Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite Pentahydrate

Article abstract of DOI:10.1021/acs.joc.8b02541

A practical method for the preparation of (diacetoxyiodo)arene ArI(OAc)₂ is described. The use of commercially available sodium hypochlorite pentahydrate (NaClO·5H₂O) enabled safe, rapid, and inexpensive oxidation of iodoarenes with electron-withdrawing and -donating substituents. The method allows tandem divergent access to synthetically useful organo-λ³-iodanes such as hydroxyl(tosyloxy)iodobenzene, iodosylbenzene, iodonium ylide, etc.

Full text of DOI:10.1021/acs.joc.8b02541

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Featured Article
Safer Synthesis of (Diacetoxyiodo)arenes using
Sodium Hypochlorite Pentahydrate (NaClO•5H2O)
Ayumi Watanabe, Kazunori Miyamoto, Tomohide Okada, Tomotake Asawa, and Masanobu Uchiyama
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02541 • Publication Date (Web): 03 Nov 2018
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Safer Synthesis of (Diacetoxyiodo)arenes using Sodium Hypochlorite Pentahydrate
(NaClO•5H2O)
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Ayumi Watanabe,1 Kazunori Miyamoto,1,* Tomohide Okada,2 Tomotake Asawa,2 and Masanobu
Uchiyama1,3,*
1Graduate School of Pharmaceutical Sciences, The University of Tokyo
2R&D Department of Chemicals, Nippon Light Metal Company, Ltd.
3Cluster for Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN
ABSTRACT: A practical method for the preparation of (diacetoxyiodo)arene ArI(OAc)2 is
described. The use of commercially available NaClO•5H2O enabled safe, rapid, and inexpensive
oxidation of iodoarenes with electron-withdrawing and -donating substituents. The method allows
tandem divergent access to synthetically useful organo λ3-iodanes such as
hydroxyl(tosyloxy)iodobenzene, iodosylbenzene, iodonium ylide, etc.
Introduction
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(Diacetoxyiodo)arene ArI(OAc)2 2 is one of the most synthetically useful oxidizing agents in the
hypervalent organo-λ3-iodane family.1 The parent compound (diacetoxyiodo)benzene (2a) has
enjoyed widespread application as a powerful and versatile oxidant and an excellent platform for
construction of other di(hetero)iodoarenes, mainly because of its high thermal stability (storable
indefinitely on the bench-top), non-explosive character and low toxicity. It can oxidize a wide range
of functionalities, including alkenes, alkynes, alcohols, phenols, amines, sulfides, and carbonyl
compounds under mild conditions.1,2 However, despite its importance in synthetic organic chemistry,
2a is still rather costly (available commercially at ca. 320 $/mol)3a compared to the precursor,
iodobenzene (1a) (ca. 40 $/mol).3a This is partly because of the limitations of current synthetic
methods (Scheme 1). For instance, a representative preparation method involves oxidation of
iodoarenes 1 with excess amount of peracetic acid (3) in AcOH at 40 °C. This method requires strict
temperature control: at lower temperature, the reaction rate slows down significantly, while at
higher temperature over-oxidation to pentavalent iodine species occurs.4a More importantly, 3 is an
explosive compound and has been the cause of serious accidents.4b,c In 1989, McKillop and Kemp
reported a safer and more convenient method for the synthesis of 1 using sodium perborate
tetrahydrate (4) in AcOH.5a Although this method is potentially applicable to variously
functionalized iodoarenes, it generally requires the use of an excess amount of oxidant 4 (≥ 10 eq)
and tedious work-up.5b Sodium periodate (5) oxidation in Ac2O/AcOH is a promising method, but is
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limited to electron-rich or weakly electron-deficient substrates 1.6 A combination of CrO3/H2SO4 in
Ac2O-AcOH can oxidize highly electron-deficient iodoarenes such as p-nitroiodobenzene (1b),7a
but this method requires special precautions to prevent explosions,7b and cannot be applied to
electron-rich substrates.7 In 2008, Togo and co-workers reported a simple and efficient method for
the synthesis of 2 using m-chloroperbenzoic acid (6) in AcOH (Scheme 1).8 This method shows
wide applicability to both electron-rich and -deficient iodoarenes 1, but the relatively high cost of 6
(ca. 244 $/mol)3a limits its applicability for large-scale synthesis. Although Kitamura’s method
using potassium peroxydisulfate (7) is economical (K2S2O8 costs ca. 11$/mol),3b this method
requires an excess of strong acid, such as H2SO4 or CF3SO3H, to activate 7.9 In this context, there is
an urgent need for a safer, inexpensive, and operationally simple method for the preparation of 2
that is compatible with various iodoarenes (1). We report herein a new, practical preparation method
for 2 using sodium hypochlorite pentahydrate (NaClO•5H2O) 8 as an oxidant, providing convenient
access to various synthetically useful hypervalent iodine(III) reagents.
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Scheme 1. Synthesis of (diacetoxyiodo)arene 2: comparison between previous methods and the
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present method.
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Results and Discussion
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NaClO•5H2O (8) is a classical oxidant discovered about 100 years ago.10 Little attention was paid to
it as a reagent for organic synthesis until 2013,11 but now 8 is widely available from various
suppliers at low cost (ca. 15 $/mol).3b Considering its high purity and potent oxidation ability, we
thought that the use of 8 for the preparation of 2 could overcome the above-mentioned difficulties
in the oxidation of iodoarenes 1. Indeed, 8 has already attracted attention as a clean and inexpensive
oxidant for alcohols, 1,2-diols, thiols, sulfides, and phenols.11
We commenced this study by examining the direct oxidation of 1 with 8. Exposure of 8 (2
mmol) to equimolar iodobenzene (1a) in the absence of solvent resulted in the recovery of 1a after
1 hour at room temperature. This result indicates that the oxidation ability of 8 is insufficient under
weakly basic conditions. However, when the reaction was carried out in AcOH, a pale yellow
precipitate was formed within 10 min, and 2a was obtained in 91% yield by means of a simple
filtration-evaporation sequence (Table 1, entry 1). This reaction was not sensitive to the reagent
concentration in the range of 0.3–2.6 M (entries 2–4). The optimized conditions could be easily
scaled-up to 70 mmol (1a, 14 g) (entry 5). In a large-scale reaction, no significant evolution of heat
was observed. Interestingly, when 4% aqueous NaClO solution was used instead of 8, 2a was not
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obtained at all, but a large amount of iodylbenzene PhIO2 (9a) was produced instead (entry 6),
which is consistent with Zhdankin’s report.12 It is worth noting that the yield of 2a was proportional
to the concentration of aqueous NaClO solution (entries 1, 6–9; Figure 1), suggesting that H2O may
promote the over-oxidation of 2a to 9a (see also Scheme 3). Ca(ClO)2•3H2O also served as a good
oxidant, but the reaction rate was slower, probably because of the lower solubility of this reagent in
AcOH (entry 10). NaClO•2.5H2O also afforded 2a in 91% yield under the same conditions. Use of
a co-solvent was found to be effective to reduce the required amount of AcOH. Thus, in MeCN and
CH2Cl2, the amount of AcOH could be reduced to 3.0 or 2.1 equivalents without any decrease in
yield (entries 11–13), while the use of ethyl acetate, dimethyl carbonate, and acetone resulted in fair
yields (entries 14–16). However, toluene was not effective for this reaction (entries 17 and 18).
Propionic acid was also available for this transformation (entry 19).
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Further studies on the scope and limitations indicated that this method is a powerful tool for
rapid preparation of various (diacetoxyiodo)arenes. The optimized conditions are widely applicable
not only to highly electron-deficient 4- and 3-nitroiodobenzenes (1b and c),
3,5-bis(trifluoromethyl)iodobenzene (1d), and pentafluoroiodobenzene (1e), but also to
electron-rich 4-methoxyiodobenzene (1j), iodomesitylene (1k), and 1-iodonaphthalene (1l),
affording the products in good to high yields (Table 2). It should be noted that the oxidation of 1b
with 6 was completed after only 10 min under our conditions, whereas when m-CPBA 6 was used,
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the reaction required an elevated temperature (55 °C) and a prolonged reaction time (48 h).8 Other
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recyclable iodoarenes 1m–o were also good substrates.13
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Table 1. Reaction of 1a with NaClO•5H2O 8.a
entry
1a
oxidant
solvent
(M)
time
(min)
10
5
2a yield
(%)
91
(mmol)
1
2
2
2
8
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
MeCN
1.3
0.3
0.7
2.6
1.3
1.3
1.3
1.3
1.3
1.3
1.3
8
70
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2
8
5
78
4
2
8
10
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69
5
70
2
8
79
6
4% NaClO aq.
12% NaClO aq.
20% NaClO aq.
30% NaClO aq.
Ca(ClO)2•3H2Oc
8
0b
7
2
14
8
2
44
9
2
65
10
11d
2
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2
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12e
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8
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MeCN
CH2Cl2
AcOEt
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(MeO)2CO
acetone
toluene
toluene
MeCN
a Unless otherwise noted, reactions were carried out using exactly 1.0 eq of 8 in AcOH at room
temperature under air. PhIO2 9a (90%) was obtained instead of 2a. 0.6 eq. d AcOH (3.0 eq).
b
c
e
AcOH (2.1 eq). f EtCO2H (3.0 eq). g PhI(OCOEt)2 10 was obtained.
Figure 1. Relationship between concentration of NaClO and yield of 2a.
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Table 2. Synthesis of (diacetoxyiodo)arene 2.a
5
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7
8
9
NaClO•5H2O
8
OAc
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Ar
Ar
I
I
optimized conditions
OAc
1
2
AcO I OAc
AcO I OAc
AcO I OAc
AcO I OAc
AcO I OAc
F
F
NO2
F3C
CF3
F
F
NO2
F
CO2Me
2b
2c
2d
2e
87%b
2f
76%c
76%
91%
63%
AcO I OAc
AcO I OAc
AcO I OAc
AcO I OAc
AcO I OAc
Me
Me
Br
F
Me
Me
2k
OMe
2g
2h
(78%)d
2i
2j
61%c
100%
69%
(74%)d
78%
(89%)d
(73%)c,d
AcO I OAc
I OH
AcO I OAc
OAc
I
OAc
I
OAc
OAc
CO2
t-Bu
2o
65%c
n
2n
81%d,e
2l
2m
85%c
75%
a Reaction conditions: 1 (2 mmol), 8 (1–1.4 eq), AcOH (1.5 mL), rt, air, 10 min. b 8 (2 eq). c ca. 5–
10% of µ-oxo dimers were contaminated. d AcOH (3 eq) in MeCN or CH2Cl2 (1.5 mL) was used. e
Yield was determined by iodometry.
Our strategy can be extended to the divergent preparation of various hypervalent λ3-iodanes
(Scheme 2). Thus, after reaction of 1a with 8 (1 eq) and AcOH (3 eq) in MeCN for 10 min (same as
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Table 1, entry 11), the 2a obtained can be used directly for further transformations without
purification. Thus, treatment of TsOH•H2O, CF3CO2H, and NaOH resulted in the formation of
hydroxy(tosyloxy)iodobenzene (11), bis(trifluoroacetoxy)iodobenzene (12), and iodosylbenzene
(13) in fairly good yields; all of these compounds are important reagents in current synthetic
organic chemistry.14 Furthermore, reaction with dimedone and p-nitrobenzenesulfonamide under
basic conditions afforded iodonium ylide 14 and imino-λ3-iodane 15 in good to high yields.15
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O O
S
N– I+
p-NO2C6H4
Ph
15 73%
TsO
I
OH
TsOH•H2O
(1.0 eq)
O O
S
KOH
(3.5 eq)
rt, 12 h
p-NO2C6H4
NH2
(1.0 eq)
rt,
5 min
78%
11
I
8 (1.0 eq)
AcOH (3.0 eq)
CF3COOH
(6.5 eq)
I
AcO
I
OAc
F3CCOO
OCOCF3
rt, 10 min
MeCN, rt, 10 min
1a
2a
12
I
83%
NaOH
(4.5 eq)
O
O
K2CO3
(3.2 eq)
rt,
30 min
O
rt,
10 min
(1.0 eq)
O
n
–
I+
70%
13
Ph
O
88%
14
Scheme 2. Divergent synthesis of various hypervalent iodine(III) reagents.
A plausible reaction mechanism is illustrated in Scheme 3. (1) Nucleophilic attack of iodoarene
1 to hypochloric acid (HOCl) 16 generated by the reaction between 8 and acetic acid,16 to form
acetoxy(chloro)-λ3-iodane intermediate 17, followed by (2) ligand exchange with acetate ion results
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in the formation of the more stable 2. On the other hand, in the presence of a large amount of water,
(3) a competitive ligand exchange yielding more electron-rich dihydroxy-λ3-iodane 18 might occur.
18 thus generated would probably undergo further chlorination with 8 to afford pentavalent
iodylarene 9.
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+
+
+
AcONa
5H2O
AcOH
Cl OH
pKa = 7.3
16
NaClO•5H2O
pKa = 4.8
8
(2)
AcO IIII Cl AcONa
(1)
AcO IIII OAc
II
AcOH
+
16
R
R
R
NaCl
H2O
1
2
17
(3)
O
HO IIII OH
IV
O
R
H2O
8
or
2
17
R
AcOH
or
HCl
18
9
Scheme 3. Proposed reaction mechanism.
In conclusion, we have developed a very convenient method for the rapid, safe and efficient
synthesis of (diacetoxyiodo)arenes 2 using sodium hypochlorite pentahydrate (8) and acetic acid. It
is noteworthy that this method can be scaled up safely, since neither toxic molecular chlorine nor
explosive peracetic acid was detected under the reaction conditions employed. This method
provides a practical and rapid route to various synthetically useful organo λ3-iodanes. Further
studies on the preparation of tri/pentavalent organoiodine reagents with hypochlorite salt, as well as
applications of this concept to iodoarene-catalyzed oxidation reactions are under investigation.
EXPERIMENTAL SECTION
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IR spectra were recorded on a FT-IR instrument. H NMR, C NMR, and F NMR spectra were
obtained on 500 MHz spectrometer. Chemical shifts (δ) are reported in parts per million (ppm)
downfield from internal Me4Si. Low mass spectra (MS) were measured on TOF-MS with an ESI
probe. Melting points were determined with melting points apparatus and are uncorrected.
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(Diacetoxyiodo)arenes 2 from Iodoarenes 1: General Procedure without Solvent
To a vigorously stirred solid of NaClO•5H2O 8 (329 mg, 2.0 mmol) was added iodoarene 1 (2
mmol) and AcOH (1.5 mL) at room temperature under air and the mixture was stirred for 10
minutes. After addition of CH2Cl2 (ca. 20 mL, it can be replaced by other solvent such as AcOEt or
CHCl3. If large amount of insoluble residue remained, addition of EtOH (ca. 5 mL) was very
effective to re-dissolve it), the reaction mixture was filtered (removes NaCl and water) and solvents
were removed under reduced pressure to give a pale yellow solid, which was washed several times
with hexane or hexane-toluene by decantation to give (diacetoxyiodo)arene 2 in almost pure form.
Further purification was achieved by 1) a short boiling of the crude 2 in AcOEt-Ac2O (>10:1) until
it becomes clear solution and cooled to room temperature, 2) recrystallization by addition of excess
hexane/Et2O-hexane at 5 ºC or -20 ºC. Otherwise, the crude 2 was purified by following procedure.
The crude residue (after evaporation) was added AcONa (4 mmol) and stirred in AcOEt (5 mL) at
room temperature for 30 min, followed by the filtration and concentration under reduced pressure to
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give pure 2 as a white solid. In several cases, small amount of corresponding µ-oxo dimer
[ArI(OAc)–O–I(OAc)Ar] could not be separated.
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(Diacetoxyiodo)arenes 2 from Iodoarenes 1: General Procedure with Solvent
To a vigorously stirred suspension of NaClO•5H2O 8 (329 mg, 2.0 mmol) in appropriate solvent
(1.5 mL) was added iodoarene 1 (2 mmol) and AcOH (343 µL, 6.0 mmol) at room temperature
under air and the mixture was stirred for 10 minutes. After addition of CH2Cl2 (ca. 20 mL, it can be
replaced by other solvent such as AcOEt or CHCl3. If large amount of insoluble materials remained,
addition of EtOH (ca. 5 mL) was very effective to re-dissolve it), the reaction mixture was filtered
(removes NaCl and water) and solvents were removed under reduced pressure to give a pale yellow
solid, which was washed several times with hexane or hexane-toluene by decantation to give
(diacetoxyiodo)arene 2 in almost pure form. Analytically pure sample of 2 was obtained by
following the above-mentioned procedures (general procedure without solvent).
Large-scale synthesis of 2a
In a well-ventilated food, to a vigorously stirred solid of NaClO•5H2O 8 (11 g, 70 mmol) in a 1 L
beaker was added iodobenzene (7.5 mL, 67 mmol) in AcOH (100 mL) at room temperature under
air. After 10 minutes, CH2Cl2 (200 mL) and toluene (200 mL) were added and separated aqueous
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phase was removed and filtered. The filtrate was concentrated to a half of its original volume (ca.
50 mL) under reduced pressure to yield white suspension, which was then added excess hexane
(~200 mL) and filtered to give 2a (17 g, 79%) as a white solid. Analytically pure sample of 2a was
obtained by following the above-mentioned procedures (general procedure without solvent).
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(Diacetoxyiodo)benzene (2a):5b colorless prisms (586 mg, obtained from 2 mmol of starting
material, purity 97% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.09 (dd, J = 8.4, 1.2 Hz, 2H),
7.62 (tt, J = 7.4, 1.2 Hz, 1H), 7.60 (dd, J = 8.4, 7.6 Hz, 2H), 2.01 (s, 6H); 13C{1H} NMR (125 MHz,
CDCl3): δ = 176.3, 134.8, 131.6, 130.8, 121.5, 20.2.
4-Nitro(diacetoxyiodo)benzene (2b):8 colorless prisms (558 mg, obtained from 2 mmol of starting
material, purity 97% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.32 (d, J = 9.1 Hz, 2H), 8.30
(d, J = 9.1 Hz, 2H), 2.04 (s, 6H); 13C{1H} NMR (125 MHz, CDCl3): δ = 176.7, 149.4, 136.0, 126.7,
125.6, 20.2.
3-Nitro(diacetoxyiodo)benzene (2c):5b colorless prisms (668 mg, obtained from 2 mmol of starting
material, purity 95% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.94 (m, 1H), 8.44 (m, 1H),
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8.40 (m, 1H), 7.72 (t, J = 8.2 Hz, 1H), 2.04 (s, 6H); C{1H} NMR (125 MHz, CDCl3): δ = 176.8,
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148.6, 140.4, 131.5, 130.1, 126.3, 120.6, 20.3.
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3,5-Bis(trifluoromethyl)(diacetoxyiodo)benzene (2d):8 white microcrystalline solid (577 mg,
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obtained from 2 mmol of starting material, purity 100% by iodometry); H NMR (500 MHz,
CDCl3): δ = 8.50 (s, 2H), 8.07 (s, 1H), 2.05 (s, 6H); 19F NMR (470 MHz, CDCl3): δ = -62.88 (s,
6F); C{1H} NMR (125 MHz, CDCl3): δ = 177.0, 135.0, 133.8 (q, JCF = 34.7 Hz), 125.5 (br s),
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122.2 (q, 1JCF = 273.0 Hz), 121.0, 20.3.
2,3,4,5,6-Pentafluoro(diacetoxyiodo)benzene (2e): white microcrystalline solid (717 mg, obtained
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from 2 mmol of starting material, purity 97% by iodometry); mp 89–91 ºC; H NMR (500 MHz,
CDCl3): δ = 2.01 (s, 6H); 19F NMR (CDCl3, 470 Hz): δ = -120.90– -121.10 (m, 2F), -144.59 (tt, J =
20.7, 4.5 Hz, 1F), -156.42– -156.59 (m, 2F); C{1H} NMR (125 MHz, CDCl3): d = 178.2, 146.8–
13
146.4 (m), 146.0–145.6 (m), 144.7–144.4 (m), 143.9–143.5 (m), 138.5–138.0 (m), 136.4–136.0 (m),
95.9 (t, JCF = 26.5 Hz), 20.0; HRMS (ESI, positive) m/z calcd for C10H6F5INaO4 [(M + Na)+]
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434.9129, found 434.9110.
4-Methoxycarbonyl(diacetoxyiodo)benzene (2f):8 white microcrystalline solid (638 mg, obtained
from 2 mmol of starting material, purity 91% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.01
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(d, J = 9.1 Hz, 2H), 6.96 (d, J = 9.1 Hz, 2H), 3.86 (s, 3H), 2.00 (s, 6H); 13C{1H} NMR (125 MHz,
CDCl3): δ = 176.5, 165.5, 134.9, 133.0, 131.8, 125.7, 52.7, 20.3.
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4-Bromo(diacetoxyiodo)benzene (2g):17 colorless prisms (593 mg, obtained from 2 mmol of
starting material, purity 96% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 7.95 (d, J = 8.0 Hz,
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2H), 7.62 (d, J = 8.0 Hz, 2H), 2.01 (s, 6H); C{1H} NMR (125 MHz, CDCl3): δ = 176.5, 136.5,
134.2, 126.8, 119.6, 20.3.
4-Fluoro(diacetoxyiodo)benzene (2h):5b white microcrystalline solid (530 mg, obtained from 2
mmol of starting material, purity 99% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.08 (dd, J
= 8.9 Hz, 4JHF = 5.2 Hz, 2H), 7.18 (dd, J = 8.9 Hz, 3JHF = 8.2 Hz, 2H), 2.01 (s, 6H); 19F NMR (470
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MHz, CDCl3): δ = -105.68 (s, 1F); C{1H} NMR (125 MHz, CDCl3): δ = 176.5, 164.3 (d, JCF
=
254.3 Hz), 137.6 (d, 3JCF = 9.0 Hz), 118.6 (d, 2JCF = 22.4 Hz), 115.5 (d, 4JCF = 3.3 Hz), 20.3.
4-Methyl(diacetoxyiodo)benzene (2i):5b white microcrystalline solid (598 mg, obtained from 2
mmol of starting material, purity 95% by iodometry); 1H NMR (500 MHz, CDCl3): δ =7.97 (d, J =
8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 2.44 (s, 3H), 2.00 (s, 6H); 13C{1H} NMR (125 MHz, CDCl3):
δ = 176.3, 142.5, 134.8, 131.6, 118.2, 21.3, 20.2.
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4-Methoxy(diacetoxyiodo)benzene (2j):18 white microcrystalline solid (485 mg, obtained from 2
mmol of starting material, purity 88% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.01 (d, J =
9.0 Hz, 2H), 6.97 (d, J = 9.0 Hz, 2H), 3.87 (s, 3H), 2.00 (s, 6H); 13C{1H} NMR (125 MHz, CDCl3):
δ = 176.4, 162.1, 137.1, 116.6, 111.6, 55.6, 20.3.
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2,4,6-Trimethyl(diacetoxyiodo)benzene (2k):19 white microcrystalline solid (728 mg, obtained
from 2 mmol of starting material, purity 99% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 7.10
(s, 2H), 2.71 (s, 6H), 2.36 (s, 3H), 1.97 (s, 6H); 13C{1H} NMR (125 MHz, CDCl3): δ = 176.5, 143.2,
141.3, 129.5, 128.9, 26.7, 21.2, 20.3.
1-(Diacetoxyiodo)naphthalene (2l):20 white microcrystalline solid (558 mg, obtained from 2 mmol
of starting material, purity 98% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.50 (dd, J = 7.5,
0.8 Hz, 1H), 8.13 (d, J = 8.3 Hz, 1H), 8.10 (d, J = 8.5 Hz, 1H), 7.91 (d, J = 8.3 Hz, 1H), 7.75–7.70
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(m, 1H), 7.67–7.62 (m, 1H), 7.53 (t, J = 7.8 Hz, 1H), 1.93 (s, 6H); C{1H} NMR (125 MHz,
CDCl3): δ = 176.6, 137.1, 134.4, 133.5, 131.3, 129.6, 129.2, 129.1, 127.6, 126.6, 125.3, 20.2.
4-tert-Butyl(diacetoxyiodo)benzene (2m):21 white microcrystalline solid (718 mg, obtained from 2
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mmol of starting material, purity 90% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 7.99 (d, J =
8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 2.01 (s, 6H), 1.35 (s, 9H); 13C{1H} NMR (125 MHz, CDCl3):
δ = 176.4, 155.5, 134.5, 128.2, 118.1, 31.1, 20.4.
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4,4’-Bis(diacetoxyiodo)biphenyl (2o):22 white microcrystalline solid (874 mg, obtained from 2
mmol of starting material, purity 98% by iodometry); 1H NMR (500 MHz, CDCl3): δ = 8.20 (d, J =
13
8.5 Hz, 4H), 7.67 (d, J = 8.5 Hz, 4H), 2.04 (s, 6H); C{1H} NMR (125 MHz, CDCl3): δ = 176.8,
142.7, 135.6, 129.7, 121.2, 20.2.
(Dipropionyloxyiodo)benzene (10):23 colorless prisms (518 mg, obtained from 2 mmol of starting
1
material, purity 96% by iodometry); H NMR (500 MHz, CDCl3): δ = 8.08 (dd, J = 8.5, 1.0 Hz, 2H),
7.59 (tt, J = 7.5, 1.0 Hz, 1H), 7.49 (dd, J = 8.5, 7.5 Hz, 2H), 2.28 (q, J = 7.6 Hz, 4H), 1.07 (t, J = 7.6
Hz, 6H); 13C{1H} NMR (125 MHz, CDCl3): δ = 179.5, 134.8, 131.6, 130.8, 121.7, 27.2, 9.8.
Synthesis of 3-Iodosylbenzoic Acid (2n)
To a vigorously stirred suspension of NaClO•5H2O 8 (329 mg, 2.0 mmol) and 3-iodobenzoic acid
(1n) (496 mg, 2 mmol) in MeCN (1.5 mL) was added AcOH (344 µL, 3.0 mmol) slowly at room
temperature under air and the mixture was stirred for 10 minutes. After the reaction mixture was
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added H2O (10 mL), the solid thus generated was filtered and washed twice with H2O (10 mL),
followed by twice with acetone (10 mL) and Et2O (10 mL) (removes NaCl, starting materials, and
water). The residue was dried at room temperature in the dark overnight to give 3-iodosylbenzoic
acid (2n) (435 mg (98% purity), 81%) as a pale yellow solid. The purity of 2p (98%) was
determined by common iodometric titration using 10% KI aqueous solution, AcOH, and 0.1 M
Na2S2O3 aqueous solution.
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3-Iodosylbenzoic acid (2n):24 ATR-FTIR (neat) ν = 3082, 1650, 1622, 1265, 1171, 745, 707, 534
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cm-1; H NMR (CDCl3-TFA 20:1): δ = 8.95–8.93 (m, 1H), 8.51–8.45 (m, 2H), 7.83–7.79 (m, 1H);
13C{1H} NMR (125 MHz, CDCl3): δ = 169.9, 140.3, 136.9, 135.2, 132.4, 132.1, 127.3.
Synthesis of Hydroxy(tosyloxy)iodobenzene 11
To a vigorously stirred suspension of NaClO•5H2O 8 (329 mg, 2.0 mmol) and iodobenzene (1a)
(224 µL, 2 mmol) in MeCN (1.5 mL) was added AcOH (343 µL, 6.0 mmol) slowly at room
temperature under air and the mixture was stirred for 10 minutes. After addition of CH2Cl2 (20 mL),
the mixture was filtered and solvents were removed under reduced pressure to give a pale yellow
solid, which was added p-toluenesulfonic acid monohydrate (380 mg, 2 mmol) in MeCN (1.5 mL)
and stirred at room temperature for 10 minutes. After addition of Et2O (10 mL), the resulting white
precipitate was collected by filtration. The residue was washed several times with acetone (5 mL)
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and Et2O (5 mL) to give hydroxy(tosyloxy)iodobenzene 11 (612 mg, yield 78%) as a
microcrystalline solid.
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Hydroxy(4-toluenesulfonyloxy)iodobenzene (11):25 1H NMR (500 MHz, CD3CN): δ = 8.10 (br d,
J = 7.3 Hz, 2H), 7.66 (t, J = 7.5 Hz, 1H), 7.56–7.49 (m, 2H), 7.50 (d, J = 8.1 Hz, 2H), 7.20 (d, J =
8.1 Hz, 2H); 13C{1H} NMR (125 MHz, CDCl3): δ = 146.0, 138.2, 135.0, 132.9, 131.6, 128.6, 126.0,
124.0, 21.3.
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Synthesis of Bis(trifluoroacetoxy)iodobenzene (12)
To a vigorously stirred suspension of NaClO•5H2O 8 (330 mg, 2.0 mmol) and iodobenzene (1a)
(224 µL, 2 mmol) in MeCN (1.5 mL) was added AcOH (342 µL, 6.0 mmol) slowly at room
temperature under air and the mixture was stirred for 10 minutes. After addition of CH2Cl2 (20 mL),
the reaction mixture was added trifluoroacetic acid (1.49 g, 13 mmol) and chlorobenzene (10 mL)
and concentrated under reduced pressure. The residue was washed several times with hexane by
decantation to give bis(trifluoroacetoxy)iodobenzene (12) (503 mg, 83%) as a microcrystalline
solid.
Bis(trifluoroacetoxy)iodobenzene (12):26 1H NMR (CDCl3, 500 MHz): δ = 8.22 (dd, J = 8.4, 1.0
Hz, 2H), 7.75 (tt, J = 7.5, 1.0 Hz, 1H), 7.62 (dd, J = 8.4, 7.5 Hz, 2H); 19F NMR (CDCl3, 470 MHz):
δ -73.45 (s, 6F); 13C{1H} NMR (125 MHz, CDCl3): δ 161.1 (q, 2JCF = 40.8 Hz), 135.2, 133.7, 132.0,
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122.8, 112.9 (q, 1JCF = 289 Hz).
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One-pot Synthesis of Iodosylbenzene (13)
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To a vigorously stirred suspension of NaClO•5H2O 8 (330 mg, 2.0 mmol) and iodobenzene (1a)
(224 µL, 2 mmol) in MeCN (1.5 mL) was added AcOH (344 µL, 6.0 mmol) slowly at room
temperature under air and the mixture was stirred for 10 minutes. After addition of 3 M NaOH
aqueous solution (3 mL, 9 mmol), the mixture was stirred for 10 minutes. The yellow solid thus
generated was filtered and washed three times with H2O (10 mL), followed by acetone (5 mL) and
Et2O (5 mL). The residue was dried under reduced pressure overnight to give iodosylbenzene (13)
(320 mg (97% purity), 70%) as light yellow powder. The purity of 13 was determined by common
iodometric titration using 10% KI aqueous solution, AcOH, and 0.1 M Na2S2O3 aqueous solution.
Iodosylbenzene (13):27 mp 208 ºC (dec); ATR-FTIR (neat) ν = 3048, 1672, 1567, 1470, 1439, 1172,
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1047, 995, 800–650, 460 cm-1; H NMR (MeOH-d4, 500 MHz): δ = 8.01 (br d, J = 7.3 Hz, 1.2H),
8.0 (br d, J = 6.7 Hz, 0.8H), 7.7–7.5 (m, 3H). The splitted peaks in 1H NMR spectrum are probably
responsible for the formation of (dimethoxyiodo)benzene-d6 and its µ-oxo dimer [PhI(OCD3)OI(O
CD3)Ph].
Synthesis of Iodonium Ylide 14
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To a vigorously stirred suspension of NaClO•5H2O 8 (467 mg, 2.8 mmol) and iodobenzene (1a)
(318 µL, 2.8 mmol) in MeCN (1.5 mL) was added AcOH (480 µL, 8.4 mmol) slowly at room
temperature under air and the mixture was stirred for 10 minutes. After addition of CH2Cl2 (20 mL),
the mixture was filtered and solvents were removed under reduced pressure to give a pale yellow
solid, which was added dimedone (390 mg, 2.8 mmol), K2CO3 (1.26 g, 9.1 mmol), and EtOH (2.8
mL). After stirring the mixture at room temperature for 30 minute, the resulting orange suspension
was added 5 mL of water and extracted with CH2Cl2 (5 mL X 4). The combined organic phase was
dried over Na2SO4, filtered, and solvents were removed under reduced pressure to give iodonium
ylide 14 (842 mg, 88%) as a white microcrystalline solid.
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5,5-Dimethyl-2-(phenyl-λ3-iodanylidene)cyclohexane-1,3-dione (14):28 1H NMR (CDCl3, 500
MHz): δ = 7.83 (d, J = 8.0 Hz, 2H), 7.52 (t, J = 7.5 Hz, 1H), 7.36 (dd, J = 8.0, 7.5 Hz, 2H), 2.51 (s,
13
4H), 1.07 (s, 6H); C{1H} NMR (125 MHz, CDCl3): δ = 188.4, 133.8, 131.5, 131.3, 112.0, 94.6,
50.6, 32.0, 28.1.
Synthesis of Imino-λ3-iodane 15
To a vigorously stirred suspension of NaClO•5H2O 8 (328 mg, 2.0 mmol) and iodobenzene (1a)
(224 µL, 2.0 mmol) in MeCN (1.5 mL) was added AcOH (340 µL, 6.0 mmol) slowly at room
temperature under air and the mixture was stirred slowly at room temperature under air and the
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mixture was stirred for 10 minutes. After addition of CH2Cl2 (20 mL), the mixture was filtered and
solvents were removed under reduced pressure to give a pale yellow solid, which was added a
mixture of p-nitrobenzenesulfonamide (404 mg, 2.0 mmol) and KOH (393 mg, 7.0 mmol) in MeOH
(4.7 mL). After stirring the mixture overnight (12 h), the resulting suspension was filtered and
washed with cold MeOH several times to give imino-λ3-iodane 15 (594 mg, 73%) as pale yellow
powder.
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[N-(4-Nitrophenylsulfonyl)imino](phenyl)-λ3-iodane (15):29 ATR-FTIR (neat) ν = 3102, 3069,
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1521, 1346, 1269, 1121, 1077, 851, 733, 616, 545, 463 cm-1; H NMR DMSO-d6, 500 MHz): δ =
13
8.14–7.97 (m, 2H), 7.81–7.68 (m, 4H), 7.39 (t, J = 7.4 Hz 1H), 7.23 (t, J = 7.4 Hz, 2H); C{1H}
NMR (125 MHz, DMSO-d6): δ = 151.5, 147.9, 133.4, 130.3, 130.0, 127.4, 123.6, 118.4.
ACKNOWLEDGMENTS
This work was supported by grants from JSPS KAKENHI (S) (17H06173), KAKENHI (B)
(17H03017), NAGASE Science & Technology Development Foundation, Sumitomo Foundation.
ASSOCIATED CONTENT
The Supporting Information is available free of charge on the ACS Publications website at DOI:
xxx
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REFERENCES
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Ochiai, M. In Chemistry of Hypervalent Compounds; Akiba, K.-y., Ed.; Wiley-VCH: New York,
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Weinheim, 1992. (f) Zhdankin, V. V. Hypervalent Iodine Chemistry: Preparation, Structure and
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Yoshimura, A.; Zhdankin, V. V. Advances in Synthetic Applications of Hypervalent Iodine
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(Diacetoxyiodo)benzene: More Than an Oxidant. Aust. J. Chem. 2017, 70, 338–340. (j) Varvoglis,
A. Aryliodine(III) dicarboxylates. Chem. Soc. Rev. 1981, 10, 377–407. (k) Moriarty, R. M.; Chany,
C. J.; Kosmeder, J. W.; Du Bois, J. Phenyliodine(III) Bis(trifluoroacetate). Encyclopedia of
Reagents for Organic Synthesis; John Wiley & Sons: Hoboken, NJ. 2009.
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2 For recent examples, oxidation of (a) Olefin, Zhong, W.; Yang, J.; Meng, X.; Li, Z.
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o-Hydroxystilbenes into Benzo- and Naphthofurans. Synthesis 2012, 44, 1171–1177. (j) Carboxylic
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3 (a) Data from Sigma-Aldrich Chemical Corporation. (b) Data from FUJIFILM Wako Pure
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12 (a) IBX ester was prepared from corresponding 2-iodobenzoate ester using aq. NaClO in AcOH.
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16 Formation of hypochloric acid 16 under chloride ion-free conditions at low pH was confirmed
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19 Ye, C.; Twamley, B.; Shreeve, J. M. Straightforward Syntheses of Hypervalent Iodine(III)
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24 Yusubov, M. S.; Gilmkhanova, M. P.; Zhdankin, V. V.; Kirschning, m-Iodosylbenzoic Acid as a
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26 Zagulyaeva, A. A.; Yusubov, M. S.; Zhdankin, V. V. A General and Convenient Preparation of
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