390
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 2, February, 2015
Khachatryan et al.
analysis was performed on an Eurovector EuroEA 3000 CHNSꢀ
analyzer.
the fraction with b.p. 87—93 C (5 Torr) was collected. The yield
was 69 g (49%), nD20 1.4840.12,13
,ꢀEnones 2a—h (general procedure). A solution of sodium
hydroxide (1 g, 0.025 mol) in water (10 mL) was added dropwise
to a mixture of aldehyde (0.2 mol), the corresponding methyl
ketone (0.2 mol) or acetone (0.1 mol), and ethanol (100 mL) at
25—30 C. The mixture was allowed to stand for 2 h under the
specified conditions and then cooled to 0 C. The precipitate
that formed was filtered, washed with water, dried, and recrysꢀ
tallized from the appropriate solvent.
5ꢀIsopropylꢀ3ꢀmethylcyclohexꢀ2ꢀenone (11b). The synthesis
according to the same procedure starting from isobutyraldehyde
(72 g, 1 mol), ethyl acetoacetate (260 g, 2 mol), and potassium
carbonate (21 g, 0.15 mol) gave product 11b in a yield of 80 g
(52%), b.p. 115—120 C (10 Torr), nD20 1.4880.12
References
This procedure was used to synthesize 3ꢀphenylꢀ1ꢀ(2ꢀthiꢀ
enyl)propꢀ2ꢀenꢀ1ꢀone (2c), 1,5ꢀbis(2,4ꢀdichlorophenyl)pentaꢀ
1,4ꢀdienꢀ3ꢀone (2d), 1,5ꢀbis(4ꢀbutoxyphenyl)pentaꢀ1,4ꢀdienꢀ3ꢀ
one (2e), 1,5ꢀbis(4ꢀpentyloxyphenyl)pentaꢀ1,4ꢀdienꢀ3ꢀone (2f),
1,5ꢀbis(4ꢀchlorophenyl)pentaꢀ1,4ꢀdienꢀ3ꢀone (2g), and 1,5ꢀbisꢀ
(4ꢀmethylphenyl)pentaꢀ1,4ꢀdienꢀ3ꢀone (2h). The solvents used
for the recrystallization, the yields, and physicochemical conꢀ
stants of the reaction products are given in Table 1.
6ꢀAcetylcyclohexꢀ2ꢀenones 4a—h (general procedure). A mixꢀ
ture of ,ꢀenone (0.1 mol), acetylacetone (0.1 mol), the corꢀ
responding solvent (100 mL), and potassium carbonate (2 g,
0.014 mol) was refluxed with vigorous stirring for 2—3 h. After
cooling to 0 C, the precipitate that formed was separated, washed
with a 5% hydrochloric acid solution, and recrystallized from
the appropriate solvent.
1. N. M. Morlyan, D. S. Khachatryan, S. M. Gabrielyan, Sh. O.
Badanyan, A.s. 1074859 USSR; Byul. Izobret. [Inventor Bull.],
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2. N. M. Morlyan, D. S. Khachatryan, Sh. O. Badanyan, Arm.
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Khim. Zh. [Arm. Chem. J.], 1980, 33(9), 733 (in Russian).
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5. D. S. Khachatryan, N. M. Morlyan, R. G. Mirzoyan, Sh. O.
Badanyan, Arm. Khim. Zh. [Arm. Chem. J.], 1981, 34(8), 672
(in Russian).
6. D. S. Khachatryan, A. A. Vardapetyan, G. A. Panosyan,
R. G. Mirzoyan, N. M. Morlyan, Zh. Org. Khim., 1990, 26,
2092 [J. Org. Chem. USSR (Engl. Transl.), 1990, 26].
7. D. S. Khachatryan, A. A. Vardapetyan, V. N. Tkachenko,
N. M. Morlyan, Tez. dokl. III Vsesoyuz. soveshchaniya po
khimicheskim reaktivam [Abstrs of Papers, III AllꢀUnion Conf.
on Chemical Reagents], Ashkhabad, 1989, Pꢀ107 (in Russian).
8. I. I. Boiko, T. I. Boiko, A. A. Vardapetyan, G. V. Novitskaya,
D. S. Khachatryan, N. M. Morlyan, K. K. Koshelev, A.s.
1704446 USSR; Byul. Izobret. [Inventor Bull.], 2000, 9
(in Russian).
9. V. I. Zelenov, A. V. Chernova, L. I. Lysenko, Zh. Obshch.
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2009, 79].
10. J. K. F. Geirsson, A. D. Gudmundsdottir, Synthesis, 1990,
11, 993.
This procedure was used to synthesize 6ꢀacetylꢀ3ꢀ[2ꢀ(4ꢀ
methoxyphenyl)vinyl]ꢀ5ꢀ(4ꢀmethoxyphenyl)cyclohexꢀ2ꢀenone
(4a), 6ꢀacetylꢀ3,5ꢀdiphenylcyclohexꢀ2ꢀenone (4b), 6ꢀacetylꢀ5ꢀ
phenylꢀ3ꢀ(2ꢀthienyl)cyclohexꢀ2ꢀenone (4c), 6ꢀacetylꢀ3ꢀ[2ꢀ(2,4ꢀ
dichlorophenyl)vinyl]ꢀ5ꢀ(2,4ꢀdichlorophenyl)cyclohexꢀ2ꢀenone
(4d), 6ꢀacetylꢀ3ꢀ[2ꢀ(4ꢀbutoxyphenyl)vinyl]ꢀ5ꢀ(4ꢀbutoxyphenyl)ꢀ
cyclohexꢀ2ꢀenone (4e), 6ꢀacetylꢀ3ꢀ[2ꢀ(4ꢀpentyloxyphenyl)ꢀ
vinyl]ꢀ5ꢀ(4ꢀpentyloxyphenyl)cyclohexꢀ2ꢀenone (4f), 6ꢀacetylꢀ3ꢀ
[2ꢀ(4ꢀchlorophenyl)vinyl]ꢀ5ꢀ(4ꢀchlorophenyl)cyclohexꢀ2ꢀenꢀ
one (4g), and 6ꢀacetylꢀ3ꢀ[2ꢀ(4ꢀmethylphenyl)vinyl]ꢀ5ꢀ(4ꢀmethꢀ
ylphenyl)cyclohexꢀ2ꢀenone (4h).
The solvents, yields, physicochemical constants, 1H NMR
spectroscopic data, and mass spectrometric data for compounds
4a—h are given in Tables 2 and 3.
5ꢀEthylꢀ3ꢀmethylcyclohexꢀ2ꢀenone (11a). A mixture of proꢀ
panal (58 g, 1 mol), ethyl acetoacetate (260 g, 2 mol), and potasꢀ
sium carbonate (21 g, 0.15 mol) was kept at 40—50 C for 1 h,
refluxed for 5 h, and cooled to 20 C. Then a solution of sodium
hydroxide (100 g) in water (300 mL) and ethanol (250 mL) were
added, and the mixture was refluxed for 4 h. Ethanol with water
were distilled off to the vapor temperature of 80 C to collect
~400 mL of the distillate. The reaction mixture was cooled to
room temperature, neutralized with concentrated HCl (250 mL)
to pH 5—6, again refluxed for 30 min, and cooled to room temꢀ
perature. The organic layer was separated and distilled in vacuo;
11. L. I. Smith, G. F. Roualt, J. Am. Chem. Soc., 1943, 65, 631.
12. W. F. Whitmore, C. W. Roberts, J. Org. Chem., 1948, 13, 31.
13. D. Jyothi, S. H. Prasad, Indian J. Chem., Sect. B, 2008,
47, 630.
14. S. Tsuboi, T. Uno, A. Тakeda, Chem. Lett., 1978, 7, 1325.
Received August 8, 2014;
in revised form October 31, 2014