Oxone/KI-Mediated Nitration of Alkenes and Alkynes: Synthesis of Nitro- and β-Iodonitro-Substituted Alkenes

Article abstract of DOI:10.1002/ejoc.201402750

Oxone (2KHSO₅·KHSO₄·K₂SO₄) was used to promote the nitration of alkenes and alkynes with sodium nitrite (NaNO₂) and potassium iodide (KI). This stable, easy-to-handle, and environmentally benign oxidant was used under mild conditions (room temperature) and provided short reaction times. Styrene derivatives that did not contain electron-donating groups afforded the corresponding nitro alkenes in moderate to good yields, whereas aliphatic alkenes and electron-deficient alkenes were not good substrates. Under similar reaction conditions, aryl alkynes yielded β-iodonitro alkenes. Oxone (2KHSO₅·KHSO₄·K₂SO₄) was used to promote the reactions of alkenes and alkynes with sodium nitrite (NaNO₂) and potassium iodide (KI) to afford the corresponding nitro and β-iodonitro-substituted alkenes, respectively, in moderate to good yields.

Full text of DOI:10.1002/ejoc.201402750

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FULL PAPER
DOI: 10.1002/ejoc.201402750
Oxone®/KI-Mediated Nitration of Alkenes and Alkynes: Synthesis of
Nitro- and β-Iodonitro-Substituted Alkenes
Sornsiri Hlekhlai,[a] Natthapol Samakkanad,[a] Tassaporn Sawangphon,[a]
Manat Pohmakotr,[a] Vichai Reutrakul,[a] Darunee Soorukram,[a] Thaworn Jaipetch,[b] and
Chutima Kuhakarn*[a]
Keywords: Synthetic methods / Green chemistry / Alkenes / Alkynes / Oxidation / Nitration
Oxone® (2KHSO5·KHSO4·K2SO4) was used to promote the
nitration of alkenes and alkynes with sodium nitrite (NaNO2)
and potassium iodide (KI). This stable, easy-to-handle, and
environmentally benign oxidant was used under mild condi-
tions (room temperature) and provided short reaction times.
Styrene derivatives that did not contain electron-donating
groups afforded the corresponding nitro alkenes in moderate
to good yields, whereas aliphatic alkenes and electron-
deficient alkenes were not good substrates. Under similar re-
action conditions, aryl alkynes yielded β-iodonitro alkenes.
refluxing conditions, the formation of undesired (E) and (Z)
isomers, expensive reagents, and lengthy reaction times
might be encountered.
Introduction
Nitro alkenes are an important class of nitro compounds
that can be synthetically useful for the preparation of a vari-
ety of organic compounds for use in various fields.[1] Nitro
alkene-containing molecules have also been reported to ex-
hibit important biological activities.[2] The nitro group has
an activating effect on the adjacent carbon-carbon double
bond, which enables the nitro alkene to serve as a Michael
acceptor[3] and an electron-deficient dienophile partner[4] in
a cycloaddition reaction. Furthermore, the nitro group can
be transformed into other important functionalities, al-
lowing the nitro group to serve as a transient activating
functional group.[5] Several synthetic methods have been re-
ported for the synthesis of nitro alkenes. Among them, the
Henry reaction followed by a dehydration is a classical
method for the preparation of nitro alkenes.[6] Alternatively,
nitro alkenes can be prepared by the direct nitration of alk-
enes with MNO2 (M = Na, K, or Ag),[7a–7j] nitrogen dioxide
(NO2),[7k] nitric oxide (NO)[7l–7n] or clay-supported nitrat-
ing reagents[7o] as well as by the decarboxylative nitration
of α,β-unsaturated carboxylic acids.[8] Although these pro-
cedures have been well described, significant developments
in both the nitration of alkenes and decarboxylative ni-
tration have recently received much attention.[9] However,
several drawbacks including gaseous and harsh conditions,
The development of environmentally benign, experimen-
tally simple, and efficient synthetic strategies continues to
attract interest and is an important subject of research be-
cause of economical, environmental, and green chemistry
objectives. Oxone® (2KHSO5·KHSO4·K2SO4) is a colorless,
granular, free-flowing, solid peroxygen compound that
serves as powerful non-chlorine oxidizing agent that is
stable, easy-to-handle, nontoxic, and relatively inexpensive.
Additionally, the byproducts associated with Oxone® are
generally recognized as environmental safe. Because of its
stability, high efficiency, experimentally simple procedures,
mild reaction conditions, and generation of minimal chemi-
cal waste, Oxone® has found many synthetic applica-
tions.[10] Because the direct installation of a nitro moiety at
an olefinic carbon is a powerful method to access nitro alk-
enes, we developed a convenient, practical, and environ-
mentally benign synthetic method for the nitration of alk-
enes. We then chose Oxone® as a benign oxidant to mediate
the nitration of alkenes and alkynes.
Results and Discussion
As a part of our ongoing interest in oxidative transfor-
mation reactions,[11] we herein report an eco-friendly reac-
tion that uses the sodium nitrite (NaNO2)/Oxone®/KI com-
bination to effect the nitration of alkenes and alkynes (see
Scheme 1).
[a] Department of Chemistry and Center of Excellence for
Innovation in Chemistry (PERCH-CIC), Faculty of Science,
Mahidol University,
Rama VI Road, Bangkok 10400, Thailand
E-mail: chutima.kon@mahidol.ac.th
http://chemistry.sc.mahidol.ac.th
[b] Mahidol University, Kanchanaburi Campus,
Saiyok, Kanchanaburi 71150, Thailand
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201402750.
Scheme 1. Synthesis of nitro alkenes using NaNO2/Oxone®/KI.
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p-Bromostyrene (1a) was chosen as a model substrate to
Having established the optimum reaction conditions (see
examine the optimum reaction conditions (see Table 1). Ini- Table 1, Entry 3), the halide source was next examined. An
tially, the treatment of a mixture of p-bromostyrene (1a, 0.5 array of halide sources were screened, which included NaI,
mmol), Oxone® (1 equiv.), and KI (1.0 equiv.) in CH2Cl2 Et4NI, KBr, and NaCl, and the results are summarized in
(2 mL) with a solution of NaNO2 (3 equiv.) in H2O (1 mL) Table 2. The iodide anion promoted the reaction more ef-
resulted in the generation of heat and the vigorous evol- ficiently than the bromide and chloride ions. Potassium iod-
ution of gas. Monitoring by TLC analysis revealed that 1a ide (KI) promoted the reaction most efficiently.
still remained, and the desired nitro alkene 2a was isolated
in 15% yield (see Table 1, Entry 1). Thus, we treated the
Table 2. Optimization of the halide sources.[a]
reaction mixture with NaNO2 in a portionwise manner. A
suspended mixture of 1a (0.5 mmol), Oxone® (1 equiv.),
and KI (1.0 equiv.) in CH2Cl2 (2 mL) was treated with a
solution of NaNO2 (1 equiv.) in water (1 mL) at room tem-
perature. After the reaction was stirred for 15 min, ad-
ditional solid NaNO2 (4 equiv., 1 equiv. every 15 min) was
introduced to the reaction vessel. After the last portion of
solid NaNO2 was added, the reaction mixture was stirred
for an additional 0.5 h. After a routine aqueous workup, 2a
was obtained in the low yield of 29% (see Table 1, Entry 2).
Employing an excess amount of Oxone® (2.4 equiv.) led to
a dramatic increase in the yield to give nitro alkene 2a in
Entry
Halide source
Yield [%][b]
1
2
3
4
5
KI
NaI
Et4NI
KBr
NaCl
88
78
55
27
trace
[a] Compound 1a (0.5 mmol), Oxone® (2.4 equiv.), and halide
source (1 equiv.) were suspended in CH2Cl2 (2 mL), and then a
88% isolated yield (see Table 1, Entry 3). When the reaction solution of NaNO2 (1 equiv.) in water (1 mL) was added at room
temperature. The reaction was stirred for 15 min, and then solid
NaNO2 (4 equiv., 1 equiv. every 15 min) was added portionwise.
[b] Isolated yield.
was carried out with a higher ratio of water to dichloro-
methane, a mixture of nitro alkene 2a and β-iodonitro com-
pound 3a was obtained in a ratio of 7:2 (2a/3a, by integra-
tion of the 1H NMR signals, see Table 1, Entry 4). However,
On the basis of these results (see Tables 1 and 2), the
the mixture slowly turned brown, and 3a was converted into optimized reaction conditions were further employed to ex-
2a upon standing at room temperature. Inferior results were plore the generality and functional group compatibility of
obtained when the reactions were conducted in Et2O/H2O this reaction. The nitration of styrene derivatives was pri-
and ClCH2CH2Cl/H2O (see Table 1, Entries 5 and 6). In- marily examined (see Table 3). Under the standard reaction
creasing the stoichiometric amount of either Oxone® (from conditions, some substrates gave a mixture of nitro alkene
2.4 equiv. to 4 equiv.) or KI (from 1 equiv. to 2 equiv.) led 2 and the corresponding β-iodonitro compound 3. In these
to lower yields of 2a (see Table 1, Entries 7 and 8). Finally, cases, the mixture was treated with aqueous NaOH (10 m,
a dramatic decrease in the reaction yield was observed when 1 mL) upon completion of the reaction (1.5 h), and the re-
KI was employed in a substoichiometric amount (see sulting mixture was heated at reflux for 1 h. Halogen-substi-
Table 1, Entry 9). However, in all cases, (E)-nitro alkene 2a tuted styrene derivatives, which included the 4-Br, 4-Cl, 3-
was obtained as a single isomer.
Cl, 2-Cl, 4-F, and 3-F substituents, as well as styrene under-
Table 1. Optimization of reaction conditions.[a]
Entry
Oxone® [equiv.]
KI [equiv.]
NaNO2 [equiv.]
Solvent [v/v]
2a/3a[b]
% Yield 2a[c]
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
2
0.5
3[d]
5
5
5
5
5
5
5
5
CH2Cl2/H2O (2:1)
CH2Cl2/H2O (2:1)
CH2Cl2/H2O (2:1)
CH2Cl2/H2O (1:2)
Et2O/H2O (2:1)
ClCH2CH2Cl/H2O (2:1)
CH2Cl2/H2O (2:1)
CH2Cl2/H2O (2:1)
CH2Cl2/H2O (2:1)
–
–
–
7:2
–
–
–
–
–
15
29
88
–
32
68
56
72
49
2.4
2.4
2.4
2.4
4
2.4
2.4
[a] Unless otherwise noted, 1a (0.5 mmol), Oxone®, and KI were suspended in the organic solvent, and then a solution of NaNO2
(1 equiv.) in water was added at room temperature. The reaction was stirred for 15 min, and then solid NaNO2 (4 equiv., 1 equiv. every
15 min) was added portionwise. [b] After chromatographic purification, the product ratio was determined by analyzing the integration of
1
the H NMR (300 MHz) signals for the mixture. [c] Isolated yield. [d] A solution of NaNO2 in water was added to the reaction vessel in
one portion.
2
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Oxone®/KI-Mediated Nitration of Alkenes and Alkynes
went the reaction to provide the corresponding nitro alk-
The nitration reactions of aliphatic alkenes as well as an
enes 2a–2g in good yields (75–88%, see Table 3, Entries 1– α,β-unsaturated ester were also investigated, and the results
7). Styrenes that contained strong electron-withdrawing are summarized in Table 4. Under the reported reaction
groups such as –NO2 and –CHO readily underwent the re- conditions, aliphatic alkenes gave poorer results than those
action to give the corresponding nitro alkenes 2h–2j in observed with styrene derivatives, and the corresponding
moderate yields (53–69%, see Table 3, Entries 8–10). Both nitro alkenes 2p–2r were afforded in low yields (23–34%
ClCH2– and acetoxy (AcO–) substituents were well toler- yields) without isomerizing into their corresponding allylic
ated under the standard reaction conditions to provide 2k nitro compounds. 1-Phenylcyclohexene gave 6-nitro-1-phen-
and 2l in 73 and 62% yield, respectively (see Table 3, En- ylcyclohexene (2s), an allylic nitrocyclohexene, as the prod-
tries 11 and 12).
uct in 47% yield instead of α,β-unsaturated 1-nitro-2-phen-
ylcyclohexene.[12] We reasoned that this exception, in the
case of 1-phenylcyclohexene, resulted from the restricted
conformation within the cyclohexane ring that is required
for the elimination of HI. Compound 2s was also produced
when the nitration reaction of 1-phenylcyclohexene was car-
ried out under ultrasonic conditions with NaNO2/ceric am-
monium nitrate (CAN)/AcOH in a sealed tube at 600 W.[7i]
6-Nitro-1-phenylcyclohexene (2s) was reported to be ther-
modynamically more stable than 1-nitro-2-phenylcyclohex-
ene, its α,β-unsaturated isomer, because the steric interac-
tion between the nitro and phenyl group in the latter com-
pound hinders either group from conjugating well with the
olefinic moiety.[13] In contrast to the reaction of 1-phenyl-
cyclohexene, those of cyclohexene and norbornene did not
perform well, and unidentified spots on the TLC plate and
complex 1H NMR patterns were observed. Attempts to
conduct the nitration of α,β-unsaturated carbonyl com-
pounds were also unsatisfactory. Among several substrates
examined, the reaction of tert-butyl acrylate gave the corre-
sponding β-nitro derivative 2t in only 16% yield. Although
the reactions of aliphatic alkenes and electron-deficient alk-
enes looked clean (TLC analysis indicated recovery of start-
Table 3. Nitration reaction of styrene derivatives.[a]
Entry
R
R1
R2
Product 2 Yield [%][b]
1
2
4-BrC6H4
4-ClC6H4
3-ClC6H4
2-ClC6H4
4-FC6H4
3-FC6H4
C6H5
4-O2NC6H4
3-O2NC6H4
3-OHCC6H4
4-(ClCH2)C6H4
4-AcOC6H4
4-tBuC6H4
C6H5
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
2a
2b
2c
2d
2e
2f
88
80
87
83
80
82
75
53
69
68
73
62
35
68[d]
42
3[c]
4[c]
5
6[c]
7[c]
8
2g
2h
2i
9
10
11[c]
12
13[c]
14[c]
15[c]
2j
2k
2l
2m
2n
2o
1-naphthyl
[a] Compound 1 (0.5 mmol), Oxone® (2.4 equiv.), and KI (1 equiv.)
were suspended in CH2Cl2 (2 mL), and then a solution of NaNO2 ing material, product, and baseline substance), they resulted
(1 equiv.) in water (1 mL) was added at room temperature. The re-
in a poor mass recovery of the crude mixture (less than
action was stirred for 15 min, and then solid NaNO2 (4 equiv.,
40% of the theoretical yield).
1 equiv. every 15 min) was added portionwise. [b] Isolated yield.
[c] After 1.5 h, aqueous NaOH (10 m, 1 mL) was added, and the
mixture was heated at reflux for 1 h. [d] Yield of (E) isomer only.
Table 4. Nitration reaction of aliphatic alkenes and α,β-unsaturated
ester.[a,b]
Unfortunately, the reaction was incompatible with styr-
ene derivatives that contained an electron-donating substit-
uent. The reactions of 4-methylstyrene and 4-methoxystyr-
ene showed unidentified spots on the TLC plate, but the
starting materials were completely consumed. This is prob-
ably a result of competing reactions such as a benzylic oxi-
dation or the iodination or nitration of the aromatic ring.[11]
4-tert-Butylstyrene gave a low yield (35% yield) of the cor-
responding nitro alkene 2m (see Table 3, Entry 13). The ste-
[a] Compound 1 (0.5 mmol), Oxone® (2.4 equiv.), and KI (1 equiv.)
rically hindered β-methylstyrene gave a mixture of (E) and
1
were suspended in CH2Cl2 (2 mL), and then a solution of NaNO2
(1 equiv.) in water (1 mL) was added at room temperature. The re-
action was stirred for 15 min, and then solid NaNO2 (4 equiv.,
1 equiv. every 15 min) was added portionwise. [b] Isolated yields are
(Z) isomers (E/Z, 8:1, by integration of the H NMR sig-
nals) in 78% yield. The single (E) isomer was obtained in
68% yield after preparative thin layer chromatography (see
Table 3, Entry 14). 1-Vinylnaphthalene gave the corre- provided. [c] After 1.5 h, solid LiOH·H2O (10 equiv.) was added,
and the mixture was heated at reflux for 1 h. [d] 1-Phenylcyclo-
hexene was employed as the starting material.
sponding nitro alkene 2o in 42% yield (see Table 3, En-
try 15). Finally, 2-vinylpyridine and 4-vinylpyridine, both
vinyl-substituted heteroaromatic compounds, were exam-
ined. Unfortunately, the desired nitro alkenes were not de-
tected. The crude residues contained insoluble mixtures, ported.[14] As an extension of the present work, it was of
and the starting materials were recovered. interest to study the nitration of alkynes, and the results are
The synthesis of β-iodonitro alkenes has rarely been re-
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summarized in Table 5. Under the standard reaction condi- oxybenzene (6) was obtained (30% yield) as a significant
tions for styrene derivatives, the reaction of phenylacetylene competing product. This may be attributed to the strong
afforded β-iodonitro alkene 5a in 62% yield as a mixture of electron-releasing properties of the methoxy group
(E) and (Z) isomers (see Table 5, Entry 1). Next, arylacetyl- (MeO–), which facilitated the iodination reaction. Ad-
enes that contained substituents with different electronic ditionally, the formation of 6 suggests that molecular iodine
properties, such as Me–, MeO–, Br–, F–, and –NO2, were (I2) was generated under the reaction conditions. This was
evaluated (see Table 5, Entries 2–8). In all cases, the corre- confirmed by the isolation of 6 in quantitative yield without
sponding β-iodonitro alkenes 5b–5h were obtained in low the formation of 5c when 4-ethynylanisole was exposed to
to moderate yields (20–70% yields) and as an inseparable the standard reaction conditions, but I2 (1 equiv.) was em-
mixture of (E) and (Z) isomers. In the case of 4-ethynylanis- ployed in place of KI/Oxone®. In the case of 1-phenyl-
ole (see Table 5, Entry 3), (E)-1-(1,2-diiodovinyl)-4-meth- propyne, the reaction proceeded smoothly to give the corre-
sponding product 5i as a mixture of isomers in 53% yield
(see Table 5, Entry 9). On the basis of the spectroscopic
data of β-iodonitro alkene 5b, which was derived from 4-
Table 5. Nitration reaction of arylacetylenes.[a]
ethynyltoluene (4b), the major isomer was confirmed to
have the (E) configuration in which the iodine atom was
oriented anti to the nitro group (NOE experiments, see Sup-
porting Information). The stereochemistry of compounds
5a and 5c–5i were then assigned on the basis of those of 5b.
Entry
R
R1
Product 5 Yield [%][b]
E/Z[c]
Finally, the aliphatic alkynes 1-octyne and 4-octyne failed
to provide the desired β-iodonitro alkene products. The
crude reaction mixture showed an imbalance of the reco-
vered mass, and the starting alkynes could not be recovered.
Although no detailed mechanistic studies have been car-
ried out, on the basis of the above experimental results, two
pathways involving radical and ionic mechanisms are poss-
ibly taking place (see Schemes 2 and 3). For a radical ni-
tration, the oxidation of KI with Oxone® takes place in the
first step to generate an electrophilic iodine species (i.e.,
IOH or I2).[15] Although it is probably generated under our
reaction conditions, molecular iodine (I2 in place of KI/
Oxone®) was not capable of mediating the nitration reac-
tion of styrene, and no reaction took place with the styrene
1
2
3
4
5
6
7
8
9
C6H5
H
H
H
H
H
H
H
H
Me
5a
5b
5c
5d
5e
5f
5g
5h
5i
62
70
5.6:1
4.8:1
4.2:1
6.7:1
9.1:1
5.9:1
6.3:1
3.4:1
4.7:1
4-MeC6H4
4-MeOC6H4
4-BrC6H4
2-BrC6H4
4-FC6H4
3-FC6H4
4-O2NC6H4
C6H5
20[d]
63
57
65
48
26
53
[a] Compound 4 (0.5 mmol), Oxone® (2.4 equiv.), and KI (1 equiv.)
were suspended in CH2Cl2 (2 mL), and then a solution of NaNO2
(1 equiv.) in water (1 mL) was added at room temperature. The re-
action was stirred for 15 min, and then solid NaNO2 (4 equiv.,
1 equiv. every 15 min) was added portionwise. [b] Isolated yield.
[c] The E/Z ratios were determined from by 1H NMR analysis (300
or 400 MHz). [d] (E)-1-(1,2-Diiodovinyl)-4-methoxybenzene (6)
was isolated in 30% yield.
1
unconsumed (by H NMR analysis of the crude mixture).
Scheme 2. Proposed radical nitration of alkenes and alkynes.
Scheme 3. Proposed ionic nitration of alkenes and alkynes.
4
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Oxone®/KI-Mediated Nitration of Alkenes and Alkynes
The subsequent reaction of the electrophilic iodine species
with NaNO2 leads to the formation of the I–NO2 species.[7f]
Thus, the nitryl radical (·NO2), which is generated from the
I–NO2 species, preferentially undergoes a reaction at the
less-hindered side of the alkene or alkyne to generate the
more stable secondary or vinylic radical, respectively. The
radical intermediate is then trapped by the iodine atom to
lead to β-iodonitro alkane 3 or β-iodonitro alkene adduct
5. In some cases with the formation of a β-iodonitro alkane
3, there is the spontaneous elimination of HI. Otherwise
thetwo-stepreactionsequenceinonepotrequiresabase-inducedde-
hydroiodination to give the corresponding nitro alkene
product 2. In support of the radical mechanism, the
nitration reaction of p-bromostyrene (1a) was carried out
in the presence of the radical inhibitor TEMPO [(2,2,6,6-
tetramethylpiperidin-1-yl)oxyl, 1 equiv.]. As a result, the
yield of nitro alkene 2a was drastically reduced to 34%
yield, and the p-bromostyrene (1a) still remained (by TLC
analysis prior to the aqueous workup). Although this obser-
vation implies that the reaction may proceed through a rad-
ical pathway, the lower yield of 2a might result from com-
peting reactions of TEMPO with Oxone® or other gener-
ated reactive species.[16]
Experimental Section
General Methods: All reagents were obtained from commercial
sources and used without further purification. Preparative and thin
layer chromatography was carried out on TLC alumina sheets with
silica gel 60 F254 (Merck). Column chromatography was performed
with silica gel (Merck) and a hexanes/acetone mixture as the eluent,
and all solid compounds were recrystallized from a hexanes/
CH2Cl2 mixture. Melting points were recorded with a digital Elec-
trothermal Melting 9100 apparatus. The 1H and 13C NMR spectro-
scopic data were recorded with Bruker 300 (300 MHz) and Bruker
400 (400 MHz) spectrometers, and CDCl3 or [D6]acetone was used
1
as the solvent. The H NMR chemical shifts are reported in ppm
by using tetramethylsilane (TMS) as the internal standard. The 13
C
NMR chemical shifts are reported in ppm by using the residual
non-deuterated solvent peak as the internal standard. The IR spec-
tra were recorded with a Perkin–Elmer EX FTIR spectrometer. The
mass spectra were recorded with a Thermo Finnigan Polaris Q
mass spectrometer. The high resolution mass spectra were recorded
with an HR-TOF-MS Micromass model VQTOF2 mass spectrom-
eter.
General Procedure A – One-Step Synthesis of Nitro Olefins and β-
Iodo Nitro Alkenes: To a mixture of the alkene or alkyne
(0.5 mmol), Oxone® (368.9 mg, 1.2 mmol), and KI (83.5 mg,
1.0 mmol) was added dichloromethane (2 mL). To this solution was
slowly added a solution of NaNO2 (34.5 mg, 0.5 mmol) in water
(1 mL). The mixture was stirred at room temperature for 15 min,
and then solid NaNO2 (4 equiv., 1 equiv. every 15 min) was added
portionwise. After the final amount of NaNO2 was introduced, the
mixture was stirred for an additional 15 min. The reaction was then
quenched by the addition of saturated aqueous sodium thiosulfate
(5 mL). The resulting mixture was further stirred and then ex-
tracted with EtOAc (3ϫ 10 mL). The combined organic extracts
were washed with water (10 mL) and brine (10 mL). The organic
layer was dried with anhydrous MgSO4 and concentrated under
reduced pressure. The residue was purified by column chromatog-
raphy (hexanes/acetone).
Although, the radical nitration pathway can convert alk-
enes into nitro alkenes, the cationic nitration pathway
should not be excluded. The inferior results obtained when
electron-deficient-substituted styrene derivatives, aliphatic
alkenes, α,β-unsaturated carbonyl compounds, and elec-
tron-deficient-substituted arylacetylenes were employed as
substrates suggest the involvement of an electrophilic ni-
tronium ion (+NO2), which is generated from the reaction
of Oxone® and NaNO2 as the reactive electrophile.[11c]
Thus,
the
nitronium ion attacks the alkene or alkyne to lead to a sec-
ondary or vinylic cation, which is then trapped by an iodide
ion to yield β-iodonitro alkane 3 or β-iodonitro alkene ad-
duct 5. Subsequent HI elimination or base-mediated HI eli-
mination of β-iodonitro alkane 3 gives nitro alkene 2 as the
product.
General Procedure B – Two-Step Synthesis of Nitro Olefins: To a
mixture of the alkene (0.5 mmol), Oxone® (368.9 mg, 1.2 mmol),
and KI (83.5 mg, 1.0 mmol) was added dichloromethane (2 mL).
To this solution was slowly added a solution of NaNO2 (34.5 mg,
0.5 mmol) in water (1 mL). The mixture was stirred at room tem-
perature for 15 min, and then solid NaNO2 (4 equiv., 1 equiv. every
15 min) was added portionwise. After the final amount of NaNO2
was introduced, the mixture was stirred for an additional 15 min.
Aqueous NaOH (10 m, 1 mL) was then added, and the resulting
mixture was heated at reflux for 1 h. The reaction was then
quenched by the addition of saturated aqueous sodium thiosulfate
(5 mL). The resulting mixture was further stirred and then ex-
tracted with EtOAc (3ϫ 10 mL). The combined organic extracts
were washed with water (10 mL) and brine (10 mL). The organic
layer was dried with anhydrous MgSO4 and concentrated under
reduced pressure. The residue was purified by column chromatog-
raphy (hexanes/acetone).
Conclusions
In summary, we have reported a convenient, mild, and
rapid method for the nitration of alkenes into their corre-
sponding nitro alkenes. Styrene derivatives that did not con-
tain electron-donating groups yielded the corresponding
nitro alkenes in moderate to good yields, whereas aliphatic
and electron-deficient alkenes gave deficient results. In ad-
dition, this method can be applied to the synthesis of β-
iodonitro alkenes by starting from phenylacetylenes. De-
spite the limited scope of substrates, in view of the conve-
nient and mild reaction conditions (room temperature) as
well as the relatively inexpensive reagents, the present ap-
proach is a significant alternative to existing methods for
the synthesis of nitro alkenes and β-iodonitro alkenes,
which are an important class of compounds in organic
chemistry.
General Procedure C – Two-Step Synthesis of Nitro Olefins: To a
mixture of the alkene (0.5 mmol), Oxone® (368.9 mg, 1.2 mmol),
and KI (83.5 mg, 1.0 mmol) was added dichloromethane (2 mL).
To this solution was slowly added a solution of NaNO2 (34.5 mg,
0.5 mmol) in water (1 mL). The mixture was stirred at room tem-
perature for 15 min, and then solid NaNO2 (4 equiv., 1 equiv. every
15 min) was added portionwise. After the final amount of NaNO2
was introduced, the mixture was stirred for an additional 15 min.
Solid LiOH·H2O (209.8 mg, 5.0 mmol) was then added, and the
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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5

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C. Kuhakarn et al.
FULL PAPER
resulting mixture was heated at reflux for 1 h. The reaction was
then quenched by the addition of saturated aqueous sodium thio-
sulfate (5 mL). The resulting mixture was further stirred and then
extracted with EtOAc (3ϫ 10 mL). The combined organic extracts
were washed with water (10 mL) and brine (10 mL). The organic
layer was dried with anhydrous MgSO4 and concentrated under
reduced pressure. The residue was purified by column chromatog-
raphy (hexanes/acetone).
7.59–7.52 (m, 3 H, ArH, CH), 7.18–7.13 (m, 2 H, ArH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 164.9 (d, J = 253.0 Hz, C), 137.8
(CH), 136.8 (CH), 131.3 (d, J = 9.0 Hz, 2 CH), 126.3 (C), 116.8
(d, J = 22.0 Hz, 2 CH) ppm. IR (KBr): ν = 3113, 3047, 1637, 1595,
˜
1504, 1415, 1346 cm–1. HRMS (ESI-TOF): calcd. for
C8H6FNNaO2 [M + Na]+ 190.0280; found 190.0273.
(E)-1-Fluoro-3-(2-nitrovinyl)benzene (2f):[17c] 3-Fluorostyrene (1f,
61.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure B. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2f (69.6 mg,
(E)-1-Bromo-4-(2-nitrovinyl)benzene (2a):[9e] 4-Bromostyrene (1a,
92.3 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2a (102.5 mg,
1
82% yield) as a yellow viscous oil. H NMR (300 MHz, CDCl3): δ
= 7.88 (d, J = 13.7 Hz, 1 H, CH), 7.48 (d, J = 13.7 Hz, 1 H, CH),
88% yield) as a yellow solid, m.p. 153–154 °C; ref.[9e] m.p. 152– 7.40–7.33 (m, 1 H, ArH), 7.28–7.25 (m, 1 H, ArH), 7.19–7.09 (m,
1
153 °C. H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 13.7 Hz, 1
H, CH), 7.61–7.56 (m, 3 H, ArH, CH), 7.42 (dt, J = 8.5, 2.1 Hz, 2
2 H, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 162.9 (d, J =
247.2 Hz, C), 138.1 (CH), 137.6 (d, J = 2.8 Hz, CH), 132.1 (d, J =
H, ArH) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.8 (CH), 137.4 7.9 Hz, C), 131.0 (d, J = 8.3 Hz, CH), 125.1 (d, J = 3.0 Hz, CH),
(CH), 132.7 (2 CH), 130.4 (2 CH), 128.9 (C), 126.8 (C) ppm. IR 119.0 (d, J = 21.2 Hz, CH), 115.4 (d, J = 22.3 Hz, CH) ppm. IR
(KBr): ν = 3105, 1635, 1587, 1519, 1501, 1336 cm–1. HRMS (ESI-
(neat): ν = 3111, 1641, 1584, 1520, 1448, 1347 cm–1. HRMS (ESI-
˜
˜
TOF): calcd. for C8H6BrNNaO2 [M + Na]+ 249.9480; found TOF): calcd. for C8H6FNNaO2 [M + Na]+ 190.0280; found
249.9477.
190.0287.
(E)-1-Chloro-4-(2-nitrovinyl)benzene (2b):[9g] 4-Chlorostyrene (1b,
69.3 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2b (73.4 mg,
80% yield) as a yellow solid, m.p. 109–110 °C; ref.[9g] m.p. 110–
(E)-(2-Nitrovinyl)benzene (2g):[9g] Styrene (1g, 52.1 mg, 0.5 mmol)
and NaNO2 (172.5 mg, 2.5 mmol) were employed as described in
general procedure B. Purification by column chromatography
(SiO2, 10% acetone in hexanes) gave 2g (55.9 mg, 75% yield) as a
yellow solid, m.p. 59–60 °C; ref.[9g] m.p. 55–58 °C. 1H NMR
(400 MHz, CDCl3): δ = 8.01 (d, J = 13.7 Hz, 1 H, CH), 7.59 (d, J
1
111 °C. H NMR (300 MHz, CDCl3): δ = 7.97 (d, J = 13.7 Hz, 1
H, CH), 7.57 (d, J = 13.7 Hz, 1 H, CH), 7.50 (d, J = 8.5 Hz, 2 H, = 13.7 Hz, 1 H, CH), 7.56–7.43 (m, 5 H, ArH) ppm. 13C NMR
ArH), 7.44 (d, J = 8.5 Hz, 2 H, ArH) ppm. 13C NMR (75 MHz, (100 MHz, CDCl3): δ = 139.0 (CH), 137.1 (CH), 132.1 (CH), 130.0
CDCl3): δ = 138.3 (C), 137.6 (CH), 137.4 (CH), 130.2 (2 CH), 129.7 (C), 129.4 (2 CH), 129.1 (2 CH) ppm. IR (KBr): ν = 3110, 1633,
˜
(2 CH), 128.5 (C) ppm. IR (KBr): ν = 3105, 1634, 1593, 1519, 1490,
1578, 1515, 1449, 1343 cm–1. HRMS (ESI-TOF): calcd. for
C8H8NO2 [M + H]+ 150.0555; found 150.0560.
(E)-1-Nitro-4-(2-nitrovinyl)benzene (2h):[17d] 4-Nitrostyrene (1h,
˜
1339 cm–1. HRMS (ESI-TOF): calcd. for C8H6ClNNaO2 [M +
Na]+ 205.9985; found 205.9986.
(E)-1-Chloro-3-(2-nitrovinyl)benzene (2c):[17a] 3-Chlorostyrene (1c, 74.5 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
69.3 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure B. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2c (79.9 mg,
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2h (51.5 mg,
53% yield) as a yellow solid, m.p. 109–110 °C; ref.[17d] m.p. 106–
107 °C. 1H NMR (300 MHz, [D6]acetone): δ = 8.32 (dt, J = 9.0,
2.3 Hz, 2 H, ArH), 8.22–8.08 (m, 4 H, ArH, CH) ppm. 13C NMR
1
87% yield) as a yellow viscous oil. H NMR (300 MHz, CDCl3): δ
= 7.95 (d, J = 13.7 Hz, 1 H, CH), 7.61–7.54 (m, 2 H, ArH, CH),
7.51–7.39 (m, 3 H, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = (75 MHz, [D6]acetone): δ = 150.3 (C), 141.5 (CH), 137.7 (C), 137.0
138.1 (CH), 137.4 (CH), 135.4 (C), 131.9 (CH), 131.8 (C), 130.6
(CH), 131.3 (2 CH), 124.9 (2 CH) ppm. IR (KBr): ν = 3112, 1604,
˜
(CH), 128.7 (CH), 127.2 (CH) ppm. IR (neat): ν = 3110, 1639, 1535, 1494, 1466, 1346 cm–1. HRMS (ESI-TOF): calcd. for
˜
1568, 1520, 1474, 1345 cm–1. HRMS (ESI-TOF): calcd. for
C8H6ClNNaO2 [M + Na]+ 205.9985; found 205.9986.
C8H6N2NaO4 [M + Na]+ 217.0225; found 217.0219.
(E)-1-Nitro-3-(2-nitrovinyl)benzene (2i):[17b] 3-Nitrostyrene (1i,
(E)-1-Chloro-2-(2-nitrovinyl)benzene (2d):[9e] 2-Chlorostyrene (1d, 74.5 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
69.3 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure B. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2d (76.2 mg,
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2i (67.0 mg,
69% yield) as a yellow solid, m.p. 120–121 °C; ref,[17b] m.p. 125 °C.
1H NMR (300 MHz, CDCl3): δ = 8.44 (s, 1 H, ArH), 8.37 (d, J =
8.4 Hz, 1 H, ArH), 8.07 (d, J = 13.7 Hz, 1 H, CH), 7.90 (d, J =
7.6 Hz, 1 H, ArH), 7.73–7.67 (m, 2 H, ArH, CH) ppm. 13C NMR
1
83% yield) as a yellow viscous oil. H NMR (300 MHz, CDCl3): δ
= 8.40 (d, J = 13.7 Hz, 1 H, CH), 7.62–7.57 (m, 2 H, ArH, CH),
7.50 (br. dd, J = 8.0, 1.5 Hz, 1 H, ArH), 7.43 (td, J = 7.2, 1.7 Hz,
1 H, ArH), 7.34 (br. td, J = 8.7, 1.6 Hz, 1 H, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.8 (C), 139.3 (CH), 136.2 (CH), 134.4
(75 MHz, CDCl3): δ = 138.8 (CH), 136.0 (C), 135.1 (CH), 132.8
(CH), 131.8 (C), 130.6 (CH), 126.2 (CH), 123.4 (CH) ppm. IR
(CH), 130.7 (CH), 128.6 (CH), 128.4 (C), 127.4 (CH) ppm. IR (KBr): ν = 3104, 1530, 1509, 1440, 1350 cm–1. HRMS (ESI-TOF):
˜
(neat): ν = 3112, 1634, 1591, 1526, 1471, 1443, 1340 cm–1. HRMS
calcd. for C8H6N2NaO4 [M + Na]+ 217.0225; found 217.0227.
˜
(ESI-TOF): calcd. for C8H6ClNNaO2 [M + Na]+ 205.9985; found
205.9991.
(E)-3-(2-Nitrovinyl)benzaldehyde (2j):[9e] 3-Vinylbenzaldehyde (1j,
66.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2j (60.2 mg,
(E)-1-Fluoro-4-(2-nitrovinyl)benzene (2e):[17b] 4-Fluorostyrene (1e,
61.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
1
68% yield) as a yellow solid, m.p. 91–92 °C; ref,[9e] m.p. 90 °C. H
chromatography (SiO2, 10% acetone in hexanes) gave 2e (66.9 mg, NMR (300 MHz, CDCl3): δ = 10.00 (s, 1 H, CHO), 8.01–7.92 (m,
80% yield) as a yellow solid, m.p. 102–103 °C; ref.[17b] m.p. 100 °C.
3 H, ArH, CH), 7.74 (d, J = 7.8 Hz, 1 H, ArH), 7.62–7.57 (m, 2
1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J = 13.7 Hz, 1 H, CH), H, ArH, CH) ppm. 13C NMR (75 MHz, CDCl3): δ = 191.0 (CH),
6
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Oxone®/KI-Mediated Nitration of Alkenes and Alkynes
138.4 (CH), 137.4 (CH), 137.2 (C), 134.3 (CH), 132.8 (CH), 131.1
7.93 (d, J = 7.5 Hz, 1 H, ArH), 7.75 (d, J = 7.2 Hz, 1 H, ArH),
(C), 130.2 (CH), 129.5 (CH) ppm. IR (KBr): ν = 3111, 1640, 1578, 7.67–7.56 (m, 3 H, ArH, CH), 7.52 (t, J = 7.8 Hz, 1 H, ArH) ppm.
˜
1526, 1493, 1445, 1350 cm–1. HRMS (ESI-TOF): calcd. for
C9H7NNaO3 [M + Na]+ 200.0324; found 200.0332.
13C NMR (100 MHz, CDCl3): δ = 138.5 (CH), 136.1 (CH), 133.7
(C), 132.5 (CH), 131.5 (C), 129.0 (CH), 127.7 (CH), 127.0 (C),
126.8 (CH), 126.4 (CH), 125.4 (CH), 122.9 (CH) ppm. IR (KBr):
(E)-1-(Chloromethyl)-4-(2-nitrovinyl)benzene (2k):[9e] 4-Vinylbenzyl
chloride (1k, 76.3 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol)
were employed as described in general procedure B. Purification by
column chromatography (SiO2, 10% acetone in hexanes) gave 2k
ν = 3111, 1632, 1505, 1395, 1339 cm–1. HRMS (ESI-TOF): calcd.
˜
for C12H9NNaO2 [M + Na]+ 222.0531; found 222.0528.
(E)-[(3-Nitroallyl)oxy]benzene (2p):[7n] Allyl phenyl ether (1p,
(72.6 mg, 73% yield) as a yellow solid, m.p. 105–106 °C; ref.[9e] m.p. 67.6 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
1
107–108 °C. H NMR (300 MHz, CDCl3): δ = 7.9 (d, J = 13.7 Hz,
ployed as described in general procedure C. Purification by column
1 H, CH), 7.53–7.46 (m, 3 H, ArH, CH), 7.40 (d, J = 8.3 Hz, 2 H, chromatography (SiO2, 5% acetone in hexanes) gave 2p (20.6 mg,
1
ArH), 4.53 (s, 2 H, CH2) ppm. 13C NMR (75 MHz, CDCl3): δ =
141.5 (C), 138.1 (CH), 137.5 (CH), 130.1 (C), 129.5 (2 CH), 129.4
23% yield) as a yellow viscous oil. H NMR (400 MHz, CDCl3): δ
= 7.41 (dt, J = 13.3, 3.4 Hz, 1 H, CH), 7.35–7.31 (m, 3 H, ArH),
(2 CH), 45.2 (CH ) ppm. IR (KBr): ν = 3116, 1637, 1569, 1501, 7.04 (t, J = 7.4 Hz, 1 H, CH), 6.93 (dd, J = 8.8, 0.9 Hz, 2 H, ArH),
˜
2
1445, 1347 cm–1. HRMS (ESI-TOF): calcd. for C9H8ClNNaO2 [M
4.81 (dd, J = 3.3, 2 Hz, 2 H, CH2) ppm. 13C NMR (100 MHz,
CDCl3): δ = 157.4 (C), 140.3 (CH), 136.7 (CH), 129.8 (2 CH), 122.0
+ Na]+ 220.0141; found 220.0142.
(CH), 114.5 (2 CH), 63.6 (CH ) ppm. IR (neat): ν = 3131, 2909,
˜
(E)-4-(2-Nitrovinyl)phenyl Acetate (2l):[7f] 4-Acetoxystyrene (1l,
81.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2l (64.2 mg,
62% yield) as a yellow solid; m.p. 147–148 °C. 1H NMR (300 MHz,
CDCl3): δ = 8.00 (d, J = 13.7 Hz, 1 H, CH), 7.60–7.53 (m, 3 H,
2
1589, 1534, 1492, 1437, 1362 cm–1. HRMS (ESI-TOF): calcd. for
C9H9NNaO3 [M + Na]+ 202.0480; found 202.0479.
(E)-[(5-Nitropent-4-en-1-yl)oxy]benzene (2q): (Pent-4-en-1-yloxy)-
benzene (1q, 72.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol)
were employed as described in general procedure C. Purification by
ArH, CH), 7.21 (d, J = 8.4 Hz, 2 H, ArH), 2.33 (s, 3 H, CH3) ppm. column chromatography (SiO2, 5% acetone in hexanes) gave 2q
1
13C NMR (75 MHz, CDCl3): δ = 168.8 (C), 153.5 (C), 138.0 (CH), (26.9 mg, 26% yield) as a yellow viscous oil. H NMR (400 MHz,
137.1 (CH), 130.4 (2 CH), 127.6 (C), 122.8 (2 CH), 21.1
CDCl3): δ = 7.38–7.27 (m, 3 H, ArH, CH), 7.03 (dt, J = 13.4,
1.5 Hz, 1 H, CH), 6.96 (t, J = 7.4 Hz, 1 H, ArH), 6.89 (dd, J =
(CH ) ppm. IR (KBr): ν = 3106, 1746, 1603, 1561, 1502, 1349 cm–1.
˜
3
MS: m/z (%) = 207 (3) [M]+, 165 (51), 148 (8), 118 (100), 89 (25). 8.8, 1.0 Hz, 2 H, ArH), 4.02 (t, J = 5.8 Hz, 2 H, CH2), 2.51 (ddd,
HRMS (ESI-TOF): calcd. for C10H9NNaO4 [M + Na]+ 230.0429;
found 230.0441.
J = 14.8, 7.3, 1.5 Hz, 2 H, CH2), 2.05–1.98 (m, 2 H, CH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 158.5 (C), 141.8 (CH), 139.9
(CH), 129.6 (2 CH), 121.0 (CH), 114.4 (2 CH), 66.3 (CH2), 27.6
(E)-1-(tert-Butyl)-4-(2-nitrovinyl)benzene (2m): 4-tert-Butylstyrene
(1m, 80.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were
employed as described in general procedure B. Purification by col-
umn chromatography (SiO2, 10% acetone in hexanes) gave 2m
(CH ), 25.4 (CH ) ppm. IR (neat): ν = 3103, 3041, 2930, 1600,
˜
2
2
1587, 1524, 1497, 1355 cm–1. MS: m/z (%) = 207 (98) [M]+, 161
(33), 94 (100), 77 (21), 63 (54). HRMS (ESI-TOF): calcd. for
C11H13NNaO3 [M + Na]+ 230.0793; found 230.0795.
1
(35.9 mg, 35% yield) as a yellow viscous oil. H NMR (400 MHz,
CDCl3): δ = 8.00 (d, J = 13.7 Hz, 1 H, CH), 7.58 (d, J = 13.7 Hz, (E)-(3-Nitroallyl)benzene (2r):[17e] Allylbenzene (1r) (59.1 mg,
1 H, CH), 7.50 (d, J = 8.9 Hz, 2 H, ArH), 7.47 (d, J = 8.9 Hz, 2
0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were employed as de-
scribed in general procedure C. Purification by column chromatog-
H, ArH), 1.34 (s, 9 H, 3 CH3) ppm. 13C NMR (100 MHz, CDCl3):
δ = 156.2 (C), 139.1 (CH), 136.4 (CH), 129.1 (2 CH), 127.2 (C), raphy (SiO2, 2% acetone in hexanes) gave 2q (27.7 mg, 34% yield)
126.4 (2 CH), 35.1 (C), 31.0 (3 CH ) ppm. IR (neat): ν = 3109, as a yellow viscous oil. 1H NMR (400 MHz, CDCl3): δ = 7.46–
˜
3
2964, 1633, 1606, 1521, 1464, 1415, 1338 cm–1. MS: m/z (%) = 205 7.28 (m, 4 H, ArH, CH), 7.19 (br. d, J = 7.6 Hz, 2 H, ArH), 6.92
(1) [M]+, 190 (16), 160 (11), 143 (57), 128 (49), 115 (100), 103 (20), (dt, J = 13.3, 1.7 Hz, 1 H, CH), 3.59 (dd, J = 7.0, 1.4 Hz, 2 H,
91 (25). HRMS (ESI-TOF): calcd. for C12H15NNaO2 [M + Na]+
228.1000; found 228.0997.
(E)-(2-Nitroprop-1-en-1-yl)benzene (2n):[17b] trans-β-Methylstyrene
(1n, 59.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were
employed as described in general procedure B. Purification by pre-
parative thin layer chromatography (SiO2, 2% EtOAc in hexanes)
CH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 141.0 (CH), 140.4
(CH), 135.7 (C), 129.1 (2 CH), 128.7 (2 CH), 127.4 (CH), 34.6
(CH ) ppm. IR (KBr): ν = 3105, 2923, 1524, 1496, 1454, 1353 cm–1.
˜
2
HRMS (ESI-TOF): calcd. for C9H9NNaO2 [M + Na]+ 186.0531;
found 186.0532.
6-Nitro-1-phenylcyclohexene (2s):[17f] 1-Phenylcyclohexene (1s,
gave 2n (55.2 mg, 68% yield) as a yellow solid, m.p. 62–63 °C; 79.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
1
ref.[17b] m.p. 62 °C. H NMR (400 MHz, CDCl3): δ = 8.09 (s, 1 H, ployed as described in general procedure C. Purification by column
CH), 7.46–7.42 (m, 5 H, ArH), 2.46 (d, J = 0.8 Hz, 3 H, CH3) ppm. chromatography (SiO2, 5% acetone in hexanes) gave 2s (47.8 mg,
1
13C NMR (100 MHz, CDCl3): δ = 147.8 (C), 133.5 (CH), 132.4 47% yield) as a yellow viscous oil. H NMR (400 MHz, CDCl3): δ
(C), 130.0 (2 CH), 129.9 (CH), 128.9 (2 CH), 14.0 (CH3) ppm. IR = 7.43–7.16 (m, 5 H, ArH), 6.39 (t, J = 4.1 Hz, 1 H, CH), 5.53 (t,
(KBr): ν = 3058, 2925, 1519, 1449, 1387, 1324 cm–1. HRMS (ESI-
TOF): calcd. for C9H9NNaO2 [M
186.0520.
J = 4.6 Hz, 1 H, CH), 2.44–2.32 (m, 2 H, CH2), 2.25–2.07 (m, 2
H, CH2), 1.80–1.65 (m, 2 H, CH2) ppm. 13C NMR (100 MHz,
CDCl3): δ = 138.8 (C), 133.8 (CH), 131.3 (C), 128.6 (2 CH), 127.7
(CH), 125.5 (2 CH), 83.0 (CH), 29.0 (CH2), 25.4 (CH2), 17.3
˜
+
Na]+ 186.0531; found
(E)-1-(2-Nitrovinyl)naphthalene (2o):[9g] 1-Vinylnaphthalene (1o,
77.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure B. Purification by column
chromatography (SiO2, 10% acetone in hexanes) gave 2o (41.8 mg,
42% yield) as a yellow solid, m.p. 85–87 °C; ref.[9g] m.p. 84–86 °C.
(CH ) ppm. IR (neat): ν = 3058, 2940, 1547, 1496, 1446, 1374 cm–1.
˜
2
HRMS (ESI-TOF): calcd. for C12H13NNaO2 [M + Na]+ 226.0844;
found 226.0839.
tert-Butyl (E)-3-Nitroacrylate (2t): tert-Butyl acrylate (1t, 64.1 mg,
1H NMR (400 MHz, CDCl3): δ = 8.84 (d, J = 13.4 Hz, 1 H, CH), 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were employed as de-
8.14 (d, J = 8.2 Hz, 1 H, ArH), 8.01 (d, J = 8.2 Hz, 1 H, ArH),
scribed in general procedure C. Purification by column chromatog-
Eur. J. Org. Chem. 0000, 0–0
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C. Kuhakarn et al.
H of A, CH), 7.70 (s, 1 H of B, CH), 7.57–7.50 (m, 4 H of A, B,
as a yellow viscous oil. H NMR (400 MHz, CDCl3): δ = 7.59 (d, ArH), 7.40 (dt, J = 8.7, 2.0 Hz, 2 H of B, ArH), 7.18 (dt, J = 8.7,
J = 13.5 Hz, 1 H, CH), 7.01 (d, J = 13.5 Hz, 1 H, CH), 1.53 (s, 9 2.4 Hz, 2 H of A, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ =
H, 3 CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 161.7 (C), 148.4 143.3 (2 CH, A, B), 138.2 (C, B), 137.3 (C, A), 132.1 (2 CH, B),
FULL PAPER
raphy (SiO2, 5% acetone in hexanes) gave 2t (13.9 mg, 16% yield)
1
(CH), 129.5 (CH), 83.8 (C), 27.9 (3 CH ) ppm. IR (neat): ν = 2925, 131.8 (2 CH, A), 130.4 (2 CH, B), 128.8 (2 CH, A), 125.9 (C, B),
˜
3
2854, 1733, 1564, 1372 cm–1. MS: m/z (%) = 173 (3) [M]+, 148 124.6 (C, A), 112.2 (2 C, A, B) ppm. IR (KBr): ν = 3100, 1604,
˜
(100), 147 (20), 121 (13). HRMS (ESI-TOF): calcd. for 1516, 1482, 1395, 1330, 815 cm–1. MS: m/z (%) = 353 (11) [M]+,
C7H11NNaO4 [M + Na]+ 196.0586; found 196.0586.
274 (10), 183 (90), 180 (58), 75 (100), 74 (79). HRMS (APCI-TOF):
calcd. for C8H6BrINO2 [M + H]+ 353.8627; found 353.8620.
(1-Iodo-2-nitrovinyl)benzene (5a):[14c] Phenylacetylene (4a, 51.0 mg,
0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were employed as de-
scribed in general procedure A. Purification by column chromatog-
raphy (SiO2, 5% acetone in hexanes) gave a mixture of the (E) and
(Z) isomers (i.e., A and B, respectively) of 5a (86.8 mg, 62% yield.
1-Bromo-2-(1-iodo-2-nitrovinyl)benzene (5e): 1-Bromo-2-ethyn-
ylbenzene (4e, 90.5 mg, 0.5 mmol) and NaNO2 (172.5 mg,
2.5 mmol) were employed as described in General Procedure A.
Purification by column chromatography (SiO2, 5% acetone in hex-
anes) gave a mixture of the (E) and (Z) isomers (i.e., A and B,
respectively) of 5e (100.9 mg, 57% yield; E/Z, 9.1:1) as a yellow
1
E/Z, 5.6:1) as a yellow viscous oil. H NMR (400 MHz, CDCl3): δ
= 7.74 (s, 1 H of A, CH), 7.67 (s, 1 H of B, CH), 7.53 (dd, J = 7.4,
1.6 Hz, 2 H of B, ArH), 7.44–7.30 (m, 8 H of A, B, ArH) ppm. 13
C
1
solid; m.p. 56–57 °C. H NMR (300 MHz, CDCl3): δ = 7.79 (s, 1
NMR (100 MHz, CDCl3): δ = 143.2 (CH, B), 142.9 (CH, A), 138.5
(2 C, A, B), 131.2 (CH, B), 130.2 (CH, A), 129.1 (2 CH, B), 128.9
(2 CH, B), 128.5 (2 CH, A), 127.3 (2 CH, A), 113.8 (2 C, A,
H of A, CH), 7.61 (d, J = 7.9 Hz, 2 H of A, B, ArH), 7.48 (s, 1 H
of B, CH), 7.40–7.35 (m, 2 H of A, B, ArH), 7.28–7.19 (m, 4 H of
A, B, ArH) ppm. 13C NMR (75 MHz, CDCl3): δ = 145.6 (CH, B),
144.8 (CH, A), 140.0 (C, B), 139.5 (C, A), 133.6 (CH, B), 133.2
(CH, A), 131.2 (CH, B), 130.8 (CH, A), 129.3 (CH, B), 127.7 (CH,
A), 127.6 (CH, B), 127.5 (CH, A), 121.2 (C, B), 119.8 (C, A), 111.7
B) ppm. IR (KBr): ν = 3101, 1592, 1525, 1488, 1444, 1335, 961,
˜
692 cm–1. HRMS (ESI-TOF): calcd. for C8H6INNaO2 [M + Na]+
297.9341; found 297.9334.
(2 C, A, B) ppm. IR (KBr): ν = 3107, 1622, 1521, 1459, 1423, 1334,
˜
1-(1-Iodo-2-nitrovinyl)-4-methylbenzene (5b): 4-Ethynyltoluene (4b,
58.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 5% acetone in hexanes) gave a mixture of
the (E) and (Z) isomers (i.e., A and B, respectively) of 5b (104.5 mg,
845 cm–1. MS: m/z (%) = 353 (6) [M]+, 273 (100), 258 (32), 244
(41). HRMS (APCI-TOF): calcd. for C8H6BrINO2 [M + H]+
353.8627; found 353.8622.
1-Fluoro-4-(1-iodo-2-nitrovinyl)benzene (5f): 1-Ethynyl-4-fluoro-
benzene (4f, 60.0 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol)
were employed as described in general procedure A. Purification
by column chromatography (SiO2, 5% acetone in hexanes) gave a
mixture of the (E) and (Z) isomers (i.e., A and B, respectively) of
5f (95.2 mg, 65% yield; E/Z, 5.9:1) as a yellow semisolid. 1H NMR
(300 MHz, CDCl3): δ = 7.73 (s, 1 H of A, CH), 7.63 (s, 1 H of B,
CH), 7.56–7.51 (m, 2 H of B, ArH), 7.35–7.29 (m, 2 H of A, ArH),
7.14–7.04 (m, 4 H of A, B, ArH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 164.3 (d, J = 252.1 Hz, C, B), 163.3 (d, J = 250.7 Hz,
C, A), 143.1 (2 CH, A, B), 135.4 (d, J = 3.4 Hz, C, B), 134.3 (d, J
= 3.6 Hz, C, A), 131.1 (d, J = 8.8 Hz, 2 CH, B), 129.6 (d, J =
8.7 Hz, 2 CH, A), 116.0 (d, J = 20.9 Hz, 2 CH, B), 115.8 (d, J =
1
70% yield; E/Z, 4.8:1) as a yellow solid; m.p. 55–57 °C. H NMR
(400 MHz, CDCl3): δ = 7.64 (s, 1 H of A, CH), 7.59 (s, 1 H of B,
ArH), 7.36 (d, J = 8.2 Hz, 2 H of B, ArH), 7.18–7.10 (m, 6 H of
A, B, ArH), 2.33 (s, 3 H of B, CH3), 2.30 (s, 3 H of A, CH3) ppm.
13C NMR (100 MHz, CDCl3): δ = 142.5 (2 CH, A, B), 140.8 (2 C,
A, B), 135.5 (2 C, A, B), 129.6 (2 CH, B), 129.2 (2 CH, A), 129.1
(2 CH, B), 127.5 (2 CH, A), 114.5 (2 C, A, B), 21.4 (CH3, A), 21.3
(CH , B) ppm. IR (KBr): ν = 3099, 1604, 1520, 1501, 1333,
˜
3
811 cm–1. MS: m/z (%) = 289 (2) [M]+, 162 (16), 119 (29), 115 (100),
91 (25), 89 (22). HRMS (ESI-TOF): calcd. for C9H8INNaO2 [M +
Na]+ 311.9497; found 311.9508.
1-(1-Iodo-2-nitrovinyl)-4-methoxybenzene (5c): 4-Ethynylanisole (4c,
66.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by prepar-
ative thin layer chromatography (SiO2, 3% acetone in hexanes) gave
a mixture of the (E) and (Z) isomers (i.e., A and B, respectively)
22.1 Hz, 2 CH, A), 112.5 (C, A), 108.7 (C, B) ppm. IR (KBr): ν =
˜
3105, 1598, 1502, 1406, 1333, 1236, 893 cm–1. MS: m/z (%) = 293
(1) [M]+, 123 (100), 120 (72), 74 (43). HRMS (ESI-TOF): calcd.
for C8H5FINNaO2 [M + Na]+ 315.9247; found 315.9247.
1
of 5c (30.5 mg, 20% yield; E/Z, 4.2:1) as a yellow viscous oil. H
1-Fluoro-3-(1-iodo-2-nitrovinyl)benzene (5g): 1-Ethynyl-3-fluoro-
benzene (4g, 60.0 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol)
were employed as described in general procedure A. Purification
by column chromatography (SiO2, 5% acetone in hexanes) gave a
mixture of the (E) and (Z) isomers (i.e., A and B, respectively) of
5g (70.3 mg, 48% yield; E/Z, 6.3:1) as a yellow semisolid. 1H NMR
(300 MHz, CDCl3): δ = 7.72 (s, 1 H of A, CH), 7.67 (s, 1 H of B,
CH), 7.41–6.99 (m, 8 H of A, B, ArH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 162.4 (d, J = 247.7 Hz, C, B), 162.1 (d, J = 247.1 Hz,
C, A), 143.8 (CH, B), 143.5 (CH, A), 141.3 (d, J = 7.8 Hz, C, B),
140.3 (d, J = 8.3 Hz, C, A), 130.5 (d, J = 8.3 Hz, CH, B), 130.3 (d,
J = 8.4 Hz, CH, A), 124.5 (d, J = 3.1 Hz, CH, B), 122.8 (d, J =
3.2 Hz, CH, A), 118.1 (d, J = 21.1 Hz, CH, B), 117.2 (d, J =
21.0 Hz, CH, A), 116.5 (d, J = 23.7 Hz, CH, B), 114.5 (d, J =
23.6 Hz, CH, A), 111.1 (d, J = 2.4 Hz, C, A), 107.8 (C, B) ppm.
NMR (400 MHz, CDCl3): δ = 7.71 (s, 1 H of A, CH), 7.66 (s, 1 H
of B, CH), 7.52 (d, J = 8.8 Hz, 2 H of B, ArH), 7.31 (d, J = 8.8 Hz,
2 H of A, ArH), 6.93–6.87 (m, 4 H of A, B, ArH), 3.86 (s, 3 H of
B, CH3), 3.84 (s, 3 H of A, CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 161.2 (2 C, A, B), 142.0 (CH, A), 141.7 (CH, B), 131.0
(2 CH, B), 130.2 (2 C, A, B), 129.9 (2 CH, A), 114.9 (2 C, A, B),
114.3 (2 CH, B), 113.8 (2 CH, A), 55.6 (CH3, B), 55.4 (CH3,
A) ppm. IR (neat): ν = 3068, 2929, 1603, 1525, 1503, 1462, 1328,
˜
1254 cm–1. MS: m/z (%) = 305 (11) [M]+, 135 (100), 132 (62), 89
(26). HRMS [atmospheric pressure chemical ionization (APCI)-
TOF]: calcd. for C9H9INO3 [M + H]+ 305.9627; found 305.9622.
1-Bromo-4-(1-iodo-2-nitrovinyl)benzene (5d): 1-Bromo-4-ethyn-
ylbenzene (4d, 90.5 mg, 0.5 mmol) and NaNO2 (172.5 mg,
2.5 mmol) were employed as described in general procedure A. Pu-
rification by column chromatography (SiO2, 5% acetone in hex- IR (KBr): ν = 3103, 1583, 1527, 1482, 1434, 1335, 1228 cm–1. MS:
˜
anes) gave a mixture of the (E) and (Z) isomers (i.e., A and B,
m/z (%) = 294 (100) [M + 1]+, 166 (15), 134 (57), 120 (48), 107 (34).
respectively) of 5d (111.5 mg, 63% yield; E/Z, 6.7:1) as a yellow
HRMS (ESI-TOF): calcd. for C8H5FINNaO2 [M + Na]+ 315.9247;
1
solid; m.p. 95–96 °C. H NMR (300 MHz, CDCl3): δ = 7.73 (s, 1 found 315.9257.
8
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

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Oxone®/KI-Mediated Nitration of Alkenes and Alkynes
20677; d) M. A. Reddy, N. Jain, D. Yada, C. Kishore, V. J.
1-(1-Iodo-2-nitrovinyl)-4-nitrobenzene (5h): 1-Ethynyl-4-nitrobenz-
ene (4h, 73.6 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were
employed as described in general procedure A. Purification by col-
umn chromatography (SiO2, 5% acetone in hexanes) gave a mixture
of the (E) and (Z) isomers (i.e., A and B, respectively) of 5h
(41.6 mg, 26% yield; E/Z, 3.4:1) as a yellow solid; m.p. 114–116 °C.
1H NMR (400 MHz, CDCl3): δ = 8.30–8.25 (m, 4 H of A, B, ArH),
7.79 (s, 1 H of A, CH), 7.70 (d, J = 8.1 Hz, 2 H of B, ArH), 7.46 (dt,
J = 8.8, 2.2 Hz, 3 H of A, B, ArH, CH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 148.2 (2 C, A, B), 145.0 (2 C, A, B), 144.8 (CH, B),
144.3 (CH, A), 129.9 (2 CH, B), 128.0 (2 CH, A), 124.0 (2 CH, B),
Reddy, P. S. Reddy, A. Addlagatta, S. V. Kalivendi, B. Sreedhar,
J. Med. Chem. 2011, 54, 6751–6760; e) L. Q. Lu, J. R. Chen,
W. Xiao, Acc. Chem. Res. 2012, 45, 1278–1293.
a) D. J. P. Bates, M. O. Lively, M. J. Gorczynski, S. B. King,
A. J. Townsend, C. S. Morrow, Biochemistry 2009, 48, 4159–
4169; b) L. Villacorta, F. J. Schopfer, J. Zhang, B. A. Freeman,
Y. E. Chen, Clin. Sci. 2009, 116, 205–218.
a) G. H. Posner, R. D. Crouch, Tetrahedron 1990, 46, 7509–
7530; b) N. Mase, K. Watanabe, H. Yoda, K. Takabe, F.
Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2006, 128, 4966–
4967.
[2]
[3]
[4]
[5]
123.9 (2 CH, A), 109.8 (2 C, A, B) ppm. IR (KBr): ν = 3111, 1586,
a) A. G. M. Barrett, Chem. Soc. Rev. 1991, 20, 95–127; b) E.
Ghera, T. Yechezkel, A. Hassner, J. Org. Chem. 1993, 58, 6716–
6724.
˜
1524, 1514, 1402, 1343, 1316, 833 cm–1. MS: m/z (%) = 320 (1)
[M]+, 304 (26), 273 (20), 191 (36), 150 (28), 119 (53), 92 (82), 75
(100). HRMS (ESI-TOF): calcd. for C8H5IN2NaO4 [M + Na]+
342.9192; found 342.9183.
a) C. Palomo, J. M. Aizpurua, F. P. Cossio, J. M. Garcia, M. C.
Lopez, M. Oiarbide, J. Org. Chem. 1990, 55, 2070–2078; b) R.
Ballini, M. Petrini, Tetrahedron 2004, 60, 1017–1047; c) J. R.
Hwu, T. Josephrajan, S.-C. Tsay, Synthesis 2006, 3305–3308; d)
A. Corma, P. Serna, H. Garcia, J. Am. Chem. Soc. 2007, 129,
6358–6359; e) D. P. Gavin, J. C. Stephens, ARKIVOC (Gaines-
ville, FL, U.S.) 2011, 407–421; f) B. Zheng, H. Wang, Y. Han,
C. Liu, Y. Peng, Chem. Commun. 2013, 49, 4561–4563.
a) C. H. Heathcock, in: Comprehensive Organic Synthesis (Eds.:
B. M. Trost, I. Fleming, C. H. Heathcock), Pergamon Elsevier,
Oxford, UK, 1991, vol. 2, p. 133; b) R. Ballini, R. Castagnani,
M. Petrini, J. Org. Chem. 1992, 57, 2160–2162; c) J. M. Rodríg-
uez, M. D. Pujol, Tetrahedron Lett. 2011, 52, 2629–2632.
For the employment of MNO2 as a nitrating reagent, see: a)
A. Hassner, J. E. Kropp, G. J. Kent, J. Org. Chem. 1969, 34,
2628–2632; b) S. Ranganathan, S. K. Kar, J. Org. Chem. 1970,
35, 3962–3964; c) E. J. Corey, H. Estreicher, J. Am. Chem. Soc.
1978, 100, 6294–6295; d) J. Barluenga, M. A. Rodríguez, P. J.
Campos, G. Asensio, J. Chem. Soc., Chem. Commun. 1987,
1491–1492; e) J. Barluenga, M. A. Rodríguez, P. J. Campos, J.
Chem. Soc., Perkin Trans. 1 1990, 2807–2809; f) P. J. Campos,
B. García, M. A. Rodríguez, Tetrahedron 2000, 41, 979–982; g)
W. W. S y, A . W. B y, Tetrahedron Lett. 1985, 26, 1193–1196; h)
S. S. Jew, H. D. Kim, Y. S. Cho, C. H. Cook, Chem. Lett. 1986,
1747–1748; i) J. R. Hwu, K.-L. Chen, S. Ananthan, H. V. Patel,
Organometallics 1996, 15, 499–505; j) D. Ghosh, D. E. Nichols,
Synthesis 1996, 195–197; for the employment of NO2 as a ni-
trating reagent, see: k) H. Suzuki, T. Mori, J. Org. Chem. 1997,
62, 6498–6502; for the employment of NO as a nitrating rea-
gent, see: l) T. Mukaiyama, E. Hata, T. Yamada, Chem. Lett.
1995, 505–506; m) E. Hata, T. Yamada, T. Mukaiyama, Bull.
Chem. Soc. Jpn. 1995, 68, 3629–3636; n) I. Jovel, S. Prateep-
tongkum, R. Jackstell, N. Vogl, C. Weckbecker, M. Beller, Adv.
Synth. Catal. 2008, 350, 2493–2497; for the employment of a
clay-supported nitrating reagent, see: o) R. S. Varma, K. P.
Naicker, P. J. Liesent, Tetrahedron Lett. 1998, 39, 3977–3980.
a) J. P. Das, P. Sinha, S. Roy, Org. Lett. 2002, 4, 3055–3058; b)
A. Messere, A. Gentili, I. Garella, F. Temussi, B. D. Blasio, A.
Fiorentino, Synth. Commun. 2004, 34, 3317–3324; c) A. S. Rao,
P. V. Srinivas, K. S. Babu, J. M. Rao, Tetrahedron Lett. 2005,
46, 8141–8143; d) A. K. Bose, S. N. Ganguly, M. S. Manhas,
W. He, J. Speck, Tetrahedron Lett. 2006, 47, 3213–3215; e) S.
Ramgopal, K. Ramesh, A. Chakradhar, N. M. Reddy, K. C.
Rajanna, Tetrahedron Lett. 2007, 48, 4043–4045; f) G. I. Niki-
shin, L. L. Sokova, V. D. Makhaev, N. I. Kapustina, Russ.
Chem. Bull. 2008, 57, 118–123.
(1-Iodo-2-nitroprop-1-en-1-yl)benzene (5i): (Prop-1-yn-1-yl)benzene
(4i, 58.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by column
chromatography (SiO2, 5% acetone in hexanes) gave a mixture of
the (E) and (Z) isomers (i.e., A and B, respectively) of 5i (77.0 mg,
53% yield; E/Z, 4.7:1) as a yellow viscous oil. 1H NMR (400 MHz,
CDCl3): δ = 7.40–7.24 (m, 10 H of A, B, ArH), 2.62 (s, 3 H of A,
CH3), 2.16 (s, 3 H of B, CH3) ppm. 13C NMR (100 MHz, CDCl3):
δ = 151.1 (2 C, A, B), 142.9 (C, B), 140.1 (C, B), 129.4 (CH, A),
129.3 (CH, B), 128.7 (2 CH, B), 128.6 (2 CH, A), 128.1 (2 CH, B),
127.3 (2 CH, A), 103.5 (2 C, A, B), 24.4 (CH3, A), 18.3 (CH3,
[6]
[7]
B) ppm. IR (KBr): ν = 3057, 2922, 1523, 1488, 1442, 1378,
˜
1334 cm–1. MS: m/z (%) = 289 (1) [M]+, 272 (7), 162 (19), 115 (100),
105 (72). HRMS (ESI-TOF): calcd. for C9H8INNaO2 [M + Na]+
311.9497; found 311.9496.
(E)-1-(1,2-Diiodovinyl)-4-methoxybenzene (6): 4-Ethynylanisole (4c,
66.1 mg, 0.5 mmol) and NaNO2 (172.5 mg, 2.5 mmol) were em-
ployed as described in general procedure A. Purification by prepar-
ative thin layer chromatography (SiO2, 3% acetone in hexanes) gave
6 (57.9 mg, 30% yield) as a yellow solid; m.p. 40 °C. 1H NMR
(400 MHz, CDCl3): δ = 7.34 (d, J = 8.8 Hz, 2 H, ArH), 7.20 (s, 1
H, CH), 6.88 (d, J = 8.8 Hz, 2 H, ArH), 3.83 (s, 3 H, CH3) ppm.
13C NMR (100 MHz, CDCl3): δ = 159.7 (C), 135.2 (C), 130.2 (2
CH), 113.6 (2 CH), 96.6 (C), 79.8 (CH), 55.3 (CH3) ppm. IR (KBr):
ν = 3057, 2924, 1604, 1503, 1465, 1296, 1255 cm–1. MS: m/z (%) =
˜
386 (100) [M]+, 260 (20), 133 (7). HRMS (ESI-TOF): calcd. for
C9H9I2O [M + H]+ 386.8743; found 386.8759.
Supporting Information (see footnote on the first page of this arti-
1
cle): NOE data for 5b and copies of H and 13C NMR spectra of
all reported compounds.
[8]
Acknowledgments
The authors thank the Thailand Research Fund (TRF-
DBG5480017), the Center of Excellence for Innovation in Chemis-
try (PERCH-CIC), the Office of the Higher Education Commis-
sion, Mahidol University under the National Research Universities
Initiative and the Development and Promotion of Science and
Technology Talent Project (DPST), and the Institute for the Pro-
motion of Teaching Science and Technology for financial support.
[9]
For recent developments in the nitration of alkenes and decarb-
oxylative nitration, see a) T. Taniguchi, T. Fujii, H. Ishibashi,
J. Org. Chem. 2010, 75, 8126–8132; b) T. Taniguchi, T. Fujii,
H. Ishibashi, Org. Biomol. Chem. 2011, 9, 653–655; c) P. K.
Kancharla, Y. S. Reddy, S. Dharunam, Y. D. Vankar, J. Org.
Chem. 2011, 76, 5832–5837; d) S. Maity, S. Manna, S. Rana,
T. Naveen, A. Mallick, D. Maiti, J. Am. Chem. Soc. 2013, 135,
3355–3358; e) S. Maity, T. Naveen, U. Sharma, D. Maiti, Org.
Lett. 2013, 15, 3384–3387; f) T. Naveen, S. Maity, U. Sharma,
[1] a) G. G. Graboski, A. G. M. Berrett, Chem. Rev. 1986, 86, 751–
762; b) H. Feuer, A. T. Nielsen (Eds.), Nitro Compounds: Re-
cent Advances in Synthesis and Chemistry, VCH, New York,
1990; c) H. Uehara, R. Imashiro, G. Hernandez-Torres, C. F.
Barbas III, Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20672–
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: O42750
/KAP1
Date: 02-10-14 14:22:11
Pages: 11
C. Kuhakarn et al.
FULL PAPER
D. Maiti, J. Org. Chem. 2013, 78, 5949–5954; g) B. V. Rokade, [13]
K. R. Prahhu, Org. Biomol. Chem. 2013, 11, 6173–6716; h) S.
F. G. Bordwell, E. W. Garbisch Jr., J. Org. Chem. 1963, 28,
1765–1769.
Manna, S. Jana, T. Saboo, A. Maji, D. Maiti, Chem. Commun.
2013, 49, 5286–5288; i) M. Al-Masum, N. Saleh, T. Islam, Tet-
rahedron Lett. 2013, 54, 1141–1144.
[14]
a) T. E. Stevens, W. D. Emmons, J. Am. Chem. Soc. 1958, 80,
338–341; b) M. S. Yusubov, I. A. Perederina, V. D. Filimonov,
T.-H. Park, K.-W. Chi, Synth. Commun. 1998, 28, 833–836; c)
E. N. Tveryakova, Y. Y. Miroshnichenko, I. A. Perederina,
M. S. Yusubov, Russ. J. Org. Chem. 2007, 43, 152–153.
[10] a) M. C. Marcotullio, F. Epifano, M. Curini, Trends Org.
Chem. 2003, 10, 21–34; b) K. Moriyama, M. Takemura, H.
Togo, Org. Lett. 2012, 14, 2414–2417; c) B. Yu, A.-H. Liu, L.-
N. He, B. Li, Z.-F. Diao, Y.-N. Li, Green Chem. 2012, 14, 957–
962; d) H. Hussain, I. R. Green, I. Ahmed, Chem. Rev. 2013,
113, 3329–3371; e) A. Yoshimura, K. R. Middleton, A. D. To-
dora, B. J. Kastern, S. R. Koski, A. V. Maskaev, V. V. Zhdan-
kin, Org. Lett. 2013, 15, 4010–4013; f) B. Poladura, A. Marti-
nez-Castaneda, H. Rodriguez-Solla, R. Llavona, C. Concellon,
V. del Amo, Org. Lett. 2013, 15, 2810–2813; g) F. Drouet, G.
Masson, J. Zhu, Org. Lett. 2013, 15, 2854–2857.
[11] For a benzylic oxidation reaction, see: a) K. Moriyama, M.
Takemura, H. Togo, Org. Lett. 2012, 14, 2414–2417; for the
iodination of an aromatic ring, see: b) K. V. V. K. Mohan, N.
Narender, S. J. Kulkarni, Tetrahedron Lett. 2004, 45, 8015–
8018; for the nitration of a ring, see: c) M. A. Zolfigol, M.
Bagherzadeh, E. Madrakian, E. Ghaemi, A. Taqian-Nasab, J.
Chem. Res., Synop. 2001, 140–142.
®
[15]
Oxone was reported to be capable of oxidizing the iodide ion
to iodine/hypoiodide. For details, see: a) A. Yoshimura, C. Zhu,
K. R. Middleton, A. D. Todora, B. J. Kastern, A. V. Maskaev,
V. V. Zhdankin, Chem. Commun. 2013, 49, 4800–4802; b) M. C.
Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M.
Curini, Synthesis 2006, 2760–2766; c) M. Curini, F. Epifano,
M. C. Marcotullio, F. Montanari, Synlett 2004, 368–370.
[16] C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett. 2000, 2,
1172–1175.
[17] a) J. Park, C. Song, K. Choi, T. Sim, B. Moon, E. J. Roh, Bio-
org. Med. Chem. Lett. 2013, 23, 5515–5518; b) S. Jalal, S. Sar-
kar, K. Bera, S. Maiti, U. Jana, Eur. J. Org. Chem. 2013, 4823–
4828; c) J. Liu, X.-R. Zhu, J. Ren, W.-D. Chen, B.-B. Zeng,
Synlett 2013, 24, 2740–2742; d) L. Rokhom, G. Bez, Tetrahe-
dron Lett. 2013, 54, 5500–5504; e) A. G. Myer, J. K. Barbay, B.
Zhong, J. Am. Chem. Soc. 2001, 123, 7207–7219; f) O. A. Iv-
anova, E. B. Averina, E. M. Budynina, A. A. Korlyukov, M. Y.
Antipin, T. S. Kuznetsova, T. S. Zefirov, Russ. J. Org. Chem.
2005, 41, 1292–1297.
[12] 1-Nitro-2-phenylcyclohexene was reported to be obtained from
the reaction of 1-phenylcyclohexene with NaNO2/I2/ethylene
glycol in EtOAc/H2O at 0 °C to room temperature for 72 h (see
ref.[7h]). When we used the identical reaction conditions, styrene
gave nitro alkene 2g in 78% yield, whereas 1-phenylcyclohexene
Received: June 13, 2014
Published Online: ᭿
1
yielded 6-nitro-1-phenylcyclohexene (2s, by H and 13C NMR
analyses of the crude reaction mixture).
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Job/Unit: O42750
/KAP1
Date: 02-10-14 14:22:11
Pages: 11
Oxone®/KI-Mediated Nitration of Alkenes and Alkynes
Nitration
S. Hlekhlai, N. Samakkanad,
T. Sawangphon, M. Pohmakotr,
V. Reutrakul, D. Soorukram, T. Jaipetch,
C. Kuhakarn* .................................. 1–11
Oxone® (2KHSO5·KHSO4·K2SO4) was
used to promote the reactions of alkenes
and alkynes with sodium nitrite (NaNO2)
and potassium iodide (KI) to afford the
corresponding nitro and β-iodonitro-sub-
stituted alkenes, respectively, in moderate
to good yields.
Oxone®/KI-Mediated Nitration of Alkenes
and Alkynes: Synthesis of Nitro- and β-
Iodonitro-Substituted Alkenes
Keywords: Synthetic methods
/ Green
chemistry / Alkenes / Alkynes / Oxidation /
Nitration
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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