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KiMYA PROBLEML9RÎ № 1 2018
ISSN 2221-8688
UDC 547.789
THE SYNTHESIS AND MOLECULAR CRYSTALLINE STRUCTURE OF ETHYL-1-ACETYL-3-(4-CHLOROPHENYL) -2,2-DICYANOCYCLOPROPANE CARBOXYLATE
A.I. Ismiyev, K.E. Hajiyeva, R.K. Askerov, A.M. Maharramov
Baku State University
Z.Xalilov str., 23, Baku AZ1148, Azerbaijan Republic, e-mail: [email protected]
Three-component condensation reaction of malonodinitrile, 4-chloro- benzaldehyde and ethyl 4-chloro-3-oxobutanoate has been analyzed to establish that in the presence of NaOH base, the reaction proceeds by Knoevenagel-Michael-Perkin cascade carbocyclization to form ethyl-1-acetyl-3-(4-chlorophenyl)-2,2-dicyanocyclopropane carboxylate. The structure of the reaction product examined through with X-ray analysis
Keywords: three-component condensation reactions, malonodinitrile, cyclopropane carboxylates.
INTRODUCTION
It should be noted that multicomponent reactions, involving simultaneous interaction of, at least, three compounds and forming one final product together with parts of all the initial components, contribute to the development of new methods to synthesize polyfunctional carbo- and hetero-cycles with useful properties. Typically, the developed multicomponent reactions proceed in one-step ("one-pot"), by using commercially available substrates and reagents, which significantly reduce the cost of final products as well as harmful environmental consequences of the
synthesis occurrence [1-5]. A large number of multicomponent reactions have been discovered, analyzed and described.
Among variety of multicomponent reactions, of particular interest are reactions that include compounds like malonodinitrile, alkyl cyanoacetates, etc. with active methylene group. These compounds together with nitrile groups have great synthetic potentials and through changing the structure of other reagents that react with them it is possible to synthesize many structured complex carbo and heterocyclic compounds [6-11].
RESULTS
The current research work examined the three-component condensation reaction based on the interaction of malonodinitrile (1), 4-chlorobenzaldehyde (2) and ethyl 4-chloro-3-oxobutanoate (3), which has not been described in the literature. As a base
component of reaction, an equimolecular amount of NaOH was used. It revealed that 72% of ethyl ethyl-1 -acetyl-3 -(4-chlorophenyl)-2,2-dicyanocyclopropane carboxylate (4) was obtained as a result of reaction (Scheme 1).
CN
Cl
O O O
+ NC^^CN +
H H3C Y OC2H5
I II Cl
III
NC
NaOH
Cl
COOC2H5
C—CH3
// 3 O
IV
Scheme 1. The reaction between malonodinitrile, 4-chlorobenzaldehyde and ethyl 4-
chl oro-3 -oxobutanoate.
A.I. ISMIYEV et al.
59
The reaction product is, perhaps, carbocyclization which proceeds by means of Knoevenagel-Michael-Perkin cascade step-by-step mechanism (Scheme 2).
Knevenagel
NC H ®OH NC
X
NC' H -H2O NC
,)e <AC
NC NC
Mixael
OO
r\r H
Cr H^ -H2O NC
"OH
OO
H3C "*OC9H,
NC
Perkin
2 5 ©
OH
-H2O
OO
y\
NC
H4-C1
OO
OC2H5
OO
6H4-C1 C1C
H4-C1
CN
NC
C1-C
/ O'
COOC2H5 CH3
Scheme 2: Proposed mechanism of the reaction.
To prove the molecular structure of the compound synthesized, we used X-ray diffraction method. Single crystals for X-ray diffraction analysis were obtained by crystallization of compound IV from ethanol.
Note that the crystals are monoclinic: a=8.176(3) Â, b=10.443(4) Â, c=18.375(7)Â, a=B=y=90°, V=1568.8(10) Â3, spatial group P21 21 21, Z=4. The structure deciphered by the direct method and specified by the least
squares in respect of F in the anisotropic approximation for non-hydrogen atoms. The coordinates of the remaining H atoms are calculated geometrically and specified in the model of the "rider."
All calculations were carried out through the use of SHELXTL software package [12].
A perspective view of the molecule IV together with the numeration of non-hydrogen atoms shown in Fig. 1.
Figure 1. A perspective view of molecule IV together with the numeration of non-hydrogen atoms
H
25
C2H5
In the molecular structure IV, there is a angle between the plane of phenyl and the chiral center where carbon atom C3 crystallizes cyclopropane fragment is 87.27 ° in the space group P21 21 21. Note that the
Table 1. Basic crystallographic data anc specifying parameters of compound IV
Parameters IV
Empirical formula C16H13Cl2N2O3
Molecular weight, M 316.73
Temperature, K 296
Dimensions of the crystal, mm3 0.220 x 0.170 x 0.160
Shingonia Monoclinic
Spatial group P2i2i2i
a, A 8.176(3)
b, A 10.443(4)
c, A 18.375(7)
a, deg. 90.00
P, deg. 90.00
Y, deg. 90.00
V, A3 1568.8(10)
Z 4
d(calc.), g/sm H, mm-1 1.341
0.257
F(000) 656
Data collection area for 0, deg 25
Measured reflections 6525
Independent reflections 1301
Number of parameters to be specified 199
R 1 [I>2o(I)] 0.2096
wR2(all data) 0.5963
GOOF 1.009
Tmin; Tmax 0.355; 0.746
Residual electron density (pmin/pmax)/e.A-3 -0.901 / 1.484
The monitoring of reaction as well as the purity of the synthesized compound were specified by thin layer chromatography on Sulifol plates (eluent acetone-hexane 1: 1) and subsequent evaporation with iodine vapor (UV detector).
The infrared spectrum was recorded on Fourier spectrometer Varian 3600 FT-IR Excalibur Series in KBr tablets.
1 13
H and С NMR spectra was recorded on Brucker AC-300 devices (300 and 75 MHz, respectively).
TAL PART
Note that the X-ray diffraction analysis of compound IV was carried out on a Brucker SMART APEXII CCD diffractometer (MoKCE - radiation, graphite monochromator, (p- and ro-scanning). Measured 6525 diffraction reflections, 9max = 25 Intensities of symmetrically equivalent reflections were averaged. As a result of averaging, 2755 independent diffraction reflections with R (int) = 0.0664 were obtained to implement decoding and specifying the crystal structure (Table 1).
A.I. ISMIYEV et al.
61
Ethyl-1-acetyl-3-(4-chlorophenyl)-2,2-dicyanocyclopropane carboxylate (IV)
Added to a solution of 1.40 g (10 mmol) 4-chlorobenzaldehyde (I) and 0.66 g (10 mmol) malonodinitrile (II) in 15 ml of ethanol were 0.3 g (10.71 mmol) 1 ml of aqueous solution of KOH, and then mixed. Also, 1.64 g (10 mmol) of ethyl 4-chloro-3-oxobutanoate (III) was added to the rapidly formed precipitated solution. After mixing it at room temperature for 6 hours, the reaction mixture was rinsed with water. The formed precipitate was filtered off, dried and
recrystallized from ethanol. The yield of reaction is 2.2 grams (69%), m.p =1300C
IR spectrum (y, sm-1): 2200, 2250 (CN), 1720 (С=О), 1650(C=0)
1H spectrum (DMS0-d6, ppm ): 1,29 (3H,t,CH3), 2.1(1H,s,CH), 4.2(2H, m, O-CH2), 7.24(2H,CH,arom), 7.41(2H,CH, arom)
13C spectrum (DMS0-d6): 12, 15, 20, 28, 62, 109, 110, 115, 126, 127, 128, 129, 131, 143,163
REFERENCES
1. Simon C., Constantieux T., Rodriguez J. Utilisation of 1,3-Dicarbonyl Derivatives in Multicomponent Reactions. European Journal of Organic Chemistry. 2004, no. 24, pp. 49574980
2. Ganem B. Strategies for Innovation in Multicomponent Reaction Design. Acc. Chem. Res. 2009, vol. 42, no. 3, pp. 463-472.
3. Hugel H. Microwave Multicomponent Synthesis. Molecules. 2009, vol. 14, no.12, pp. 4936-4972.
4. Eckert H. Diversity Oriented Synthesis of Conventional Heterocycles by Smart Multicomponent Reactions (MCRs) of the Last Decade. Molecules. 2012, vol. 17, no. 9, pp. 1074-1102.
5. Chebanov V.A., Desenko S.M. Multicomponent heterocyclization reactions with controlled selectivity. Himija geterociklicheskih soedinenij - Chemistry of Heterocyclic Compounds. 2012, no. 4, pp. 607-625. (In Russian).
6. Litvinov V.P. Recyclisation of carbo-and heterocyclic compounds involving malononitrile and its derivatives. Uspehi himii - Russian Chem. Rev. 1999, vol. 68, no. 1, pp. 45-60.
7. Shestopalov A.M., Shestopalov A.A., Rodinovskaya R.A. Multicomponent reactions of carbonyl compounds and derivatives of
cyanoacetic acid: synthesis of carbo-and heterocycles. Synthesis. 2008, no. 1, pp.1-25.
8. Allen EE., Zhu C., Panek J.S. et al. Multicomponent Condensation Reactions via ortho-Quinone Methides. Organic Letters. 2017, vol.19, no. 7, pp. 1878-1881.
9. Kamalraja J., Perumal P.T. Microwave assisted InCl3 mediated regioselective synthesis of highly functionalized indolylpyran under solvent-free condition and its chemical transformation to indolyltriazolylpyran hybrids. Tetrahedron Letters. 2014, no. 55, 3561-3564.
10. Ismiev A.I., Guliyeva N.A., Nagiyev F.N., Magerramov A.M. Synthesis of new nitrogen-containing derivatives of diethyl 4-hydroxy-4-methyl-2-aryl-6-oxocyclohexane-1,3-dicarboxylates. Kimya Problemleri - Chemical Problems. 2016, no. 1, pp. 74-79. (in Azerbaijan).
11. A.I.Ismiev, N.A.Guliyeva, S.I.Nazarov, A.M.Magerramov Three-component condensation reactions of diacetyl substituted ketoles of cyclohexane series with phenacylbromide and thiosemicarbazide. Kimya Problemleri - Chemical Problems. 2015, no. 4, pp. 428-431. (in Azerbaijan).
12. Sheldrick, G. M.: SHELXTL. Structure Determination Software Suite. Version 6.12. Bruker AXS, Madison, Wisconsin, USA 2001.
СИНТЕЗ И МОЛЕКУЛЯРНАЯ КРИСТАЛЛИЧЕСКАЯ СТРУКТУРА ЭТИЛ-1-АЦЕТИЛ-3-(4-ХЛОРОФЕНИЛ)-2,2- ДИЦИАНЦИКЛОПРОПАНКАРБОКСИЛА ТА
А.И. Исмиев, К.Е. Гаджиева, Р.К. Аскеров, А.М. Магеррамов
Бакинский Государственный Университет AZ1148Баку, ул. ЗХалилова, 23; e-mail: [email protected]
Исследована трехкомпонентная реакция конденсации с участием малонодинитрила, 4-хлорбензальдегида и этил-4-хлор-3-оксобутаноата. Установлено, что в присутствии основания NaOH реакция протекает как реакция каскадной карбоциклизации Кневенагеля-Михаэля-Перкина с образованием этил-1-ацетил-3-(4-хлорфенил)-2,2-дицианциклопропан кар-боксилата. Строение продукта реакции установлено методом рентгеноструктурного анализа
Ключевые слова: трехкомпонентные реакции конденсации, малонодинитрил, циклопропанкарбоксилаты
ETiL 1-ASETiL-3-(4-XLORFENiL)-2,2-DiSiANTSiKLOPROPAN KARBOKSiLATINSiNTEZi Vd MOLEKULYAR KRiSTALLiK QURULUgU
A.i. ismiyev, K.E. Haciyeva, R.K. dsgzrov, A.M. M9h9rr9mov
Baki Dövldt Universiteti AZ 1148 Baki, Z.Xdlilov küg., 23; e-mail: [email protected]
Malonodinitril, 4-xlorbenzaldehid vd etil 4-xlor-3-oksobutanoatin i§tiraki ild ügkomponentli kondensld^md reaksiyasi tddqiq edilmi§dir. Мйэууэп edilmi§dir ki, reaksiya NaOH dsasinin i§tirakinda Knevenagel-Mixael-Perkin kaskad karbotsiklld§md reaksiyasi kimi geddrdk etil 1-asetil-3-(4-xlorfenil)-2,2-disiantsiklopropankarboksilatin alinmasi ild ndticdldnir. Reaksiya mdhsulunun qurulu§u rentgen qurulu§ analizi üsulu ild tdsdiq edilmi§dir Agar sözlar : ügkomponentli reaksiyalar, malonodinitril, tsiklopropan karboksilatlar
Received 19.01.2018.
