Convenient synthesis of α-nitrooximes mediated by OXONE

Article abstract of DOI:10.1039/c4ra11703d

A novel OXONE mediated direct difunctionalization of alkenes with NaNO₂ in aqueous acetonitrile for the synthesis of α-nitrooximes was developed. The α-nitrooximes were readily prepared in moderate to high yields at room temperature under mild reaction conditions. The present protocol offers an easy and environmentally benign approach to access various α-nitrooximes derived from styrene derivatives.

Full text of DOI:10.1039/c4ra11703d

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Convenient synthesis of a-nitrooximes mediated by
®
OXONE †
Cite this: RSC Adv., 2014, 4, 59726
a
a
a
Napasawan Chumnanvej, Natthapol Samakkanad, Manat Pohmakotr,
a
b
a
a
Vichai Reutrakul, Thaworn Jaipetch, Darunee Soorukram and Chutima Kuhakarn*
Received 3rd October 2014
Accepted 28th October 2014
®
A novel OXONE mediated direct difunctionalization of alkenes with NaNO
2
in aqueous acetonitrile for the
synthesis of a-nitrooximes was developed. The a-nitrooximes were readily prepared in moderate to high
yields at room temperature under mild reaction conditions. The present protocol offers an easy and
environmentally benign approach to access various a-nitrooximes derived from styrene derivatives.
DOI: 10.1039/c4ra11703d
www.rsc.org/advances
direct access for the formation of C–N bonds from alkenes has
Introduction
long been a challenge of interest to the synthetic community.
7
1,2-Difunctionalizations of the carbon–carbon double bonds in
In contrast to the synthesis of oximes from alkenes, the
8
alkenes are among the most powerful transformations in synthesis of a-nitrooximes has been less studied (Scheme 1).
chemical synthesis. They are challenging synthetic trans- Scheinbaum employed the reaction of olens with nitrous
formations in organic chemistry, used for the introduction of anhydride (N
O ) generated by the reaction of nitric oxide and
2 3
functional groups into an unactivated alkene moiety as well as air, followed by the treatment of the initially obtained pseudo-
8c
for the enhancement of molecular complexity. In recent years, nitrosites with ZnCl (Scheme 1, Path A). The preformed
2
novel metal-catalyzed and metal-free methods for the difunc- peroxynitrite-promoted reaction of styrene, leading to a mixture
tionalization of alkenes have been reported, such as dioxyge- of a-nitrooxime, nitrate, benzaldehyde, a-nitroacetophenone
1
2
3
4
8b
nation, oxyamination, oxythiolation, oxyphosphorylation,
and a nitroalkene was reported by Grossi (Scheme 1, Path B).
5
and diamination. In particular, the introduction of two vicinal Also, a solvent-free synthesis of pseudonitrosites, which can
carbon–nitrogen bonds provides powerful access to vicinal undergo tautomerization to a-nitrooxime, was reported by
8a
diamines which are important scaffolds found in pharmaceu- Shaabani and co-workers (Scheme 1, Path C). Despite signi-
tically important compounds, materials and ligands in catalysis cant developments, available methods toward a-nitrooxime
6
(
Fig. 1). Therefore, the development of new reactions that allow synthesis required gaseous reagents or tedious experimenta-
8
c,9
tions for the preparation of the requisite reagent.
With
continuous research efforts aiming at 1,2-difunctionalizations
10
of alkenes and alkynes, we report herein an alternative,
convenient and efficient synthesis of a-nitrooximes from
alkenes by employing commercially available reagents (NaNO
and OXONE ) (Scheme 1). OXONE is found in many synthetic
2
®
®
applications, due to its stability, high efficiency and mild
Fig.
1 Representative examples of some important compounds
containing the diamine moiety.
a
Department of Chemistry and Center of Excellence for Innovation in Chemistry
(
PERCH-CIC), Faculty of Science, Mahidol University, Rama VI Road, Bangkok
1
0400, Thailand
b
Mahidol University, Kanchanaburi Campus, Saiyok, Kanchanaburi 71150, Thailand
†
Electronic supplementary information (ESI) available. See DOI:
0.1039/c4ra11703d
Scheme 1 Methods for a-nitrooxime synthesis.
1
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reaction conditions, as well as the minimization of organic water to CH
3
CN, lower yields of 2a were obtained (Table 1, entry
11
chemical waste.
9). The reaction was less efficient upon a decrease or increase of
®
the amount of either NaNO or OXONE employed (Table 1,
2
entries 10–13). It is worth mentioning that in the reactions
shown in Table 1, entry 8 was carried out by employing a single
portion of NaNO (4 equiv.) in the reaction vessel; a vigorous
2
Results and discussion
Initially, the reaction of 4-bromostyrene (1a) with NaNO
2
/
reaction took place with the observation of heat generation as
well as fuming of brownish gaseous species.
®
OXONE was chosen as a model reaction in order to nd the
optimized reaction conditions. The selected results of the
optimization experimentation are summarized in Table 1. In a
With the above optimal reaction conditions in hand (Table 1,
entry 8), the scope and limitations of the reaction were evalu-
ated by employing a range of structurally different styrene
derivatives. It should be noted that, except for 2r, the a-nitro-
typical reaction procedure, 1a, NaNO (half of the total amount
2
®
employed) and OXONE were suspended in an organic solvent,
1
followed by the slow addition of water. Aer the reaction was
oximes were obtained as a mixture of two isomers ( H NMR
stirred at room temperature for 45 min, a second half portion of
analysis of the crude mixtures or aer chromatographic puri-
2
NaNO was added and the reaction was further stirred for an

cation). Upon column chromatographic purication, in some
additional 45 min. Aer chromatographic purication by
column chromatography, the corresponding a-nitrooxime 2a
was isolated as a single isomer ( H NMR analysis) along with a
nitroalkene 3a (E isomer) as a competing product. The a-
nitrooxime 2a and nitroalkene 3a could be readily separated by
cases, the a-nitrooximes were isolated as a single isomer. The
results are summarized in Table 2. Halogen-substituted styrene
derivatives including Br, Cl and F at the para-, meta-, or ortho-
positions gave the corresponding products in moderate to good
yields (59–84% yields) (Table 2, entries 1–6). Furthermore, 4-
nitrostyrene and 3-nitrostyrene also gave moderate yields (62–
1
simple column chromatography. In the initial experiment, 1a
®
was allowed to react with NaNO
2
(4 equiv.) and OXONE (2
66% yields) (Table 2, entries 7 and 8). A sensitive formyl group
equiv.). A screening of the solvents indicated that a combina-
tion of acetonitrile and water gave the best results, affording the
desired a-nitrooxime 2a in 84% isolated yield (Table 1, entries
and a chloromethyl group were found to be well accommodated
and each of their corresponding products were obtained as a
single isomer (Table 2, entries 9 and 10). Electron-releasing
substituted styrenes including 4-Me-, 4-MeO-, and 4-tBu-
substituted styrenes appeared less efficient, yielding the corre-
sponding a-nitrooximes in moderate yields (45–59% yields)
1–8). When the reactions were carried out with a lower ratio of
a
Table 1 Reaction optimization
(
Table 2, entries 11–13). 4-Acetoxystyrene afforded its corre-
sponding a-nitrooxime in 71% yield (Table 2, entry 14). More-
over, the reactions involving simple styrene, 1-
a
vinylnaphthalene, and b-substituted styrene derivatives which
include b-methylstyrene and 1,2-dihydronaphthalene, were also
successful, yielding the respective products in moderate yields
(
44–63% yields) (Table 2, entries 15–18). Finally, 2-vinyl-
thiophene gave the corresponding a-nitrooxime derivative in
3% yield (Table 2, entry 19) while 2-vinyl- and 4-vinylpyridines
led to unidentied complex mixtures. It should be noted that in
all cases, the corresponding nitroalkenes (E isomers) were also
obtained in varying quantities (2–21% yields). Unfortunately,
the present protocol was found to be incompatible with
aliphatic alkenes including 1-octene and cyclohexene; complex
b
Yield
7
(%)
®
OXONE
(equiv.)
NaNO
(equiv.)
2
Solvent
(v/v)
c
Entry
2a
3a
1
2
3
4
5
6
7
8
9
2
2
2
2
2
2
2
2
2
2
2
1
4
4
4
4
4
4
4
4
4
4
2
3
4
4
CH
ClCH
EtOAc : H
Acetone : H
Toluene : H
iPrOH : H O (1 : 2)
MeOH : H O (1 : 2)
2
Cl
2
: H
Cl : H
O (1 : 2)
O (1 : 2)
O (1 : 2)
2
O (1 : 2)
37
40
52
55
43
22
—
84
68
9
8
19
7
2
CH
2
2
O (1 : 2)
2
2
10 mixtures were observed in the TLC analyses with poor mass
2
13
—
—
6
recovery.
2
While no detailed mechanistic studies were carried out, to
follow the reaction pathway, some control experiments were
conducted. Thus, the reaction with p-bromostyrene (1a) was
2
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
CN : H
CN : H
CN : H
CN : H
CN : H
CN : H
2
O (1 : 2)
2
O (2 : 1)
2
O (1 : 2)
2
O (1 : 2)
2
O (1 : 2)
2
O (1 : 2)
5
1
1
1
1
0
1
2
3
10 carried out in the presence of radical inhibitors, including
44
47
45
2
19
13
TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxyl, 1 equiv.] and
BHT (3,5-di-tert-butyl-4-hydroxytoluene, 1 equiv.) (Scheme 2). It
was found that the a-nitrooxime 2a was obtained in much lower
yields, 19% yield and 32% yield, respectively. Since both the
TEMPO and BHT experiments only lower the reaction yields
a
2
Reaction conditions: 1a (0.5 mmol), NaNO (half of the total amount
employed), and OXONE were suspended in an organic solvent,
followed by the slow addition of water. Aer the reaction was stirred
®
at room temperature for 45 min, a second half portion of NaNO
2
was rather than cease the reaction, the control experiments do not
added and the reaction was further stirred for an additional 45 min.
fully indicate a radical mechanism. On the basis of previous
b
c
Isolated yield. In all cases, 2a was obtained as a single isomer aer
8
b,c
reports,
a mechanistic proposal is predicted as shown in
chromatographic purication.
®
Scheme 3. Primarily, a nitrite anion is oxidized by OXONE ,
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Paper
a
Table 2 Evaluation of scope and limitations of the reaction
b
Substrate
Product; yield (%)
c
Entry
Ar ¼
R ¼
a-Nitrooxime, 2 (isomer ratio)
Nitroalkene, 3
d
1
2
3
4
5
6
7
8
9
4-BrC
6
H
4
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
2a; 84 (single isomer)
3a; 6
3b; 10
3c; 3
3d; 6
3e; 7
3f; 2
3g; 5
3h; 3
3i; 7
3j; 7
3k; 21
3l; 5
3m; 8
3n; 9
3o; 5
3p; 15
3q; 12
4-ClC
3-ClC
2-ClC
6
6
6
H
4
H
4
H
4
2b; 73 (27.6 : 1)
2c; 74 (14.4 : 1)
2d; 59 (1.7 : 1)
2e; 69 (11.5 : 1)
2f; 75 (32.3 : 1)
2g; 66 (19.0 : 1)
2h; 62 (21.2 : 1)
4-FC
3-FC
6
H
H
4
6
4
4-O
3-O
2
NC
NC
6
H
H
H
4
4
2
6
d
3-OHCC
4-(ClCH
4-MeC
4-MeOC
4-tBuC
4-AcOC
6
4
2i; 56 (single isomer)d
10
11
12
13
14
15
16
17
2
)C
6
H
4
2j; 60 (single isomer)
2k; 45 (10.8 : 1)
2l; 51 (single isomer)
2m; 59 (5.5 : 1)
2n; 71 (14.4 : 1)
6
H
4
d
6
H
4
6
H
4
6
H
4
d
C
6
H
5
2o; 63 (single isomer)
1-Naphthyl
2p; 44 (1.7 : 1)
2q; 52 (2.3 : 1)
C
6
H
5
CH
3
e
1
8
9
2r; 56 (single isomer)
3r; 0
3s; 0
1
1-Thienyl
H
2s; 73 (1 : 1)
a
®
Reaction conditions: 1 (0.5 mmol), NaNO
2
(2 equiv.) and OXONE (2 equiv.) were suspended in CH
3
CN (1 mL), followed by the slow addition of
water (2 mL). Aer the reaction was stirred at room temperature for 45 min, NaNO
2
(2 equiv.) was added and the reaction was further stirred for an
b
c
additional 45 min. Isolated yield; in most cases their corresponding nitroalkenes (E isomers) were isolated in the range of 2–21% yields. The
1
d 1
isomeric ratio was determined by H NMR analysis.
H NMR spectral data of the crude mixtures exhibited a mixture of two isomers;
e 1
compound (isomer ratio): 2a (11.0 : 1); 2i (10.5 : 1); 2j (10 : 1); 2l (9.2 : 1); 2o (9.9 : 1).
A H NMR spectrum of the crude mixture exhibited a
single isomer.
generating unstable peroxynitrous acid (HPN, HOONO). Under tautomerization, leading to the observed a-nitrooxime 2. It is
®
the reaction conditions (OXONE , pK
acid decomposes, leading to a reactive species which is believed obtained has a Z conguration (the methylnitro group syn to the
to be nitrous anhydride (N ). Alternatively, sodium nitrite hydroxy group). In comparison with a closely related system, the
under relatively acidic conditions in situ generates nitrous acid
HNO ) which undergoes decomposition to furnish several resonate at a lower eld than those of the E isomer due to the
a
ꢀ 2), the peroxynitrous believed that the major isomer of a-nitrooxime 2 that was
2 3
O
1
H NMR signals of the methylene protons of the Z isomer
(
2
12
electrophilic species including NO, NO , N O and N O . The deshielding effect of the electronegative oxygen atom. As the
2
2
3
2 4
nitrous anhydride reacts with styrene and its derivatives to corresponding nitroalkene 3 was isolated as a by-product, it is
generate a more stable benzylic radical A and nitric oxide (NO).
Subsequent coupling of the benzylic radical A with nitric oxide
then gives a C-nitroso derivative which easily undergoes
Scheme 2 Control experiments.
Scheme 3 Plausible reaction pathway.
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likely to be derived from the benzylic radical A generating a dried (anhydrous MgSO
4
), ltered and vacuumed (aspirator).
®
benzyl cation via a one-electron oxidation with OXONE fol- The residue was puried by column chromatography (SiO2)
lowed by a deprotonation process. Although the radical mech- using acetone/hexanes as the eluent to provide the corre-
anistic pathway shown in Scheme 3 can direct alkenes to a- sponding product.
nitrooximes, we cannot exclude the possibility of the ionic
1-(4-Bromophenyl)-2-nitroethanone oxime (2a). White solid
+
ꢂ
mechanism proceeding via the nitronium ion ( NO
as a nitrating species. The failure of aliphatic alkenes to (30% acetone in hexanes) R
undergo the reaction suggests the involvement of the cationic 9.18 (br s, 1H), 7.57 (dd, J ¼ 6.7, 2.0 Hz, 2H), 7.49 (dd, J ¼ 6.7, 2.0
2
) which acts (109.7 mg, 84% yield); mp ¼ 97–98 C (CH
2
Cl
2
/hexanes); TLC
1
f
¼ 0.26; H NMR (400 MHz; CDCl
3
) d
1
3
3
intermediate. The formation of nitroalkene 3 also suggests the Hz, 2H), 5.62 (s, 2H) ppm. C NMR (100 MHz; CDCl ) d 147.8
+
involvement of the nitronium ion ( NO ) to serve as a reactive (C), 132.3 (2 ꢁ CH), 131.9 (C), 127.7 (2 ꢁ CH), 125.0 (C), 68.1
2
electrophile. Thus, the nitronium ion reacts with the styrene (CH ) ppm; IR (KBr) n 3232 (O–H), 1636 (C]N), 1558 and 1375
2
ꢃ1
+
substrates, leading to a benzylic cation B which upon elimina- (NO ) cm ; MS m/z (%) relative intensity 258 (M , 55), 181 (57),
2
tion of a proton yields nitroalkene 3 (Scheme 3).
169 (100), 102 (59), 89 (73); HRMS (APCI-TOF) calcd for
+
C
8
H
1
8
BrN
-(4-Chlorophenyl)-2-nitroethanone oxime (2b).
viscous oil (79.6 mg, 73% yield); TLC (30% acetone in hexanes)
2 3
O [M + H] 258.9718, found 258.9719.
8
a
Yellow
Conclusion
1
R
f
¼ 0.29; H NMR (400 MHz; CDCl
3
, isomeric ratio 27.6 : 1,
In summary, we have developed a convenient synthesis of a-
minor isomer marked*) d 9.87 (br s, 1H of major and minor
isomers), 7.54 (dd, J ¼ 6.8, 2.0 Hz, 2H of major and minor
isomers), 7.38 (dd, J ¼ 6.8, 2.0 Hz, 2H of major and minor
nitrooximes from styrene derivatives by employing a new
®
combination of the inorganic salt OXONE and sodium nitrite.
The reaction readily proceeded at ambient temperature and
conveniently employed inexpensive and environmentally
benign reagents. The reaction offers easy access to the 1,2-
difunctionalization of alkenes through the formation of C–N
bonds, albeit limited to styrene derivatives.
1
3
isomers), 5.62 (s, 1.93H), 5.40* (s, 0.07H) ppm. C NMR (100
MHz; CDCl
3
) d 147.4 (C), 136.4 (C), 131.4 (C), 129.7* (2 ꢁ CH),
29.2 (2 ꢁ CH), 128.9* (2 ꢁ CH), 127.3 (2 ꢁ CH), 77.8* (CH ),
8.1 (CH ) ppm (some peaks of the minor isomer could not be
1
6
2
2
1
3
detected by C NMR due to their low intensity); IR (KBr) n 3235
ꢃ1
(O–H), 1596 (C]N), 1562 and 1379 (NO ) cm ; HRMS (APCI-
2
Experimental
+
TOF) m/z calcd for C H ClN O [M + H] 215.0223, found
8
8
2 3
General information
215.0213.
1
1-(3-Chlorophenyl)-2-nitroethanone oxime (2c). Yellow
viscous oil (79.9 mg, 74% yield); TLC (30% acetone in hexanes)
H NMR spectra were recorded with a Bruker DPX-300 (300
MHz) or a Bruker Ascend™ 400 (400 MHz) spectrometer in
CDCl
acetone-d
internal standard. C NMR spectra were recorded with a Bruker
DPX-300 (75 MHz) or a Bruker Ascend™ 400 (100 MHz) spec-
trometer in CDCl
deuterated solvent peak as an internal standard. IR spectra
were recorded with a Perkin Elmer 683 GX FTIR System spec-
trometer. High resolution mass spectra were recorded with a
Bruker micro TOF spectrometer. Melting points were recorded
with a digital Electrothermal Melting 9100 apparatus and
uncorrected. Column chromatography was performed using
Merck silica gel (Art 7734). Other common solvents (dichloro-
methane, hexanes, ethyl acetate, and acetone) were distilled
before use.
1
R
f
¼ 0.31; H NMR (400 MHz; CDCl
3
, isomeric ratio 14.4 : 1,
3
using tetramethylsilane as an internal standard or in
using a residual non-deuterated solvent peak as an
minor isomer marked*) d 9.39 (br s, 1H of major and minor
isomers), 7.63 (t, J ¼ 1.8 Hz, 0.94H), 7.60* (t, J ¼ 1.8 Hz, 0.06H),
6
1
3
7
5
1
(
(
.49–7.34 (m, 3H of major and minor isomers), 5.62 (s, 1.87H),
1
3
.39* (s, 0.13H) ppm. C NMR (100 MHz; CDCl ) d 147.6 (C),
3
3 6
or acetone-d using a residual non-
35.1 (C), 134.7 (C), 130.5 (CH), 130.3 (CH), 130.0* (CH), 128.5*
CH), 126.3 (CH), 126.2* (CH), 124.5* (CH), 124.3 (CH), 77.8*
CH ), 68.2 (CH ) ppm (some peaks of the minor isomer could
2
2
1
3
not be detected by C NMR due to their low intensity); IR (KBr)
n 3274 (O–H), 1630 (C]N), 1559 and 1373 (NO
%) relative intensity 214 (M , 6), 137 (100), 125 (68), 102 (64), 75
40); HRMS (APCI-TOF) calcd for C H ClN NaO [M + Na]
ꢃ1
2
) cm ; MS m/z
+
(
(
2
+
8
7
2
3
37.0043, found 237.0041.
-(2-Chlorophenyl)-2-nitroethanone oxime (2d). Yellow
viscous oil (64.0 mg, 59% yield); TLC (30% acetone in hexanes)
1
1
R
f
¼ 0.31; H NMR (400 MHz; CDCl
3
, isomeric ratio 1.7 : 1,
General procedure for the synthesis of a-nitrooxime
minor isomer marked*) d 9.71 (br s, 0.63H), 9.02* (br s, 0.37H),
A mixture of the styrene derivative (0.5 mmol), sodium nitrite 7.53–7.33 (m, 4H of major and minor isomers), 5.60 (s, 1.25H),
®
13
(
68.9 mg, 1 mmol) and OXONE (307.4 mg, 1 mmol) was sus- 5.42* (s, 0.75H) ppm. C NMR (100 MHz; CDCl
pended in acetonitrile (1 mL). To this mixture was slowly added 147.9* (C), 132.6* (C), 132.5 (C), 131.7 (CH), 131.5 (CH), 131.3
O (2 mL) at room temperature. Aer the reaction mixture was (C), 131.2* (CH), 130.6* (CH), 130.0 (CH), 129.8* (CH), 129.7*
3
) d 148.8 (C),
H
2
stirred at room temperature for 45 min, a second portion of (C), 127.5 (CH), 127.0* (CH), 77.4* (CH
sodium nitrite (68.9 mg, 1 mmol) was introduced and the (neat) n 3272 (O–H), 1622 (C]N), 1558 and 1373 (NO
resulting mixture was further stirred for an additional 45 min. m/z (%) relative intensity 215 (M + 1, 100), 137 (31), 102 (41), 75
), 70.2 (CH
) ppm; IR
) cm ; MS
2
2
ꢃ1
2
+
+
8 7 2 3
The reaction mixture was diluted by the addition of water (5 mL) (19); HRMS (APCI-TOF) calcd for C H ClN NaO [M + Na]
and was extracted with EtOAc (3 ꢁ 15 mL). The combined 237.0043, found 237.0042.
2
organic layers were washed with H O (20 mL) and brine (20 mL),
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-(4-Fluorophenyl)-2-nitroethanone oxime (2e).
Paper
8a
1
Yellow (CH), 130.6* (CH), 125.0* (CH), 124.8 (CH), 124.4* (CH), 121.5
viscous oil (70.0 mg, 69% yield); TLC (30% acetone in hexanes) (CH), 78.7* (CH
), 68.8 (CH
, isomeric ratio 11.5 : 1, isomer could not be detected by C NMR due to their low
minor isomer marked*) d 9.57 (br s, 1H of major and minor intensity); IR (KBr) n 3314 (O–H), 1575 (C]N), 1533 and 1378
) ppm (some peaks of the minor
2
2
1
13
R
f
¼ 0.31; H NMR (400 MHz; CDCl
3
ꢃ1
+
isomers), 7.62–7.58 (m, 2H of major and minor isomers), 7.15– (NO
2
) cm ; MS m/z (%) relative intensity 225 (M , 1), 148 (100),
.09 (m, 2H of major and minor isomers), 5.63 (s, 1.84H), 5.40* 102 (56), 89 (41); HRMS (ESI-TOF) calcd for C NaO [M +
7
(
8
H
7
N
3
5
1
3
+
s, 0.16H) ppm. C NMR (100 MHz; CDCl ) d 164.0 (d, J ¼ 249.9 Na] 248.0283, found 248.0276.
3
Hz, C), 147.7 (d, J ¼ 8.2 Hz, C), 130.6* (d, J ¼ 8.5 Hz, 2 ꢁ CH),
3-(1-(Hydroxyimino)-2-nitroethyl)benzaldehyde (2i). Yellow
ꢂ
1
29.1 (d, J ¼ 3.1 Hz, C), 128.3 (d, J ¼ 8.5 Hz, 2 ꢁ CH), 116.2 (d, solid (59.2 mg, 56% yield); mp ¼ 118–119 C (EtOAc/hexanes);
1
J ¼ 21.8 Hz, 2 ꢁ CH), 115.9* (d, J ¼ 21.8 Hz, 2 ꢁ CH), 78.0* TLC (30% acetone in hexanes) R
¼ 0.19; H NMR (400 MHz;
f
(CH
2
), 68.5 (CH
2
) ppm (some peaks of the minor isomer could acetone-d
6
) d 11.80 (s, 1H), 10.11 (s, 1H), 8.33 (t, J ¼ 1.5 Hz, 1H),
1
3
not be detected by C NMR due to their low intensity); IR (KBr) 8.13 (ddd, J ¼ 7.8, 1.8, 1.2 Hz, 1H), 8.01 (dt, J ¼ 7.6, 1.3 Hz, 1H),
ꢃ1
13
n 3279 (O–H), 1602 (C]N), 1549 and 1376 (NO
(
2
) cm ; HRMS 7.71 (t, J ¼ 7.7 Hz, 1H), 5.98 (s, 2H) ppm. C NMR (100 MHz;
+
8 7 2 3
6
APCI-TOF) m/z calcd for C H FN NaO [M + Na] 221.0338, acetone-d ) d 192.6 (CH), 148.0 (C), 137.9 (C), 136.2 (C), 132.3
found 221.0337.
(CH), 131.0 (CH), 130.3 (CH), 127.7 (CH), 68.8 (CH
2
) ppm; IR
) cm ; MS
ꢃ1
1
-(3-Fluorophenyl)-2-nitroethanone oxime (2f). Yellow (KBr) n 3203 (O–H), 1610 (C]N), 1554 and 1381 (NO
viscous oil (74.2 mg, 75% yield); TLC (30% acetone in hexanes) m/z (%) relative intensity 208 (M , 6), 131 (90), 103 (76), 77 (100);
2
+
1
+
R
f
¼ 0.31; H NMR (400 MHz; CDCl
, isomeric ratio 32.3 : 1, HRMS (ESI-TOF) calcd for C H N NaO [M + Na] 231.0382,
3
9 8 2 4
minor isomer marked*) d 8.71 (br s, 1H of major and minor found 231.0375.
isomers), 7.45–7.38 (m, 3H of major and minor isomers), 7.18–
1-(4-(Chloromethyl)phenyl)-2-nitroethanone oxime (2j). Pale
ꢂ
7
(
.13 (m, 1H of major and minor isomers), 5.64 (s, 1.94H), 5.40* yellow solid (68.4 mg, 60% yield); mp ¼ 83–84 C (CH
2 2
Cl /
1
3
1
s, 0.06H) ppm. C NMR (100 MHz; CDCl ) d 163.0 (d, J ¼ 245.8 hexanes); TLC (30% acetone in hexanes) R
f
¼ 0.24; H NMR (400
3
Hz, C), 147.5 (d, J ¼ 2.6 Hz, C), 135.1 (d, J ¼ 7.9 Hz, C), 130.7 (d, MHz; CDCl ) d 8.76 (br s, 1H), 7.64 (d, J ¼ 8.3 Hz, 2H), 7.46 (d,
3
13
J ¼ 8.2 Hz, CH), 121.8 (d, J ¼ 2.9 Hz, CH), 117.4 (d, J ¼ 21.2 Hz, J ¼ 8.3 Hz, 2H), 5.65 (s, 2H), 4.60 (s, 2H) ppm. C NMR (100
), 68.0 (CH
) ppm MHz; CDCl
some peaks of the minor isomer could not be detected by
NMR due to their low intensity); IR (KBr) n 3274 (O–H), 1610 H), 1605 (C]N), 1574 and 1383 (NO
CH), 113.2 (d, J ¼ 23.5 Hz, CH), 77.9* (CH
2
2
3
) d 148.0 (C), 139.7 (C), 133.0 (C), 129.2 (2 ꢁ CH),
1
3
(
C
126.5 (2 ꢁ CH), 68.1 (CH
2
), 45.4 (CH
2
) ppm; IR (KBr) n 3227 (O–
ꢃ1
) cm ; MS m/z (%) relative
2
ꢃ1
+
(
1
C]N), 1558 and 1376 (NO
2
) cm ; MS m/z (%) relative intensity intensity 228 (M , 3), 151 (100), 115 (44), 100 (30); HRMS (APCI-
+
+
+
99 (M + 1, 100), 198 (M , 31), 180 (3), 121 (82), 109 (59); HRMS TOF) calcd for C
9
H
10ClN
2-Nitro-1-(p-tolyl)ethanone oxime (2k). Yellow viscous oil
(43.9 mg, 45% yield); TLC (30% acetone in hexanes) R
¼ 0.36;
, isomeric ratio 10.8 : 1, minor isomer
2 3
O [M + H] 229.0380, found 229.0375.
+
8a
(
APCI-TOF) calcd for C H FN NaO [M + Na] 221.0338, found
8 7 2 3
221.0331.
f
1
1
-(4-Nitrophenyl)-2-nitroethanone oxime (2g). Pale yellow
H NMR (400 MHz; CDCl
3
ꢂ
solid (75.2 mg, 66% yield); mp ¼ 123–124 C (EtOAc/hexanes); marked*) d 9.37 (br s, 1H of major and minor isomers), 7.42 (d,
1
TLC (30% acetone in hexanes) R
f
¼ 0.21; H NMR (400 MHz; J ¼ 8.1 Hz, 2H of major and minor isomers), 7.15 (d, J ¼ 8.1 Hz,
acetone-d
1.99 (s, 1H of major and minor isomers), 8.23 (dd, J ¼ 7.1, 2.0 0.17H), 2.30 (s, 3H of major and minor isomers) ppm. C NMR
Hz, 2H of major and minor isomers), 7.99 (dd, J ¼ 7.1, 2.0 Hz, (100 MHz; CDCl ) d 148.5 (C), 140.9 (C), 131.3* (C), 130.0 (C),
H of major and minor isomers), 5.89 (s, 1.90H), 5.68* (s, 0.10H) 129.8 (2 ꢁ CH), 129.4* (2 ꢁ CH), 129.0* (C), 128.3* (2 ꢁ CH),
6
, isomeric ratio 19.0 : 1, minor isomer marked*) d 2H of major and minor isomers), 5.56 (s, 1.83H), 5.31* (s,
1
3
1
3
2
1
3
ppm. C NMR (100 MHz; acetone-d ) d 149.0 (C), 147.4 (C), 126.8* (C), 126.1 (2 ꢁ CH), 78.1* (CH
2 2 3
), 68.5 (CH ), 21.5* (CH ),
) ppm; IR (KBr) n 3292 (O–H), 1611 (C]N), 1546 and
6
1
41.0 (C), 130.6* (2 ꢁ CH), 127.7 (2 ꢁ CH), 124.4 (2 ꢁ CH), 21.4 (CH
24.0* (2 ꢁ CH), 78.6* (CH ), 68.4 (CH
) ppm (some peaks of 1377 (NO
+
3
ꢃ1
1
2
2
2
) cm ; HRMS (ESI-TOF) m/z calcd for C
9
H
10
N
2
NaO
3
1
3
the minor isomer could not be detected by C NMR due to their [M + Na] 217.0589, found 217.0595.
8a
low intensity); IR (KBr) n 3364 (O–H), 1599 (C]N), 1567 and
1-(4-Methoxyphenyl)-2-nitroethanone oxime (2l).
Pale
Cl
ꢃ1
+
ꢂ
1380 (NO
2
) cm ; MS m/z (%) relative intensity 225 (M , 2), 147 yellow solid (56.0 mg, 51% yield); mp ¼ 109–110 C (CH
2
2
/
1
(
100), 102 (33), 89 (98); HRMS (ESI-TOF) calcd for C
8
H
7
N
3
NaO
5
hexanes); TLC (20% acetone in hexanes) R
MHz; acetone-d
f
¼ 0.26; H NMR (400
+
[M + Na] 248.0283, found 248.0282.
6
) d 11.22 (s, 1H), 7.72 (dd, J ¼ 6.9, 2.2 Hz, 2H),
13
1
-(3-Nitrophenyl)-2-nitroethanone oxime (2h). Pale yellow 6.98 (dd, J ¼ 6.9, 2.2 Hz, 2H), 5.84 (s, 2H), 3.83 (s, 3H) ppm.
C
ꢂ
solid (69.8 mg, 62% yield); mp ¼ 98–99 C (CH Cl /hexanes); NMR (100 MHz; acetone-d
6
) d 161.7 (C), 148.2 (C), 128.2 (2 ꢁ
2
2
1
TLC (30% acetone in hexanes) R
acetone-d
1.93 (s, 0.95H), 11.51* (s, 0.05H), 8.63 (t, J ¼ 1.7 Hz, 1H of HRMS (ESI-TOF) m/z calcd for C
major and minor isomers), 8.32–8.29 (m, 1H of major and found 211.0720.
f
¼ 0.26; H NMR (400 MHz; CH), 127.5 (C), 114.8 (2 ꢁ CH), 68.9 (CH
2
), 55.6 (CH
3
) ppm; IR
ꢃ1
, isomeric ratio 21.2 : 1, minor isomer marked*) d (KBr) n 3229 (O–H), 1606 (C]N), 1559 and 1380 (NO
) cm
;
6
2
+
1
H N O [M + H] 211.0719,
9 11 2 4
minor isomers), 8.24–8.21 (m, 1H of major and minor isomers),
1-(4-(tert-Butyl)phenyl)-2-nitroethanone oxime (2m). Yellow
ꢂ
7
1
1
.77 (t, J ¼ 8.0 Hz, 1H of major and minor isomers), 6.00 (s, solid (70.3 mg, 59% yield); mp ¼ 102–103 C (CH
2 2
Cl /hexanes);
¼ 0.32; H NMR (400 MHz;
1
3
1
.91H), 5.81* (s, 0.09H) ppm. C NMR (100 MHz; acetone-d ) d TLC (30% acetone in hexanes) R
f
6
49.5 (C), 147.5 (C), 137.0 (C), 135.6* (CH), 132.9 (CH), 131.0 CDCl
3
, isomeric ratio 5.5 : 1, minor isomer marked*) d 9.27 (br
s, 0.85H), 8.81* (br s, 0.15H), 7.57 (d, J ¼ 8.5 Hz, 2H of major and
59730 | RSC Adv., 2014, 4, 59726–59732
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minor isomers), 7.46 (d, J ¼ 8.5 Hz, 2H of major and minor isomers), 6.10 (q, J ¼ 6.9 Hz, 0.70H), 5.82* (q, J ¼ 6.9 Hz, 0.30H),
1
3
isomers), 5.66 (s, 1.69H), 5.41* (s, 0.31H), 1.33 (br s, 9H of major 1.86 (d, J ¼ 6.9 Hz, 2.09H), 1.75* (d, J ¼ 6.9 Hz, 0.91H) ppm.
C
1
3
and minor isomers) ppm. C NMR (100 MHz; CDCl ) d 153.9 NMR (100 MHz; acetone-d ) d 153.3 (C), 152.3* (C), 134.8 (C),
3
6
(
(
(
C), 148.4 (C), 130.0 (C), 128.1* (2 ꢁ CH), 126.1 (2 ꢁ CH), 125.9 132.1*(C), 130.2 (CH), 130.0* (CH), 129.4 (2 ꢁ CH), 129.1* (2 ꢁ
), 68.4 (CH
) ppm (some peaks of the minor isomer could not be 17.1* (CH
2 ꢁ CH), 125.7* (2 ꢁ CH), 78.1* (CH
2
2
), 34.9 (C), 31.1 CH), 129.0* (2 ꢁ CH), 127.4 (2 ꢁ CH), 86.2* (CH), 78.3 (CH),
3 ꢁ CH
3
3
), 15.4 (CH
3
) ppm; IR (KBr) n 3237 (O–H), 1648 (C]
1
3
ꢃ1
detected by C NMR due to their low intensity); IR (KBr) n 3300 N), 1546 and 1386 (NO
2
) cm ; MS m/z (%) relative intensity 194
ꢃ1
+
2
(O–H), 1608 (C]N), 1558 and 1374 (NO ) cm ; MS m/z (%) (M , 2), 130 (26), 117 (70), 115 (100), 103 (32), 77 (65); HRMS
+
+
9 10 2 3
relative intensity 236 (M , 6), 221 (52), 175 (35), 158 (100), 130 (ESI-TOF) calcd for C H N NaO [M + Na] 217.0589, found
(
2
+
40); HRMS (ESI-TOF) calcd for C H N NaO [M + Na]
217.0587.
1
2
16
2
3
1
4
59.1059, found 259.1058.
4
2-Nitro-3,4-dihydronaphthalen-1(2H)-one oxime (2r). Pale
ꢂ
-(1-(Hydroxyimino)-2-nitroethyl)phenyl acetate (2n). Yellow brown solid (57.7 mg, 56%); mp ¼ 138–139 C (CH Cl /hexanes,
2
2
ꢂ
1
14
ꢂ
solid (85.7 mg, 71% yield); mp ¼ 114–115 C (EtOAc/hexanes); lit. mp 140–142 C); TLC (20% acetone in hexanes) R
f
¼ 0.28;
1
TLC (30% acetone in hexanes) R
acetone-d
f
¼ 0.20; H NMR (400 MHz;
H NMR (400 MHz; CDCl
3
) d 11.86 (br s, 1H), 10.61 (d, J ¼ 7.9
6
, isomeric ratio 14.4 : 1, minor isomer marked*) d Hz, 1H), 9.82–9.62 (m, 2H), 9.58 (d, J ¼ 7.5 Hz, 1H), 8.09 (t, J ¼
1
1.35 (s, 1H of major and minor isomers), 7.63 (d, J ¼ 8.3 Hz, 2H 4.7 Hz, 1H), 3.93–3.79 (m, 1H), 3.76–3.68 (m, 1H), 3.59–3.50 (m,
13
of major and minor isomers), 7.03 (d, J ¼ 8.3 Hz, 2H of major 1H), 3.16–3.03 (m, 1H). C NMR (100 MHz; CDCl
3
) d 147.8 (C),
and minor isomers), 5.66 (br s, 1.87H), 5.44* (br s, 0.13H), 2.14 137.4 (C), 130.3 (CH), 128.7 (CH), 128.1 (C), 127.3 (CH), 124.5
1
3
(br s, 3H of major and minor isomers) ppm. C NMR (100 MHz; (CH), 76.9 (CH), 27.8 (CH ), 25.0 (CH ); IR (KBr) n 3300 (O–H),
2 2
ꢃ1
acetone-d ) d 169.5 (C), 152.9 (C), 148.0 (C), 132.6 (C), 130.7* (2 1598 (C]N), 1547 and 1375 (NO ) cm ; MS m/z (%) relative
6
2
+
ꢁ
CH), 128.0 (2 ꢁ CH), 122.9 (2 ꢁ CH), 122.5* (2 ꢁ CH), 79.2* intensity 206 (M , 1), 160 (10), 142 (23), 128 (36), 115 (100), 89
+
(
CH
isomer could not be detected by C NMR due to their low 229.0589, found 229.0584.
intensity); IR (KBr) n 3278 (O–H), 1604 (C]N), 1570 and 1369
2 2 3 10 2 3
), 69.0 (CH ), 20.9 (CH ) ppm (some peaks of the minor (31); HRMS (ESI-TOF) calcd for C10H N NaO [M + Na]
1
3
15
2-Nitro-1-(thiophen-2-yl)ethanone oxime (2s). Yellow solid
ꢃ1
+
ꢂ
15
(
1
NO
2
) cm ; MS m/z (%) relative intensity 238 (M , 7), 196 (21), (51.2 mg, 73%); mp ¼ 218–219 C (CH
2
Cl
2
/hexanes, lit. mp 218
ꢂ
1
19 (31), 107 (100), 77 (25); HRMS (ESI-TOF) calcd for
C); TLC (30% acetone in hexanes) R ¼ 0.38; H NMR (400 MHz;
f
+
C H N NaO [M + Na] 261.0487, found 261.0480.
CDCl , isomeric ratio 1 : 1, minor isomer marked*) d 9.29 (br s,
1
0
10
2
5
3
13
2
-Nitro-1-phenylethanone oxime (2o). Yellow solid (59.1 0.53H), 7.65 (d, J ¼ 4.8 Hz, 0.51H), 7.48 (d, J ¼ 3.9 Hz, 0.54H),
ꢂ
13
mg, 63% yield); mp ¼ 95–96 C (CH
2
Cl
2
/hexanes, lit. mp 95 7.38* (d, J ¼ 4.8 Hz, 0.49H), 7.28* (d, J ¼ 3.9 Hz, 0.47H), 7.13 (dd,
ꢂ
1
C); TLC (30% acetone in hexanes) R
f
¼ 0.24; H NMR (400 MHz; J ¼ 4.8, 3.9 Hz, 0.54H), 7.07* (dd, J ¼ 4.8, 3.9 Hz, 0.49H), 5.64 (s,
CDCl
5
3
) d 8.65 (br s, 1H), 7.65–7.63 (m, 2H), 7.47–7.43 (m, 3H), 0.93H), 5.54 (s, 1H) (some peaks of the minor isomer could not
1
3
1
13
.66 (s, 2H) ppm. C NMR (100 MHz; CDCl ) d 148.5 (C), 133.0 be detected by H NMR due to their low intensity). C NMR (75
3
(
C), 130.4 (CH), 129.0 (2 ꢁ CH), 126.2 (2 ꢁ CH), 68.3 (CH
2
) ppm; MHz; CDCl
3
) d 144.3* (C), 142.4 (C), 136.6* (C), 132.3* (CH),
ꢃ1
IR (KBr) n 3222 (O–H), 1636 (C]N), 1559 and 1383 (NO ) cm
MS m/z (%) relative intensity 180 (M , 3), 134 (11), 103 (100), 91 126.2 (CH), 77.4 (CH ), 68.0* (CH ); IR (KBr) n 3265 (O–H), 1637
;
129.6 (C), 129.4 (CH), 128.6* (CH), 127.6 (CH), 127.4* (CH),
2
+
2
2
ꢃ1
+
(65), 77 (42); HRMS (ESI-TOF) calcd for C H N NaO [M + Na]
(C]N), 1557 and 1375 (NO ) cm ; MS m/z (%) relative intensity
186 (M , 11), 140 (14), 109 (37), 97 (100); HRMS (ESI-TOF) calcd
8
8
2
3
2
+
2
03.0433, found 203.0434.
+
1-(Naphthalen-1-yl)-2-nitroethanone oxime (2p). Yellow for C
6
H
6
N
2
NaO
3
S [M + Na] 208.9997, found 208.9996.
viscous oil (51.1 mg, 44% yield); TLC (30% acetone in hexanes)
1
R
f
¼ 0.22; H NMR (400 MHz; CDCl
minor isomer marked*) d 9.61 (br s, 0.63H), 8.84* (br s, 0.37H),
.01–7.88 (m, 3H of major and minor isomers), 7.68–7.37 (m, 4H We thank the Thailand Research Fund (TRF-DBG5480017), the
of major and minor isomers), 5.63 (s, 1.26H), 5.46* (s, 0.74H) Center of Excellence for Innovation in Chemistry (PERCH-CIC),
3
, isomeric ratio 1.7 : 1,
Acknowledgements
8
1
3
ppm. C NMR (100 MHz; CDCl ) d 149.3* (C), 149.1 (C), 133.8 the Office of the Higher Education Commission, Mahidol
3
(C), 133.5* (C), 130.83 (C), 130.79* (C), 130.6 (CH), 130.5* (CH), University under the National Research Universities Initiative
1
1
1
7
1
29.4 (C), 128.8 (CH), 128.7* (CH), 127.4* (CH), 127.3 (CH), for nancial support.
27.1* (CH), 126.9* (C), 126.57* (CH), 126.55 (CH), 125.4 (CH),
25.20 (CH), 125.18* (CH), 125.1* (CH), 124.5 (CH), 79.0* (CH
1.6 (CH ) ppm; IR (neat) n 3273 (O–H), 1592 (C]N), 1558 and
372 (NO ) cm ; MS m/z (%) relative intensity 230 (M , 14), 184
2
),
Notes and references
2
ꢃ1
+
2
1 For selected dioxygenation, see: (a) C. J. R. Bataille and
T. J. Donohoe, Chem. Soc. Rev., 2011, 40, 114; (b) Q. Xue,
J. Xie, P. Xu, K. Hu, Y. Cheng and C. Zhu, ACS Catal., 2013,
3, 1365; (c) M. J. Rawling and N. C. O. Tomkinson, Org.
Biomol. Chem., 2013, 11, 1434; (d) B. C. Giglio,
V. A. Schmidt and E. J. Alexanian, J. Am. Chem. Soc., 2011,
133, 13320; (e) M.-K. Zhu, J.-F. Zhao and T.-P. Loh, J. Am.
Chem. Soc., 2010, 132, 6284; (f) A. Wang, H. Jiang and
(31), 166 (100), 152 (47), 115 (19); HRMS (ESI-TOF) calcd for
+
C H N NaO [M + Na] 253.0589, found 253.0588.
1
2
10
2
3
2
-Nitro-1-phenylpropan-1-one oxime (2q). Yellow solid (50.5
ꢂ
mg, 52% yield); mp ¼ 96–97 C (EtOAc/hexanes); TLC (30%
1
acetone in hexanes) R
isomeric ratio 2.3 : 1, minor isomer marked*) d 11.29 (s, 0.70H),
0.86* (s, 0.30H), 7.64–7.39 (m, 5H of major and minor
f
¼ 0.29; H NMR (400 MHz; acetone-d
6
,
1
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RSC Adv., 2014, 4, 59726–59732 | 59731

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RSC Advances
Paper
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2
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3
For selected oxysulfonylation and oxysulfenylation, see: (a)
F.-L. Yang, F.-X. Wang, T.-T. Wang, Y.-J. Wang and
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W. Wei and J.-X. Ji, Angew. Chem., Int. Ed., 2011, 50, 9097.
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59732 | RSC Adv., 2014, 4, 59726–59732
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