Selenium-catalyzed deoxygenative reduction of aliphatic nitro compounds with carbon monoxide

Article abstract of DOI:10.1246/bcsj.20090347

A reduction method of aliphatic nitro compounds to oximes using carbon monoxide was developed. When aliphatic nitro compounds were treated with carbon monoxide in the presence of a selenium catalyst, the corresponding oximes were formed in moderate to good yields.

Full text of DOI:10.1246/bcsj.20090347

8
16
Bull. Chem. Soc. Jpn. Vol. 83, No. 7, 816–818 (2010)
Short Articles
cat.Se
OH
N
Selenium-Catalyzed Deoxygenative
Reduction of Aliphatic Nitro
NO2
R2
K CO
2
3
+
CO
R1
R1
R2
DMA
Compounds with Carbon Monoxide
Scheme 1. Selenium-catalyzed reductive deoxygenation of
aliphatic nitro compounds with carbon monoxide.
Yutaka Nishiyama,* Sadatatsu Ikeda,
Hiroaki Nishida, and Rui Umeda
oximes by the reductive deoxygenation of aliphatic nitro
compounds has already been reported, however these methods
have some disadvantages, namely (i) contamination of another
reduction products, (ii) handling of agents unstable against
moisture or air, (iii) limitation of substrates, and (iv) harsh
reaction conditions.
Department of Chemistry and Materials Engineering,
Faculty of Chemistry, Materials and Bioengineering,
Kansai University, Suita, Osaka 564-8680
When 4-nitro-4-phenyl-1-butene (1a) was allowed to react
with carbon monoxide (5 atm) in the presence of a catalytic
amount of selenium (20 mol %) and three equivalent amounts
of potassium carbonate in N,N-dimethylacetamide (DMA) at
Received December 28, 2009
E-mail: nishiya@kansai-u.ac.jp
2
5 °C for 0.5 h, reductive deoxygenation of 1a smoothly
A reduction method of aliphatic nitro compounds to
oximes using carbon monoxide was developed. When
aliphatic nitro compounds were treated with carbon mon-
oxide in the presence of a selenium catalyst, the correspond-
ing oximes were formed in moderate to good yields.
proceeded to give 4-phenylbuten-4-one oxime (2a) in 98%
yield without the formation of other nitrogen-containing
compounds, such as amine, azo, azoxy, and nitroso (Entry 1
in Table 1). To determine the optimized reaction conditions, 1a,
which was chosen as a model compound, was treated with
carbon monoxide in the presence of a selenium catalyst under
various reaction conditions, and these results are shown in
Table 1. When a tertiary amine, such as triethylamine and
N-methylpyrrolidine was used as a base, the reductive deoxy-
genation of 1a hardly proceeded under the same reaction
conditions as Entry 1, and 1a was recovered (Entries 2 and 3).
In the case of DBU having a stronger basicity than that of
triethylamine and N-methylpyrrolidine, 2a was obtained in 72%
yield (Entry 4). The use of N,N-dimethylformamide (DMF),
acetonitrile, THF, and benzene instead of DMA as the solvent
significantly decreased the yield of 2a (Entries 5­8). Decreasing
the amount of selenium as a catalyst (5 mol %) was successfully
attained by extending the reaction time (Entries 9 and 10). When
the reaction was carried out under an atmosphere of carbon
monoxide, the yield of 2a decreased (Entry 11).
Carbon monoxide is widely accepted as a useful reducing
agent as well as an extremely important agent for introducing
1
carbonyl functions into organic molecules. As to the synthetic
reactions utilizing the reducing ability of carbon monoxide,
transition-metal complexes are usually employed as the catalyst
for the reduction or reductive carbonylation of various organic
compounds with carbon monoxide. Recently, we and Chinese
chemists have shown that elemental selenium, a non-transition
metal, acts as a unique catalyst for the reduction or reductive
carbonylation of aromatic nitro compounds with carbon
monoxide giving the corresponding nitrogen-containing com-
2
,3
pounds.
On the continuous study of the utility of carbon monoxide in
organic synthesis, we now find that aliphatic nitro compounds
are selectively reduced by carbon monoxide in the presence of
a selenium catalyst under mild reaction temperature and carbon
monoxide pressure producing the corresponding oximes in
moderate to good yields (Scheme 1).4 The preparation of
In order to determine the scope and limitations of the
preparation of aliphatic oximes by the reductive deoxygenation
of nitro compounds with carbon monoxide, various aliphatic
nitro compounds were treated with carbon monoxide in the
,5
Table 1. Selenium-Catalyzed Reductive Deoxygenation of 4-Nitro-4-phenyl-1-butene (1a) with Carbon Monoxidea)
OH
cat.Se
base
NO2
N
CO
solvent
1
a
2a
Entry
Solvent
Base
Yield/%b)
Entry
Solvent
Base
Yield/%b)
1
2
DMA
DMA
K2CO3
Et3N
98 (85)
9
7
8
9
0
THF
C6H6
DMA
DMA
DMA
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
7
0
81
99
51
c)
3
DMA
N Me
7
c),d)
e)
1
11
4
5
6
DMA
DMF
CH3CN
DBU
K2CO3
K2CO3
72
53
30
a) Reaction conditions: 1a (0.30 mmol), Se (0.06 mmol), base (0.90 mmol), solvent (3 mL), and CO (5 atm) at 25 °C for
0.5 h. b) GC yield. The number in parenthesis shows the isolated yield. c) Se (0.015 mmol). d) For 3 h. e) CO (1 atm).
Published on the web June 30, 2010; doi:10.1246/bcsj.20090347

Y. Nishiyama et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 7 (2010)
817
Table 2. Synthesis of Various Oximesa)
CO2
NO
R2
tautomerization
Entry
Substrate
Product
Yield/%b)
Se
CO
R1
OH
N
NO2
Ar
NOH
NO2
Ar
SeCO
1
2
3
Ar = p-CH3C6H4 1b
Ar = p-CF3C6H4 1c
2b
2c
2d
90 (76)
94 (73)
98 (72)
R1
R2
R1
R2
2
1
Ar = p-ClC6H4
1d
Scheme 2. A plausible catalytic reaction pathway.
OH
N
NO2
4c)
1e
2e
77
54
(
(
)6
(
(
)6
tion of nitro compound by hydrogen selenide, which was gen-
7
erated by the reaction of SeCO with H O, cannot be ruled out.
2
5d)
1f
OH 2f
In summary, we found that the reaction of aliphatic nitro
compounds with carbon monoxide in the presence of selenium
catalyst gave the corresponding oximes in moderate to good
yields with high selectivity.
)5
)5
NO2
N
OH
NO2
N
6d),e)
1g
2g
77 (64)
Experimental
General Procedures.
were recorded on 270 and 67.5 MHz spectrometers using
The 1H and 13C NMR spectra
7d)
OH
(
)6 NO2
NO2
1h
2h
94 (83)
33
(
)6
N
N
OH
CDCl as the solvent with tetramethylsilane as the internal
8
Ph
1i
2i
3
Ph
standard. The IR spectra were recorded on an FT-IR spec-
trometer. Gas chromatography (GC) was carried out using a
flame-ionizing detector-equipped instrument and a capillary
column (0.25 mm © 1200 mm).
a) Reaction conditions: substrate (0.30 mmol), Se (0.06 mmol),
K2CO3 (0.90 mmol), DMA (3 mL), and CO (5 atm) at 25 °C for
0
.5 h. b) GC yield. The numbers in parenthesis show the iso-
lated yields. c) CO (20 atm) for 5 h. d) For 3 h. e) CO (50 atm).
Reagents. Selenium powder, amines, K CO , and nitro-
2
3
cyclohexane were commercially available and were used
without further purification. The nitro compounds were
prepared by literature methods and modification of these
methods. Other chemical agents were obtained commercially
and were purified if necessary by distillation.
presence of a selenium catalyst (20 mol %) under the same
reaction conditions as that of Entry 1 in Table 1. These results
are shown in Table 2. 4-(p-Methylphenyl)-, 4-(p-trifluoro-
methylphenyl)-, and 4-(p-chlorophenyl)-substituted 4-nitro-1-
butenes were reductively deoxygenated by carbon monoxide
to give the corresponding oximes 2b­2d in 90, 94, and 98%
yields, respectively (Entries 1­3). The conversion of the 4-
nitro-1-undecene (1e) into 1-undecen-4-one oxime (2e) was
successfully achieved using this system (Entry 4). When 2-
nitrooctane (1f) and 1-nitrooctane (1h), which have no carbon­
carbon double bond, were allow to react with carbon monoxide
under mild reaction conditions, the yields of the corresponding
oximes 2f and 2h decreased, however the product yields of 2f
and 2h were improved by extending the reaction time (Entries 5
and 7). Similarly, nitrocyclohexane (1g) was reduced by carbon
monoxide in the presence of a selenium catalyst to give
cyclohexanone oxime (2g), which is an important intermediate
in the preparation of nylon-6, in 77% yield (Entry 6). In the
case of nitrophenylmethane, the yield of oxime 2i was low due
to the formation of various by-products (Entry 8).
8
General Procedure for Selenium-Catalyzed Reaction of
Aliphatic Nitro Compounds with Carbon Monoxide. In a
50 mL stainless steel autoclave were placed nitro compound
(0.30 mmol), selenium (4 mg, 0.06 mmol), K CO (124 mg,
2
3
0.90 mmol), and DMA (3 mL) and magnetic stirring bar. The
apparatus was flushed three times and charged at 5­50 atm with
carbon monoxide. The mixture was stirred at room temperature
for 0.5­3 h. After the reaction, the carbon monoxide was purged
in a well-ventilated hood. Aq. HCl was added to the reaction
mixture, and the resultant solution was extracted with ethyl
acetate (25 mL © 3). The organic layer was dried over MgSO4.
The resulting mixture was filtered and the filtrate was then
concentrated. Purification of the residue by column chromatog-
raphy on silica gel afforded the corresponding oxime. The
product was characterized by comparing its spectral data with
9
10
11
those of authentic sample or previous reports 2a, 2d, 2f, 2g,
11
12
A method for the preparation of carbonyl selenide (SeCO)
via the acidolysis of secondary amine salts of the selenocarba-
mates generated by the reaction of elemental selenium with
carbon monoxide and secondary amine has already been
2h, and 2i. The structures of the products 2b, 2c, and 2e were
assigned by their H and C NMR, IR, and mass spectrum.
1
13
(E)-1-(p-Methylphenyl)-3-butene-1-one Oxime (2b):
1
H NMR (270 MHz, CDCl ): ¤ 9.53 (br, 1H), 7.52 and 7.18
3
6
shown. It was then proposed that the reductive deoxygenation
(AA¤BB¤, J = 5.4 Hz, 4H), 6.00­5.89 (m, 1H), 5.19­5.08 (m,
1
3
of the nitro group of 1 with SeCO to generate the nitroso is the
first step in this reaction. The tautomerization of nitroso
compounds smoothly proceeded under the reaction conditions
to give the oximes 2 (Scheme 2). When potassium carbonate,
which was dried at 150 °C, was used, the yield of oxime was
decreased (40%). Thus, another pathway including the reduc-
2H), 3.59 (d, J = 4.1 Hz, 2H), 2.35 (s, 3H); C NMR (67.5
MHz, CDCl3): ¤ 21.2, 31.0, 117.0, 126.2, 129.2, 132.2, 132.7,
139.3, 156.7; IR (KBr): 514, 592, 769, 816, 943, 1051, 1115,
¹
1
1187, 1304, 1324, 1438, 1515, 1610, 1638, 3293 cm ; GC MS
+
m/z 175 (M ).
(Z)-1-(p-Methylphenyl)-3-butene-1-one Oxime (2b):

8
18
Bull. Chem. Soc. Jpn. Vol. 83, No. 7 (2010)
© 2010 The Chemical Society of Japan
1
H NMR (270 MHz, CDCl ): ¤ 8.89 (br, 1H), 7.41 and 7.22
109. b) Y. Nishiyama, Y. Naitoh, N. Sonoda, Synlett 2004, 886.
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3
(AA¤BB¤, J = 5.4 Hz, 4H), 5.88­5.78 (m, 1H), 5.14­5.06 (m,
2
H), 3.29 (d, J = 4.6 Hz, 2H), 2.37 (s, 3H); 13C NMR (67.5
MHz, CDCl ): ¤ 21.3, 39.8, 117.8, 127.9, 128.9, 130.0, 133.2,
3
3
a) X. Zhang, H. Jing, J. Mol. Catal. A: Chem. 2009, 302,
1
9
1
39.0, 156.5; IR (KBr): 475, 518, 574, 640, 659, 719, 747, 812,
02, 930, 980, 1020, 1065, 1109, 1190, 1245, 1326, 1397, 1426,
1
37. b) X. Liu, S. Lu, J. Mol. Catal. A: Chem. 2009, 300, 36. c) X.
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513, 1611, 1644, 1655, 3247 cm ; GC MS m/z 175 (M ).
E)-1-(p-Trifluoromethylphenyl)-3-butene-1-one Oxime
(
1
(2c): H NMR (270 MHz, CDCl ): ¤ 9.12 (br, 1H), 7.66 and
3
7
.55 (AA¤BB¤, J = 6.8 Hz, 4H), 5.91­5.77 (m, 1H), 5.13­5.02
13
(m, 2H), 3.53 (dt, J = 1.7, 5.4 Hz, 2H); C NMR (67.5 MHz,
CDCl ): ¤ 21.5, 30.9, 117.6, 125.4, 125.5, 125.5, 126.7, 131.5,
3
1
9
3
56.0; IR (KBr): 501, 577, 610, 670, 754, 773, 836, 901, 931,
76, 1017, 1076, 1120, 1161, 1322, 1408, 1427, 1618, 1645,
¹
1
+
234 cm ; GC MS m/z 229 (M ).
Z)-1-(p-Trifluoromethylphenyl)-3-butene-1-one Oxime
(
2
003, 24, 731. n) J. Mei, S. Lu, Cuihua Xuebao 2003, 24, 321.
1
(2c): H NMR (270 MHz, CDCl ): ¤ 8.91 (br, 1H), 7.61 and
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S. Lu, Cuihua Xuebao 2002, 23, 321. q) J. Mei, S. Lu, Huaxue
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Yang, S. Lu, Chihua Xuebao 1999, 20, 224. u) Y. Yang, S. Lu,
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3
7
.51 (AA¤BB¤, J = 5.4 Hz, 4H), 5.79­5.69 (m, 1H), 5.08­5.02
13
(m, 2H), 3.23 (dt, J = 0.8, 4.6 Hz, 2H); C NMR (67.5 MHz,
CDCl ): ¤ 39.7, 118.6, 125.1, 125.2, 125.2, 125.3, 128.4,
3
1
1
2
32.3, 155.7; IR (KBr): 511, 834, 951, 1013, 1051, 1095, 1294,
¹1
320, 1399, 1438, 1495, 1596, 1638, 3294 cm ; GC MS m/z
+
4
The preparation of oximes by the reduction of aliphatic
29 (M ).
E)-1-Undecene-4-one Oxime (2e): 1H NMR (270 MHz,
nitro compounds, see: a) A. Gissot, S. N’Gouela, C. Matt, A.
Wagner, C. Mioskowski, J. Org. Chem. 2004, 69, 8997. b) V. M.
Danilenko, A. A. Tishkov, S. L. Ioffe, I. M. Lyapkalo, Y. A.
Strelenko, V. A. Tartakovsky, Synthesis 2002, 635. c) J. R. Hwu,
W. N. Tseng, H. V. Patel, F. F. Wong, D.-N. Horng, B. R. Liaw,
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Tetrahedron 1990, 46, 7413. f) M. Bartra, P. Romea, F. Urpí, J.
Vilarrasa, Tetrahedron 1990, 46, 587. g) D. H. R. Barton, I.
Fernandez, C. S. Richard, S. Z. Zard, Tetrahedron 1987, 43, 551.
h) G. A. Olah, S. C. Narang, L. D. Field, A. P. Fung, J. Org. Chem.
(
CDCl ): ¤ 7.77 (br, 1H), 5.91­5.76 (m, 1H), 5.18­5.10 (m, 2H),
2
1
CDCl ): ¤ 14.1, 22.6, 26.1, 29.0, 29.2, 31.7, 32.4, 33.9, 117.3,
1
MS m/z 182 (M ).
Z)-1-Undecene-4-one Oxime (2e): 1H NMR (270 MHz,
CDCl ): ¤ 8.47 (br, 1H), 5.93­5.78 (m, 1H), 5.18­5.06 (m, 2H),
3
.94 (dt, J = 1.4, 7.0 Hz, 2H), 2.34 (t, J = 7.7 Hz, 2H), 1.31­
.23 (m, 10H), 0.88 (t, J = 6.6 Hz, 3H); 13C NMR (67.5 MHz,
3
¹
1
32.1, 159.4; IR (KBr): 914, 969, 1637, 2928, 3247 cm ; GC
+
(
3
3
.13 (dt, J = 1.5, 6.5 Hz, 2H), 2.19 (t, J = 7.6 Hz, 2H), 1.3­1.2
13
(m, 10H), 0.88 (t, J = 6.6 Hz, 3H); C NMR (67.5 MHz,
1
983, 48, 2766. i) P. A. Wehrli, B. Schaer, Synthesis 1977, 649.
j) J. R. Hanson, Synthesis 1974, 1. k) J. F. Knifton, J. Org. Chem.
973, 38, 3296. l) H. H. Baer, W. Ramk, Can. J. Chem. 1972, 50,
1292. m) W. K. Seifert, P. C. Condit, J. Org. Chem. 1963, 28, 265.
It was reported that aliphatic nitro compounds were reduced
CDCl ): ¤ 14.1, 21.5, 22.6, 25.5, 27.3, 29.0, 29.8, 31.7, 117.6,
1
MS m/z 182 (M ).
3
¹
1
33.4, 167.7; IR (KBr): 916, 976, 1655, 2928, 3247 cm ; GC
1
+
5
This research was supported by a Grant-in-Aid for Science
Research, and Strategic Project to Support the Formation of
Research Bases at Private Universities from the Ministry of
Education, Culture, Sports, Science and Technology of Japan.
by carbon monoxide in the presence of selenium catalyst, however
there are some disadvantages on these methods: (i) high pressure
(50 atm) of carbon monoxide, (ii) high reaction temperature (130­
150 °C), (iii) low yield (<49%) and low selectivity, and (iv)
limitation of the substrate. see: J. J. McCoy, J. G. Zajacek, K. E.
Fuger, U.S. Patent 3989755, 1976.
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