First authentication of Kostanecki's triketone and multimolecular reaction of aromatic aldehydes with acetophenone

Article abstract of DOI:10.1002/hlca.200800413

A double-component, multimolecular reaction between acetophenone and aromatic aldehydes was achieved under catalysis by the solid-base mixture NaOH/K₂CO₃, and Kostanecki's triketone, supposed to exist for more than 110 years, was suc

Full text of DOI:10.1002/hlca.200800413

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First Authentication of Kostaneckiꢀs Triketone and Multimolecular Reaction
of Aromatic Aldehydes with Acetophenone
by Zixing Shan*, Xiaoyun Hu, Lin Hu, and Xitian Peng
Department of Chemistry, Wuhan University, Wuhan, 430072, Hubei, P. R. China
(fax: þ 86-27-68754067; e-mail: zxshan@whu.edu.cn)
A double-component, multimolecular reaction between acetophenone and aromatic aldehydes was
achieved under catalysis by the solid-base mixture NaOH/K2CO3, and Kostaneckiꢀs triketone, supposed
to exist for more than 110 years, was successfully separated for the first time as an accompaniment of a
pentane-1,5-dione or a 1,2,3,4,5-pentasubstituted cyclohexanol (Scheme 1) and authenticated by
spectroscopic and single-crystal X-ray diffraction analysis. Thus, the multimolecular-reaction mechanism
of the formation of 1,2,3,4,5-pentasubstituted cyclohexanols from 1-phenylalkan-1-ones and aromatic
aldehydes was fully validated based on the results (Scheme 3).
1. Introduction. – Reaction of an aldehyde with an alkanone is one of the most
extensively applied reactions in organic syntheses. A great number of investigations
have revealed that in most cases, the alkanone undergoes a two-component,
bimolecular reaction with the aldehyde to form an a,b-unsaturated ketone [1] or a b-
hydroxy ketone [2], while reports on multimolecular reactions between them are rather
scarce. As far as the reactions of acetophenone (¼1-phenylethanone) with aromatic
aldehydes are concerned, four classes of products, shown in Fig. 1, have been separated
and characterized, i.e., chalcones, b-hydroxy ketones, pentane-1,5-diones, and penta-
substituted cyclohexanols [1 – 4]. Kostaneckiꢀs triketone, belonging to a class of five-
molecular reaction products from acetophenone and aromatic aldehydes, has never
been successfully separated and substantiated1) although its structure was supposed to
be 4-benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (CAS Registry number 7149-37-3)
as early as in 1896 [5]. This might be due to the fact that linear triketones are unstable
compounds, and their synthesis is difficult to control.
Kostaneckiꢀs triketone is a key intermediate in the formation of multifunctional
1,2,3,4,5-pentasubstituted cyclohexanols. Surely, this does not mean that the linear
triketone is impossible to be isolated as a self-existent chemical entity. The known
reactions of acetophenone and aromatic aldehydes were carried out almost always in
aqueous or alcoholic caustic-base solutions [8] or in the presence of a solid-supported
catalyst [9]; probably, these reaction conditions were unsuitable for the formation of
1
)
In the literature, some authors purported that they had prepared the Kostaneckiꢀs triketone, the
m.p. being 2568 [5][6] and 1898 [7], respectively; however, later, the structure of the compound with
m.p. 1898 was established as 2,4-dibenzoyl-1,3,5-triphenylcyclohexanol [8], while the structure of the
compound with m.p. 2568 has not been elucidated to date.
ꢁ 2009 Verlag Helvetica Chimica Acta AG, Zꢂrich

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Fig. 1. Five classes of possible products from the reaction of aromatic aldehydes and acetophenone
this class of triketones. Considering that the two-component solid-base system NaOH/
K2CO3 has been successfully applied to a highly chemoselective preparation of
1,2,3,4,5-pentasubstituted cyclohexanols [10], we attempted to prepare Kostaneckiꢀs
triketone by such a solvent-free reaction of acetophenone with aromatic aldehydes or
chalcone (¼1,3-diphenylprop-2-en-1-one). Thus we now could isolate successfully two
Kostaneckiꢀs triketones, 4-benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (KTO-1) and
4-benzoyl-3,5-bis(2-methoxyphenyl)-1,7-diphenylheptane-1,7-dione (KTO-2), as by-
products of 2,4-dibenzoyl-1,3,5-triphenylcyclohexanol (PCH-1) and 3-(2-methoxy-
phenyl)-1,5-diphenylpentane-1,5-dione (PDO), respectively. In the present work, we
describe the preparation and characterization of these two Kostaneckiꢀs triketones as
well as a plausible mechanism for the formation of 1,2,3,4,5-pentasubstituted cyclo-
hexanols.
2. Results and Discussion. – 2.1. Preparation of Kostaneckiꢀs Triketones. A mixture
NaOH/K2CO3 2 :1 was finely ground and then added to a mixture of benzaldehyde and
acetophenone while grounding discontinuously for about 4 h at room temperature
(Scheme 1). The obtained nonsticking yellow solid powder was extracted with AcOEt,
and the residue obtained after concentration of the extract was heated to reflux in
EtOH, then cooled to ca. 508 and filtrated. The resulting insoluble solid was
recrystallized in AcOEt to afford 2,4-dibenzoyl-1,3,5-triphenylcyclohexanol [11]
(PCH-1) in 91% yield; the EtOH solution was concentrated and the residue separated
by column chromatography (silica gel) to afford a trace of Kostaneckiꢀs triketone 4-
benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (KTO-1). A similar reaction of 2-
methoxybenzaldehyde with acetophenone gave Kostaneckiꢀs triketone 4-benzoyl-3,5-
bis(2-methoxyphenyl)-1,7-diphenylheptane-1,7-dione (KTO-2) in 3% yield and 3-(2-

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Helvetica Chimica Acta – Vol. 92 (2009)
methoxyphenyl)-1,5-diphenylpentane-1,5-dione [12] (PDO) in more than 80% yield
after recrystallization in EtOH (Scheme 1). On the other hand, acetophenone reacted
with 4-methoxybenzaldehyde under similar conditions to furnish 2,4-dibenzoyl-3,5-
bis(4-methoxyphenyl)-1-phenylcyclohexanol (PCH-2) in 93% yield [10]. These facts
reveal that the products of the solvent-free reaction are not only in close relationship
with the substituent at the aromatic aldehyde but also with the position of the
substituent at the aromatic ring.
Scheme 1. Preparation of Kostaneckiꢀs Triketones KTO-1 and KTO-2 from Acetophenone and Aromatic
Benzaldehydes via a Solvent-Free Reaction
Attempts to upgrade the KTO-1 and KTO-2 yield by increasing the NaOH loading
in the mixed-solid catalyst and by changing the molar ratio of both the reactants did not
meet with success. Nevertheless, the yields of Kostaneckiꢀs triketones KTO-1 and KTO-
2 were upgraded to 12% and 5%, respectively, when acetophenone was allowed to
react with the chalcones 1,3-diphenylprop-2-en-1-one or 3-(2-methoxyphenyl)-1-
phenylprop-2-en-1-one under the same condition as described above (Scheme 2); the
chalcones were synthesized from acetophenone and benzaldehyde or 2-methoxybenz-
aldehyde.
The reaction of acetophenone and chalcone (¼1,3-diphenylprop-2-en-1-one)
affords 1,3,5-triphenylpentane-1,5-dione in 86% yield in the presence of solid NaOH
as catalyst [12]. This is in striking contrast to the above result and reveals that the two-
component solid-base catalyst NaOH/K2CO3 has a different catalytic activity from that
of solid NaOH.
The above results indicate that under catalysis with the two-component solid-base
system, Kostaneckiꢀs triketones KTO-1 and KTO-2 can be synthesized in low yield from
acetophenone and 2-methoxybenzaldehyde, 1,3-diphenylprop-2-en-1-one, or 3-(2-
methoxyphenyl)-1-phenylprop-2-en-1-one. The low yields of KTO-1 and KTO-2 and

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Scheme 2. Preparation of Kostaneckiꢀs Triketones KTO-1 and KTO-2 from Acetophenone and
Chalcones via a Solvent-Free Reaction
the concomitant formation of 2,4-dibenzoyl-1,3,5-triphenylcyclohexanol or 3-(2-
methoxyphenyl)-1,5-diphenylpentane-1,5-dione display the diverse idiosyncrasy of
the two Kostaneckiꢀs triketones.
2.2. Properties and Crystal Structure of Kostaneckiꢀs Triketones. KTO-1 and KTO-2
are colorless crystalline compounds with a defined melting point and have similar
spectroscopic properties. The stretching vibrations of the CO groups are at 1677 cmꢀ1
(strong sharp band) for KTO-1 and 1640 – 1700 cmꢀ1 (strong broad band) for KTO-2.
Their 1H-NMR spectra (Fig. 2) show four sets of resonances in a 1:1:1:4 intensity ratio
in the upper-field region, which correspond to the seven aliphatic H-atoms, and the
geminal H-atoms at C(2) and C(6) (4 H) are not equivalent, as revealed by a
complicated coupling pattern. In addition, the chemical shifts of the aliphatic H-atoms
of KTO-2 always appear at lower field than the corresponding ones of KTO-1, implying
that the presence of the 2-MeO group increases the deshielding effect of the benzene
ring. The 13C-NMR spectra of KTO-1 and KTO-2 reveal the chemical shifts for three
CO groups at d 195 – 205; among them, the two at d 195 – 200 are attributed to C(1)O
and C(7)O, and the one near d 204.5 to the CO group bound at C(4). The other five
aliphatic C-atoms are at d 55 – 35. These are basic characteristics of Kostaneckiꢀs
triketones.
The composition and structure of the two Kostaneckiꢀs triketones were also
confirmed by the single-crystal X-ray diffraction analysis of KTO-12). A single crystal
suitable for X-ray crystallographic analysis was obtained by slow recrystallization in
2
)
CCDC-695978 contains the supplementary crystallographic data for this paper. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif.

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Fig. 2. 1H-NMR Spectra (CDCl3, 300 MHz) of KTO-1 (bottom) and KTO-2 (top)
AcOEt. The structure of KTO-1 (Fig. 3) showed that the Ph groups at C(9) and C(17)
are in a relative ꢃtrans-arrangementꢀ to each other; energetically, this conformation may
be unfavorable for the isomerization into a cyclohexanol. However, experiment
established that pure KTO-1 can undergo cyclization into 2,4-dibenzoyl-1,3,5-
triphenylcyclohexanol (PCH-1) in the presence of the two-component solid-base
catalyst. Perhaps a base-catalyzed epimerization at the benzylic positions C(9) or C(17)
takes place prior to cyclization.
The bond distances and bond angles of the aliphatic molecular skeleton of KTO-1
are summarized in the Table 1. The three carbonyl groups have almost identical bond
distances (ca. 1.215 ꢄ) and form nearly identical bond angles with the adjacent atoms
(ca. 119.58), meaning that they are in almost the same environment. The data indicate
that KTO-1 belongs to the orthorhombic crystal system, and its space group is Pbcn.
2.3. Formation Mechanism of the Pentasubstituted Cyclohexanol. As described
above (Scheme 1), acetophenone reacted with 2-methoxybenzaldehyde or benzalde-
hyde in the presence of the two-component solid-base catalyst to afford 3-(2-
methoxyphenyl)-1,5-diphenylpentane-1,5-dione (PDO) or 2,4-dibenzoyl-1,3,5-triphe-
nylcyclohexanol (PCH-1) in high yield as well as small amounts of the Kostaneckiꢀs
triketones KTO-1 and KTO-2, meaning that the solid catalyst NaOH/K2CO3 is
especially favorable for a multimolecular reaction between an alkyl arylketone and an

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Fig. 3. X-Ray crystal structure of 4-benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (KTO-1). Arbitrary
atom numbering.
Table. Selected Bond Distances and Bond Angles of KTO-1. For atom numbering, see Fig. 3.
Bond distance [ꢄ]
C(7)ꢀO(1)
1.217(4)
C(24)ꢀO(3)
1.215(5)
C(38)ꢀO(2)
1.216(4)
C(7)ꢀC(8)
C(8)ꢀC(9)
C(9)ꢀC(10)
C(9)ꢀC(16)
1.565(4)
1.496(4)
1.528(4)
1.526(4)
C(16)ꢀC(24)
1.508(5)
C(16)ꢀC(17)
1.555(4)
C(17)ꢀC(18)
1.518(5)
C(17)ꢀC(37)
1.523(5)
C(24)ꢀC(25)
C(31)ꢀC(38)
C(37)ꢀC(38)
1.480(4)
1.490(5)
1.505(4)
Bond angle [8]
C(1)ꢀC(7)ꢀC(8)
119.0(3)
C(7)ꢀC(8)ꢀC(9)
113.8(3)
C(8)ꢀC(9)ꢀC(16)
112.5(2)
C(10)ꢀC(9)ꢀC(8)
113.7(3)
C(10)ꢀC(9)ꢀC(16)
C(17)ꢀC(16)ꢀC(9)
C(18)ꢀC(17)ꢀC(37)
C(25)ꢀC(24)ꢀC(16)
110.2(3)
115.3(3)
111.2(3)
120.8(4)
C(24)ꢀC(16)ꢀC(17)
110.7(3)
C(24)ꢀC(16)ꢀC(9)
109.4(3)
C(37)ꢀC(17)ꢀC(16)
111.5(3)
C(31)ꢀC(38)ꢀC(37)
119.2(3)
O(1)ꢀC(7)ꢀC(1)
O(1)ꢀC(7)ꢀC(8)
O(2)ꢀC(38)ꢀC(31)
O(2)ꢀC(38)ꢀC(37)
119.5(3)
121.5(3)
120.4(3)
120.4(3)
O(3)ꢀC(24)ꢀC(25)
119.2(4)
O(3)ꢀC(24)ꢀC(16)
119.9(3)

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aromatic aldehyde. The pentane-1,5-dione PDO is formed via a three-molecule
reaction between acetophenone (2 equiv.) and 2-methoxybenzaldehyde (1 equiv.),
while Kostaneckiꢀs triketones KTO-1 and KTO-2 and the pentasubstituted cyclo-
hexanols PCH-1 and PCH-2 are formed via a five-molecule reaction between
acetophenone (3 equiv.) and an aromatic aldehyde (2 equiv. of benzaldehyde or 2-
methoxybenzaldehyde). The reactions of Scheme 2 further reveal that the chalcone is a
key building block of these multimolecular-reaction products. The Kostaneckiꢀs
triketone is always generated as by-product of a pentane-1,5-dione or of a
pentasubstituted cyclohexanol, meaning that in this kind of reaction, Kostaneckiꢀs
triketone plays a dual role. On the one hand, Kostaneckiꢀs triketone is a product of the
reaction of a pentane-1,5-dione and a chalcone, which can be generated in situ from
acetophenone and an aromatic aldehyde. On the other hand, Kostaneckiꢀs triketone is a
precursor of the pentasubstituted cyclohexanols. The structure of the chalcone
influences considerably the efficiency of the formation of pentane-1,5-diones and
Kostaneckiꢀs triketone as well as the course of the reactions. Most of the chalcones
bearing a halo and electron-donating group readily give pentane-1,5-diones and
Kostaneckiꢀs triketone, but these dione and trione products are unstable under the
experimental conditions, and are immediately transformed into the pentasubstituted
cyclohexanols. However, in the case of 2-methoxychalcone, the presence of the 2-MeO
group not only stops the reaction with acetophenone at the stage of the pentane-1,5-
dione but also hinders the further reaction of the latter with acetophenone to form
Kostaneckiꢀs triketone and its transformation into a pentasubstituted cyclohexanol.
The above results clearly indicate that Kostaneckiꢀs triketone is an intermediate
between pentane-1,5-dione and the pentasubstituted cyclohexanol, and this intermedi-
ate is often elusive due to its sensitivity to experimental conditions. The successful
isolation and characterization of all three possible intermediates of the formation of
1,2,3,4,5-pentasubstituted cyclohexanols by us, in particular of Kostaneckiꢀs triketone,
provides a direct gist for the elucidation of the formation mechanism of the
pentasubstituted cyclohexanols from acetophenone and aromatic aldehydes
(Scheme 3). The possibility of an epimerization at C(3) and C(5) of the molecular
skeleton of Kostaneckiꢀs triketone, i.e., the epimerization from the ꢃtrans-arrangementꢀ
as established for KTO-1 by its crystal structure (Fig. 3) to the ꢃcis-arrangementꢀ of the
Ph groups at C(3) and C(5), would produce an intermediate suitable for cyclization to
the pentasubstituted cyclohexanol.
3. Conclusions. – In summary, we validate for the first time the existence of
Kostaneckiꢀs triketone in the reaction of aromatic aldehydes with 1-phenylalkan-1-ones
through spectroscopic and single-crystal X-ray diffraction analysis, after the triketone
was supposed to exist for more than 110 years. Kostaneckiꢀs triketones are either
difficult to form owing to the composition of the aldehyde or chalcone, or instable
under the experimental conditions and transformed rapidly into multisubstituted
cyclohexanols via an intramolecular addition. The successful separation and character-
ization of Kostaneckiꢀs triketone not only afford a practical gist for the establishment of
the formation mechanism of 1,2,3,4,5-pentasubstituted cyclohexanols from 1-phenyl-
alkan-1-ones and aromatic aldehydes but also provide a reliable model for under-
standing the reactions of alkyl heteroaryl ketones [4c][4d][13] with aromatic aldehydes

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Scheme 3. Mechanism of the Formation of 1,2,3,4,5-Pentasubstituted Cyclohexanols
or heteroaromatic aldehydes and the reactions of chalcones with active-methylene
compounds, such as alkyl heteroaryl ketones, nitroalkanes [14], alkanenitriles [15],
alkyl cyanoacetates [16], malononitrile [17], etc., to form multisubstituted cyclohexanol
derivatives.
We thank the National Natural Science Foundation of China (20372053 and 20672083) for financial
support.
Experimental Part
General. Commercially available starting materials and solvents were used without further
purification if not specified. All known products were confirmed by comparison with those of the
authentic samples. M.p.: VEB-Wagetechnik-Rapio-PHMK05 instrument; uncorrected. IR Spectra:
.
Testscan Shimadzu FTIR 8000; KBr disc; selected characteristic peaks in cmꢀ1 1H- and 13C-NMR
Spectra: Varian-Mercury-VX-300 spectrometer; chemical shifts d in ppm rel. to internal Me4Si
(¼0 ppm); field lock by external referencing to the relevant deuteron resonance. MS: VG-ZAB-HF-
3F spectrometer; in m/z (rel. %).
Preparation and Characterization of Kostaneckiꢀs Triketones. The finely ground mixture of NaOH
(0.34 g, 8.5 mmol) and K2CO3 (0.6 g, 4.2 mmol) was added to a mixture of acetophenone (1 g, 8.3 mmol)

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and chalcone (3.48 g, 16.7 mmol) and ground continuously at r.t. until the liquid disappeared (ca. 20 –
30 min), and then ground from time to time for ca. 4 h to furnish a nonsticking yellow solid powder.
This solid was washed with H2O, and the insoluble residue was refluxed in EtOH (80 ml) for 2 h. The
temp. was reduced to ca. 508, the mixture filtered, and the filtrate cooled to r.t. to yield precipitated 4-
benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (KTO-1; 0.53 g, 12%). Colorless crystals. M.p. 144 – 1468.
1H-NMR (CDCl3, 300 MHz): 7.90 (d, J ¼ 7.5, 2 H); 7.72 (d, J ¼ 7.5, 2 H); 7.54 – 7.22 (m, 11 H); 7.16 – 7.01
(m, 10 H); 4.56 (t, J ¼ 6.3, 1 H); 4.12 – 4.02 (m, 1 H); 3.94 – 3.87 (m, 1 H); 3.72 – 3.33 (m, 4 H). 13C-NMR
(CDCl3, 75 MHz): 204.3; 198.9; 198.6; 142.1; 141.3; 139.8; 137.4; 137.3; 133.2; 132.6; 128.9; 128.8; 128.7;
128.7; 128.5; 128.4; 128.3; 128.2; 128.1; 128.0; 55.4; 42.6; 42.5; 41.9; 40.1. Anal. calc. for C38H32O3: C 85.04,
H 6.01; found: C 84.82, H 5.95.
The EtOH filtrate removed from KTO-1 was concentrated to give a small amount of PCH-1. The
solid, insoluble in hot EtOH, was recrystallized from AcOEt to yield pure 2,4-dibenzoyl-1,3,5-
triphenylcyclohexanol (PCH-1; 1.6 g, 36%). M.p. 188 – 1908 ([18]: 1898). IR: 3442s (OH), 1696s, 1677s,
1
1660s (C¼O). H-NMR (CDCl3, 300 MHz): 7.78 (d, J ¼ 7.8, 2 H); 7.45 (d, J ¼ 7.5, 2 H); 6.94 – 7.30 (m,
18 H); 6.81 (t, J ¼ 6.6, 3 H); 5.71 (d, J ¼ 12, 1 H); 5.21 (s, OH); 4.37 (t, J ¼ 4.5, 1 H); 4.12 – 4.20 (m, 2 H);
3.41 (t, J ¼ 12, 1 H); 2.05 (d, J ¼ 8.4, 1 H). 13C-NMR (CDCl3, 75 MHz): 208.5; 207.0; 147.1; 141.9; 140.4;
139.5; 138.5; 133.1; 132.1; 129.0; 128.4; 128.4; 128.3; 128.0; 128.0; 127.9; 127.6; 127.1; 126.8; 125.4; 53.0;
50.4; 48.3; 42.4; 38.6.
A similar reaction of acetophenone (1.200 g, 10 mmol) with 2-methoxybenzaldehyde (0.680 g,
5 mmol) yielded 3-(2-methoxyphenyl)-1,5-diphenylpentane-1,5-dione (PDO) and 4-benzoyl-3,5-bis(2-
methoxyphenyl)-1,7-diphenylheptane-1,7-dione (KTO-2).
Data of PDO: Yield 63%. M.p. 113 – 1148 ([12]: 1158). IR: 1678s, 1634m. 1H-NMR (300 MHz,
CDCl3 þ D2O): 3.38 – 3.53 (m, 2 CH2); 3.77 (s, MeO); 4.30 (quint., J ¼ 7.50, HꢀC(3)); 6.81 – 6.89 (m,
2 H); 7.14 – 7.22 (m, 2 H); 7.41 – 7.56 (m, 6 H); 7.98 (d, J ¼ 9, 4 H). 13C-NMR (75 MHz, CDCl3): 199.5;
157.3; 137.3; 133.1; 131.6; 128.7; 128.4; 127.9; 120.9; 111.0; 55.5; 55.4; 43.3; 33.0. ES-MS (MeOH), 381
(100, [M þ Na]þ).
Data of KTO-2: Yield 5%. M.p. 164 – 1668. 1H-NMR (300 MHz, CDCl3): 3.54 (s, MeOꢀC(2)); 3.61 –
3.77 (m, 2 CH2); 3.80 (s, MeO); 4.10 – 4.00 (m, CH); 4.50 – 4.40 (m, CH); 4.94 – 4.87 (m, CH); 6.47 (d, J ¼
8.10, 1 H); 6.55 (t, J ¼ 7.20, 2 H); 6.71 (d, J ¼ 8.10, 1 H); 6.95 – 6.82 (m, 4 H); 6.98 (t, J ¼ 9.00, 1 H); 7.15 (t,
J ¼ 7.50, 2 H); 7.52 – 7.29 (m, 8 H); 7.80 (d, J ¼ 7.50, 2 H); 7.95 (d, J ¼ 7.50, 2 H). 13C-NMR (CDCl3,
75 Hz): 204.7; 199.4; 199.3; 157.3; 157.2; 139.5; 137.7; 137.6; 132.9; 132.8; 132.2; 131.0; 130.5; 129.5; 128.6;
128.5; 128.4; 128.2; 127.9; 127.8; 127.6; 120.7; 120.4; 111.0; 110.4; 55.5; 54.8; 50.8; 40.2; 38.5; 35.9. ES-MS
(MeOH): 619 (100, [M þ Na]þ). Anal. calc. for C40H36O5: C 80.51, H 6.08; found: C 80.42, H 6.02.
Crystal Structure of KTO-1. X-Ray diffraction intensity data collection and cell refinement for 4-
benzoyl-1,3,5,7-tetraphenylheptane-1,7-dione (KTO-1) was performed on an automated Bruker-
SMART-1K-CCD diffractometer equipped with a graphite monochromated MoKa radiation (l
0.71073 ꢄ). The crystal structure was solved by the direct method and refined by full-matrix least
squares for all unique data with SHELX-97.
Crystal Data of KTO-1: Empirical formula, C38H32O3; Mr, 536.64; crystal size, 0.50 ꢁ 0.34 ꢁ 0.32 mm;
calculated density, 1.196 g/cm3; volume (V), 5959.4(8) ꢄ3; crystal system, orthorhombic; space group,
Pbcn; Z ¼ 8; unit cell dimensions, a ¼ 13.0844 (11) ꢄ, b ¼ 22.6482 (18) ꢄ, c ¼ 20.1066 (16) ꢄ, a ¼ 908, b ¼
908, g ¼ 908; absorption coefficient (m), 0.074 mmꢀ1; index ranges: ꢀ 15 ꢂ h ꢂ 15, ꢀ 26 ꢂ k ꢂ 21, ꢀ 23 ꢂ
l ꢂ 23; F(000), 2272; g.o.f., 1.033; T 273(2) K; m(MoKa) ¼ 0.71073 mmꢀ1
.
REFERENCES
`
[1] L. Chaisen, A. Claparede, Ber. Dtsch. Chem. Ges. 1881, 14, 2460; J. G. Schmidt, Ber. Dtsch. Chem.
Ges. 1881, 14, 1459; M. Kalesse, Topics Curr. Chem. 2005, 244 (Natural Products Synthesis II), 43; R.
Mestres, Green Chem. 2004, 6, 583; J. H. Furhopp, G. Li, in ꢃOrganic Synthesisꢀ, 3rd edn., Wiley –
VCH, Weinheim, 2003, p. 44; M. M. Green, H. A. Wittcoff, ꢃOrganic Chemistry Principles and
Industrial Practiceꢀ, Wiley – VCH, Weinheim, 2003; M. B. Smith, J. March, ꢃAdvanced Organic
Chemistryꢀ, 5th edn., Wiley – Interscience, New York, 2001, p. 1218; F. A. Carey, R. J. Sundberg,

Helvetica Chimica Acta – Vol. 92 (2009)
1111
ꢃAdvanced Organic Chemistry Part Bꢀ, 4th edn., Kluwer Academic/Plenum Press, NewYork, 2000,
p. 57.
[2] D. B. Kimball, L. A. Silks, III, Curr. Org. Chem. 2006, 10, 1975; ꢃModern Aldol Reactionsꢀ, Ed. R.
Mahrwald, Wiley – VCH, Weinheim, 2004, Vols. 1 and 2; C. Palomo, M. Oiarbide, J. M. Garcꢅa,
Chem. Soc. Rev. 2004, 33, 65.
[3] C. B. Smith, C. L. Raston, A. N. Sobolev, Green Chem. 2005, 7, 650; N. M. Smith, C. L. Raston, C. B.
Smith, A. N. Sobolev, Green Chem. 2007, 9, 1185; G. W. V. Cave, C. L. Raston, J. L. Scott, Chem.
Commun. 2001, 2159; H. Wu, L. Lu, Y. Shen, Y. Wan, K. Yu, Synth. Commun. 2006, 36, 1193; T.
Kobayashi, H. Kawate, H. Kakiuchi, H. Kato, Bull. Chem. Soc. Jpn. 1990, 63, 1937.
[4] a) H. Kessler, S. Mronga, B. Kutscher, A. Mꢂller, W. S. Sheldrick, Liebigs Ann. Chem. 1991, 1337;
b) H. Noguchi, Chem. Eng. News 1995, 51; c) G. W. V. Cave, C. L. Raston, Chem. Commun. 2000,
2199; d) G. W. V. Cave, C. L. Raston, J. Chem. Soc., Perkin Trans. 1 2001, 3258.
[5] S. v. Kostanecki, G. Rossbach, Ber. Dtsch. Chem. Ges. 1896, 29, 1488.
[6] E. M. Hodnett, W. W. Ross, Proc. Oklahoma Acad. Sci. 1951, 32, 69.
[7] R. Georgi, A. Schwyzer, J. Prakt. Chem. 1913, 86, 273.
[8] B. S. Furniss, A. J. Hannaford, P. W. G. Smith, A. R. Tachell, ꢃVogelꢀs Textbook of Practical Organic
Chemistryꢀ, 5th edn., Longmann Scientific & Technical, UK, 1989, p. 1034; F. L. Ansari, S. Nazir, H.
Noureen, B. Mirza, Chem. Biodiversity 2005, 2, 1656.
[9] M. Lakshmi Kantam, B. Veda Prakash, C. Venkat Reddy, Synth. Commun. 2005, 35, 1971; B. M.
Choudary, M. L. Kantam, C. R. V. Reddy, B. Bharathi, F. Figueras, J. Catal. 2003, 218, 191; M. J.
Climent, A. Corma, S. Iborra, A. Velty, J. Catal. 2004, 221, 474; B. Siebenhaar, B. Casagrande, in
ꢃSynthetic Methods of Organometallic and Inorganic Chemistyꢀ, Ed. W. A. Hermann, Georg Thieme
Verlag, New York, 2002, Vol. 10, p. 114; M. Lakshmi Kantam, P. Sreekanth, P. Lakshmi Santhi,
Green Chem. 2000, 2, 47; S. S. Chaphekar, S. D. Samant, J. Chem. Technol. Biotechnol. 2004, 79, 769;
R. S. Natekar, S. D. Samant, Indian J. Chem., Sect. B 1996, 35, 1347.
[10] X. Luo, Z. Shan, Tetrahedron Lett. 2006, 47, 5623.
[11] K. Inoue, H. Noguchi, M. Hidai, Y. Uchida, Yukagaku 1983, 32, 219 (Chem. Abstr. 1983, 99, 53275);
B. K. Vasilyev, N. P. Bagrina, V. I. Vysotskii, S. V. Lindeman, Yu. T. Struchkov, Acta Crystallogr.,
Sect. C 1990, 46, 2265.
[12] W.-Y. Liu, J.-F. Li, Y.-X. Ma, Y.-M. Liang, Gaodeng Xuexiao Huaxue Xuebao 2001, 22, 141.
[13] G. W. V. Cave, M. J. Hardie, B. A. Roberts, C. L. Raston, Eur. J. Org. Chem. 2001, 3227; H. L.
Anderson, S. Anderson, J. K. M. Sanders, J. Chem. Soc., Perkin Trans. 1 1995, 2231; Y. G. Yin, K. K.
Cheung, W. T. Wong, Chin. Chem. Lett. 1998, 9, 329.
[14] O. Correc, K. Guillou, J. Hamelin, L. Paquin, F. Texier-Boulleta, L. Toupet, Tetrahedron Lett. 2004,
45, 391; J. P. Jiang, J. Gao, W. B. Shen, W. X. Chen, Acta Chim. Sin. 1992, 50, 1134; J. Y. Gao, W. X.
Chen, K. Jiang, Acta Chim. Sin. 1982, 40, 91.
[15] M. M. Al-Arab, B. S. Ghanem, M. M. Olmstead, Synthesis 1992, 10, 1003; M. M. Al-Arab, D. T.
Hani, S. G. Bader, M. O. Marilyn, Synthesis 1990, 12, 1157.
[16] A. I. Darwish, Egypt. J. Chem. 2002, 45, 695; M. M. Al-Arab, B. S. Ghanem, A. O. Fitton,
Tetrahedron 1989, 45, 6545; A. M. Mansilla, M. C. Pardo, Tetrahedron Lett. 1981, 22, 4845.
[17] L.-C. Rong, X.-Y. Li, F. Yang, H.-Y. Wang, D.-Q. Shi, Acta Crystallogr., Sect. E 2006, 62, o1766; A. I.
Darwish, Egypt. J. Chem. 2001, 44, 373; J. Mirek, Chem. Scr. 1988, 28, 295; P. Victory, J. I. Borrell, A.
Vidal-Ferran, C. Seoane, J. L. Soto, Tetrahedron Lett. 1991, 32, 5375; S. K. El-Sadany, S. M. Sharaf,
A. I. Darwish, A. A. Youssef, Indian J. Chem., Sect. B 1991, 30, 567.
[18] W. Dilthey, E. Floret, Justus Liebigs Ann. Chem. 1924, 440, 89.
Received November 16, 2008