Condensation of 2-acylcyclohexane-1,3-diones with aromatic aldehydes

Article abstract of DOI:10.1134/S1070363212010203

Condensation of 2-propanoyl-, 2-butanoyl-, and 2-pentanoylcyclohexane-1,3- diones with aromatic aldehydes in the presence of secondary amines (diethylamine, pyrrolidine, morpholine, piperidine, and hexamethyleneimine) leads to the formation of the corresponding 2-[1-(dialkylamino)-2-alkyl-3-aryl- 2- propylidene]cyclohexane-1,3-diones and derivatives of 4H-chromen-4,5(6H)- dione. A primary screening of some of the resulting enamino derivatives for fungicidal activity has been performed.

Full text of DOI:10.1134/S1070363212010203

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 1, pp. 122–130. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © D.B. Rubinov, T.A. Zheldakova, R.A. Zheldakova, I.L. Rubinova, A.V. Baranovski, F.A. Lakhvich, 2012, published in Zhurnal
Obshchei Khimii, 2012, Vol. 82, No. 1, pp. 126–134.
Condensation of 2-Acylcyclohexane-1,3-diones
with Aromatic Aldehydes
D. B. Rubinova, T. A. Zheldakovaa, R. A. Zheldakovab,
I. L. Rubinovaa, A. V. Baranovskia, and F. A. Lakhvichb
a Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus,
ul. Kuprevicha 5/2, Minsk, 220141 Belarus
b Belarusian State University, Minsk, 220030, Belarus
e-mail: rub_irin@mail.ru
Received October 19, 2010
Abstract—Condensation of 2-propanoyl-, 2-butanoyl-, and 2-pentanoylcyclohexane-1,3-diones with aromatic
aldehydes in the presence of secondary amines (diethylamine, pyrrolidine, morpholine, piperidine, and
hexamethyleneimine) leads to the formation of the corresponding 2-[1-(dialkylamino)-2-alkyl-3-aryl-2-
propylidene]cyclohexane-1,3-diones and derivatives of 4H-chromen-4,5(6H)-dione. A primary screening of
some of the resulting enamino derivatives for fungicidal activity has been performed.
DOI: 10.1134/S1070363212010203
2-Acylcyclohexane-1,3-diones (cyclic β-triketones)
(I) are interesting both as conventional synthons
widely used in organic synthesis [1] and also natural
substances and their analogs with diverse biological
activity [2]. Compounds of this class were intensively
developed in connection with the expansion of
application of a number of environmentally friendly
herbicide preparations on their basis [3]. Many natural
compounds related to the alicyclic β-triketones contain
in the acyl side chain an arylpropenoyl fragment. They
are formed by condensation of 2-acetylcycloalkane-
1,3-diones (I, R3 = H) with aromatic aldehydes [2]. In
order to search for new compounds with pesticidal
activity it seems promising to investigate condensation
of aromatic aldehydes with the triketones of β-
cyclohexane series (Ia–Id), containing an acyl side
chain longer than acetyl.
derivatives of 4H-chromene-4,5(6H)-dione IVa–IVe.
The ratio of reaction products depends on the amount
of the taken secondary amine. With 0.5 equivalents of
amine the yield of enamino derivatives IIIa–IIIe was
45–50%, of chromenediones IVa–IVe, 30–40%,
calculated with respect to the parent triketone. With
equimolar amount of secondary amine only enamines
III formed in the reaction in almost quantitative yield.
This fact suggests that chromenediones IV formed in
the reaction enter further reaction with the amine
giving enaminodiketones III.
In the direct interaction of chromenediones IVb,
IVc, and IVe with piperidine the corresponding piperi-
dine enamine derivativas IIIc, IIIe, and IIIk were
identified with the physicochemical and spectral
properties coinciding with those of the samples obtained
in the condensation reaction. This result confirms that
in the course of the reaction of triketones I with aromatic
aldehyde the enaminodiketones III are formed actually
from the chromenediones IV. The formation of
chromenediones IVa–IVe themselves can be ascribed
to the intramolecular cyclization of β-triketones IIB or
their precursors β'-hydroxytriketones IIA. Note that in
this reaction we could not get chromenediones IV
using other common catalysts of the aldol-crotonic
condensation, including sodium hydroxide, triethyl-
amine, trifluoroacetic acid, and hydrogen chloride.
From the published data [1,2,4–9 the formation is
expectable in this reaction of 2-(2-alkyl-3-aryl-2-
propenoyl)cyclohexane-1,3-diones (IIB). However, it
appeared that the condensation of triketones Ia–Id
with benzaldehyde, anisaldehyde, veratric aldehyde, p-
hydroxybenzaldehyde, and piperonal under the
conditions of catalysis by secondary amine bases
(diethylamine, pyrrolidine, piperidine, hexamethylene-
imine, morpholine) resulted in a mixture of the
enaminodiketones IIIa–IIIl cis- and trans-isomers and
122

CONDENSATION OF 2-ACYLCYCLOHEXANE-1,3-DIONES
123
O
O
O
O
O
OH
Ar
O
O
R3
_H2O
+H2O
ArCHO
Ar
R1
R2
R1
R2
R1
R2
R3
R3
HNR4R5
O
O
IIB
Iа_Id
IIA
O
O
O
NR4R5
R3
Ar
5
4
4a
8a
Ar
6
7
3
2
R1
R2
+
R1
R2
R3
O
8
O
IIIа_IIIl
IVа_IVe
I, R1 = R2 = R3 = СН3 (а); R1 = R2 = СН3, R3 = С2Н5 (b); R1 = H, R2 = 2,4,6-(CH3)3C6H2, R3 = СН3 (c); R1 = H, R2 = 2,4,6-
(CH3)3C6H2, R3 = С2Н5 (d); III, R1 = R2 = R3 = СН3, R4 = R5 = С2Н5, Ar = С6Н5 (а); R1 = R2 = СН3, R3 = R4 = R5 = С2Н5,
Ar = С6Н5 (b); R1 = R2 = R3 = СН3, R3 = С3Н7, R4 + R5 = –(CH2)5–, Ar = C6H5 (c); R1 = R2 = R3 = СН3, R4 + R5 = –(CH2)6–,
Ar = 3,4-(OCH2O)C6H3 (d); R1 = H, R2 = 2,4,6-(CH3)3C6H2, R3 = СН3, R4 + R5 = –(CH2)5–, Ar = 4-СН3ОС6Н4 (e); R1 = H,
R2 = 2,4,6-(CH3)3C6H2, R3 = С2Н5, R4 + R5 = –(CH2)5–, Ar = 3,4-(OCH2O)C6H3 (f); R1 = R2 = R3 = СН3, R4 + R5 =
–(CH2)2O(CH2)2–, Ar = 4-СН3ОС6Н4 (g); R1 = R2 = СН3, R3 = С3H7, R4 + R5 = –(CH2)2O(CH2)2–, Ar = 3,4-(СН3О)2С6Н3
(h); R1 = R2 = R3 = СН3, R4 + R5 = –(CH2)5–, Ar = 4-СН3ОС6Н4 (i); R1 = R2 = СН3, R3 = С2Н5, R4 + R5 = –(CH2)6–, Ar =
3,4-(OCH2O)C6H3 (j); R1 = R2 = СН3, R3 = С2Н5, R4 + R5 = –(CH2)5–, Ar = С6Н5 (k); R1 = R2 = R3 = СН3, R4 + R5 =
–(CH2)4–, Ar = 4-НОС6Н4 (l); IV, R1 = R2 = R3 = СН3, Ar = С6Н5 (а); R1 = R2 = СН3, R3 = С2Н5, Ar = С6Н5 (b); R1 = R2 =
R3 СН3, R3 = С3Н7, Ar = C6H5 (c); R1 = R2 = R3 = СН3, Ar = 3,4-(–OCH2O–)C6H3 (d); R1 = H, R2 = 2,4,6-(CH3)3C6H2, R3 =
СН3, Ar = 4-СН3ОС6Н4 (e).
1
According to H NMR spectra, chromenediones
IVa–IVe are mixtures of diastereomers at the 2 and 3
positions of pyranone ring in the case of the
compounds of dimedone series IVa–IVd, and at the 2,
3, and 7 positions in the case of compound IVd which
has a mesityl substituent. Judging from the value of the
vicinal constants of protons at C2 and C3 (10–11 Hz)
typical of the trans-location of substituents, we
conclude that the 2,3-trans-isomers prevail.
The structure of chromenedions IVa–IVe can be
regarded as that of the intramolecular enol ether of β-
O
O
O
O
N
O
R3
Ar
N
H
Ar
R1
R2
R1
R2
R3
IIIc, IIIe, IIIk
IVb, IVc, IVe
N
H
O
O
O
NHR4
NH2R4
Ar
R3
Ar
R1
R2
IIIа, IIIe, IIIi
R1
R2
R3
O
IIIm_IIIo
N
V
III, R1 = R2 = R3 = СН3, R4 = C3Н7, Ar = 3,4-(OCH2O)C6H3 (m); R1 = R2 = R3 = СН3, R4 = CH2C6H5, Ar = C6H5 (n); R1 =
H, R2 = 2,4,6-(CH3)3C6H2, R3 = СН3, R4 = 4-CH3C6H4, Ar = 4-СН3ОС6Н4 (o).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

124
RUBINOV et al.
Impact of enamines IIIc, IIId, IIIf, IIIh, and IIIj on the growth of fungi
Coefficient of inhibition of fungal growth RF, %
Fungi strain
control
0
IIIc
IIId
IIIf
IIIh
IIIj
а
а
Alternaria alternata
Aspergillus niger
Botridis cineria
40
40
45
а
а
а
0
0
0
0
0
0
20
40
20
30
0
20
50
10
10
10
20
30
45
50
20
0
20
25
10
35
10
20
Fusarium oxysporum
Monilia sp.
20
а
Mucor sp.
а
Penicillum lividum
a Stimulation of fungal growth.
30
40
triketone of cyclohexane series, and on this basis it is
presumable that by their electronic and chemical
properties these compounds should be similar to the
methyl ethers of enol of 2-acylcyclohexane-1,3-dione,
which react readily with amines affording enamine
derivatives at the ring [10].
The ratio of cis- and trans-isomers of enamines
IIIa–IIIl in the mixture is defined primarily by the
length of the acyl side chain of the triketone. For 2-
propanoyl derivatives Ia and Ib the preferred
formation of (E)-isomers (IIIa, IIId, IIIe, IIIi, and
IIIl) is typical while 2-butanoyl and 2-pentanoyl
derivatives of cyclohexane-1,3-dione Ib and Id form in
this reaction predominantly (Z)-isomers IVb, IVc, IVf,
IVh, IVj, and IVk. The amine and aldehyde structure
much less affects the ratio of isomeric reaction
products.
The analysis of IR spectra of chromenediones IVa–
IVe shows their coincidence in the carbonyl region
with the spectra of the methyl ethers of 2-acylcyclo-
hexane-1,3-dione enol: the absorbtion of noncom-
jugated carbonyl group of the acyl side chain (in
chromenediones it corresponds to 4-keto group) occurs
at 1705–1710 cm–1, the absorption of conjugated car-
bonyl group of the ring (5-keto group in chromene-
dione), at 1640–1650 cm–1, and the absorption of
conjugated double bonds (C4a–C8a), at 1610–1620 cm–1.
Chromatographic mobility of cis-isomers of
enamines III is higher compared with the trans-
compounds, so their mixtures can be separated by
chromatography. However, the minor condensation
products readily isomerized in the course of separation,
and we failed to obtain pure samples. Even when the
main reaction product was isolated as a chromato-
graphically pure crystalline compound, after prepara-
tion a sample for NMR studies the minor component
appeared in an hour.
However, we have not found such a resemblance to
the enol methyl ethers in the chemical behavior of
chromenediones IVa–IVe. As noted above, in the
reaction of compounds IVb, IVc, and IVe with
piperidine a mixture was isolated of (Z)–(E)-isomers of
exocyclic derivatives IIIk, IIIl and IIIm, which
corresponds to the nucleophilic attack of amine on the
carbonyl group of the pyran ring. We did not observe
formation in this reaction of regioisomeric endocyclic
enaminodiketones V expected in the reaction of amine
with chromenedione along the mechanism of vinyl
substitution. This line of reaction is unusual also taking
in mind that the formation of exocyclic enamino-
diketones with tertiary amino group in the case of 2-
acylcyclohexane-1,3-diones has been described only
for their interaction with the pyrrolidine [11].
The exocyclic position of enamine fragment and the
assignment of configuration to isomers was made on
the basis of two-dimensional 13C–15N HMBC spectro-
scopy. In the NOESY experiments with compounds
IIIc and IIId no interaction was observed between the
protons of enamine fragment and methylene protons of
cyclohexanedione,
indicating
that
they
are
considerably distant from each other. In the NOESY
spectrum of the cis-isomer of piperidine enamino-
diketone IIIc, whose chromatographic mobility is
higher, the interaction was observed of two of the four
piperidine methylene protons (CH2NCH2) at 3.37 and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

CONDENSATION OF 2-ACYLCYCLOHEXANE-1,3-DIONES
125
3.57 ppm with the ortho-protons of the phenyl group.
These protons are likely to be located on one side of
the plane of the piperidine ring. Analogous interaction
was not observed in the NOESY spectra of trans-
isomers of compounds IIIc and IIId showing lower
chromatographic mobility. In the 13C NMR spectrum
of an isomer of enaminodiketone IIId with lower
chromatographic mobility coupling of the carbon in
the methyl group of side chains with olefinic protons is
registered, with the constant equal to 8.4 Hz, which,
according to [12], corresponds to the trans-isomer.
It turned out that studied compounds IIIc, IIId,
IIIf, IIIh, and IIIj in a concentration of 100 g ml–1
showed an activity against these strains of phyto-
pathogenic fungi, mainly by inhibiting their growth.
The mycelial growth inhibition rate varies in the range
of 10–50%. The maximum effect (50%) showed
compound IIId against Botridis cineria and IIIf
against Fusarium oxysporum.
The azepanyl derivative IIIj showed within 48–72
h stimulating rather than inhibiting activity toward all
tested strains except for Monilia sp. The morpholine
enamine IIIk stimulated the growth of Alternaria
alternata. Most resistant to the action of the studied
compounds were fungi Mucor sp. (the lack of effect, a
slight inhibition by the compounds IIIh and IIIi, and
stimulation at the action of IIIj) and Monilia sp., the
degree of its suppression usually does not exceed 40%.
1
Analysis of H NMR spectra shows that for the cis-
isomers of enaminodiketones IIIa–IIIl is characteristic
an upfield shift of all signals of proton-containing
groups compared with the trans-isomer, except for the
olefinic proton. In the 13C NMR spectra of the com-
pounds of dimedone series we observed coincidence of
respective chemical shifts of carbon atoms of
methylene and carbonyl groups of the ring, and in the
1H NMR spectra the methylene protons of cyclo-
hexane-1,3-dione fragment appear as a broad four-
proton singlet. In the IR spectra of the trans-isomers of
enaminodiketones IIIa–IIIl a very strong broad
absorption band is observed of the conjugated
exocyclic keto group at 1550–1570 cm–1 and a strong
absorption band of conjugated double bond at 1505–
1520 cm–1. In the spectra of cis-isomers the absorption
at 1505–1520 cm–1 is much less intense or non-
observable, and there is a very intense broad absorp-
tion band at 1580–1590 cm–1 belonging, apparently,
both to the conjugated carbonyl groups and to the
conjugated double bond.
Inhibition of growth of colonies was calculated
according to Abbott:
D
control – Dexp
× 100,
RF =
Dcontrol
where RF is growth inhibition compared with control,
%; Dcontrol is the diameter of growing mycelium in
control test; Dexp is the diameter of growing mycelium
in an experiment.
The results of the primary screening of the
fungicidal activity of the cyclic β-triketone derivatives
indicate the prospects of finding substances with
fungicidal activity in this series of compounds.
The enaminodiketones III proved to be very stable
chemically. Refluxing of compounds IIIc, IIIe and
IIIk in a mixture of acetic and hydrochloric acid for
16 h resulted in the formation of the respective
chromenediones IVb, IVc, and IVe in the yield of 40–
50%. At the action of propylamine, benzylamine, or p-
toluidine on enaminodiketones IIIa, IIIe, or IIIi in
toluene at 110°C over 6–8 h respective enamino-
diketones IIIm–IIIo formed, the products of trans-
amination, in the yield of 50–60%.
EXPERIMENTAL
IR spectra of solids were recorded on a Bomem
Michelson FT IR 100 instrument from the tablets with
KBr, of oily substances, from the films. The NMR
spectra were recorded on a Bruker Avance 500
1
spectrometer (operating frequency 500 MHz for H
and 125 MHz for 13C) from solutions in deuteron-
chloroform (TMS reference). The mass spectra were
obtained on an HPLS-MS/MS system comprising an
ACCELA chromatograph with a LCQ Fleet mass
detector, in the APCI ionization mode with detection
of positive ions. Melting points were determined on a
Boetius block. The reaction course was monitored and
the purity of all compounds obtained was checked by
TLC on the Alufolien Kieselgel F 254 plates (Merck).
The plates were developed in UV light and then
sprayed with a solution of ferric chloride. For
We tested some of the synthesized compounds for
the fungicidal activity in accordance with the proce-
dure in [13, 14]. The test objects were strains of
alternariosis (Alternaria alternate), aspergillosis
(Aspergillus niger), gray mold of vegetable crops
(Botrytis cinerea), root rot (fusariosis) (Fusarium
oxysporum), as well as fungi Mucor sp., Monilia sp.,
and Penicillum lividum.
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126
RUBINOV et al.
chromatography were used Kieselgel 60 HF 254 TLC-
standard (Merck) and Kieselgel 60 (Fluka).
q (2H, CH3CH2, J 7.5), 2.68 br.s (4H, 4-CH2, 6-CH2),
3.89 q and 4.17 q [4H, (CH3CH2)2N, J 7.0], 6.83 s (1H,
C=CH), 7.35–7.43 m (5H, C6H5). 13C NMR spectrum,
δ, ppm: 187.88 s, 187.88 s, 185.48 s, 136.91 s, 136.42
d, 133.85 s, 129.40 d, 129.40 d, 129.33 d, 128.83 d,
128.83 d, 108.96 s, 50.63 t, 50.30 t, 46.98 t, 46.98 t,
32.25 s, 28.47 q, 28.24 q, 23.76 t, 13.89 q, 13.41 q,
13.21 q. Found, %: C 78.11, H 8.95; N 4.09. [M + 1]+
354. C23H31NO2. Calculated, %: C 78.15, H 8.84; N
3.96. M 353.51.
Condensation of 2-acylcyclohexane-1,3-diones
with aromatic aldehydes. a.To a solution of 0.05 mol
of triketones I in 50 ml of toluene was added 0.055
mol of an aromatic aldehyde (benzaldehyde, anisal-
dehyde, veratric aldehyde, p-hydroxybenzaldehyde, or
piperonal) and 0.025 mol of a secondary amine (di-
ethylamine, pyrrolidine, morpholine, piperidine, or
hexamethyleneimine). The reaction mixture was re-
fluxed for 12–24 h with a water separator, then after
cooling it was diluted with 50 ml of toluene, extracted
with 2×50 ml of 20% hydrochloric acid and 50 ml of
water. The toluene solution was dried over anhydrous
magnesium sulfate, passed through a thin layer of
silica gel, and evaporated on a rotary evaporator. The
residue was crystallized from ethyl acetate–petroleum
ether. Oily products were isolated by column
chromatography on silica gel (eluent ethyl acetate–
petroleum ether). The chromenediones IVa–IVe were
obtained in 30–40% yield.
5,5-Dimethyl-2-[(Z)-1-(piperidyl)-2-propyl-3-
phenyl-2-propenilydene]-1,3-cyclohexane-1,3-dione
(IIIc). Yield 46%, mp 172–173°C. IR spectrum, cm–1:
1
1630 w, 1570 v.s, 1510 m, 1510 m, 1400. H NMR
spectrum, δ, ppm: 0.93 br.s (7H, CH3CCH3,
NCH2CHAHB), 0.95 t (3H, CH3CH2, J 7.2), 1.40–1.60
m (6H, CH3CH2, NCH2CHAHBCH2CHAHB), 1.73 m
(1H, NCH2CH2CH2CHAHB), 2.24 br.s (4H, 4-CH2, 6-
CH2), 2.27 m and 2.46 m (2H, CH3CH2CHAHB), 3.37
m and 3.47 m (2H, CH2NC HAHB), 3.57 (2H,
CHAHBNCH2), 6.71 (1H, C=CH), 7.20–7.30 m (5H,
C6H5). 13C NMR spectrum, δ, ppm: 193.28 s, 193.28 s,
176.35 s, 137.93 s, 136.39 s, 132.80 d, 129.04 d,
129.04 d, 128.42 d, 128.42 d, 127.73 s, 109.86 s, 56.57
t, 52.57 t, 52.57 t, 52.02 t, 40.71 t, 30.77 c, 28.61 q,
28.61 q, 25.27 t, 25.04 t, 23.60 t, 21.22 t, 14.30 q.
Found, %: C 79.48, H 8.89; N 3.72. [M + 1]+ 380.
C25H33NO2. Calculated, %: C 79.11, H 8.76; N 3.69. M
379.54.
The combined aqueous layers were extracted with
2×25 ml of chloroform. The combined organic layers
were washed with 50 ml of water, dried with
anhydrous magnesium sulfate, and evaporated on a
rotary evaporator. The residue was crystallized from
ethyl acetate–petroleum ether to afford enamino-
diketones IIIa–IIIe, IIIl in 45–50% yield.
5,5-Dimethyl-2-[(E,Z)-1-(diethylamino)-2-methyl-
3-phenyl-2-propylidene]cyclohexane-1,3-dione (IIIa).
Yield 45%. Oily substance. IR spectrum, cm–1: 1630
2-[(E)-1-(1-Azepanyl)-3-(1,3-benzodioxol-5-yl)-2-
methyl-2-propylidene]-5,5-dimethylcyclohexane-
1,3-dione (IIId). Yield 50%, mp 182–183°C. IR
spectrum, cm–1: 1620 m, 1600 w, 1570 v.s, 1500 v.s.
1H NMR spectrum, δ, ppm: (E-isomer) 1.08 s (6H,
CH3CCH3), 1.79 m and 1.88 m [8H, NCH2(CH2)4CH2],
2.26 d (3H, CH3C = CH, J 1.1 Hz), 2.30 br.s (4H, 4-
CH2, 6-CH2), 3.76 m and 3.82 m (4H, CH2NCH2), 5.98
s (2H, OCH2O), 6.48 br.s (1H, CH3C=CH), 6.80 d
[1H, (5'-H)-C6H3, J 8.1 Hz], 6.84 d.d [1H, (6'-H)-
C6H3 , J1 1.8 Hz, J2 1.4 Hz], 6.90 d [1H, (2'-H)-C6 H3,
J 1.4 Hz]. 13C NMR spectrum, δ, ppm: 193.32 s,
193.32 s, 181.48 s, 147.73 s, 147.43 s, 134.38 s,
134.19 d, 130.19 s, 124.36 d, 112.57 s, 109.31 d,
108.39 d, 101.31 t , 57.11 t, 54.19 t, 52.01 t, 52.01 t,
31.20 s, 29.63 t, 29.02 t, 28.69 q, 28.69 q, 26.92 t,
26.59 t, 19.45 q. Found, %: C 73.47, H 7.75; N 3.35.
[M + 1]+ 410. C25H31NO4. Calculated, %: C 73.32, H
7.63; N 3.42. M 409.52.
1
m, 1575 v.s, 1510 s. H NMR spectrum, δ, ppm:
(Z):(E) = 1:1; (Z)-isomer, 0.78 s (6H, CH3CCH3), 1.06
t and 1.27 t (6H, CH3CH2)2N, J 7.2 Hz), 2.18 d (3H,
CH3C=CH, J 1.2 Hz), 2.35 s (4H, 4-CH2, 6-CH2),
3.47-3.75 m [4H, (CH3CH2)2N], 6.84 br.s (1H,
CH3C=CH), 7.10—.35 m (5H, C6H5); (E)-isomer, 1.08
s (6H, CH3CCH3), 1.31 t and 1.33 t (6H, CH3CH2)2N,
J 7.2 Hz), 2.29 d (3H, CH3C=CH, J 1.0 Hz), 2.31 s
(4H, 4-CH2, 6-CH2), 3.63 m [4H, (CH3CH2)2N], 6.56 d
(1H, CH3C=CH), 7.10–7.35 m (5H, C6H5). Found, %:
C 77.91, H 8.85; N 4.21. [M + 1]+ 340. C22H29NO2.
Calculated, %: C 77.84, H 8.61; N 4.13. M 339.48.
5,5-Dimethyl-2-[(Z)-1-(diethylamino)-3-phenyl-
2-ethyl-2-propylidene]cyclohexane-1,3-dione (IIIb).
Yield 42%, mp 149–150°C. IR spectrum, cm–1: 1660
1
v.s, 1615 s, 1585 v.s, 1555 m. H NMR spectrum, δ,
ppm: 1.13 s (6H, CH3CCH3), 1.16 t (3H, CH3CH2,
5-Mesityl-2-[(E,Z)-2-methyl-3-(4-methoxyphenyl)-
1-(1-piperidyl)-2-propylidene]cyclohexane-1,3-
J 7.5), 1.45 t and 1.51 t [6H, (CH3CH2)2N, J 7.0], 2.57
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

CONDENSATION OF 2-ACYLCYCLOHEXANE-1,3-DIONES
127
dione (IIIe). Yield 50 %, mp 177–180°C. IR spec-
substance. IR spectrum, cm–1: 1710 v.s, 1640 m, 1570
1
1
trum, cm–1: 1640 m, 1590 v.s, 1520 m, 1250 v.s. H
v.s. H NMR spectrum, δ, ppm: (Z):(E) = 2:1; Z-
NMR spectrum, δ, ppm: (Z):(E) = 3:2; Z-isomer, 1.59–
1.89 m [6H, NCH2(CH2)3], 2.16 br.s [6H, 2',6'-(CH3)2-
C6H2], 2.20 s (3H, 4'-CH3C6H2), 2.25 br.s (3H,
CH3C=CH), 2.32 m (2H, 4-CHA, 6-CHB), 2.74 m (2H,
4-CHB, 6-CHB), 3.51–3.70 m (4H, CH2NCH2), 3.77 s
(3H, OCH3), 3.91 m (1H, 5-CH), 6.63 s (1H, C=CH),
6.76 s (2H, C6H2), 6.80 d [2H, (3',5'-H2)-C6H4, J 8.7 Hz],
7.01 d [2H (2',6'-H2)-C6H4, J 8.7 Hz]; E-isomer, 1.74–
1.89 m [6H, NCH2(CH2)3], 2.24 (3H, 4'-CH3C6H2),
2.32 br.s (3H, CH3C=CH), 2.38 br.s [6H, 2',6'-(CH3)2-
C6H2], 2.46 d.d (2H, 4-CHA, 6-CHA, J1 16.8 Hz, J2
3.7 Hz), 3.08 m ( 2H, 4-CHB, 6-CHB), 3.58–3.72 m
(4H, CH2NCH2), 3.77 m (1H, 5-CH), 3.82 s (3H,
OCH3), 6.61 br.s (1H , C=CH), 6.83 s (2H, C6H2), 6.90
d (2H, (3',5'-H2)-C6H4, J 8.7 Hz), 7.35 d [2H, (2',6'-
H2)-C6H4, J 8.7 Hz]. Found, %: C 78.86, H 8.05; N
3.13. [M + 1]+ 472. C31H37NO3. Calculated, %: C
78.95, H 7.91; N 2.97. M 471.64.
isomer, 0.74 t (3H, CH3CH2, J 7.1 Hz), 1.11 s and 1.13
s (6H, CH3CCH3), 1.21–1.62 m (4H, CH3CH2CH2),
2.36 s (2H, 6-CH2), 2.60 m (1H, 3-CH), 2.61 s (2H, 8-
CH2), 5.66 d (1H, 2-CH, J 3.0 Hz), 7.33–7.43 m (5H,
C6H5); E-isomer, 0.79 t (3H, CH3 CH2 , J 7.2 Hz), 1.07
s and 1.09 s (6H, CH3CCH3), 1.21–1.62 m (4H,
CH3CH2CH2), 2.31 s (2H, 6-CH2), 2.50 s (2H, 8-CH2),
2.82 m (1H, 3-CH), 5.31 d (1H, 2-CH, J 9.7 Hz), 7.33–
7.43 m (5H, C6H5). Found, %: C 76.99, H 7.90. [M +
1]+ 313. C20H24O3. Calculated, %: C 76.89, H 7.74. M
312.40.
2-(1,3-Benzodioxo-5-yl)-3,7,7-trimethyl-7,8-di-
hydro-2H-chromen-4,5-(3H,6H)dione (IVd). Yield
36%. Oily substance. IR spectrum, cm–1: 1710 v.s,
1
1660 m, 1570 v.s, 1510 s, 1500 s. H NMR spectrum,
δ, ppm: E-isomer, 0.93 t (3H, CH3, J 6.74 Hz), 1.10 s
(6H, CH3CCH3), 2.33 s (2H, 6-CH2), 2.50 s (2H, 8-
CH2), 2.81 m (1H, 3-CH), 4.96 d (H, 2-CH, J
12.82 Hz), 6.02 s (2H, OCH2O), 6.84 s and 6.88 s (3H,
C6H3). Found, %: C 69.38, H 6.25. [M + 1]+ 329.
C19H20O5. Calculated, %: C 69.50, H 6.14. M 328.36.
3,7,7-Trimethyl-2-phenyl-7,8-dihydro-2H-chro-
men-4, 5(3H,6H)dione (IVa). Yield 39%, mp 124–
125°C. IR spectrum, cm–1: 1700 v.s, 1640 m, 1570 v.s
1H NMR spectrum, δ, ppm: (Z):(E) = 1:4; Z-isomer,
1.13 d (3H, CH3, J 6.6 Hz), 1.11 s (6H, CH3CCH3),
2.37 s (2H, 6-CH2), 2.63 s (2H, 8-CH2), 2.70 m (1H, 3-
CH), 5.64 d (1H, 2-CH, J 3.1 Hz), 7.33–7.46 m (5H,
C6H5); E-isomer, 0.94 d (3H, CH3, J 6.8 Hz), 1.10 s
(6H, CH3CCH3), 2.34 s (2H, 6-CH2), 2.52 s (2H, 8-
CH2), 2.86 m (1H, 3-CH), 07.05 d (1H, 2-CH, J 12.7
Hz), 7.33–7.46 m (5H, C6H5). Found, %: C 76.18, H
7.15. [M + 1]+ 285. C18H20O3. Calculated, %: C 76.03,
H 7.09. M 284.35.
7-Mesityl-3-methyl-2-(4-methoxyphenyl)-7,8-di-
hydro-2H-chromen-4,5-(3H,6H)-dione (IVe). Yield
37%. mp 182–185°C. IR spectrum, cm–1: 1705 v.s,
1
1640 m, 1620 m, 1570 s, 1520 m, H NMR spectrum,
δ, ppm: (four diastereomers) 0.94 d, 0.96 d, 1.00 d and
1.01 d (3H, CH3, J 7.0 Hz), 2.25 s (3H, 4'-CH3C6H2),
2.37 br.s [6H, 2',6'-(CH3)2C6H2], 2.51–2.65 m (2H, 6-
CHA, 8-CHA), 2.86–2.97 m (1H, 3-CH), 3.03–3.11 m
(1H, 6-CHB), 3.21–3.37 m (1H, 8-CHB), 3.78–3.87 m
(1H, 7-CH), 3.84 s (3H, OCH3), 5.03 d (0.56H, J
13.3 Hz), 5.9 d (0.29H, J 12.6 Hz), 5.63 d (0.1H, J
3.1 Hz) and 5.66 d (0.05H, J 3.7 Hz) (1H, 2-CH); 6.85
s (2H, C6H2), 6.94–7.01 m [2H, 3'',5''-(H2)-C6H4],
7.52–7.36 m [2H, 2'',6''-(H2)-C6H4]. Found, %: C
77.16, H 7.11. [M + 1]+ 405. C26H28O4. Calculated, %:
C 77.20, H 6.98. M 404.51.
7,7-Dimethyl-2-phenyl-3-ethyl-7,8-dihydro-2H-
chromen-4,5(3H,6H)dione (IVb). Yield 35%, mp
113–115°C. IR spectrum, cm–1: 1710 v.s, 1645 m,
1570 v.s. 1H NMR spectrum, δ, ppm: (Z):(E) = 2:1; Z-
isomer, 0.85 t (3H, CH3CH2, J 7.5 Hz), 1.13 s and 1.14
s (6H, CH3CCH3), 1.52–1.65 m (2H, CH3CH2), 2.37 s
(2H, 6-CH2), 2.52 m (1H, 3-CH), 2.61 s (2H, 8-CH2),
5.67 d (1H, 2-CH, J 3.1 Hz), 7.34–7.44 m (5H, C6H5);
E-isomer, 0.88 t (3H, CH3 CH2, J 7.5 Hz), 1.09 s and
1.10 s (6H, CH3CCH3), 1.40 m (2H, CH3CH2), 2.32 s
(2H, 6-CH2), 2.50 s (2H, 8-CH2) , 2.78 m (1H, 3-CH),
5.33 d (1H, 2-CH, J 10.2 Hz), 7.33–7.44 m (5H,
C6H5). Found, %: C 76.18, H 7.15. [M + 1]+ 299.
C19H22O3. Calculated, %: C 76.48, H 7.43. M 298.38.
b. To a solution of 0.05 mol of triketone I in 50 ml
of toluene was added 0.055 mol of aromatic aldehyde
and 0.05 mole of a secondary amine. The reaction
mixture was refluxed for 8–10 h with a water separa-
tor. After cooling, the reaction mixture was placed in a
freezer, the precipitated crystals were filtered off,
washed with 20 ml of cold toluene, recrystallized from
ethyl acetate–petroleum ether, and then dried in a
vacuum. Yield of the enaminodiketones III 85–95%.
Enaminodiketone IIId described above was obtained
by method b in 90% yield.
7.7-Dimethyl-3-propyl-2-phenyl-7,8-dihydro-2H-
chromen-4,5(3H,6H)-dione (IVc). Yield 35%. Oily
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

128
RUBINOV et al.
2-[(Z)-3-(1,3-Benzodioxol-5-yl)-1-(1-piperidyl)-2-
(1H, C=CH), 6.81 d [1H, (3')-H-C6H3, J 8.3], 6.86 d
[1H, (2')-H-C6 H3, J 8.3], 7.01 s [1H, (6')-H-C6H3].
Found, %: C 70.64, H 8.05; N 3.09. [M + 1]+ 442.
C26H35NO5. Calculated, %: C 70.72, H 7.99; N 3.17. M
441.56.
ethyl-2-propylidene]-5-mesitylcyclohexane-1,3-dione
(IIIf). Yield 95%, mp 236–238°C (ether). IR spectrum,
1
cm–1: 1660 m, 1590 v.s, 1500 s. H NMR spectrum, δ,
ppm: 1.15 t (3H, CH3CH2, J 7.4 Hz), 1.54–1.84 m [6H,
NCH2(CH2)3], 2.23 s (3H, 4'-CH3C6H2), 2.31 br.s [6H,
2',6'-(CH3)2C6H2], 2.35 d.d (1H, 4-CHA, J1 12.6 Hz, J2
4.5 Hz), 2.48 br.s (1H, 6-CHA), 2.56 m (2H, CH3CH2),
2.96 m (1H, 4 CHB, 6-CHB), 3.51–3.72 m (5H, 5-CH,
CH2NCH2), 5.95 s (2H, OCH2O), 6.64 s (1H, C=CH),
6.77 s [2H, (5',6'-H2)C6H3], 6.80 s (2H, C6H2), 6.83 s
[1H, (2'-H)C6H3]. Found, %: C 76.74, H 7.68; N 2.91.
[M + 1]+ 500. C32H37NO4. Calculated, %: C 76.92, H
7.46; N 2.80. M 499.64.
5,5-Dimethyl-2-[(E,Z)-2-methyl-3-(4-methoxy-
phenyl)-1-(1-piperidyl)-2-propylidene]cyclohexane-
1,3-dione (IIIi). Yield 92%, mp 125–126°C. IR
spectrum, cm–1: 1610 m, 1580 v.s, 1570 v.s, 1565 v.s,
1535 m, 1510 m, 1250 v.s. 1H NMR spectrum, δ, ppm:
(Z):(E) = 1:1; Z-isomer, 0.63 br.s and 0.87 br.s (6H,
CH3CCH3), 1.51–1.85 m [6H, CH2N(CH2)3], 2.10 br.s
(4H, 4-CH2, 6-CH2), 2.20 d (3H, CH3C=CH, J 1.3 Hz),
3.45 m (1H, CHAHBNCHAHB), 3.51–3.60 m (2H,
CHAHBNCHAHB), 3.77 s (3H, OCH3), 3.85 m (1H,
CHAHBNCHAHB), 6.57 br.s (1H, CH3C=CH), 6.76 d
[2H, 3',5'-(H2)-C6H4, J 8.7 Hz], 7.00 d [2H, 2',6'-(H2)-
C6H4, J 8.7 Hz]; E-isomer, 1.08 s (6H, CH3CCH3),
1.49–1.83 m [6H, CH2N(CH2)3], 2.29 br.s (3H,
CH3C =CH), 2.31 br.s (4H, 4-CH2, 6-CH2), 3.55 m
and 3.65 m (4H, CH2NCH2), 3.81 s (3H, OCH3), 6.54 s
(1H, CH3C=CH), 6.87 d [2H, 3',5'-(H2)-C6H4, J 8.8 Hz],
5,5-Dimethyl-2-[(E,Z)-2-methyl-3-(4-methoxy-
phenyl)-1-(4-morpholinyl)-2-propylidene]cyclohexane-
1,3-dione (IIIg). Yield 87%, mp 158–159°C. IR spec-
trum, cm–1: 1605 m, 1580 v.s, 1510 s, 1400, 1240 s. 1H
NMR spectrum, δ, ppm: (Z):(E) = 4:1; Z-isomer, 0.85
br.s (6H, CH3CCH3), 2.13 d (3H, CH3C=CH, J 1.3 Hz),
2.19 br.s (4H, 4-CH2, 6-CH2), 3.37–3.58 m (4H,
CH2NCH2), 3.70–4.00 m (4H, CH2OCH2), 3.78 s (3H,
OCH3), 6.64 br.s (1H, CH3C=CH), 6.80 d [2H, 3',5'-
(H2)C6H4, J 8.8 Hz]; 7.7 d [2H, 2',6'-(H2)C6H4, J
8.8 Hz]; E-isomer, 1.08 s (6H, CH3CCH3), 2.28 d (3H,
CH3C=CH, J 1.0 Hz), 2.32 br.s (4H, 4-CH2, 6-CH2),
3.46 t (4H, CH2NCH2, J 5.0 Hz), 3.83 t (4H,
CH2OCH2, J 5.0 Hz), 3.82 s (3H, OCH3), 6.55 br.s
(1H, CH3C=CH), 6.88 d [2H, 3',5'-(H2)C6H4 J 8.8 Hz],
7.31 d [2H, 2',6'-(H2)-C6H4, J 8.8 Hz]. 13C NMR
spectrum, δ, ppm: Z-isomer, 193.56 br, 176.07, 159.62,
134.35, 130.44, 130.02, 130.02, 128.65, 114.06,
114.06, 109.79, 66.28, 66.10, 55.80, 55.45, 52.55 ,
52.55, 51.05, 30.68, 28.41 br, 24.14; E-isomer, 193.82
br, 180.73, 159.62, 134.56, 132.60, 130.02, 130.02,
128.54, 114.06, 114.06, 112.55, 66.99, 66.65, 55.66,
52.55, 52.55, 52.25, 51.77, 31.05, 28.73, 28.73, 19.79.
Found, %: C 72.11, H 7.85; N 3.77. [M + 1]+ 384.
C23H29NO4. Calculated, %: C 72.04, H 7.62; N 3.65. M
383.49.
13
7.31 d [2H, 2',6'-(H2)-C6H4, J 8.8 Hz]. C NMR spec-
trum, δ, ppm: Z-isomer, 193.56, 193.56, 176.24,
159.19, 133.11, 130.82, 129.94, 129.94, 128.53, 113.67,
113.67, 109.97, 56.17, 55.32, 52.33, 52.33, 51.53,
30.49, 28.59 br, 26.05, 25.93, 24.30, 23.53. Found, %:
C 75.71, H 8.09, N 3.80. [M + 1]+ 382. C24H31NO3.
Calculated, %: C 75.56; H 8.19; N 3.67. M 381.52.
2-[(E,Z)-1-(1-Azepanyl)-3-(1,3-benzodioxol-5-yl)-
2-ethyl-2-propylidene]-5,5-dimethylcyclohexane-1,3-
dione (IIIj). Yield 93%. Oily substance. IR spectrum,
1
cm–1: 1570 v.s, 1500, 1490 o.s. H NMR spectrum, δ,
ppm: (Z):(E) = 3:2; Z-isomer, 0.99 s (6H, CH3CCH3),
1.05 t (3H, CH3CH2, J 7.5 Hz), 1.16–1.30 m and 1.48–
1.80 m [8H, NCH2(CH2)4CH2], 2.25–2.34 m (1H,
CHAHBCH3), 2.28 s (4H, 4-CH2, 6-CH2), 2.40–2.48 m
(1H, CHAHBCH3), 3.02 m (1H, CHAHBNCHCHD), 3.64
d.d (1H, CHAHBNCHCHD, J1 15.2 Hz, J2 7.9 Hz), 3.80
d.d (1H, CHAHBNCHCHD, J1 15.3 Hz, J2 10.2 Hz),
3.94 m (1H, CHAHBNCHCHD), 5.93 s and 5.94 s (2H,
OCH2O), 6.58 s (1H, C=CH), 6.74 d [1H, (5'-H)C6H3,
J 7.9 Hz], 6.79 d [1H, (6'-H)C6 H3, J 7.9 Hz], 6.81 br.s
[1H, (2'-H)-C6H3]; E-isomer, 1.02 s (6H, CH3CCH3),
1.14 t (3H, CH3CH2, J 7.5 Hz), 1.70–1.90 m [8H,
NCH2(CH2)4CH2], 2.38 br.s (4H, 4-CH2, 6-CH2), 2.54
q (2H, CH3CH2, J 7.5 Hz), 4.2 m (4H, CH2NCH2),
5.97 s (2H, OCH2O), 6.75 s (1H, CH3C=CH), 6.80 d
[1H, (5'-H)-C6H3, J 8.5 Hz], 6.93 d [1H, (6'-H)-C6H3, J
8.5 Hz], 6.95 br.s [1H, (2'-H)-C6H3]. Found, %: C
5,5-Dimethyl-2-[(Z)-3-[3,4-dimethoxyphenyl]-1-
(morpholinyl)-2-propyl-2-propenilydene]-1,3-cyclo-
hexane-1,3-dione ( IIIh). Yield 95%, mp 147–151°C.
IR spectrum, cm–1: 1640, 1590 v.s, 1520 v.s, 1250 v.s.
1H NMR spectrum, δ, ppm: 0.91 t (3H, CH3CH2, J
7.3), 1.02 s (6H, CH3CCH3), 1.39 m (2H, CH3CH2),
2.24 m (1H, CH3CH2CHA), 2.32 s (4H, 4-CH2, 6-CH2),
2.36 m (1H, CH3CH2CHB), 2.97 m, 3.14 m, 3.38 m,
and 3.95 m (4H, CH2NCH2), 3.51 m and 3.64 m (4H,
CH2 CH2), 3.80 s and 3.88 s (6H, (OCH3)2), 6.75 s
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CONDENSATION OF 2-ACYLCYCLOHEXANE-1,3-DIONES
129
73.67, H 9.15; N 3.23. [M + 1]+ 424. C26H33NO4.
Calculated, %: C 73.73; H 7.85; N 3.31. M 423.54.
substance. IR spectrum, cm–1: 1650 s, 1550 v.s, 1500
m. 1H NMR spectrum, δ, ppm: 0.86 t (3H,
NCH2CH2CH3, J 7.4 Hz), 1.07 s (6H, CH3CCH3), 1.17
t (3H, CH2CH3, J 7.4 Hz), 1.34–1.47 m (2H,
NCH2CH2CH3), 2.16 m (1H, CHAHBCH3), 2.34 s and
2.46 s (4H, 4-CH2, 6-CH2), 2.43 m (1H, CHAHBCH3),
3.00 m (1H, NCHAHB), 3.24 m (1H, NCHAHB), 5.90 s
(2H, OCH2O ), 6.33 br.s (1H, C=CH), 6.62–6.68 m
(3H, C6H3), 13.17 br.s (1H, NH···O). Found, %: C
71.37, H 7.65; N 3.60. [M + 1]+ 370. C22H27NO4.
Calculated, %: C 71.52, H 7.37; N 3.79. M 369.46.
5,5-Dimethyl-2-[(Z)-1-(piperidyl)-3-phenyl-2-ethyl-
2-propenylidene]-1,3-cyclohexane-1,3-dione (IIIk).
Yield 89%, mp 173–178°C. IR spectrum, cm–1: 1630
1
w, 1580 v.s, 1540 m, 1500 w. H NMR spectrum, δ,
ppm: 0.88 br.s (6H, CH3CCH3), 1.01 m [1H,
N(CH2CH2)2CHA], 1.12 t (3H, CH3CH2, J 7.4), 1.43–
1.76 m [5H, N(CH2CH2)2CHB], 2.22 br.s (4H, 4-CH2,
6-CH2), 2.33 m (1H, CH3CHA), 2.56 m (1H, CH3CHB),
5.98 s (2H, OCH2O), 3.37–3.65 m (4H, CH2NCH2),
6.69 s (1H, C=CH), 7.17–7.31 m (5H, C6H5). En-
aminodiketone IIIk) was also obtained with the yield
48%, along with chromenedione IVb (yield 31%), by
the method a.
2-[(E,Z)-1-(benzylamino)-2-methyl-3-phenyl-2-
propylidene]-5,5-dimethylcyclohexane-1,3-dione
(IIIn). Yield 60%. Oily substance. IR spectrum, cm–1:
1650 s, 1580 v.s, 1550 v.s. 1H NMR spectrum, δ, ppm:
(Z):(E) = 2:1; Z-isomer, 1.06 s (6H, CH3CCH3), 2.12 d
(3H, CH3C=CH, J 1.3 Hz), 2.34 s and 2.45 s (4H, 4-
CH2, 6-CH2), 4.63 br.d (2H, NHCH2Ph, J2 6.0 Hz),
6.21 br.s (1H, CH3C=CH), 7.00–7.38 m (10H,
C6H5CH2C6H5), 13.45 br.s (1H, NH); E-isomer, 1.04 s
and 1.06 s (6H, CH3CCH3), 2.07 d (3H, CH3C=CH, J
1.3 Hz), 2.34 s and 2.44 s ( 4H, 4-CH2, 6-CH2), 4.22
d.d (1H, NHCHACHBPh, J1 15.3 Hz, J2 5.0 Hz), 4.55
d.d (1H, NHCHACHBPh, J1 15.3 Hz, J2 6.0 Hz), 6.51
2-[(E)-3-(4-Hydroxyphenyl)-2-methyl-1-(pyrro-
li-inyl)-2-propenilydene]-5,5-dimethyl-1,3-cyclo-
hexane-1,3-dione (IIIl). Yield 95%, mp 199–203°C.
IR spectrum, cm–1: 1610 m, 1570 v.s, 1540 v.s, 1510
v.s. 1H NMR spectrum, δ, ppm: 1.10 s (6H,
CH3CCH3), 2.05 m and 2.12 m (4H, NCH2CH2CH2),
2.22 s (3H, CH3C=CH), 2.36 s (4H, 4-CH2, 6-CH2),
3.73 t and 3.78 t (4H, CH2NCH2, J 6.8), 6.45 s (1H,
C=CH), 6.69 d and 6.95 d (4H, C6H4, J 8.6), 10.03 br.s
(1H, OH).
br.d (1H, CH3C=CH), 7.00–7.38
m
(10H,
C6H5CH2C6H5), 13.36 br.s (1H, NH). Found, %: C
80.47, H 7.15; N 3.58. [M + 1]+ 374. C25H27NO2.
Calculated, %: C 80.40, H 7.29; N 3.75. M 373.49.
Reaction of chromenediones IVb, IVc, and IVe
with piperidine. To a solution of 2 mmol of a chro-
menedione in 50 ml of toluene was added 2.2 mmol of
piperidine. The reaction mixture was refluxed with a
water separator for 6–8 h, cooled to room temperature,
passed through a thin layer of silica gel, and eva-
porated in a rotary evaporator. The residue was crystal-
lized from ethyl acetate–petroleum ether. The yields of
enaminodiketones: IIIc, 82%, IIId, 95% IIIk, 88%.
5-Mesityl-2-[(E,Z)-2-methyl-3-(4-methoxyphenyl)-
1-(4-toluidine)-2-propenilydene]-1,3-cyclohexane-
1,3-dione (IIIo). Yield 55%, mp 157°C. IR spectrum,
1
cm–1: 1650 s, 1600, 1540 v.s, 1510 m. H NMR
spectrum, δ, ppm: 2.01 d and 2.07 d [3H, 4'-(CH3)-
C6H4, J 1.3 Hz], 2.25 s and 2.27 s (3H, 4'-CH3C6H2),
2.32 s and 2.34 s (3H, CH3C=CH), 2.42 br.s [6H, 2',6'-
(CH3)2C6H2], 2.55–2.72 m (2H, 4-CHA, 6-CHA), 2.96–
3.11 m (1H, 4-CHB), 3.23–3.33 m (1H, 6-CHB), 3.62
m and 3.86 m (1H, 5-CH), 3.82 s (3H, OCH3), 6.18 s
and 6.25 s (1H, C=CH), 6.68–7.15 m (10H, aromatic),
14.42 br (1H, NH···O). Found, %: C 80.42, H 7.05; N
2.98. [M + 1]+ 494. C33H35NO3. Calculated, %: C
80.29, H 7.15; N 2.84. M 493.64.
Transamination of enaminodiketones IIIa, IIIe
and IIIi. To a solution of 2 mmol of a enamino-
diketone IIIa, IIIe, or IIIi in 25 ml of toluene was
added 2.4 mmol of an amine. The reaction mixture was
refluxed for 6–8 h without access of air moisture,
cooled to room temperature, passed through a thin
layer of silica gel, and evaporated on a rotary eva-
porator. By column chromatography of the residue on
silica gel (ethyl acetate–petroleum ether) respective
enaminodiketone IIIm–IIIo were isolated. Yield 50–
60%.
Hydrolysis of enaminodiketones (IIIc, IIIe, and
IIIk). To a mixture of 10 ml of acetic acid and 2 ml of
concn. hydrochloric acid was added 2 mmol of a
enaminodiketone. The mixture was refluxed for 16 h,
then cooled, 50 ml of water was added, and the
mixture was extracted with 2×50 ml of toluene. The
combined organic solution was washed with water,
2-[(E)-3-(1,3-Benzodioxol-5-yl)-2-methyl-1-(n-
propylamino)-2-propenilydene]-5,5-dimethyl-1,3-
cyclohexane-1,3-dione (IIIm). Yield 52%. Oily
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130
RUBINOV et al.
7. Budnikova, M.V., Zheldakova, T.A., Rubinov, D.B.,
and Mikhal’chuk, A.L., Zh. Obshch. Khim., 2002,
vol. 72, no. 6, p. 1053.
washed with 25 ml of saturated sodium carbonate
solution, dried over magnesium sulfate, passed through
a thin layer of silica gel, and evaporated on a rotary
evaporator. The residue was crystallized from ethyl
acetate–petroleum ether. Yield of chromenediones:
IVb 42%, IVc 40%, IVe 50%.
8. Quick, J. and Oterson, R., Synthesis, 1976, no. 11,
p. 745.
9. Bachmann, W.E., Cava, M.P., and Dreiding, A.S.,
J. Am. Chem. Soc., 1954, vol. 76, no. 21, p. 5554.
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