Preparation of a microsized cerium chloride-based catalyst and its application in the Michael addition of β-diketones to vinyl ketones

Article abstract of DOI:10.1039/c3nj01454a

A facile method, which does not require special equipment, was developed for the preparation of microsized cerium chloride by the thermal treatment of CeCl₃·7H₂O or the evaporation of its alcoholic solutions. The way of the preparation of the cerium chloride-based catalyst plays a decisive role in its catalytic activity. This catalyst is efficient in the Michael addition of β-diketones to vinyl ketones giving β,δ-triketones.

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PAPER
Preparation of a Microsized Cerium ChlorideꢀBased Catalyst and its
Application in Michael Addition of βꢀDiketones to Vinyl Ketones
Alexander O. Terent’ev a,b Vera A. Vil’,a Ivan A. Yaremenko,a Oleg V. Bityukov,a,b Dmitri O.
,
5
Levitsky,c Vladimir V. Chernyshev,d,e Gennady I. Nikishin,a and Fabrice Fleury.c
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/c0nj00000x
A facile method, which does not require special equipment, was developed for the preparation of
microsized cerium chloride by the thermal treatment of CeCl3×7H2O or evaporation of its alcoholic
10 solutions. The way of the preparation of the cerium chlorideꢀbased catalyst plays a decisive role in its
catalytic activity. This catalyst is efficient in the Michael addition of βꢀdiketones to vinyl ketones giving
β,δꢀtriketones.
45 twenty years ago it was found that CeCl3ꢁ7H2O in combination with
sodium iodide can act as a more active Lewis acid promoter that is
able to facilitate a variety of useful organic transformations,
whereby no precautions need to be taken to exclude moisture or
oxygen from the reaction system.17 It is supposed that the efficiency
50 of the CeCl3ꢁ7H2O ꢀ NaI system is associated with the generation of
a ceriumꢀchlorineꢀiodineꢀcontaining catalyst.
Introduction
The Michael reaction provides the commonly used and efficient
15 synthetic route to the CꢀC bond formation. The synthesis involves
the coupling of Cꢀnucleophiles with unsaturated compounds
activated by an electronꢀwithdrawing group. βꢀDicarbonyl
compounds comprise one of the largest groups of Cꢀnucleophiles.
The latter are used to prepare products that are widely used in
20 organic synthesis.
Cerium compounds are used also in redox processes. Thus, the
CeCl3×7H2O ꢀ NaBH4 system, in which cerium chloride acts as a
Lewis acid, selectively reduces the carbonyl group in enones, with
55 the C=C bond remaining intact.18 The cerium salt (CeCl3×7H2O)
catalyzes αꢀhydroxylation of βꢀdicarbonyl compounds with
oxygen.19
In the present study, we found that microsized cerium chloride
prepared from cerium chloride heptahydrate catalyzes the coupling
of βꢀdiketones with vinyl ketones. The reaction products, β,δꢀ
triketones, are used in the synthesis of cyclic peroxides exhibiting
Since anhydrous CeCl3 can be used both as a Lewis acid and the
starting compound for the synthesis of organocerium reagents,16d, 20
60 considerable attention has been given to procedures for the
dehydration of commercially available CeCl3×7H2O. It was found
that the heating above 90 °С is accompanied by the partial
hydrolysis to form CeOCl, about 80 % of water can be removed at
temperatures below 90 °С, and residual water can be removed at
65 140ꢀ150 °С in vacuo.21
1
25 antiparasitic activity and a wide range of nitrogenꢀcontaining
heterocyclic compounds, as well as oxabicyclic systems, which
2
are natural product analogues with antiparasitic activity. 3
According to the literature data, the conditions of the coupling of βꢀ
diketones with vinyl ketones may vary in a wide range. The nature
30 of the catalyst is the main factor responsible for the successful
synthesis. Traditional alkaline catalysts are of little use for this
purpose because in the presence of these catalysts, the condensation
of diketones and the polymerization of vinyl ketones become the
dominant reactions. When searching for catalysts, it was found that
In the present study, we propose a facile method for the preparation
of microsized cerium chloride from CeCl3×7H2O and consider the
effect of the surface structure on the efficiency of the catalyst in the
addition reaction of βꢀdiketones to vinyl ketones giving β,δꢀ
70 triketones. When used asꢀis, commercial CeCl3×7H2O does not
35 the reaction of βꢀdiketones with vinyl ketones is catalyzed by
4, 2a
complexes and salts of nickel
and copper,5 aluminum
compounds,6 cerium compounds,7 ionic liquids,8 and iron,9
indium,10 zirconium,11 bismuth,12 and europium 13 chlorides.
7a
catalyze this reaction. In the study, this salt acted as the catalyst
only under solventꢀfree conditions when subjected to microwave
radiation, which requires special equipment. Besides, the authors
did not report the reaction temperature and the radiation power; the
75 absence of these parameters does not allow one to obtain
reproducible results. More recently, it was found that CeCl3×7H2O,
in combination with NaI catalyzes this reaction at room
In the past decades, cerium salts have found wide application in
40 organic synthesis. Cerium(IV) compounds, particularly, ammonium
cerium nitrate, are actively used as oneꢀelectron oxidants.14
Cerium(III) chloride heptahydrate 15 has emerged as a very cheap,
waterꢀtolerant, and friendly reagent, which is able to promote a
variety of selective functional group transformations.16 About
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temperature.7b
catalyst B was prepared as follows: CeCl3×7H2O was dissolved in
The microsized CeCl3ꢀbased catalyst proposed in the present study MeOH, the solvent was evaporated, and the resulting precipitate
can be prepared without the use of additional reagents and special20 was heated at 150 °С for 2 h. The catalyst C was prepared by
equipment. This catalyst is efficient in the addition reaction of βꢀ dissolving CeCl3×7H2O in EtOH followed by the evaporation of the
5
diketones to vinyl ketones to form β,δꢀtriketones.
solvent and heating of the resulting precipitate at 150 °С for 2 h
(Fig. 2). The catalyst D was prepared by heating CeCl3×7H2O at
150 °С for 2 h (Fig. 3). The catalyst E was prepared as follows:
Results and Discussion
The work on the preparation of microsized cerium chloride and its25 CeCl3×7H2O was heated at 150 °С for 2 h and dissolved in MeOH,
application in the synthesis of β,δꢀtriketones was performed in two then silica gel was added (85 wt. % SiO2 / (SiO2 + СeСl3×7H2O)),
10 steps. In the first step, we developed a procedure for the preparation the reaction mixture was sonicated for 10 min, and the solvent was
of the active catalyst because the commercial salt CeCl3×7H2O is a evaporated at 80 °С for 1 h at 10ꢀ15 mm Hg. The catalyst F was
poor catalyst for the addition reaction. In the second step, the prepared as follows: CeCl3×7H2O was dissolved in MeOH, silica
microsized catalyst was used in the Michael addition of βꢀdiketones30 gel was added (85 wt. % SiO2 / (SiO2 + СeСl3×7H2O)), the reaction
to vinyl ketones.
mixture was sonicated for 10 min, and the solvent was evaporated
15 With the aim of developing a reproducible, facile, and scaledꢀup at 60 °С for 0.5 h at 10ꢀ15 mm Hg (Fig. 4).
procedure, we proposed several ways of the preparation of the
catalyst. The catalyst А was commercial CeCl3×7H2O (Fig. 1). The
Fig. 2. Micrograph of the catalyst C
Fig. 1. Micrograph of the commercial sample A CeCl3×7H2O
Fig. 3. Micrograph of the catalyst D
Fig. 4. Micrograph of the catalyst F
35 The Xꢀray powder diffraction study showed that the catalysts В, С, small amount of CeOCl probably formed.21 The Xꢀray powder
and D prepared by the thermal treatment of CeCl3×7H2O were diffraction also revealed that the anhydrous catalysts В, С, and D
anhydrous CeCl3 with different morphology. The preparation of the rapidly took up atmospheric moisture during storage in air and were
catalyst D from commercial cerium chloride heptahydrate resulted transformed into the crystalline phase of CeCl3×7H2O within one
in the weight loss corresponding to the practically complete45 hour.
40 dehydration of CeCl3×7H2O. According to the literature data, a The fieldꢀemission scanning electron microscopy (FEꢀSEM) study
2
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of the samples of cerium chloride showed that its structure
substantially depends on the way of the treatment. The commercial
sample of CeCl3×7H2O does not have pronounced
A
a
microstructure (Fig. 1). The catalyst С has a porous microstructure
formed by particles with a size of about 1 ꢂm (Fig. 2). The catalyst
D is composed of particle aggregates with a particle size of about 1
ꢂm (Fig. 3). The catalyst F apparently contains small particles of
cerium chloride on the surface of large silica gel grains (Fig. 4). It
should be noted that the immobilization of cerium chloride onto
5
10 silica gel with the aim of preparing the active catalyst was
described earlier. Thus, silica gelꢀsupported CeCl3×7H2OꢀNaI was
used 22 for the conjugate addition of amines to α,βꢀenones.
15
The aboveꢀdescribed catalysts A – F were used in the reaction of βꢀ
diketones 1aꢀi with methyl vinyl ketone (Scheme 1).
Scheme 1. Synthesis of β,δꢀtriketones 2aꢀi from βꢀdiketones 1aꢀi and
methyl vinyl ketone.
The conditions for the synthesis of β,δꢀtriketones were optimized
by investigating the preparation of 3ꢀacetylheptaneꢀ2,6ꢀdione 2a
20 from methyl vinyl ketone and pentaneꢀ2,4ꢀdione 1a. The influence
of the preparation procedure, the amount of the catalysts A ꢀ F, and
the reaction time on the yield of 2a was studied (Table 1).
Table 1. Synthesis of 3ꢀacetylheptaneꢀ2,6ꢀdione 2a from methyl vinyl ketone and pentaneꢀ2,4ꢀdione 1a.
25
Amount of
A ꢀ F (mol. %)
Yield of 2a based on NMR
(isolated product), %
Run
Catalyst A – F
Reaction time, h
1
2
3
4
5
A
B
C
D
D
20
20
20
20
10
5
6
6
6
6
6
3
71 (65)
85 (77)
91 (84)
91 (83)
94 (89)
15
6
7
D
D
6
6
1
8
9
10
11
12
13
D
D
20
10
10
10
10
10
12
24
24
24
24
24
89 (82)
93 (87)
87 (82)
33
69 (61)
83 (79)
D a
D b
Е c
F c
General reaction conditions: the catalyst (372.6 mg (A); 246.5 mg (ВꢀС); 12.3ꢀ246.5 mg (D); 1.179 g (Е); or 1.242 g (F)) was added to pentaneꢀ2,4ꢀ
dione 1a (0.5 g, 5 mmol), the reaction mixture was stirred at room temperature for 5 min, and then methyl vinyl ketone (385 mg, 5.5 mmol, 1.1 mole per
mole of 1а) was added. The mixture was stirred at 20 – 25 °С for 6, 12, or 24 h.
a CeCl3×7H2O was heated at 70 °С for 1 h.
30 b After the mixing of all reagents, H2O (7 mole per mole of CeCl3) was added.
c The catalyst E or F was added to a solution of pentaneꢀ2,4ꢀdione 1a (0.5 g, 5 mmol) in CH3CN (5 mL).
The amount of the catalyst also has a substantial effect on the result
In run 1, commercial CeCl3×7H2O proved to be a poor catalyst for of the reaction. In the range from 5 to 20 mol. %, the yield of 2a
this reaction. Only the specially prepared catalyst (runs 2ꢀ13) is45 changed only slightly, whereas in the presence of 1 % of the
35 suitable for the synthesis of the target product, 3ꢀacetylheptaneꢀ2,6ꢀ catalyst (run 7), the yield decreased to 15 %.
dione 2a. An increase in the surface area of the catalyst and The reaction time (6, 12, or 24 h) is of no importance. In runs 4ꢀ6
changes in its properties have a decisive effect of the yield of the and 8, 9, the yields of 3ꢀacetylheptaneꢀ2,6ꢀdione 2a differ only
product. The simple procedure for the dissolution of CeCl3×7H2O slightly.
followed by the evaporation of the liquid phase (runs 2 with B and50 Among the catalysts B, C, and D, the latter exhibits the highest
40 3 with C) resulted in a strong increase in the activity of the catalyst. activity, its preparation does not require preliminary preparation of
Thus, the yield of 2a was 71 and 85%, respectively. In runs 4ꢀ6 (the solutions, and the simple treatment of the catalyst at 150 °С ensures
catalyst D was used), the yield of 2a was even 6ꢀ9 % higher.
the reproducibility of its composition.
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A decrease in the temperature of the treatment of the catalyst to 7015 that obtained in the reaction catalyzed by thermally untreated SiO2ꢀ
°С, at which the water loss from CeCl3×7H2O is very low, has no immobilized CeCl3×7H2O (run 13, F).
significant effect on the yield of the target product (run 10). These Taking into account the data on the optimization of the reaction
experiments showed that the structure of the catalyst rather than its conditions (Table 1, run 9, catalyst D), β,δꢀtriketones 2aꢀi were
composition is mainly responsible for the activity. In run 11, water synthesized from βꢀdiketones 1aꢀi and methyl vinyl ketone,
(7 moles of H2O per mole of СeCl3) was added to the reaction20 including unsymmetrical βꢀdiketones 1b,c and βꢀdiketones
mixture containing the anhydrous catalyst D. In this case, the target containing bulky aryl and adamantly moieties 1dꢀi, in yields up to
product 2а was obtained in lower yield. Therefore, although the 89% (Table 2).
5
presence of water decreases the activity of the catalyst, it is not
10 fully suppressed.
The use of silica gel as the substrate for cerium chloride (runs 12
and 13) led to a decrease in the yield of 3ꢀacetylheptaneꢀ2,6ꢀdione
25
2а. The reaction with the use of the thermally preꢀtreated
CeCl3×7H2O (run 12, E) afforded 2а in lower yield compared to
Table 2. β,δꢀTriketones 2aꢀi synthesized from βꢀdiketones 1aꢀi and methyl vinyl ketone.
Structures of β,δꢀtriketones 2aꢀi and yields, %
O
O
O
2a, 87
O
2b, 65
2e, 82
2c, 49
2f, 89
2i, 72
O
O
2d, 81
2g, 32 (27a)
2h, 42 (55a)
General reaction conditions: the catalyst D (123.1ꢀ51.1 mg, 0.207ꢀ0.5 mmol, 0.1 mole of CeCl3 per mole of diketone 1aꢀi) was added with stirring to
30 solution of diketone 1aꢀi (0.5 g, 2.074ꢀ5.0 mmol) in 3 mL of CH3CN (in the case of 1aꢀc, the solvent was not used), the reaction mixture was stirred at
room temperature for 5 min, methyl vinyl ketone (160ꢀ385 mg, 2.281ꢀ5.50 mmol, 1.1 mole per mole of diketone 1aꢀi) was added, and the mixture was
stirred at 20–25 °С for 24 h.
a The catalyst sample F was used.
ketone occurs most efficiently in the presence of the catalysts D and
35 The addition of pentaneꢀ2,4ꢀdione 1а to 2ꢀcyclohexenꢀ1ꢀone 3 F under conditions similar to runs 9 and 13, respectively, in Table 1
catalyzed by the catalyst D gave β,δꢀtriketone 4 in 76 % yield45 (Table 3, Scheme 3).
(Scheme 2).
40 Scheme 2. Synthesis of 3ꢀ(3ꢀoxocyclohexyl)pentaneꢀ2,4ꢀdione 4 from
pentaneꢀ2,4ꢀdione 1а and 2ꢀcyclohexenꢀ1ꢀone 3.
Scheme 3. Synthesis of αꢀsubstitutedꢀ3ꢀacetylꢀ2,6ꢀdiones 6aꢀh.
The addition of αꢀsubstituted βꢀdiketones 5aꢀh to methyl vinyl
4
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For scanning electron microscopy observations,24 samples were
mounted on a 25 mm aluminum stub using conductive glue and
coated with a 10 nm thick metal layer (Pt/Pd, 80/20) by magnetron
50 sputtering. The microstructure was studied by fieldꢀemission
scanning electron microscopy (FEꢀSEM) on a Hitachi SU8000
electron microscope. The images were taken using a secondary
electron detector at an accelerating voltage of 10 kV and the
working distance of 8 ꢀ 10 mm. The morphology of the samples
55 was studied taking into account the correction for surface effects of
the conductive layer sputtering.
The TLC analysis was carried out on standard silica gel
chromatography plates. The melting points were determined on a
Kofler hotꢀstage apparatus. The chromatography and the catalyst
60 preparation were performed on silica gel (0.060–0.200 mm, 60 A,
CAS 7631ꢀ86ꢀ9, Acros). Ultrasonic bath with an operating
frequency of 22 kHz was used; the power of the generator was 85
W.
Table 3. Synthesis of αꢀsubstitutedꢀ3ꢀacetylꢀ2,6ꢀdiones 6aꢀh from methyl
vinyl ketone and αꢀsubstituted βꢀdiketones 5aꢀh.
Yield of 6aꢀh based on the isolated
product, %
Catalyst F
Run
Substituent R
Catalyst D
1
2
3
4
5
6
7
8
Me (5a)
Bu (5b)
Hexyl (5c)
71
32
34
25
66
57
48
39 a
42
51
27
34
62
77
70
62a
CH2CH2COOEt (5d)
СH2CH2CN (5e)
CH2Ph (5f)
CH2ꢀC6H4ꢀ(4)Cl (5g)
CH2ꢀC6H4ꢀ(4)NO2 (5h)
General reaction conditions: the catalyst D or F (10 mol. %; 52.4–108.0
mg (D) or 0.527ꢀ1.088 g (F)) was added with stirring to βꢀdiketone 5aꢀh
(0.5 g, 2.125 ꢀ 4.381 mmol) or a solution of βꢀdiketone 5aꢀh in CH3CN (2
mL), respectively, and then methyl vinyl ketone (2.338–4.819 mmol, 163.9
– 337.8 mg, 1.1 mole per mole of βꢀdiketone 5aꢀh) was added. The reaction
mixture was stirred at room temperature for 24 h.
5
a THF (2 mL) was added.
Ethanol, methanol, petroleum ether (PE) (40/70), MeCN, ethyl
65 acetate (EA), pentaneꢀ2,4ꢀdione, methyl vinyl ketone,
dibenzoylmethane and 2ꢀcyclohexenꢀ1ꢀone were purchased from
Acros. Cerium(III) chloride heptahydrate was purchased from Alfa
Aesar.
10 According to the aboveꢀdescribed data, structurally different β,δꢀ
triketones 2aꢀi, 4, and 6aꢀh are produced in yields from satisfactory
to good in the reactions catalyzed by the D and F. The yield of the
products depends on the type of the catalyst. Thus, the sample D
proved to be the most efficient catalyst for the synthesis of
15 unsymmetrical β,δꢀtriketones 2b,c, β,δꢀtriketones containing bulky
aryl and adamantly moieties 2dꢀi, and β,δꢀtriketone 4, whereas the
catalyst F was efficient in the synthesis of αꢀsubstituted β,δꢀ
triketones 6fꢀh with large benzyl substituents. For β,δꢀtriketones
6aꢀe no clear dependence of the yield on the nature of the catalyst
20 was observed.
70 Synthesis of diketones 1bꢀg, i and 5aꢀh.
Diketones 1b,25 1c,26 1d,27 1e,27 1f,28 1g,28 1i,29 5a,30 5b,31 5c,32
5d,33 5e,34 5f,35 5g,35 5h35 were synthesized according to the
literature.
75 6ꢀMethylheptaneꢀ2,4ꢀdione, 1b.25
Colorless oil.
1H NMR (300.13 MHz, CDCl3, δ): 0.87ꢀ0.91 (m, 6H), 2.01ꢀ2.19
(m, 6H), 2.34 (d, 0.25H, J = 7.34 Hz), 3.51 (s, 0.25H), 5.43 (s,
0.75H), 15.5 (br.s., 0.75H).
Conclusions
80 13C NMR (75.48 MHz, CDCl3, δ): 22.4, 24.2, 25.1, 26.2, 47.1,
52.6, 58.2, 100.5, 192.2, 192.7.
It was found that the catalytic activity of cerium chloride widely
used in organic chemistry depends on the preliminary thermal
25 treatment. The results of the present study suggest that this effect
can play a substantial role in the synthesis with the use of
organocerium reagents.
Procedures were developed for the preparation of the structured
microsized catalyst CeCl3 from commercial CeCl3×7H2O by
30 evaporation of its alcoholic solutions followed by the heating of the
residue at 150 °С or only by heating commercial CeCl3×7H2O at
this temperature. The efficiency of the catalysts was estimated in
the addition reaction of βꢀdiketones to vinyl ketones. The yields of
the corresponding β,δꢀtriketones reach 89 %.
7ꢀMethyloctaneꢀ3,5ꢀdione, 1c.26
Colorless oil.
85 1H NMR (300.13 MHz, CDCl3, δ): 0.86ꢀ0.91 (m, 6H), 1.01 (t,
0.6H, J = 7.34 Hz), 1.09 (t, 2.4H, J = 7.34 Hz), 1.92ꢀ2.10 (m,
2.8H), 2.24ꢀ2.36 (m, 1.8H), 2.48 (q, 0.4H, J = 7.34 Hz), 3.50 (s,
0.4H), 5.43 (s, 0.8H), 15.47 (br.s., 0.8H).
13C NMR (75.48 MHz, CDCl3, δ): 7.4, 9.5, 22.4, 24.2, 26.2, 31.7,
90 37.0, 47.2, 52.6, 57.2, 99.1, 192.4, 196.4, 204.0.
1ꢀPhenylbutaneꢀ1,3ꢀdione, 1d.27
White crystals, m.p. = 58ꢀ60 °С (m.p. = 60 °С 36).
35 Experimental
1H NMR (300.13 MHz, CDCl3, δ): 2.18 (s, 2.75H), 2.28 (s, 0.25H),
95 4.08 (s, 0.25H), 6.16 (s, 1H), 7.40ꢀ7.50 (m, 3H), 7.85ꢀ7.94 (m, 2H),
General materials and methods.
NMR spectra were recorded on a commercial instrument (300.13 16.16 (br.s., 0.75H).
MHz for H, 75.48 MHz for 13C) in CDCl3. Highꢀresolution mass 13C NMR (75.48 MHz, CDCl3, δ): 25.7, 54.6, 96.6, 126.9, 128.5,
1
128.7, 132.2, 134.8, 183.3, 193.7.
spectra (HRMS) were measured using electrospray ionization
40 (ESI).23 The measurements were done in positive ion mode
(interface capillary voltage 4500 V); the spectra were acquired in
00 1ꢀ(4ꢀMethylphenyl)butaneꢀ1,3ꢀdione, 1e.27
1
the massꢀtoꢀcharge ratio (m/z) range of 50−3000; the Colorless oil.
external/internal calibration was done with Electrospray Calibrant 1H NMR (300.13 MHz, CDCl3, δ): 2.15 (s, 2.7H), 2.26 (s,0.3H),
Solution. Solutions in MeCN were injected with a syringe (flow 2.37 (s, 3H), 4.04 (s, 0.2H), 6.12 (s, 0.9H), 7.22 (d, 2H, J = 8.07
45 rate 3 ꢃL min−1). Nitrogen was applied as a dry gas; the interface
Hz), 7.74ꢀ7.82 (m, 2H), 16.20 (br.s., 0.9H).
temperature was set at 180 °C.
105 13C NMR (75.48 MHz, CDCl3, δ): 21.5, 25.6, 54.6, 96.2, 127.0,
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129.3, 132.1, 143.0, 183.7, 193.0.
60 4ꢀAcetylꢀ5ꢀoxohexanenitrile, 5e.34
Oil.
1ꢀ(4ꢀMethoxyphenyl)butaneꢀ1,3ꢀdione, 1f.28
White crystals, m.p. = 57ꢀ59 °С (m.p. = 53 °С 36).
1Н NMR (300.13 MHz, CDCl3, δ): 2.07ꢀ2.21 (m, 7H), 2.34ꢀ2.44
5
1Н NMR (300.13 MHz, CDCl3, δ): 2.16 (s, 3H), 3.85 (s, 3H), 6.10 (m, 2.3H), 2.63 (t, 0.7H, J = 7.34 Hz), 3.82 (t, 0.6H, J = 7.33 Hz),
(s, 1H), 6.92 (d, 2H, J = 8.81 Hz), 7.83ꢀ7.93 (m, 2H), 16.30 (br.s., 16.88 (br.s., 0.4H).
1H).
65 13C NMR (75.48 MHz, CDCl3, δ): 15.1, 18.1, 22.9, 23.1, 23.6,
13C NMR (75.48 MHz, CDCl3, δ): 25.2, 26.2, 55.4, 95.7, 113.6, 29.5, 65.7, 107.1, 118.5, 118.7, 191.6, 202.3.
113.8, 127.7, 129.0, 130.5, 163.0, 163.4, 184.0, 191.5, 196.6.
10
3ꢀBenzylpentaneꢀ2,4ꢀdione, 5f.35
1ꢀ(4ꢀBromophenyl)butaneꢀ1,3ꢀdione, 1g.28
Oil.
White crystals, m.p. = 91ꢀ92 °С (m.p. = 96.5 °С 36).
70 1Н NMR (300.13 MHz, CDCl3, δ): 2.07 (s, 2H), 2.12 (s, 4H), 3.14
1Н NMR (300.13 MHz, CDCl3, δ): 2.18 (s, 3H), 4.05 (s, 0.12H), (d, 1.5H, J = 7.34 Hz), 3.65 (s, 0.5H), 4.00 (t, 0.6H, J = 7.34 Hz),
6.12 (s, 0.94H), 7.55 (d, 2H, J = 8.81 Hz), 7.71 (d, 2H, J = 8.81 7.13ꢀ7.32 (m, 5H), 16.82 (br.s., 0.4H).
15 Hz), 16.07 (br.s., 0.94H).
13C NMR (75.48 MHz, CDCl3, δ): 23.2, 29.7, 32.8, 34.2, 69.8,
13C NMR (75.48 MHz, CDCl3, δ): 25.8, 54.6, 96.6, 127.0, 128.4, 108.2, 126.2, 126.7, 127.3, 128.5, 128.6, 128.6, 137.9, 139.6, 191.8,
130.1, 131.8, 133.7, 182.2, 193.8.
75 203.5.
1ꢀ(1ꢀAdamantyl)butaneꢀ1,3ꢀdione, 1i.29
3ꢀ(4ꢀChlorobenzyl)pentaneꢀ2,4ꢀdione, 5g.35
Oil.
20 Light yellow crystals, m.p. = 57ꢀ58 °С (m.p. = 55ꢀ57 °С 29).
1Н NMR (300.13 MHz, CDCl3, δ): 1.71ꢀ2.19 (m, 18H), 3.58 (s, 1Н NMR (300.13 MHz, CDCl3, δ): 2.04 (s, 3H), 2.11 (s, 2.7H),
0.2H), 5.53 (s, 0.9H), 15.85 (br.s., 0.9H).
80 2.19 (s, 0.3H), 3.09 (d, 1H, J = 7.34 Hz), 3.61 (s, 1H), 3.95 (t, 0.5H,
13C NMR (75.48 MHz, CDCl3, δ): 25.7, 27.7, 28.0, 36.5, 37.8, J = 7.34 Hz), 7.05ꢀ7.09 (m, 2H), 7.21ꢀ7.27 (m, 2H), 16.79 (br.s.,
38.9, 40.7, 51.9, 95.5, 193.7, 198.5.
0.5H).
25
13C NMR (75.48 MHz, CDCl3, δ): 23.2, 29.7, 32.3, 33.4, 69.8,
107.9, 128.4, 128.5, 128.7, 128.8, 128.8, 129.7, 130.0, 131.4, 132.1,
85 132.6, 136.5, 138.1, 191.9, 203.1.
3ꢀMethylpentaneꢀ2,4ꢀdione, 5а.30
Oil.
1Н NMR (300.13 MHz, CDCl3, δ): 1.27 (d, 2.2H, J = 7.31 Hz),
1.78 (s, 1.6H), 2.06 (s, 2.2H), 2.14 (s, 3H), 3.62 (q, 0.6H, J = 7.31 3ꢀ(4ꢀNitrobenzyl)pentaneꢀ2,4ꢀdione, 5h.35
30 Hz), 16.37 (br.s., 0.4H).
Yellow crystals, m.p. = 89ꢀ90 °С (m.p. = 90ꢀ91 °С 37).
13C NMR (75.48 MHz, CDCl3, δ): 12.9, 21.1, 22.4, 23.3, 24.6, 1Н NMR (300.13 MHz, CDCl3, δ): 2.04 (s, 4.8H), 2.15 (s, 1.2H),
28.6, 61.9, 104.8, 190.4, 205.1, 207.3.
90 3.22 (d, 0.4H, J = 7.34 Hz), 3.75 (s, 1.6H), 4.01 (t, 0.2H, J = 7.34
Hz), 7.31 (d, 2H, J = 8.07 Hz), 8.10ꢀ8.16 (m, 2H), 16.84 (br.s.,
0.8H).
3ꢀButylpentaneꢀ2,4ꢀdione, 5b.31
35 Oil.
13C NMR (75.48 MHz, CDCl3, δ): 23.3, 29.6, 33.0, 33.5, 69.2,
1Н NMR (300.13 MHz, CDCl3, δ): 0.80ꢀ0.89 (m, 3H), 1.11ꢀ1.32 107.1, 123.8, 123.9, 128.2, 129.6, 146.7, 147.5, 191.9, 202.3.
(m, 4H), 1.77 (q, 1.4H, J = 7.32 Hz), 2.01ꢀ2.16 (m, 6.6H), 3.55 (t,95
0.7H, J = 7.32 Hz), 16.61 (br.s., 0.3H).
Catalysts preparation.
13C NMR (75.48 MHz, CDCl3, δ): 13.6, 13.7, 22.4, 22.5, 22.7, Catalyst В.
40 25.1, 27.2, 27.9, 28.9, 29.6, 32.7, 35.9, 68.8, 110.5, 190.8, 204.5.
CeCl3×7H2O (1 g) was dissolved in MeOH (10 mL), followed by
the evaporation of the solvent and heating of the resulting
100 precipitate at 150 °С for 2 h; 669 mg of the catalyst were obtained.
Catalyst С.
3ꢀHexylpentaneꢀ2,4ꢀdione, 5c.32
Oil.
1Н NMR (300.13 MHz, CDCl3, δ): 0.83 (t, 3H, J = 7.34 Hz), 1.22ꢀ CeCl3×7H2O (1 g) was dissolved in EtOH (10 mL), followed by the
45 1.26 (m, 8H), 1.78 (q, 1.5H, J = 7.34 Hz), 2.02ꢀ2.17 (m, 6.5H), 3.56 evaporation of the solvent and heating of the resulting precipitate at
(t, 0.6H, J = 7.34 Hz), 16.63 (br.s., 0.4H).
13C NMR (75.48 MHz, CDCl3, δ): 13.9, 22.4, 22.6, 22.8, 23.6
27.5, 27.5, 28.3, 28.9, 29.0, 29.2, 29.7, 30.3, 30.6, 31.4, 31.6, 69.0, CeCl3×7H2O (1 g) was heated at 150 °С for 2 h; 671 mg of the
150 °С for 2 h; 665 mg of the catalyst were obtained.
1,05 Catalyst D.
110.6, 190.8, 204.4.
catalyst were obtained.
50
Catalyst Е.
Ethyl 4ꢀacetylꢀ5ꢀoxohexanoate, 5d.33
Oil.
CeCl3×7H2O (1 g) was heated at 150 °С for 2 h, the resulting
110 powder was dissolved in MeOH (10 mL), silica gel (5.67 g) was
1Н NMR (300.13 MHz, CDCl3, δ): 1.18 (t, 3H, J = 7.33 Hz), 1.77ꢀ added (85 wt. % SiO2 / (SiO2 + СeСl3×7H2O)), the mixture was
1.86 (m, 1.4H), 2.01ꢀ2.28 (m, 7H), 2.42ꢀ2.55 (m, 1.6H), 3.68 (t, sonicated for 10 min, and the solvent was evaporated at 80 °С for 1
55 0.3H, J = 7.33 Hz), 4.02ꢀ4.10 (m, 2H), 16.68 (br.s., 0.7H).
h at 10ꢀ15 mm Hg; 6.38 g of the catalyst were obtained.
13C NMR (75.48 MHz, CDCl3, δ): 14.1, 18.8, 22.7, 22.9, 29.2, Catalyst F.
29.8, 31.5, 33.1, 34.7, 42.3, 60.2, 60.5, 67.0, 172.5, 173.1, 191.211
203.7, 208.1.
,
5
CeCl3×7H2O (1 g) was dissolved in MeOH (10 mL), silica gel (5.67
g) was added (85 wt. % SiO2 / (SiO2 + СeСl3×7H2O)), the mixture
6
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was sonicated for 10 min, and the solvent was evaporated at 60 °С (m, 13H), 3.62 (t, 0.8H, J = 7.34 Hz), 16.85 (br.s, 0.2H).
for 0.5 h at 10ꢀ15 mm Hg; 6.65 g of the catalyst were obtained.
60 13C NMR (75.48 MHz, CDCl3, δ): 20.9, 21.5, 22.3, 22.3, 22.6,
23.3, 23.9, 25.9, 29.0, 29.9, 30.0, 40.5, 43.6, 44.3, 51.2, 66.6, 109.0,
192.2, 203.9, 205.7, 207.3.
Experiment for Table 1.
5
Synthesis of 3ꢀacetylheptaneꢀ2,6ꢀdione 2a from methyl vinyl HRMS (ESI) m/z [M+Na]+: Calculated for [C12H20NaO3]+:
ketone and pentaneꢀ2,4ꢀdione 1a using catalysts A ꢀ F.
235.1305. Found: 235.1305.
The catalyst (372.6 mg (A); 246.5 mg (ВꢀС); 12.3ꢀ246.5 mg (D);65 Calculated for С12H20O3 С: 67.89 %, H: 9.5 %. Found С: 67.61 %,
1.179 g (Е); and 1.242 g (F); 1 ꢀ 20 mol. %) was added to pentaneꢀ H: 9.69 %.
2,4ꢀdione 1a (0.5 g, 5 mmol). The mixture was stirred at room IR (thin layer): 2960, 2936, 2874, 1716, 1593, 1468, 1414, 1365,
10 temperature for 5 min, and then methyl vinyl ketone (385 mg, 5.5 1168 cmꢀ1.
mmol) was added. The mixture was stirred at 20–25 °С for 6, 12, or
24 h and then filtered. The precipitate was washed with a PE : EA70 8ꢀMethylꢀ5ꢀpropionylnonaneꢀ2,6ꢀdione, 2с.
mixture (1 : 2, v/v). The solvent was evaporated using a waterꢀjet Colorless oil, nD20 = 1.4557.
vacuum pump. The product was isolated by silica gel column Rf = 0.40 (PE : EA = 5 : 1).
15 chromatography using gradient elution with 30 % to 80 % (v/v) of 1Н NMR (300.13 MHz, CDCl3, δ): 0.84ꢀ1.06 (m, 9H), 1.98ꢀ2.18
ethyl acetate in petroleum ether.
(m, 6H), 2.29ꢀ2.52 (m, 6H), 3.64 (t, 0.9H, J = 7.34 Hz), 16.88
In run 10, the catalyst was prepared by heating CeCl3×7H2O at 7075 (br.s., 0.1H)
°С for 1 h.
13C NMR (75.48 MHz, CDCl3, δ): 7.5, 21.6, 22.7, 24.0, 29.8, 35.4,
In run 11, after the mixing of all reagents, H2O (63 mg, 7 moles per 40.6, 50.9, 65.8, 205.7, 206.6, 207.4.
20 mole of CeCl3) was added.
Calculated for С13H22O3 С: 68.99 %, H: 9.80 %. Found С: 68.68 %,
In the case of the catalysts E and F, the reagents were added to a H: 10.21 %.
solution of pentaneꢀ2,4ꢀdione 1a (0.5 g, 5 mmol) in CH3CN (5 mL).80 HRMS (ESI) m/z [M+Na]+: Calculated for [C13H22NaO3]+:
249.1461. Found: 249.1462.
3ꢀAcetylheptaneꢀ2,6ꢀdione, 2a.7b
25 Colorless oil, nD20 = 1.4658.
Rf = 0.65 (PE : EA = 2 : 1).
IR (thin layer): 2960, 2940, 2874, 1717, 1594, 1463, 1410, 1367,
1166, 1037 cmꢀ1.
1Н NMR (300.13 MHz, CDCl3, δ): 1.96ꢀ2.12 (m, 10H), 2.37 (t, 2H,85 3ꢀBenzoylheptaneꢀ2,6ꢀdione, 2d. 7b
J = 7.34 Hz), 2.45ꢀ2.46 (m, 1H), 3.61 (t, 0.8H, J = 7.33 Hz), 16.62 Yellow oil, nD20 = 1.5278.
(br.s., 0.2H).
Rf = 0.56 (PE : EA = 2 : 1).
30 13C NMR (75.48 MHz, CDCl3, δ): 21.3, 21.3, 22.8, 29.1, 29.8, 1Н NMR (300.13 MHz, CDCl3, δ): 2.07ꢀ2.25 (m, 8H), 2.38ꢀ2.59
29.9, 40.4, 43.8, 66.7, 108.8, 191.0, 204.0, 207.3.
(m, 2H), 4.53 (t, 1H, J = 7.33 Hz), 7.43ꢀ7.59 (m, 3H), 7.98 (d, 2H,
90 J = 7.34 Hz).
Experiment for Table 2.
13C NMR (75.48 MHz, CDCl3, δ): 22.4, 28.5, 29.9, 40.4, 61.0,
Synthesis of β,δꢀtriketones 2aꢀi from βꢀdiketones 1aꢀi and 128.6, 128.8, 133.8, 136.1, 196.5, 203.8, 207.7.
35 methyl vinyl ketone.
The catalyst D (123.1ꢀ51.1 mg, 0.207ꢀ0.5 mmol, 10 mol. %) or, in 3ꢀ(4ꢀMethylbenzoyl)heptaneꢀ2,6ꢀdione, 2e.1c
the case of 1g and 1h, the catalyst F (367.0ꢀ394.5 mg, 10 mol.%)95 Yellow oil, nD20 = 1.5309.
was added with vigorous stirring to βꢀdiketone 1aꢀi (0.5 g, 2.07ꢀ5.0 Rf = 0.54 (PE : EA = 2 : 1).
mmol) (in the case of solid βꢀdiketones 1dꢀi, CH3CN (3 mL) was 1Н NMR (300.13 MHz, CDCl3, δ): 2.08ꢀ2.22 (m, 8H), 2.39 (s, 3H),
40 also added). The mixture was stirred at room temperature for 5 min, 2.44ꢀ2.54 (m, 2H), 4.50 (t, 1H, J = 7.34 Hz), 7.27 (d, 2H, J = 8.07
and then methyl vinyl ketone (160ꢀ385 mg, 2.281ꢀ5.50 mmol, 1.1 Hz), 7.89 (d, 2H, J = 8.07 Hz).
mole per mole of 1aꢀi) was added. The reaction mixture was stirred
00 13C NMR (75.48 MHz, CDCl3, δ): 21.6, 22.4, 28.4, 29.9, 40.5,
1
at room temperature for 24 h and filtered. The precipitate was 61.0, 128.8, 129.6, 133.7, 144.9, 196.1, 204.0, 207.8.
washed with a PE : EA mixture (1 : 2, v/v). The solvent was
45 evaporated using a waterꢀjet vacuum pump. The product was 3ꢀ(4ꢀMethoxybenzoyl)heptaneꢀ2,6ꢀdione, 2f. 1c
isolated by silica gel column chromatography using gradient elution Oil, nD20 = 1.5451.
with 30 % to 80 % (v/v) of ethyl acetate in petroleum ether. The05 Rf = 0.44 (PE : EA = 2 : 1).
1
following products were obtained: 2а, 740 mg (4.35 mmol, 87 %); 1Н NMR (300.13 MHz, CDCl3, δ): 2.09ꢀ2.25 (m, 8H), 2.39ꢀ2.61
2b, 485 mg (2.28 mmol, 65 %); 2c, 354 mg (1.57 mmol, 49 %); 2d, (m, 2H), 3.86 (s, 3H), 4.48 (t, 1H, J = 7.34 Hz), 6.94 (d, 2H, J =
50 582 mg (2.51 mmol, 81 %); 2e, 570 mg (2.32 mmol, 82 %); 2f, 607 8.81 Hz), 7.99 (d, 2H, J = 8.80 Hz).
mg (2.32 mmol, 89 %); 2g, 206 mg (0.66 mmol, 32 %); 2h, 270 mg 13C NMR (75.48 MHz, CDCl3, δ): 22.5, 28.3, 30.0, 40.6, 55.5,
(0.89 mmol, 42 %); 2i, 474 mg (1.63 mmol, 72 %).
110 61.0, 114.1, 129.2, 131.2, 164.2, 194.9, 204.2, 207.9.
Analytical data for β,δꢀtriketones 2bꢀi.
55 5ꢀAcetylꢀ8ꢀmethylnonaneꢀ2,6ꢀdione, 2b.
Yellow oil, nD20 = 1.4450.
3ꢀ(4ꢀBromobenzoyl)heptaneꢀ2,6ꢀdione, 2g.1c
White crystals, m.p. = 74ꢀ76 °С (m.p. = 70ꢀ71 °С 1c).
Rf = 0.64 (PE : EA = 2 : 1).
Rf = 0.42 (PE : EA = 5 : 1).
115 1Н NMR (300.13 MHz, CDCl3, δ): 2.11ꢀ2.22 (m, 8H), 2.48ꢀ2.60
1Н NMR (300.13 MHz, CDCl3, δ): 0.85ꢀ0.92 (m, 6H), 2.00ꢀ2.48 (m, 2H), 4.49 (t, 1H, J = 6.60 Hz), 7.62 (d, 2H, J = 8.80 Hz), 7.88
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(d, 2H, J = 8.80 Hz).
(in the case βꢀdiketone 5h, THF (2 mL) was added). Then methyl
13C NMR (75.48 MHz, CDCl3, δ): 22.3, 28.5, 29.9, 40.3, 61.0,60 vinyl ketone (163.9–337.8 mg, 2.338–4.819 mmol, 1.1 mole per
129.2, 130.2, 132.2, 134.7, 195.6, 203.7, 207.8.
mole of 5aꢀh) was added. The reaction mixture was stirred at room
temperature for 24 h and filtered. The precipitate was washed with
a PE : EA mixture (1 : 2, v/v). The solvent was evaporated using a
waterꢀjet vacuum pump. Products 6aꢀh were isolated by silica gel
65 column chromatography using gradient elution with 30 % to 80 %
5
2ꢀBenzoylꢀ1ꢀphenylhexaneꢀ1,5ꢀdione, 2h. 9a
White crystals, m.p. = 70ꢀ72 °С (m.p. = 60 °С 9a).
Rf = 0.80 (PE : EA = 2 : 1).
1Н NMR (300.13 MHz, CDCl3, δ): 2.10 (s, 3H), 2.31 (q, 2H, J = (v/v) of ethyl acetate in petroleum ether. The following products
6.60 Hz), 2.68 (t, 2H, J = 6.60 Hz), 5.47 (t, 1H, J = 6.60 Hz), 7.44 were obtained: 6а, 573.0 mg (3.110 mmol, 71 %); 6b, 369.4 mg
10 (t, 4H, J = 7.34 Hz), 7.55 (t, 2H, J = 7.34 Hz), 8.02 (d, 4H, J = 7.34 (1.632 mmol, 51 %); 6c, 234.7 mg (0.923 mmol, 34 %); 6d, 229.5
Hz). mg (0.849 mmol, 34 %); 6e, 481 mg (2.154 mmol, 66 %); 6f, 526.9
13C NMR (75.48 MHz, CDCl3, δ): 23.2, 30.0, 40.8, 54.8 (, 128.6,70 mg (2.024 mmol, 77 %); 6g, 459.2 mg (1.558 mmol, 70 %), and 6h,
128.9, 133.6, 135.8, 196.2, 208.6.
402.4 mg (1.318 mmol, 62 %).
15 3ꢀ(Adamantꢀ1ꢀylcarbonyl)ꢀ2,6ꢀheptanedione, 2i.
White crystals, m.p. = 53ꢀ55 °С.
Analytical data for αꢀsubstitutedꢀ3ꢀacetylꢀ2,6ꢀdiones 6aꢀh.
3ꢀAcetylꢀ3ꢀmethylheptaneꢀ2,6ꢀdione, 6a.9a
Rf = 0.27 (PE : EA = 5 : 1).
75 Oil.
1Н NMR (300.13 MHz, CDCl3, δ): 1.61ꢀ1.74 (m, 10H), 1.96ꢀ2.09 Rf = 0.51 (PE : EA = 2 : 1).
(m, 11H), 2.36 (q, 2H, J = 6.60 Hz), 4.06 (t, 1H, J = 6.60 Hz).
1Н NMR (300.13 MHz, CDCl3, δ): 1.27 (s, 3H), 2.02ꢀ2.06 (m,
20 13C NMR (75.48 MHz, CDCl3, δ): 23.3, 27.7, 27.9, 29.9, 36.3, 11H), 2.29 (t, 2H, J = 7.32 Hz).
37.6, 40.6, 47.7, 59.6, 204.0, 207.4, 210.6.
13C NMR (75.48 MHz, CDCl3, δ): 18.5, 26.4, 27.5, 29.8, 38.3,
Calculated for С18H26O3 С: 74.45 %, H: 9.02 %. Found С: 74.29 %,80 65.2, 207.2.
H: 9.30 %.
HRMS (ESI) m/z [M+Na]+: Calculated for [C18H26NaO3]+: 3ꢀAcetylꢀ3ꢀbutylheptaneꢀ2,6ꢀdione, 6b. 1c
25 313.1774. Found: 313.1761.
White crystals, m.p. = 42ꢀ43 °С (m.p. = 45ꢀ46 °С 1c).
IR (KBr): 3434, 3412, 2921, 2905, 2850, 1722, 1687, 1355, 1255, Rf = 0.76 (PE : EA = 2 : 1).
1152, 1012 cmꢀ1.
85 1Н NMR (300.13 MHz, CDCl3, δ): 0.86 (t, 3H, J = 7.34 Hz), 0.94ꢀ
1.05 (m, 2H), 1.26ꢀ1.33 (m, 2H), 1.81 (t, 2H, J = 7.34 Hz), 2.07ꢀ
2.11 (m, 11H), 2.22 (t, 2H, J = 7.34 Hz).
30 Synthesis of 3ꢀ(3ꢀoxocyclohexyl)pentaneꢀ2,4ꢀdione
pentaneꢀ2,4ꢀdione 1а and 2ꢀcyclohexenꢀ1ꢀone 3 (Scheme 2).
4
from 13C NMR (75.48 MHz, CDCl3, δ): 13.6, 23.0, 24.2, 25.8, 26.9,
29.8, 31.3, 38.0, 69.2, 207.1.
The catalyst D (123.2 mg, 10 mol. %, 0.5 mmol) was added with90
vigorous stirring to pentaneꢀ2,4ꢀdione (500 mg, 5 mmol). The 3ꢀAcetylꢀ3ꢀhexylheptaneꢀ2,6ꢀdione, 6c.
mixture was stirred at room temperature for 5 min, and then 2ꢀ Oil.
35 cyclohexenꢀ1ꢀone (528.6 mg, 5.5 mmol) was added. The reaction Rf = 0.28 (PE : EA = 5 : 1).
mixture was stirred at room temperature for 24 h and filtered. The 1Н NMR (300.13 MHz, CDCl3, δ): 0.82 (t, 3H, J = 5.95 Hz), 0.96ꢀ
precipitate was washed with a PE : EA mixture (1 : 2, v/v). The95 1.04 (m, 2H), 1.22ꢀ1.33 (m, 7H), 1.47ꢀ1.56 (m, 1H), 1.76ꢀ1.82 (m,
solvent was evaporated using a waterꢀjet vacuum pump. The 2H), 2.05ꢀ2.23 (m, 11H).
product was isolated by silica gel column chromatography using 13C NMR (75.48 MHz, CDCl3, δ): 13.9, 22.5, 23.7, 24.2, 26.9,
40 gradient elution with 30 % to 80 % (v/v) of ethyl acetate in 29.7, 29.9, 31.4, 31.7, 38.1, 62.9, 207.2.
petroleum ether. 3ꢀ(3ꢀOxocyclohexyl)pentaneꢀ2,4ꢀdione
obtained in 66 % yield (643 mg, 3.28 mmol).
4
was Calculated for С15H26O3 С: 70.83 %, H: 10.30 %. Found С: 70.79
100 %, H: 10.29 %.
HRMS (ESI) m/z [M+Na]+: Calculated for [C15H26NaO3]+:
277.1774. Found: 277.1778.
3ꢀ(3ꢀOxocyclohexyl)pentaneꢀ2,4ꢀdione, 4.9d
45 White crystals, m.p. = 51ꢀ52 °С (m.p. = 53ꢀ54 °С 5).
Rf = 0.71 (PE : EA = 1 : 1).
IR (thin layer): 2956, 2930, 2859, 1176, 1697, 1459, 1423, 1358,
1169 cmꢀ1.
1Н NMR (300.13 MHz, CDCl3, δ): 1.28ꢀ1.41 (m, 1H), 1.65ꢀ1.7
1905
(m, 2H), 1.97ꢀ2.05 (m, 2H), 2.13ꢀ2.39 (m, 9H), 2.59ꢀ2.70 (m, 1H), Ethyl 4,4ꢀdiacetylꢀ7ꢀoxoꢀoctanoate, 6d. 1c
3.60 (d, 1H, J = 10.27 Hz). Oil.
50 13C NMR (75.48 MHz, CDCl3, δ): 24.4, 28.8, 29.6, 29.7, 38.3, Rf = 0.39 (PE : EA = 5 : 1).
41.0, 45.2, 74.8, 202.6, 202.8, 208.9.
1Н NMR (300.13 MHz, CDCl3, δ): 1.19 (t, 3H, J = 7.34 Hz), 1.97ꢀ
110 2.28 (m, 17H), 4.05 (q, 2H, J = 7.34 Hz).
Experiment for Table 3.
13C NMR (75.48 MHz, CDCl3, δ): 14.0, 24.1, 26.1, 26.9, 28.8,
Synthesis of αꢀsubstitutedꢀ3ꢀacetylꢀ2,6ꢀdiones 6aꢀh from methyl 29.9, 37.7, 60.7, 68.4, 172.5, 206.5, 206.9.
55 vinyl ketone and αꢀsubstituted βꢀdiketones 5aꢀh.
The catalyst D or F (52.4–108.0 mg (D) or 0.527ꢀ1.088 g (F), 10 4,4ꢀDiacetylꢀ7ꢀoxooctanenitrile, 6e. 1c
mol. %) was added with stirring to βꢀdiketone 5aꢀh (0.5 g, 2.125
1
ꢀ
15 Yellow crystals, m.p. = 76ꢀ78 °С (m.p. = 74ꢀ75 °С 1c).
4.381 mmol) or a solution of 5aꢀh in CH3CN (2 mL), respectively Rf = 0.24 (PE : EA = 2 : 1).
8
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1Н NMR (300.13 MHz, CDCl3, δ): 2.10ꢀ2.26 (m, 17H).
55 d Department of Chemistry, M.V. Lomonosov Moscow State University, 1ꢀ3
13C NMR (75.48 MHz, CDCl3, δ): 12.4, 24.0, 26.7, 26.9, 29.9, Leninskie Gory, Moscow, 119991 Russian Federation.
37.3, 68.2, 118.7, 205.6, 206.2.
e A. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS,
31 Leninsky prospect, Moscow, 119071 Russian Federation.
5
3ꢀAcetylꢀ3ꢀbenzylpentaneꢀ2,4ꢀdione, 6f. 1c
White crystals, m.p. = 77ꢀ79 °С (m.p. = 79ꢀ80 °С 1c).
Rf = 0.58 (PE : EA = 2 : 1).
60
†
Electronic Supplementary Information (ESI) available: [Copies of 1H,
13C NMR, IR and HRMS spectra]. See DOI: 10.1039/c0nj00000x
1Н NMR (300.13 MHz, CDCl3, δ): 2.08ꢀ2.12 (m, 11H), 2.30 (t, 2H,
J = 7.34 Hz), 3.16 (s, 2H), 6.98 (d, 2H, J = 7.34 Hz), 7.20ꢀ7.24 (m,
10 3H).
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3ꢀAcetylꢀ3ꢀ[(4ꢀchlorophenyl)methyl]heptaneꢀ2,6ꢀdione, 6g.
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Rf = 0.53 (PE : EA = 2 : 1).
1Н NMR (300.13 MHz, CDCl3, δ): 2.06ꢀ2.13 (m, 11H), 2,28 (t, 2H,
J = 7.78 Hz), 3,11 (s, 2H), 6,92 (d, 2H, J = 8.24 Hz), 7,19 (d, 2H, J
= 8.24 Hz).
20 13C NMR (75.48 MHz, CDCl3, δ): 24.2, 27.8, 29.9, 36.8, 37.9,
69.9, 128.7, 130.9, 133.0, 134.1, 206.6.
Calculated for С16H19ClO3 С: 65.19 %, H: 6.50 %, Cl: 12.03 %.
Found С: 65.16 %, H: 6.65 %, Cl: 12.17 %.
HRMS (ESI) m/z [M+Na]+: Calculated for [C16H19ClNaO3]+:
25 317.0915. Found: 317.0905.
IR (KBr): 3416, 3390, 1720, 1691, 1492, 1370, 1360, 1167, 1147,
816 cmꢀ1.
3ꢀAcetylꢀ3ꢀ[(4ꢀnitrophenyl)methyl]heptaneꢀ2,6ꢀdione, 6h.1c
30 Yellow crystals, m.p. = 110ꢀ112 °С (m.p. = 113ꢀ114 °С 1c).
Rf = 0.33 (PE : EA = 2 : 1).
1Н NMR (300.13 MHz, CDCl3, δ): 2.09ꢀ2.13 (m, 11H), 2.31 (t, 2H,
J = 8.24 Hz), 3.24 (s, 2H), 7.17 (d, 2H, J = 8.24 Hz), 8.07 (d, 2H, J
= 8.24 Hz).
35 13C NMR (75.48 MHz, CDCl3, δ): 24.4, 27.7, 30.0, 37.1, 37.7,
70.0, 123.6, 130.6, 143.6, 206.1.
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Acknowledgments
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This work is supported by the Russian Foundation for Basic
40 Research (Grant 13ꢀ03ꢀ12074), the Program for Basic Research of
the Presidium of the Russian Academy of Sciences, and the
Ministry of Education and Science of the Russian Federation (Grant
8651). We thank the stuff of the Section of Structural Studies of the
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy
45 of Sciences, for scanning electron microscopy studies of the
samples.
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Notes and references
a
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of
Sciences, Leninsky prospect 47, Moscow, 119991 Russian Federation,
50 terentev@ioc.ac.ru.
b D. Mendeleyev University of Chemical Technology of Russia, Miusskaya
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c UFIP FREꢀCNRS 3478, DNA repair team, Université de Nantes, 2 rue de
la Houssinière, 44322 Nantes, France.
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File with the Table of Contents (TOC).
A facile method was developed for the preparation of microsized cerium chloride, which is
efficient catalyst in the Michael addition reaction.