhdankin, V.
V. J. Org. Chem. 2011, 76, 1185. (p) Merritt, E. A.;
Olofsson, B. Synthesis 2011, 517. (q) Hypervalent Iodine
Chemistry, In Topics in Current Chemistry; Vol. 224; Wirth,
T., Ed.; Springer: Berlin, 2003.
Table 2 Oxidative Reaction of Tertiary Amines with 2b and 2c
oxidant (1.4 equiv),
NaHCO3 (1.2 equiv)
N
Ar
Ar
O
CHCl3, r.t., 2 h
Entry
Ar
Oxidant
Yield (%)a
(2) (a) Varvoglis, A. Hypervalent Iodine in Organic Synthesis;
Academic Press: San Diego, 1997. Reviews:
2b
2c
1
2
48
95
(b) Kirschning, A. J. Prakt. Chem. 2000, 342, 731.
(c) Kirschning, A. J. Prakt. Chem. 1998, 340, 184.
(d) Varvoglis, A. Chem. Soc. Rev. 1981, 10, 377. Recent
reports: (e) Zhao, Y.; Yim, W.; Tan, C. K.; Yeung, Y. Org.
Lett. 2011, 13, 4308. (f) Ye, Y.; Wang, H.; Fan, R. Synlett
2011, 923. (g) Fujita, M.; Wakita, M.; Sugimura, T. Chem.
Commun. 2011, 47, 3983.
2b
2c
3
4
45
91
Me
(3) (a) McKillop, A.; Kemp, D. Tetrahedron 1989, 45, 3299.
(b) Kazmierczak, P.; Skulski, L. Synthesis 1998, 1721.
(c) Hossain, M. D.; Kitamura, T. Synthesis 2005, 1932.
(4) Zagulyaeva, A. A.; Yusubov, M. S.; Zhdankin, V. V. J. Org.
Chem. 2010, 75, 2119.
2b
2c
5
6
51
92
O2N
a Isolated yield.
(5) (a) Dohi, T.; Maruyama, A.; Yoshimura, M.; Morimoto, K.;
Tohma, H.; Kita, Y. Angew. Chem. Int. Ed. 2005, 44, 6193.
(b) Ochiai, M.; Takeuchi, Y.; Katayama, T.; Sueda, T.;
Miyamoto, K. J. Am. Chem. Soc. 2005, 127, 12244.
(c) Dohi, T.; Maruyama, A.; Minamitsuji, Y.; Takenaga, N.;
Kita, Y. Chem. Commun. 2007, 1224. (d) Merritt, E. A.;
Carneiro, V. M. T.; Silva, L. F.; Olofsson, B. J. Org. Chem.
2010, 75, 7461. (e) Dohi, T.; Nakae, T.; Ishikado, Y.; Kato,
D.; Kita, Y. Org. Biomol. Chem. 2011, 9, 6899. (f) Zhong,
W.; Liu, S.; Yang, J.; Meng, X.; Li, Z. Org. Lett. 2012, 14,
3336.
propylamino)methylarenes to give the corresponding aro-
matic aldehydes in good yields, while DIB (2b) is not
effective at room temperature. Thus, 4-nitro[(diacet-
oxy)iodo]benzene (2c) has a stronger oxidation ability
than DIB (2b). We believe the wide synthetic utility of
4-nitro[(diacetoxy)iodo]benzene (2c) compared to DIB
(2b) will open doors to a new route in organic synthesis.
In conclusion, various [(diacetoxy)iodo]arenes bearing
4-methylphenyl, phenyl, 4-nitrophenyl, 3-nitrophenyl,
4-cyanophenyl, 4-bromophenyl, 4-methoxycarbonylphe-
nyl, 3,5-bis(trifluoromethyl)phenyl, and 4-(N,N,N-tri-
methylammonium)methylphenyl groups were efficiently
prepared by the treatment of iodoarenes with MCPBA in
acetic acid. The scale-up preparation of [(diacetoxy)-
iodo]arenes is easily accomplished. The great advantage
of the present method is the easy preparation and isolation
of [(diacetoxy)iodo]arenes bearing electron-withdrawing
groups, such as 4-nitro, 3-nitro, 4-cyano, 4-methoxycar-
bonyl, and 4-(N,N,N-trimethylammonium)methyl groups.
(6) (a) Yamamoto, Y.; Togo, H. Synlett 2005, 2486.
(b) Yamamoto, Y.; Togo, H. Synlett 2006, 798.
(c) Yamamoto, Y.; Kawano, Y.; Toy, P. H.; Togo, H.
Tetrahedron 2007, 63, 4680. (d) Akiike, J.; Yamamoto, Y.;
Togo, H. Synlett 2007, 2168. (e) Kawano, Y.; Togo, H.
Synlett 2008, 217. (f) Kawano, Y.; Togo, H. Tetrahedron
2009, 65, 6251. (g) Moroda, A.; Togo, H. Synthesis 2008,
1257. (h) Ishiwata, Y.; Togo, H. Tetrahedron Lett. 2009, 50,
5354.
(7) Preparation of [(Diacetoxy)iodo]benzene (2b; Non-
Electron-Deficient Iodoarene)
To a solution of 4-iodobenzene (0.61g, 3 mmol) in AcOH (3
mL) was added MCPBA (ca. 65%, 0.88 g, 3.3 mmol). The
mixture was stirred at r.t. for 2 h. Then, H2O (30 mL) was
added to the reaction mixture and then it was extracted with
CHCl3 (3 × 20 mL). After being dried over Na2SO4,
filteration, and removal of the solvent (residue ca. 3 mL),
Et2O (20 mL) and hexane (20 mL) were added to the residue,
and the mixture was cooled to 0 °C to induce precipitation
(method A). After filtration, the solids were washed with a
mixture of Et2O and hexane to provide
Acknowledgement
Financial support in the form of a Grant-in-Aid for Scientific Re-
search (No. 20550033) from the Ministry of Education, Culture,
Sports, Science, and Technology in Japan and the Iodine Research
Project in Chiba University is gratefully acknowledged.
[(diacetoxy)iodo]benzene in 83% yield.
Preparation of 4-Nitro[(diacetoxy)iodo]benzene (2c;
Electron-Deficient Iodoarene)
References and Notes
To a solution of 4-iodonitrobenzene (0.75g, 3 mmol) in
AcOH (20 mL) was added MCPBA (ca. 65%, 0.88 g, 3.3
mmol). The mixture was stirred for 48 h at 55 °C. Then, H2O
(30 mL) was added to the reaction mixture and then it was
extracted with CHCl3 (3 × 20 mL). After being dried over
Na2SO4, filteration, and removal of the solvent (residue ca. 3
mL), Et2O (20 mL) and hexane (20 mL) were added to the
residue, and the mixture was cooled to –78 °C to induce
precipitation (method B). After filtration, the solids were
washed with a mixture of Et2O and hexane to provide
4-nitro[(diacetoxy)iodo]benzene in 81% yield.
(1) Recent reviews: (a) Togo, H.; Katohgi, M. Synlett 2001, 565.
(b) Zhdankin, V. V.; Stang, P. J. Chem Rev. 2002, 102, 2523.
(c) Stang, P. J. J. Org. Chem. 2003, 68, 2997. (d) Tohma, H.;
Kita, Y. Adv. Synth. Catal. 2004, 346. (e) Moriarty, R. M.
J. Org. Chem. 2005, 70, 2895. (f) Wirth, T. Angew. Chem.
Int. Ed. 2005, 44, 3656. (g) Richardson, R. D.; Wirth, T.
Angew. Chem. Int. Ed. 2006, 45, 4402. (h) Ochiai, M. Chem.
Rev. 2007, 7, 12. (i) Zhdankin, V. V.; Stang, P. J. Chem. Rev.
2008, 108, 5299. (j) Merritt, E. A.; Olofsson, B. Angew.
Chem. Int. Ed. 2009, 48, 9052. (k) Ochiai, M.; Miyamoto, K.
Eur. J. Org. Chem. 2008, 4229. (l) Dohi, T.; Kita, Y. Chem.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2663–2666

2666
M. Iinuma et al.
LETTER
Conditions for the Precipitation of (Diacetoxyiodo)arenes
Method A
Et2O (20 mL) and hexane (20 mL) were added to the residue,
and the mixture was cooled at 0 °C for (diacetoxy-
iodo)benzene, 4-cyano(diacetoxyiodo)benzene, and 1-
acetoxy-1,2-benziodoxole-3(1H)-one.
4-Bromo(diacetoxyiodo)benzene
Mp 116–118 °C (lit.3b mp 120–122 °C). IR (KBr): 669, 746,
804, 1380, 1411, 1644 cm–1. 1H NMR (500 MHz, CDCl3,
TMS): δ = 2.01 (s, 6 H), 7.62 (d, 2 H, J = 8.6 Hz), 7.95 (d, 2
H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS):
δ = 20.31, 119.58, 126.80, 134.15, 136.41, 176.50.
4-Bromo(diacetoxyiodo)benzene
Method B
Et2O (20 mL) and hexane (20 mL) were added to the residue,
and the mixture was cooled at –78 °C for 4-nitro[(diacet-
oxy)iodo]benzene and 3-nitro[(diacetoxy)iodo]benzene.
Method C
Et2O (20 mL) and hexane (40 mL) were added to the residue,
and the mixture was cooled at –78 °C for 4-bromo[(diacet-
oxy)iodo]benzene, 4-methoxycarbonyl[(diacet-
oxy)iodo]benzene, (diacetoxy)iodotoluene, and 3,5-
bis(trifluoromethyl)-1-[(diacetoxy)iodo]benzene.
Method D
Mp 116–118 °C (lit.3b mp 120–122 °C). IR (KBr): 669, 746,
804, 1380, 1411, 1644 cm–1. 1H NMR (500 MHz, CDCl3,
TMS): δ = 2.01 (s, 6 H), 7.62 (d, 2 H, J = 8.6 Hz), 7.95 (d, 2
H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS):
δ = 20.31, 119.58, 126.80, 134.15, 136.41, 176.50.
4-Methoxycarbonyl(diacetoxyiodo)benzene
Mp 127–130 °C. IR (KBr): 670, 755, 826, 1284, 1410, 1566,
1642, 1716 cm–1. 1H NMR (500 MHz, CDCl3, TMS):
δ = 2.02 (s, 6 H), 3.97 (s, 3 H), 8.13 (d, 2 H, J = 8.9 Hz), 8.17
(d, 2 H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS):
δ = 20.25, 52.65, 125.67, 131.74, 133.00, 134.84, 165.45,
176.45. ESI-HRMS: m/z [M + Na]+ calcd for C12H13O6INa:
402.9649; found: 402.9639.
Et2O (30 mL) was added to the residue for 4-
[(diacetoxy)iodo]benzyl-N,N,N-trimethylammonium
tosylate.
(Diacetoxyiodo)toluene
3,5-Bis(trifluoromethyl)-1-(diacetoxyiodo)benzene
Mp 102–104 °C (lit.3c mp 108–110 °C). IR (KBr): 670, 1131,
1185, 1278, 1349, 1369, 1649 cm–1. 1H NMR (125 MHz,
CDCl3, TMS): δ = 2.05 (s, 6 H), 8.09 (s, 1 H), 8.51(s, 2 H).
13C NMR (500 MHz, CDCl3, TMS): δ = 20.24, 129.03,
Mp 102–103 °C (lit.3c mp 106–108 °C). IR (KBr): 663, 1267,
1410, 1567, 1649 cm–1. 1H NMR (500 MHz, CDCl3 TMS):
δ = 2.00 (s, 6 H), 2.45 (s, 3 H), 7.30 (d, 2 H, J = 8.3 Hz), 7.97
(d, 2 H, J = 8.3 Hz). 13C NMR (125 MHz, CDCl3, TMS):
δ = 20.27, 21.43, 118.27, 131.65, 134.88, 142.57, 176.26.
(Diacetoxyiodo)benzene
123.21, 125.49, 133.73 (q, J = 34.4 Hz), 134.95, 176.97. 19
NMR (500 MHz, CDCl3, TMS): δ = –62.72 (CF3).
F
Mp 156–158 °C (lit.9 mp 161–162 °C). IR (KBr): 666, 743,
1271, 1644 cm–1. 1H NMR (500 MHz,CDCl3, TMS):
δ = 2.01 (s, 6 H), 7.49 (d, 2 H, J = 7.3 Hz), 7.60 (t, 1 H,
J = 7.4 Hz), 8.10 (d, 2 H, J = 7.5 Hz). 13C NMR (125 MHz,
CDCl3, TMS): δ = 20.32, 121.57, 130.92, 131.69, 134.90,
176.37.
4-[(Diacetoxy)iodo]benzyltrimethylammonium Tosylate
Oil. IR (neat): 566, 684, 1009, 1034, 1123, 1186, 1267,
1482, 1646 cm–1. 1H NMR (500 MHz, DMSO-d6): δ = 1.90
(s, 6 H), 2.28 (s, 3 H), 3.04 (s, 9 H), 4.60 (s, 2 H), 7.12 (d, 2
H, J = 7.8 Hz), 7.50 (d, 2 H, J = 7.7 Hz), 7.73 (d, 2 H J = 8.0
Hz), 8.07 (d, 2 H, J = 8.0 Hz). 13C NMR (125 MHz, DMSO-
d6): δ = 20.82, 21.11, 51.94, 67.05, 97.85, 125.52, 127.17,
128.16, 133.31, 134.86, 137.81, 145.59, 172.08. ESI-HRMS
(+): m/z calcd for C14H21O4NI: 394.0510; found: 394.0497.
ESI-HRMS (anion): m/z calcd for C7H7O3S: 171.0110;
found: 171.0113.
4-Nitro(diacetoxyiodo)benzene
Mp 103–104 °C (lit.3c mp 104–105 °C). IR (KBr): 673, 734,
849, 1274, 1348, 1414, 1515, 1570, 1644 cm–1. 1H NMR
(500 MHz, CDCl3, TMS): δ = 2.03 (s, 6 H), 8.28 (d, 2 H,
J = 9.1 Hz), 8.32 (d, 2 H, J = 9.3 Hz). 13C NMR (125 MHz,
CDCl3, TMS): δ = 20.27, 125.59, 126.72, 136.03, 149.40,
176.66.
1-Acetoxy-1,2-benziodoxole-3-(1H)-one
Mp 168–170 °C (lit.10 mp 164–168 °C). IR (KBr): 743,
1563, 1613 cm–1. 1H NMR (500 MHz, DMSO-d6): δ = 1.90
(s, 3 H), 7.70 (t, 1 H, J = 7.2 Hz), 7.84 (d, 1 H, J = 8.0 Hz),
3-Nitro(diacetoxyiodo)benzene
Mp 144–146 °C (lit.3b mp 148–150 °C). IR (KBr): 714, 815,
1346, 1569, 1647 cm–1. 1H NMR (500 MHz, CDCl3, TMS):
δ = 2.04 (s, 6 H), 7.73 (t, 1 H, J = 8.2 Hz), 8.40 (d, 1 H,
J = 9.7 Hz), 8.45 (d, 1 H, J = 9.3 Hz), 8.95 (s, 1 H). 13C NMR
(125 MHz, CDCl3, TMS): δ = 20.28, 120.60, 126.31,
130.07, 131.50, 140.37, 148.65, 176.78.
7.96 (t, 1 H, J = 7.6 Hz), 8.01 (d, 1 H, J = 7.5 Hz). 13
C
NMR(500 MHz, DMSO-d6): δ = 21.08, 120.45, 126.31,
130.40, 131.13, 131.52, 134.52, 167.77, 172.07.
(8) Desjardins, S.; Jacquemot, G.; Canesi, S. Synlett 2012, 23,
1497.
4-Cyano(diacetoxyiodo)benzene
(9) Leffler, J. E.; Story, L. J. J. Am. Chem. Soc. 1967, 89, 2333.
(10) Eisenberger, P.; Gischig, S.; Togni, A. Chem.–Eur. J. 2006,
12, 2579.
Mp 168–170 °C (lit.3b mp 172–173 °C). IR (KBr): 673, 821,
1009, 1270, 1650, 2227 cm–1. 1H NMR (500 MHz, CDCl3,
TMS): δ = 2.03 (s, 6 H), 7.78 (d, 2 H, J = 8.9 Hz), 8.20 (d, 2
H, J = 8.6 Hz). 13C NMR (125 MHz, CDCl3, TMS):
δ = 20.26, 115.65, 117.05, 125.20, 134.01, 135.54, 176.61.
Synlett 2012, 23, 2663–2666
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