Synthesis of α-cyanocinnamaldehydes from acrylonitrile and benzaldehydes catalyzed by Pd(OAc)2/HPMoV/FeCl3/O 2 system

Article abstract of DOI:10.1021/jo9021293

(Chemical Equation Presented) A facile direct synthesis of (E)-α-cyanocinnamaldehydes from acrylonitrile and benzaldehydes is successfully achieved in a mixed solvent of EtOH/AcOH by Pd(OAc)₂/ HPMoV/FeCl₃/O₂ catalyst syste

Full text of DOI:10.1021/jo9021293

pubs.acs.org/joc
methoxy group with hydrochloric acid is reported to lead to
Synthesis of r-Cyanocinnamaldehydes from
Acrylonitrile and Benzaldehydes Catalyzed by
Pd(OAc)2/HPMoV/FeCl3/O2 System
(E)-R-cyanocinnamaldehydes.3c Direct access to (E)-R-cyano-
cinnamaldehydes from cheap and readily available benzalde-
hydes and acrylonitrile represents a technically simple and
unexplored alternative to the existing approaches.
Sayuki Maeda, Norihide Horikawa, Yasushi Obora, and
Yasutaka Ishii*
The reaction of acrylonitrile with benzaldehyde under
potassium hydroxide has been examined by Wasserman et al.,
but desired (E)-R-cyanocinnamaldehyde was formed in a low
yield as a minor component of products.4 Therefore, this
method is not used for the purpose obtaining this compound.
Quite recently, we reported that the reaction of acrylates
with aldehydes in the presence of catalytic amounts of Pd(II),
H4PMo11VO40 (HPMo11V), and CeCl3 in a mixed solvent of
methanol and acetic acid under dioxygen produced substi-
tuted furoates in substantial yields.5 During the course of this
study, the reaction of acrylonitrile (1) with aldehydes (2)
like benzaldehyde (2a) was found to bring about the exclu-
sive formation of (E)-R-cyanocinnamaldehyde 3a in good
yield. In this paper, we report a facile direct synthesis of
(E)-R-cyanocinnamaldehydes (3) from acrylonitrile (1) and
several benzaldehydes.
Department of Chemistry and Materials Engineering, Faculty
of Chemistry, Materials and Bioengineering and High
Technology Research Center, Kansai University, Suita, Osaka
564-8680, Japan
ishii@ipcku.kansai-u.ac.jp
Received October 3, 2009
The reaction of 1 with 2a was chosen as a model reaction
and was carried out under the influence of catalytic amounts
of Pd(II), H4PMo11VO40 13H2O (HPMo11V), and Lewis
3
acid under various conditions (eq 1 and Table 1).
A facile direct synthesis of (E)-R-cyanocinnamaldehydes
from acrylonitrile and benzaldehydes is successfully
achieved in a mixed solvent of EtOH/AcOH by Pd(OAc)2/
HPMoV/FeCl3/O2 catalyst system. The reaction was found
to proceed via the cross-aldol condensation of diethyl acetal
derived from acrylonitrile with aldehydes.
In a previous reaction of acrylates with aldehydes,5 we
showed that furoates are obtained in good yields by using
a combined catalytic system consisting of Pd(OAc)2,
HPMo11V, and CeCl3. Thus, we first tried the reaction using
the same catalytic system. Namely, the reaction of 1 (2 mmol)
with 2a (10 mmol) under O2 (1 atm) in the presence of
Pd(OAc)2 (0.1 mmol), HPMo11V (35 mg, ca. 17 μmol), and
Compounds including cyanoaldehyde moieties are widely
used as precursors of pharmaceuticals, heterocyclic com-
pounds, and biologically active molecules.1 Especially, (E)-
R-cyanocinnamic aldehydes are important building blocks
for the construction of various N-heterocyclic molecules.2
There have been several reports on the synthesis of (E)-R-
cyanocinnamic aldehydes.3 For example, Basavaiah et al.
reported the synthesis of (E)-R-cyanocinnamaldehydes by the
oxidation of the corresponding allylic alcohols derived from
the Baylis-Hillman adducts.3a Yoshimatsu et al. prepared
the same compound, (E)-2-cyano-3-phenylprop-2-enal, by
R-cyanoformylation of carbonyl compounds using R-lithio-
β-ethoxyacrylonitrile obtained by lithiation of β-ethoxyacry-
lonitrile.3b The reaction of benzaldehyde with 3,3-dimetho-
xypropionitrileunder NaOMe followed by deprotection of the
CeCl3 7H2O (0.5 mmol) at 90 °C for 8 h was run, but 3a was
3
formed in poor yield (7%) (entry 1). To improve the yield of
3a, the effect of several Lewis acids such as AlCl3, ZrCl4,
GdCl3, and Gd(OTf)3 was investigated under these reaction
conditions (entries 2-5). By the use of these Lewis acids,
however, 3a was not formed, and a complex mixture of
polymeric products derived from 1 was observed. A protic
acid (p-TsOH) was also ineffective (entry 6). Among the
Lewis acids examined, FeCl3 6H2O was found to be the best
3
additive. The reaction using FeCl3 under several conditions
is shown in entries 7-9. The yield of 3a was found to be
markedly improved by excess use of 2a to 1. When 5 or
10 equiv of 2a was used with respect to 1, the desired product
3a was obtained in 88 or >99%, respectively (entries 8 and
9). When the amount of FeCl3 was reduced to 0.2 mmol, the
(1) (a) Aiai, M.; Baudy-Floc’h, M. B.; Robert, A.; Le Grel, P. Synthesis
1996, 403. (b) Hbaieb, S.; Ben Ayed, T.; Amri, H. Synth. Commun. 1997, 27,
2825. (c) Beltaief, I.; Hbaieb, S.; Besbes, R.; Amri, H.; Villieras, M.; Villieras,
J. Synthesis 1998, 1765. (d) Campi, E. M.; Dyall, K.; Fallon, G.; Jackson,
W. R.; Perlmutter, P.; Smallridge, A. J. Synthesis 1990, 855.
(2) Ciller, J. A.; Martin, N.; Seoane, C.; Soto, J. L. J. Chem. Soc., Perkin
Trans. 1 1985, 2581.
(3) (a) Basavaiah, D.; Kumaragurubaran, N.; Padmaja, K. Synlett 1999,
1630. (b) Yoshimatsu, M.; Yamaguchi, S.; Matsubara, Y. J. Chem. Soc.,
Perkin Trans. 1 2001, 2560. (c) Elliott, A. J.; Morris, P. E., Jr.; Petty, S. L.;
Williams, C. H. J. Org. Chem. 1997, 62, 8071. (d) Ravichandran, S. Synth.
Commun. 2001, 31, 2185.
(4) Wasserman, H. H.; Suryanarayana, B.; Grasetti, D. D. J. Am. Chem.
Soc. 1956, 78, 2808.
(5) Tamaso, K.; Hatamoto, Y.; Obora, Y.; Sakaguchi, S.; Ishii, Y. J. Org.
Chem. 2007, 72, 8820.
9558 J. Org. Chem. 2009, 74, 9558–9561
Published on Web 11/06/2009
DOI: 10.1021/jo9021293
r
2009 American Chemical Society

Maeda et al.
JOCNote
TABLE 1. Reaction of Acrylonitrile (1) with Benzaldehyde (2a) by
Pd(II)/HPMo11V/FeCl3/O2 System under Various Conditionsa
TABLE 2. Reaction of 3,3-Diethoxypropionitrile (4) with Benzaldehyde
(2a) by FeCl3 under Various Conditionsa
entry
Pd(II)
2a (equiv) Lewis acid conv/%b yield of 3a/%b
entry
Lewis acid
2a (equiv)
yield of 3a/%b
1
2
3
4
5
6
7
8
9
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
5
5
5
5
5
5
2
5
10
10
5
5
5
5
5
5
5
CeCl3 7H2O
3
37
>99
>99
>99
>99
>99
98
>99
>99
92
98
97
95
43
76
98
>99
7
1c
2
3
4
5
6
7
8
FeCl3
FeCl3
FeCl3
FeCl3
CeCl3
CeCl3
GdCl3
GdCl3
Gd(OTf)3
Gd(OTf)3
AlCl3
1
1
2
5
1
2
1
2
1
2
1
2
47
36
59
>99
14
27
16
29
10
19
38
79
c
AlCl3
GdCl3 6H2O
ZrCl4
c
c
c
c
3
Gd(OTf)3
p-TsOH
FeCl3 6H2O
36
83
>99 (85)
78
83
53
77
22
57
3
FeCl3 6H2O
FeCl3 6H2O
FeCl3 6H2O
3
9
3
10d Pd(OAc)2
11 Pd(acac)2
12 Pd(dba)2
13 PdCl2
10
11
12
3
FeCl3 6H2O
FeCl3 6H2O
3
AlCl3
3
a4 (2 mmol) was reacted with 2a under the influence of FeCl3 6H2O
FeCl3 6H2O
FeCl3 6H2O
3
14e 5wt%Pd/C
15f Pd(OAc)2
16g Pd(OAc)2
17 Pd(OAc)2
3
3
(0.5 mmol, 25 mol %), in EtOH (1 mL)/AcOH(5 mL) at 90 °C for 8 h.
bBased on 4 used. cAcOH (5 mL) was employed.
FeCl3 6H2O
FeCl3 6H2O
none
3
83
3
c
extent by lanthanoid Lewis acids such as CeCl3, GdCl3, and
Gd(OTf)3 to give 3a in low yields (entries 5-10). It is
interesting to note that the reaction using AlCl3 led to 3a in
relatively good yields (entries 11 and 12), although the direct
reaction of 1 with 2a by Pd(OAc)2/HPMo11V/AlCl3 system
produced only polymeric products, as shown in entry 2 in
Table 1. This indicates that AlCl3 may inhibit the acetaliza-
tion of 1 with ethanol by Pd(OAc)2/HPMo11V.
The rate of reaction of 2a with 1 was compared with that of
2a with 4 to obtain insight on the present reaction. Figure 1
shows the time dependence curves of the reaction of 2a with 1
or 4. At an early stage of the reaction, it was found that 3a is
formed faster from 2a and 4 (Figure 1, curve A) than from 2a
and 1 (Figure 1, curve B). After an induction period of about
0.5 h, the reaction of 2a with 1 was found to progress in
almost the same rate as that of 2a with 4. Therefore, the
induction time observed here may correspond to the time
needed for the generation of an active Pd species which
promotes the acetalization of 1 with ethanol in the reaction
system. This observation also indicates that the acetalization
of 1 with ethanol takes place faster or at a comparable rate to
that of the coupling of 2a with 4 under the reaction condi-
tions. Therefore, it may be concluded that excess aldehyde
must be used to prevent the polymerization as well as the
degradation of acetal 4 by the catalysts employed.
On the basis of these results, the reaction of 1 with several
aldehydes was examined and the result is shown in Table 3.
The reaction of 1 with 4-chlolobenzaldehyde (2b) and
4-methoxybenzaldehyde (2c) gave rise to the corresponding
cyanoaldehydes, 3b and 3c, in quantitative yields (entries 1
and 2). In the reaction with 4-cyanobenzaldehyde (2d) bear-
ing an electron-withdrawing group, however, the yield of
2-formyl-3-(4-cyanophenyl)-2-propenenitrile (3d) decreased
considerably (entry 3). The reaction with 2-furaldehyde led
to (E)-2-formyl-3-(2-furyl)acrylonitrile (3e) in moderate
yield (59%) (entry 4). For the reaction of 1 with cinnamalde-
hyde (2f), (2E,4E)-2-formyl-5-phenylpenta-2,4-dienenitrile (3f)
was obtained in high yield (95%) (entry 5). The reaction with
2-naphthaldehyde (2g) gave the corresponding cyanoaldehyde
(3g) in fair yield (entry 6). A striking features of the present
condensation is that the reaction takes place stereoselectively to
afford (E)-cinnamaldehyde, exclusively.
a1 (2 mmol) was reacted with 2a in the presence of Pd(II) (0.1 mmol),
HPMo11V (35 mg, ca. 17 μmol), FeCl3 6H2O (0.5 mmol), in EtOH
3
(1 mL)/AcOH (5 mL) at 90 °C for 8 h. bBased on 1 used. Number in
c
parentheses shows isolated yield. Not detected by GC. dFeCl3 6H2O
3
(0.2 mmol) was used. ePd/C (5 wt %, 213 mg) was used. fReaction was
performed at 70 °C. gReaction time was 6 h.
yield of 3a was still high (78%) (entry 10). To examine the
catalytic performance of palladium species, several palla-
dium catalysts were examined. The reaction using Pd(acac)2
produced 3a in almost the same yield as Pd(OAc)2 (entry 11),
while Pd(dba)2 (dba: dibenzylideneacetone), PdCl2, and Pd/
C afforded 3a in 53, 77, and 22% yields, respectively (entries
12-14). From these results, the Pd(OAc)2 combined with
FeCl3 was found to induce the selective coupling of 1 with 2a
leading to 3a in high yield.
The reaction at lower temperature (70 °C) resulted in a
considerable decrease of 3a (57%) (entry 15). In absence of
Lewis acid, no coupling product 3a was obtained, although
the formation of a small amount of 3,3-diethoxypropionitrile
(4) was observed (entry 17). In a previous paper, we reported
that acrylonitrile 1 undergoes efficient acetalization with
ethanol by Pd(OAc)2 in the presence of molybdovanadopho-
sphate to form 3,3-diethoxypropionitrile (4) in good yield.6
In the present reaction, it is reasonable to assume that the
acetalization of 1 with ethanol is initiated by Pd(OAc)2 and
HPMo11V and then the resulting acetal 4 reacts with 2a
under the influence of FeCl3 to give 3a.
Thus, an independent reaction of 4 with 2a in the presence
of several Lewis acids was examined in a mixed solvent of
acetic acid and ethanol under conditions (eq 2) (Table 2).
A stoichiometric reaction of 2a with 4 in the presence of
FeCl3 in acetic acid or in a mixed solvent of ethanol and
acetic acid gave 3a in 47 and 36% yields, respectively (entries
1 and 2). When 2 equiv of 2a toward 4 was employed, the
yield of 3a increased to 59% (entry 3). As expected, 3a was
obtained in quantitative yield by the use of 5 equiv of 2a
(entry 4). The reaction of 2a with 4 was prompted to some
Unfortunately, the reaction of 1 with aliphatic aldehydes
like butyraldehyde afforded a complex mixture due to the
self-condensation of aldehyde itself.
(6) Yokota, T.; Fujibayashi, S.; Nishiyama, Y.; Sakaguchi, S.; Ishii, Y.
J. Mol. Catal. A 1996, 114, 113.
J. Org. Chem. Vol. 74, No. 24, 2009 9559

Maeda et al.
JOCNote
SCHEME 1. Reaction of 4 with 2h
FIGURE 1. Time dependence curve for the formation of 3a. (A)
Reaction of 2a with 4 under the conditions shown in entry 4, Table 2.
(B) Reaction of 1 with 2a under the conditions shown in entry 8,
Table 1.
SCHEME 2. PlausibleReaction Path for the Reaction ofAcryro-
nitrile with Aldehyde by Pd(OAc)2/HPMoV/FeCl3 under O2
TABLE 3. Reaction of 1 with Aldehydes (2) by Pd(II)/HPMo11V/FeCl3/O2
Systema
action of HPMo11V/O2 reoxidation system as reported
previously.7
In conclusion, we have developed a direct route to cyano-
cinnamic aldehydes (3) from acryronitrile (1) and aldehydes
(2) in the presence of catalytic amounts of Pd(II), HPMo11V,
and FeCl3 under O2. The reaction was found to proceed via
the cross-aldol condensation of aldehydes with diethyl acetal
4 derived from acryronitrile. This method provides the direct
route to various aromatic cyanoaldehydes which are difficult
to obtain by conventional reactions.
Experimental Section
a1 (2 mmol) was reacted with 2 (10 equiv), Pd(OAc)2 (0.1 mmol, 5 mol
Compounds 3a,3,8 3b,3a,d,8 3c,8 3d,9 3e,3c 3g,3c and 3h010 were
%), HPMoV (35 mg, ca. 17 μmol), FeCl3 6H2O (0.5 mmol, 40 mol %),
3
in EtOH (1 mL)/AcOH (5 mL) at 90 °C for 8 h. bBased on 1 used. cBased
on 1 used. Numbers in parentheses show isolated yields. dtrans-Cinna-
maldehyde (5 equiv) was used.
reported previously. Heteropolyacid H4PMo11VO40 13H2O
3
(HPMo11V) was prepared according to a literature procedure.11
The conversions and yields of products were estimated by GC
from the peak areas, based on an internal standard technique
using dimethyl adipate as standard.
In contrast, the reaction of acetal 4 with aliphatic alde-
hydes like valeraldehyde (2h) in the presence of FeCl3 6H2O
Typical Procedure for Reaction of 1 with 2a (Table 1, entry 3):
To a solution of Pd(OAc)2 (22 mg, 0.1 mmol, 5 mol %), H4-
3
was found to give 5-propyl-3-cyanofuran (3h) in low yield
(24%) along with self-condensation product (E)-2-propyl-
hept-2-enal (3h0) (14%) (Scheme 1). The yield of the product
3h was increased to 50% by using Pd(OAc)2/HPMo11-
PMo11VO40 13H2O (HPMo11V) (35 mg, 17 μmol, 0.85 mol %),
3
and FeCl3 6H2O (135 mg, 0.5 mmol, 25 mol %) in EtOH
3
(1.0 mL) were added 1 (106 mg, 2 mmol), 2a (2.12 g, 20 mmol),
V/FeCl3 6H2O catalyst system. It is difficult to explain
3
(7) (a) Yokota, T.; Tani, M.; Sakaguchi, S.; Ishii, Y. J. Am. Chem. Soc.
2003, 125, 1476. (b) Tani, M.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2004, 69,
1221. (c) Yamada, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2005, 70, 5471.
(d) Yamada, T.; Sakakura, A.; Sakaguchi, S.; Obora, Y.; Ishii, Y. New J.
Chem. 2008, 32, 738. (e) Ohashi, S.; Sakaguchi, S.; Ishii, Y. Chem. Commun.
2005, 486. (f) Yamada, S.; Sakaguchi, S.; Ishii, Y. J. Mol. Catal. A 2007, 262,
48. (g) Yamada, S.; Ohashi, S.; Obora, Y.; Sakaguchi, S.; Ishii, Y. J. Mol.
Catal. A 2008, 282, 22.
clearly the reaction pathway for the formation of 3h, but
the Pd species is an important component for the formation
of 3h, as we previously reported the formation of furoates
from acrylates with aldehydes by Pd(OAc)2/HPMoV/CeCl3
system.5
(8) Yadav, L. D. S.; Sribastava, V. P.; Patel, R. Tetrahedron Lett. 2008,
49, 3142.
(9) Goehring, W.; Harrington, P. J.; Hodges, L. M.; Johnston, D. A.;
Rimmler, G. U.S. Patent Appl. 2005014792, 2005.
(10) (a) Wang, Q.; El Khoury, M.; Schlosser, M. Chem.;Eur. J. 2000, 6,
420. (b) Ishikawa, T.; Uedo, E.; Okada, S.; Saito, S. Synlett 1999, 450.
(11) Pettersson, L.; Andersson, I.; Grate, J. H.; Selling, A. Inorg. Chem.
1994, 33, 982.
A plausible reaction path for the formation of 3a from
1 and 2a is shown in Scheme 2. First, 1 undergoes the
acetalization with ethanol by palladium catalyst to give
acetal 4 on which subsequent aldol-type condensation with
2a by FeCl3 affords an R,β-unsaturated carbonyl condensate
3a. Finally, the reduced Pd(0) was reoxidized to Pd(II) by the
9560 J. Org. Chem. Vol. 74, No. 24, 2009

Maeda et al.
JOCNote
and AcOH (5 mL), and the mixture was stirred at 90 °C for
8 h under O2 (1 atm, balloon). After the reaction, GC and
GC-MS analyses were performed. Solvents were removed
under reduced pressure. The residue was then neutralized
with sodium bicarbonate and extracted with ethyl acetate
(50 mL). After concentration, the crude product was purified
by column chromatography (silica gel, hexane/ethyl acetate =
5/1), and (E)-R-cyanocinnamaldehyde (3a) was isolated as a
yellow solid.
δ 114.2 (C), 116.5 (CN), 116.9 (CN), 118.5 (C), 129.0 (CN),
130.1 (CH), 132.0 (CH), 133.9 (CH), 136.6 (C), 158.6 (CH),
188.7 (CO); GC-MS (EI) m/z (relative intensity) 182 (72) [M]þ,
154 (63), 127 (100), 103 (53).
1
3f: orange solid; H NMR (400 MHz, CDCl3) δ 7.37-7.50
(m, 5H), 7.60-7.67 (m, 2H), 7.73-7.80 (m, 1H), 9.52 (s, 1H); 13
C
NMR (100 MHz, CDCl3) δ 113.3 (C), 113.9 (C), 123.1 (CH),
128.9 (CH), 129.3 (CH), 131.9 (CH), 134.4 (C), 150.7 (CH),
158.3 (CH), 185.9 (CO); GC-MS (EI) m/z (relative intensity)
183 (100) [M]þ, 154 (79), 127 (50), 115 (27). Anal. Calcd for
C12H9ON: C, 78.67; H, 4.95; N, 7.65%. Found: C, 78.30; H,
4.99; N, 7.60%.
Reaction of 3,3-Diethoxypropionitrile (4) with Benzaldehyde
(2a) in the Presence of FeCl3 (eq 2): To a solution of FeCl3 6H2O
3
(135 mg, 0.5 mmol, 25 mol %) in a solvent of ethanol (1.0 mL)
were added 4 (286 mg, 2 mmol), 2a (1.06 g, 10 mmol), and acetic
acid (5 mL), and the mixture was stirred at 90 °C for 8 h. GC and
GC-MS analyses of the reaction mixture showed that 3a was
formed in quantitative yield.
3h: colorless liquid; 1H NMR (400 MHz, CDCl3) δ 7.81
(s, 1H), 6.20 (s, 1H), 2.61 (t, 2H), 1.67 (sext, 2H), 0.96 (t, 3 H);
13C NMR (100 MHz, CDCl3) δ13.5 (CH3), 20.9 (CH2), 29.5
(CH2), 97.9 (C), 105.9 (CH), 113.5 (C), 148.1 (CH), 158.5 (C);
GC-MS (EI) m/z (relative intensity) 135 (25) [M]þ, 106(100), 78
(14), 51 (11); HRMS (EI) m/z calcd for C8H9ON [M]þ 135.0684,
found 135.0688.
Reaction of 3,3-Diethoxypropionitrile (4) with Valeraldehyde (2h)
in the Presence of Pd(OAc)2, HPMoV, and FeCl3 (Scheme 1): To a
solution of Pd(OAc)2 (11 mg, 0.05 mmol, 5 mol %), H4PMo11-
VO40 13H2O (HPMo11V) (17.5 mg, 8.5 μmol, 0.85 mol %), and
3
FeCl3 6H2O (67.5 mg, 0.25 mmol, 25 mol %) in methanol (1.0
Acknowledgment. This work was supported by a Grant-
in-Aid for Scientific Research on Priority Areas “Advanced
Molecular Transformation of Carbon Resources” from the
Ministry of Education, Culture, Sports, Science and Tech-
nology, Japan, “High-Tech Research Center” Project for
Private Universities: matching fund subsidy from the Minis-
try of Education, Culture, Sports, Science and Technology,
2005-2009.
3
mL) were added 4 (143 mg, 1 mmol), 2h (861 mg, 10 mmol), and
acetic acid (2.5 mL), and the mixture was stirred at 70 °C for 15 h
under O2 (1 atm, balloon). After the reaction, GC and GC-MS
analyses were performed. The solvent was removed under reduced
pressure. The residue was then neutralized with sodium bicarbo-
nate and extracted with ethyl acetate (50 mL). After concentration,
the crude product was purified by column chromatography (silica
gel, n-hexane/ethyl acetate = 25/1). The products 5-propyl-3-
cyanofuran (3h) and (E)-2-propylhept-2-enal (3h0) were isolated
as colorless oils.
Supporting Information Available: Spectra data and copies
of 1H and 13C NMR of the products. This material is available
free of charge via the Internet at http://pubs.acs.org.
3d:9 yellow solid; 1H NMR (400 MHz, CD3OD) δ 8.06-8.29
(m, 5H), 8.52(s, 1H), 9.73(s, 1H);13C NMR (100 MHz, acetone-d6)
J. Org. Chem. Vol. 74, No. 24, 2009 9561