Scandium(III) trifluoromethanesulfonate catalyzed aromatic nitration with inorganic nitrates and acetic anhydride

Article abstract of DOI:10.1248/cpb.50.1060

The rare earth metal(III) trifluoromethanesulfonate (rare earth metal(III) triflate, RE(OTf)₃) was found to be an efficient catalyst for aromatic nitration with carboxylic anhydride-inorganic nitrate as the nitrating agent. In the presence of a catalytic amount of RE(OTf)₃, the nitration of substituted benzenes proceeded to afford the corresponding nitrobenzenes. Especially, scandium(III) trifluoromethanesulfonate (scandium(III) triflate, Sc(OTf)₃) is the most active catalyst among our tested Lewis acids. It was also found that acetic anhydride-Al(NO ₃) · 9H₂O is the most active nitrating agent in this system.

Full text of DOI:10.1248/cpb.50.1060

1060
Chem. Pharm. Bull. 50(8) 1060—1065 (2002)
Vol. 50, No. 8
Scandium(III) Trifluoromethanesulfonate Catalyzed Aromatic Nitration
with Inorganic Nitrates and Acetic Anhydride
Atsushi KAWADA, ,a Shigemitsu TAKEDA,b Kazumi YAMASHITA,b Hitoshi ABE,b and
*
b
Takashi HARAYAMA
a Nippon Steel Chemical Co., Ltd., Research & Development Laboratories; 46–80 Nakabaru Sakinohama, Tobata-ku,
Kitakyushu 804–8503, Japan: and b Faculty of Pharmaceutical Sciences, Okayama University; 1–1–1 Tsushima-naka,
Okayama 700–8530, Japan. Received March 20, 2002; accepted May 7, 2002
The rare earth metal(III) trifluoromethanesulfonate (rare earth metal(III) triflate, RE(OTf)3) was found to
be an efficient catalyst for aromatic nitration with carboxylic anhydride–inorganic nitrate as the nitrating agent.
In the presence of a catalytic amount of RE(OTf)3, the nitration of substituted benzenes proceeded to afford
the corresponding nitrobenzenes. Especially, scandium(III) trifluoromethanesulfonate (scandium(III) triflate,
Sc(OTf)3) is the most active catalyst among our tested Lewis acids. It was also found that acetic anhydride–
Al(NO3)·9H2O is the most active nitrating agent in this system.
Key words scandium(III) trifluoromethanesulfonate; aromatic nitration; acetyl nitrate; acetic anhydride; aluminum(III) nitrate
Nitration of aromatic compounds is one of the most funda- ganic nitrate system.
mental and useful reactions for introducing the nitrogen atom
directly into aromatic rings.1—4) This reaction generally re- Results and Discussion
quires the use of a potent mixture of concentrated or fuming
In the first place, the catalytic activity of Lewis acids was
nitric acid with sulfuric acid, a large amount of acid and its examined for the nitration of m-xylene using the acetic anhy-
waste after the aqueous work-up procedures often cause seri- dride–lithium nitrate system. These results are summarized
ous environmental problems. In order to these issues, there in Table 1. The nitration of m-xylene was carried out in a so-
have been some efforts to perform reactions in the absence of lution containing 0.3 molar equivalent of Lewis acid, 5.0
sulfric acid.5—26) For the solution of this problem, we focused molar equivalent of acetic anhydride, and 1.0 molar equiva-
on acyl nitrates, which are known as active nitrating lent of lithium nitrate (LiNO3) at room temperature. 1,3-Di-
agent.27—36) Acyl nitrates are generally produced in situ by methyl-2-nitrobenzene (1) and 1,3-dimethyl-4-nitrobenzene
the reaction of an excess of concentrated or fuming nitric (2) as nitration products were obtained. No di-nitrated prod-
acid and carboxylic anhydride, or the reaction of silver ni- ucts were observed. While it is assumed that the acetylation
trate and acid chloride. Another method for the generation of proceeds in addition to nitration under this condition, acety-
acyl nitrates is the reaction of inorganic nitrates and car- lation products were not obtained. In the absence of Lewis
boxylic anhydride, whereas, in most cases, the nitration by acids, m-xylene was not converted (Entry 1). When conven-
this method is limited to activated substrates.37) Crivello re- tional Lewis acids such as AlCl3, FeCl3, SnCl4, and
ported that the acyl nitrates generated from the mixture of BF3·Et2O were examined, the product yields were poor (En-
ammonium nitrate and trifluoroacetic anhydride and aromatic tries 2—5). The reaction was next performed using rare earth
nitration smoothly proceeded, however, the reaction of am- metal(III) compounds as the Lewis acid catalyst. While
monium nitrate with acetic anhydride did not produce nitra- ScCl3 or YbCl3 was not effective (Entries 6, 7), RE(OTf)3
tion products.38)
was effective (Entries 8, 10). Especially, when a 0.3 molar
It is known that rare earth metal(III) trifluoromethanesul- equivalent of Sc(OTf)3 was used as the catalyst, the nitration
fonates (rare earth metal(III) triflates, RE(OTf)3) have a high of m-xylene smoothly proceeded at room temperature and a
Lewis acidity compared to the corresponding rare earth 74% yield of nitration products was obtained (Entry 8). On
metal(III) halides, and are stable in water. In this decade, the other hand, in the case of no addition of acetic anhydride,
there have been many reports that RE(OTf)3 as a Lewis acid the nitration with LiNO3 in the presence of Sc(OTf)3 did not
catalyst has been successfully applied to several synthetic re- proceed (Entry 9). It is presumed that a highly reactive nitrat-
actions.39—45) Recently, we have developed RE(OTf)3 cat- ing agent such as acyl nitrate is generated in situ by the reac-
alyzed Friedel–Crafts reactions46—49) and benzyl-etherifica- tion of LiNO3 and acetic anhydride in the presence of
tion,50) and these reactions proceed smoothly using small Sc(OTf)3 as a Lewis acid. It should be noted that this nitra-
amounts of RE(OTf)3. During the course of our investiga- tion does not require strong acid condition. Table 1 also
tions about Friedel–Crafts acylation, we found that acetyl shows the difference in reactivity between the monobasic
perchlorate, the mixed anhydride of acetic acid and perchlo- acid anhydride and dibasic acid anhydride. For example, the
ric acid, which acts as an active acylating agent is generated dibasic acid anhydride such as succinic or phthalic anhydride
from acetic anhydride and lithium perchlorate in the presence produced no nitration product (Entries 11, 12). On the other
of RE(OTf)3.46—49) Based on this consideration, the efficient hand, the monobasic acid anhydrides are effective, and espe-
generation of acyl nitrate is expected between an inorgan- cially, acetic anhydride gave a good yield (Entries 8, 13).
ic nitrate and carboxylic anhydride in the presence of
Several reaction conditions were examined, and the results
RE(OTf)3, and we tried to examine the nitration of aromatic are summarized in Table 2. This table shows that the yields
compounds using the RE(OTf)3–carboxylic anhydride–inor- of the products are dependent on the solubility of the inor-
To whom correspondence should be addressed. e-mail: kawadaat@nscc.co.jp
© 2002 Pharmaceutical Society of Japan

August 2002
1061
Table 1. Lewis Acid Catalyzed Nitration with LiNO3 and Acid Anhydride
Yield/%a)
Selectivity/%b)
Entry
Lewis acid
Acid anhydride
Time/h
1ϩ2
1
2
1
2
3
4
5
6
7
8
9
10
11
12
13
None
AlCl3
FeCl3
SnCl4
BF3·Et2O
ScCl3
YbCl3
Sc(OTf)3
Sc(OTf)3
Yb(OTf)3
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
Acetic anhydride
Acetic anhydride
Acetic anhydride
Acetic anhydride
Acetic anhydride
Acetic anhydride
Acetic anhydride
Acetic anhydride
None
Acetic anhydride
Succinic anhydride
Phthalic anhydride
Benzoic anhydride
24
5
N.D.c)
Trace
15
23
17
24
24
24
24
24
2
24
2
2
20
13
24
80
87
76
Trace
Trace
74
16
19
84
81
N.D.c)
44
N.D.c)
N.D.c)
32
2
2
12
88
a) Isolated yield. b) Ratio of 1 and 2 was determined by 1H-NMR. c) Not detected.
Table 2. Nitration of m-Xylene by Sc(OTf)3–LiNO3–Acetic Anhydride
Chart 1. Possible Equation of Nitration of Aromatics by Using RE(OTf)3–
Ac2O–LiNO3
considered that this low catalytic activity of Sc(OTf)3 was
due to the basicity of lithium acetate which was generated as
a co-product in the reaction system (Chart 1).
Sc(OTf)3
eq
Time
h
Yield/%a)
Selectivity/%b)
For the study of the negative effect of the co-products, we
examined the addition of co-products to this nitration system
(Table 3). This table clearly shows that lithium acetate inter-
feres with the Sc(OTf)3-catalyzed nitration. While the nitra-
tion reaction proceeded with no addition of lithium acetate or
acetic acid (Entry 4), the reaction did not proceed in the pres-
ence of lithium acetate (Entries 1, 2). Based on this evidence,
it is concluded that the Lewis acidity of Sc(OTf)3 decreased
due to the basicity of lithium acetate and the reaction did not
proceed.
Entry
Solv.
1ϩ2
1
2
1
2
3
4
5
6
0.3
0.3
0.3
0.3
0.3
0.1
MeCN
MeNO2
C2H4Cl2
MeCN
MeCN
MeCN
2
2
2
24
48
24
74 (247)
51 (170)
62 (207)
85 (283)
82 (273)
32 (320)
20
12
11
18
17
25
80
88
89
82
83
75
a) Isolated yield. The numbers in parentheses are yields based on Sc(OTf)3. b)
Ratio of 1 and 2 was determined by 1H-NMR.
Various inorganic nitrates were then examined for the ni-
tration of m-xylene with acetic anhydride and Sc(OTf)3, and
these results are summarized in Table 4. The amount of nitro-
nium ion in the inorganic nitrate was equivalent to that of the
m-xylene. All the inorganic nitrates were effective and the
corresponding nitrated products were obtained. Especially,
the inorganic nitrates of group 3 or 13 in the periodic table
were effective and the nitration products were obtained in
good yield (Entries 7—9, 20, 21). The inorganic nitrate of Zr,
Cr, Fe, or Bi was also effective (Entries 10, 11, 13, 23). How-
ever, alkaline or alkaline earth metal nitrate has a low nitra-
tion activity, and the yields of products were very poor (En-
tries 1—6).
ganic nitrate in the reaction media employed. For example,
the nitration in acetonitrile was a homogeneous reaction and
the yield of the nitration products was 74% (Entry 1). On the
other hand, in nitromethane or dichloroethane (Entries 2, 3),
the reaction mixture was heterogeneous and the yield was
relatively low. This table also shows the effect of the amount
of catalyst and reaction time. For the nitration with a 0.3
molar equivalent of Sc(OTf)3 in acetonitrile for 24 h, the ni-
tration products were obtained in an 85% yield (Entry 4).
The yield was not further increased when the reaction time
was extended to 48 h (Entry 5). When a 0.1 molar equivalent
of Sc(OTf)3 was used, the yield was only 32% (Entry 6). We
The difference in activity of the nitration of benzene using

1062
Vol. 50, No. 8
Table 3. Negative Effect of Co-Product
Table 5. Effect of Nitric Acid Salt on Ntiration of Benzene
Entry
Inorganic nitrate
Sc(OTf)3
Yield/%a)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15c)
In(NO3)·3H2O
In(NO3)·3H2O
Bi(NO3)2·5H2O
Bi(NO3)2·5H2O
ZrO(NO3)2·2H2O
ZrO(NO3)2·2H2O
Cr(NO3)3·3H2O
Cr(NO3)3·3H2O
Fe(NO3)3·9H2O
Fe(NO3)3·9H2O
Al(NO3)3·9H2O
Al(NO3)3·9H2O
Sc(NO2)3·4H2O
Sc(NO2)3·4H2O
Sc(NO2)3·4H2O
0.1
None
0.1
None
0.1
None
0.1
None
0.1
None
0.1
None
0.1
None
None
63
32
56
32
61
Yield/%a)
1ϩ2
Selectivity/%b)
41
67
Entry
1
Additives
1
2
N.D.b)
70
AcOLi 0.9 eq.
AcOH 0.9 eq.
AcOH 0.9 eq.
AcOH 0.9 eq.
None
N.D.c)
N.D.b)
78
2
3
4
N.D.c)
52
74
N.D.b)
81
17
20
83
80
66
N.D.b)
a) Isolated yield. b) Ratio of 1 and 2 were determined by 1H-NMR. c) Not de-
tected.
a) Isolated yield. b) Not detected. c) No Ac2O was used.
Table 4. Effect of Nitric Acid Salt on Nitration of m-Xylene
effective for the nitration of benzene. In the case of the In,
Bi, Zr, or Sc salt, while the yields were low to moderate, the
nitration proceeded in the absence of Sc(OTf)3 (Entries 2, 4,
6, 14). In the case of the Cr, Fe, or Al salt, the reaction did
not proceed in the absence of Sc(OTf)3 (Entries 8, 10, 12).
On the other hand, the yield of nitrobenzene (3) increased
with the addition of Sc(OTf)3 in every case. The reaction
with Sc(NO3)3·4H2O in the absence of acetic anhydride and
Sc(OTf)3 gave no nitrated products (Entry 15). Especially,
when the inorganic nitrate of Al or Sc was used with
Sc(OTf)3 and acetic anhydride, 5 was obtained in good yield
(Entries 11, 13). We realized that Al(NO3)3·9H2O is the most
reactive inorganic nitrate in this system.
The nitration of several kinds of aromatic compounds was
examined (Table 6). Although the reaction conditions were
not yet optimized, every reaction proceeded at room tempera-
ture and corresponding mono-nitrated products were ob-
tained. While oxidation as a side reaction often occurs under
the conventional nitration conditions, no oxidation products
were observed in this reaction. The nitration of benzene and
a substituted benzene having an electron-donating group
such as anisole or alkylated benzenes proceeded in good
yield (Entries 1—4). On the other hand, the introduction of
an electron-withdrawing group such as a halogen or acetyl
group was ineffective for this nitration. While the nitration
of benzene produced a 78% yield of 3, the reaction of
chlorobenzene gave a poor yield (Entry 5). For the acetyl
group, although acetophenone gave a lower yield than
chlorobenzene did, the yield improved by the introduction of
a methoxy group and an 81% yield of nitration products
was obtained (Entries 6, 7). Interestingly, the reaction of 4-
methoxyacetophenone gave not only 3-nitro-4-methoxyace-
tophenone (13) as expected but also 4-methoxynitrobenzene
(8) (Entry 7). However, neither 2-methoxynitrobenzene (7)
nor anisole was observed in this reaction. From these results,
it is presumed that 8 is obtained not by the nitration of
Yield/%a)
Selectivity/%b)
Entry Inorganic nitrate
1ϩ2
1
2
1
2
LiNO3
NaNO3
14
25
25
4
29
16
16
25
15
14
17
17
18
17
16
17
17
17
30
17
16
16
12
16
17
18
17
14
71
84
84
75
85
86
83
83
82
83
84
83
83
83
70
83
84
84
82
84
83
82
83
86
3
KNO3
4
5
6
Mg(NO3)2·6H2O
Ca(NO2)2·4H2O
Ba(NO3)2
20
22
95
71
84
82
88
30
90
48
10
24
32
50
8
7
8
9
10
11
12
13
Sc(NO3)3·4H2O
Y(NO3)3·6H2O
Yb(NO3)3·3H2O
ZrO(NO3)2·2H2O
Cr(NO3)3·3H2O
Mn(NO3)2·6H2O
Fe(NO3)3·9H2O
14c) Co(NO3)2·6H2O
15c) Ni(NO3)2·6H2O
16
17
Rh(NO3)3
Cu(NO3)2·3H2O
18c) AgNO3
19c) Zn(NO3)2·6H2O
20
21
22
23
24
Al(NO3)3·9H2O
In(NO3)3·3H2O
Pb(NO3)2
Bi(NO3)3·5H2O
NH4NO3
92
75
50
77
21
a) Isolated yield. b) Ratio of 1 and 2 was determined by 1H-NMR. c) 0.3 eq of
Sc(OTf)3 was used.
the Sc(OTf)3–acetic anhydride–inorganic nitrate system is anisole as a de-acetylation product but by an ipso attack of
shown in Table 5. The inorganic nitrates of In, Bi, Zr, Cr, Fe, the nitronium ion.51) The reaction of 4-methoxybenzaldehyde
Al, and Sc were examined. These inorganic nitrates are also also proceeded, and a 64% yield of (4-methoxy-3-nitro-

August 2002
1063
Table 6. Nitration by Sc(OTf)3–MNO3–Ac2O
phenyl)methanediol diacetate (14) and 19% yield of (4-
methoxyphenyl)methanediol diacetate (15) were obtained
(Entry 8). For the cinnamaldehyde, (E)-3-(2-nitrophenyl)-
2-propene-1,1-diol diacetate (16), (E)-3-(4-nitrophenyl)-2-
propene-1,1-diol diacetate (17), and (E)-3-phenyl-2-propene-
1,1-diol diacetate (17) were obtained (Entry 9). Although it
is well known that the aldehyde group is easily oxidized, no
oxidation products were observed in Entries 8 and 9. These
results show that the aldehyde group is first converted to an
acylal group and then nitration occurred. For the reaction of
indoline, the acetylation of the NH group and nitration of the
aromatic ring proceeded, and N-acetylnitroindolines were ob-
tained (Entry 10). The nitration of an aromatic substituted
aliphatic alcohols was also examined (Entries 11, 12). It is
known that the nitration of an aromatic substituted aliphatic
alcohol produces the O-nitration product.52—55) While the re-
action with phenethyl alcohol yielded 13% of 2-(2-nitro-
phenyl)ethyl acetate (22), 21% of 2-(4-nitrophenyl)ethyl ac-
etate (23), and 63% of 2-phenylethyl acetate (24), the O-ni-
tration products was not observed. For the cinnamyl alcohol,
(E)-2-nitrocinnamyl acetate (25) and (E)-4-nitrocinnamyl ac-
etate (26) were obtained. These results show that the O- and
N-acetylations first proceed and then the aromatic nitration
occurrs.
Entry Conditiona)
Ar-H
Ar-NO2
b)
1
2
A
A
3
4
B
A
5
A
A
B
6c)
Conclusion
7
We have developed the RE(OTf)3 catalyzed aromatic nitra-
tion using carboxylic anhydride–inorganic nitrate as the ni-
trating agent which was found to be have the following spe-
cific features:
1) The aromatic nitration with carboxylic anhydride–metal
nitrate as the nitrating agent smoothly proceeds using a
catalytic amount of RE(OTf)3.
8d)
B
2) The nitration does not require a strong acid condition.
3) Sc(OTf)3 is the most active catalyst among the author’s
tested Lewis acids.
4) Acetic anhydride–Al(NO3)·9H2O is the most active ni-
trating.
9e)
10
11
B
B
B
5) The O- and N-nitrations do not proceed.
Experimental
Melting points were measured with a Yanagimoto micro melting point ap-
paratus. The IR spectra were recorded on a JASCO FT/IR-350. The 1H-
NMR spectra (tetramethylsilane (TMS) as an internal standard) were
recorded on a Varian VXR-500 spectrometer. Chemical shifts are given in
ppm. The Mass spectra were measured on a VG-70SE spectrometer. Ele-
mental analyses were carried out using Yanaco MT-5. For the thin-layer
chromatography (TLC) analyses throughout this study, Merck precoated
TLC plates (silica gel 60 F254) were used. Silica-gel column chromatography
was performed using Merck Kieselgel 60 (70—230 mesh).
All of the RE(OTf)3 were prepared from the corresponding rare earth
metal(III) oxide (Soekawa Chemicals Co., Ltd.) and trifluoromethanesul-
fonic acid (Kanto Chemicals Co., Ltd.) in water according to the literature
method.56,57) Acetic anhydride and acetonitrile were dried by distillation
from calcium hydride. All reagents used in this study were commercially
available.
Typical Experimental Procedure for the RE(OTf)3-Catalyzed Nitra-
tion with LiNO3 and Acetic Anhydride A typical experimental proce-
dure is described for the Sc(OTf)3-catalyzed nitration of m-xylene (Table 1,
Entry 10). Sc(OTf)3 was prepared from the scandium(III) oxide and trifluo-
romethanesulfonic acid.56,57) A mixture of Sc(OTf)3 (451 mg, 0.92 mmol),
m-xylene (320 mg, 3.0 mmol), acetic anhydride (1.4 ml, 15 mmol), and
LiNO3 (210 mg, 3.0 mmol, the amounts of nitronium ion are equivalent to
m-xylene) in acetonitrile (5 ml) was stirred at room temperature. The
progress of the reaction was monitored by TLC. After 2 h, the reaction mix-
ture was quenched by the addition of aqueous NaOH. The organic layer was
12d)
B
B
13d)
a) Condition A; Sc(OTf)3 0.1 eq., Al(NO3)3·9H2O 1.0 eq., room temperature, 2 h.
Condition B; Sc(OTf)3 0.3 eq., LiNO3 1.0 eq., room temperature, 5 h. b) The num-
bers in parentheses are isolated yields. c) Reaction time was 24 h. d) Reaction
time was 4 h. e) Reaction time was 3 h.

1064
Vol. 50, No. 8
extracted with ether, washed with brine, and dried over anhydrous MgSO4.
After removal of the solvents, the crude products were purified by column
chromatography on silica-gel using ethyl acetate–n-hexane (1 : 40) to afford
a mixture of nitrated products 1 and 2 as a yellow oil (74% yield). The iso-
mer ratio of the products determined by 1H-NMR was 1 : 2ϭ16 : 84.
Spectral data and mps of the new compounds as well as those of the less
common compounds are shown below.
5) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., J. Chem.
Soc., Chem. Commun., 1997, 613—614 (1997).
6) Ramprasad D., Waller F. J., Barrett A. G. M., Braddock D. C., U.S.
Patent 5728901 (1998) [Chem. Abstr., 128, 204692 (1998)].
7) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., Tetrahe-
dron Lett., 39, 1641—1642 (1998).
8) Waller F. J., Barrett A. G. M., Braddock D. C., Ramprasad D., McKin-
nell R. M., White J. P., Williams D. J., Ducray R., J. Org. Chem., 64,
2910—2913 (1999).
9) Waller F. J., Ramprasad D., Barrett A. G. M., Braddock D. C., Chem.
Ind. (Dekker), 75, 289—305 (1998).
4-Methoxy-3-nitroacetophenone (13)58): mp 92—94 °C (ethyl acetate); IR
(KBr) 1680, 1535, 1275, 1240 cmϪ1; 1H-NMR (CDCl3) d: 2.61 (s, 3H), 4.04
(s, 3H), 7.17 (d, 1H, Jϭ8.5 Hz), 8.18 (dd, 1H, Jϭ8.5, 2.5 Hz), 8.43 (d, 1H,
Jϭ2.5 Hz). Anal. Calcd for C9H9NO4: C, 55.38; H, 4.65; N, 7.18%. Found:
C, 55.10; H, 4.84; N, 7.15%.
(4-Methoxy-3-nitrophenyl)-methanediol Diacetate (14): mp 69—72 °C
(ethyl acetate); IR (KBr) 1740, 1535, 1350, 1245 cmϪ1; 1H-NMR (CDCl3) d:
2.14 (s, 6H), 3.99 (s, 3H), 7.12 (d, 1H, Jϭ8.5 Hz), 7.63 (s, 1H), 7.69 (dd,
10) Waller F. J., Barrett A. G. M., Braddock D. C., McKinnell R. M., Ram-
prasad D., J. Chem. Soc., Perkin Trans. 1, 1999, 867—872 (1999).
11) Barrett A. G. M., Braddock D. C., Ducray R., McKinnell R. M.,
Waller F. J., Synlett, 2000, 57—58 (2000).
1H, Jϭ8.5, 2.0 Hz), 8.04 (d, 1H, Jϭ2.0 Hz). Anal. Calcd for C12H13NO7: C, 12) Suzuki H., Murashima T., Kozai I., Mori T., J. Chem. Soc., Perkin
50.88; H, 4.63; N, 4.95%. Found: C, 50.92; H, 4.70; N, 5.00%.
Trans. 1, 1993, 1591—1957 (1993).
13) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1994, 479—484
(4-Methoxyphenyl)-methanediol Diacetate (15)59): mp 60—63 °C (ethyl
acetate); IR (KBr) 1750, 1545 cmϪ1; 1H-NMR (CDCl3) d: 2.09 (s, 6H), 3.80
(s, 3H), 6.89 (d, 2H, Jϭ8.5 Hz), 7.45 (d, 2H, Jϭ8.5 Hz), 7.62 (s, 1H). Anal. 14) Suzuki H., Murashima T., J. Chem. Soc., Perkin Trans. 1, 1994, 903—
(1994).
Calcd for C12H13NO7: C, 50.88; H, 4.63; N, 4.95%. Found: C, 50.92; H,
4.70; N, 5.00%.
908 (1994).
15) Suzuki H., Yonezawa S., Mori T., Maeda K., J. Chem. Soc., Perkin
Trans. 1, 1994, 1367—1639 (1994).
(E)-3-(2-Nitrophenyl)-2-propene-1,1-diol Diacetate (16)60)
: mp 75—
80 °C (ethyl acetate); IR (KBr) 1760, 1530, 1350, 1240, 1200, 1100, 1070, 16) Suzuki H., Mori T., Maeda K., Synthesis, 1994, 841—845 (1994).
1010 cmϪ1
;
1H-NMR (CDCl3) d: 2.15 (s, 6H), 6.19 (dd, 1H, Jϭ16.0,
17) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1995, 41—44
5.5 Hz), 7.34 (d, 1H, Jϭ5.5 Hz), 7.38 (d, 1H, Jϭ16.0 Hz), 7.4—7.7 (m, 3H),
8.0 (d, 1H, Jϭ7.5 Hz).
(1995),
18) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 1, 1995, 291—293
(E)-3-(4-Nitrophenyl)-2-propene-1,1-diol Diacetate (17)61) mp 105—
(1995).
109 °C (ether–n-hexane); IR (KBr) 1760, 1530, 1350, 1240, 1200, 1100, 19) Suzuki H., Tatsumi A., Ishibashi T., Mori T., J. Chem. Soc., Perkin
1
1070, 1010 cmϪ1; H-NMR (CDCl3) d: 2.15 (s, 6H), 6.37 (dd, 1H, Jϭ16.0,
5.5 Hz), 6.93 (d, 1H, Jϭ16.0 Hz), 7.33 (d, 1H, Jϭ6.5 Hz), 7.57 (d, 2H,
Jϭ8.5 Hz), 8.21 (d, 2H, Jϭ8.5 Hz).
Trans. 1, 1995, 339—343 (1995).
20) Suzuki H., Tomaru J., Murashima T., J. Chem. Soc., Perkin Trans. 1,
1994, 2413—2416 (1994).
(E)-3-Phenyl-2-propene-1,1-diol Diacetate (18)32): mp 81—84 °C (ethyl 21) Suzuki H., Yonezawa S., Mori T., Bull. Chem. Soc. Jpn., 68, 1535—
acetate); IR (KBr) 1760, 1680, 1625, 1490, 1455, 1375, 1245, 1195, 1130,
1060, 1000, 940, 750, 690 cmϪ1; 1H-NMR (CDCl3) d: 2.11 (s, 6H), 6.19 (dd,
1H, Jϭ16.5, 6.4 Hz), 6.90 (d, 1H, Jϭ16.5 Hz), 7.1—7.6 (m, 6H), 7.57 (d,
2H, Jϭ8.5 Hz), 8.21 (d, 2H, Jϭ8.5 Hz).
1544 (1995).
22) Suzuki Hit, Tatsumi A., Suzuki Hid, Maeda K., Synthesis, 1995,
1353—1554 (1995).
23) Suzuki H., Mori T., J. Chem. Soc., Perkin Trans. 2, 1996, 677—683
(1996).
24) Suzuki H., Yonezawa S., Nonoyama N., Mori T., J. Chem. Soc., Perkin
Trans. 1, 1996, 2385—2389 (1996).
25) Suzuki H., Mori T., J. Org. Chem., 62, 6498—6502 (1997).
1-Acetyl-7-nitroindoline (20)62): IR (KBr) 1670, 1520, 1400, 1320 cmϪ1
;
1H-NMR (CDCl3) d: 2.27 (s, 3H), 3.23 (t, 2H, Jϭ8.0 Hz), 4.24 (t, 2H,
Jϭ8.0 Hz), 7.14 (dd, 1H, Jϭ8.0, 8.0 Hz), 7.42 (ddd, 1H, Jϭ8.0, 1.5, 1.5 Hz),
7.62 (dd, 1H, Jϭ8.0, 1.5 Hz).
2-(2-Nitrophenyl)ethyl Acetate (22)63): Yellow oil; IR (neat) 1720, 1520, 26) Enya T., Suzuki H., Hisamatsu Y., Bull. Chem. Soc. Jpn., 71, 2221—
1350, 1240 cmϪ1
1.5 Hz), 4.36 (t, 2H, Jϭ8.0 Hz), 7.40 (m, 2H), 7.41 (ddd, 1H, Jϭ8.0, 8.0, 27) For example see: Deans F. B., Eaborn C., J. Chem. Soc., 1957, 498—
1.5 Hz), 7.94 (dd, 1H, Jϭ8.0, 1.5 Hz). 499 (1957).
2-(4-Nitrophenyl)ethyl Acetate (23)64): Yellow oil; IR (neat) 1720, 1520, 28) For example see: Paul M. A., J. Am. Chem. Soc., 80, 5329—5332
1350, 1240 cmϪ1 1H-NMR (CDCl3) d: 2.04 (s, 3H), 3.06 (td, 2H, Jϭ8.0,
(1958).
1.5 Hz), 4.33 (td, 2H, Jϭ8.0, 1.5 Hz), 7.40 (dd, 2H, Jϭ8.0, 1.5 Hz), 8.18 (dd, 29) For example see: Bordwell F. G., Garbisch E. W., J. Am. Chem. Soc.,
2H, Jϭ8.0, 1.5 Hz). 82, 3588—3598 (1960).
;
1H-NMR (CDCl3) d: 2.03 (s, 3H), 3.26 (td, 2H, Jϭ8.0,
2228 (1998).
;
(E)-2-Nitrocinnamyl Acetate (25): Yellow oil; IR (neat) 1740, 1520, 1345, 30) For example see: Sparks A. K., J. Org. Chem., 31, 2299—2302 (1966).
1
1230, 1440, 1030, 965, 860, 785, 740, 700 cmϪ1; H-NMR (CDCl3) d: 2.13 31) For example see: Hartshorn S. R., Moodie R. B., Schofield K., J.
(s, 3H), 4.78 (dd, 2H, Jϭ6.0, 1.5 Hz), 6.27 (dt, 1H, Jϭ16.0, 6.0 Hz), 7.14
Chem. Soc. B, 1971, 1256—1261 (1971).
(dd, 1H, Jϭ16.0, 1.5 Hz), 7.43 (ddd, 1H, Jϭ8.0, 7.5, 2.0 Hz), 7.5—7.6 (m, 32) For example see: Kurz M. E., Yang L. T. A., Zahora E. P., Adams R.
2H), 7.95 (dd, 1H, Jϭ8.0, 0.5 Hz). C., J. Org. Chem., 38, 2271—2281 (1973).
(E)-4-Nitrocinnamyl Acetate (26): Yellow oil; IR (neat) 1740, 1520, 1345, 33) For example see: Narang S. C., Thompson M. J., Aust. J. Chem., 28,
1
1230, 1440, 1030, 965, 860, 785, 740, 700 cmϪ1; H-NMR (CDCl3) d: 2.13
(s, 3H), 4.78 (dd, 2H, Jϭ6.0, 1.5 Hz), 6.46 (dt, 1H, Jϭ16.0, 6.0 Hz), 7.14
(dd, 1H, Jϭ16.0, 1.5 Hz), 7.52 (d, 2H, Jϭ8.5 Hz), 8.19 (d, 2H, Jϭ8.5 Hz).
385—389 (1975).
34) For example see: Sifniades S., J. Org. Chem., 40, 3562—3566 (1975).
35) For example see: Morzycki J. W., Lotowski Z., Stepniowska M.,
Gryszkiewicz A., Wilczewska A. Z., Tetrahedron, 53, 16161—16168
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Acknowledgements We are grateful to the SC-NMR Laboratory of
Okayama University for high-field NMR experiments.
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Methods and Mechanisms,” VCH Publishers Inc., New York, 1989,
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