SYNTHESIS OF gem-DICHLOROCYCLOPROPYLMETHYLMALONATES
201
dichlorocyclopropanes are less significant in the
reactions of O- and N-alkylation [1, 5]. As shown in
6], in some cases the use of microwave irradiation can
Synthesis of substituted malonic esters
Reaction
products
Yield,
%
[
Reactants
Т, °С Time, h
increase the yield and reduce the reaction time of C-
alkylation (Scheme 1).
II
Vа
Vb
Iа
50
80
50
7
16
7
IVа
IVb
IIIа
IIIb
IIIа
IIIb
87
82
35
30
86
75
General procedure of C-alkylation of diethyl
malonate (II). A mixture of 0.06 mol of diethyl
malonate II, 0.13 mol of chloroderivative I or V,
Ib
3
5 mL of acetonitrile, 0.006 mol of a phase transfer
IVа
CНCl
3
catalyst (TEBAC) and 0.245 mol of K CO was stirred
2
3
IVb
at 80°C for 16 h [in the case of compounds Va and Vb
the mixture was stirred at 50°C for 7 h]. The reaction
mixture was poured into water, extracted with hexane,
dried over Na SO and concentrated. The residue was
2
4
distilled in a vacuum.
Carbenylation of diethyl 2-allylmalonate IVa
and diethyl 2-(2-methylprop-2-en-1-yl)malonate
IVb. To a mixture of 0.1 mol of allylmalonate IV,
Diethyl [(2,2-dichlorocyclopropyl)methyl]malonate
(IIIa). Yield 35%, bp 170°C (5 mmHg). Physico-
2
.5 mol of chloroform, and 0.004 mol of a phase
chemical constants and parameters of NMR and mass
spectra correspond to the literature data [6].
transfer catalyst (TEBAC) was added within 1 h 200 g
of 50% NaOH solution under vigorous stirring and
heating to 50°C. The reaction mixture was stirred for
Diethyl [(2,2-dichloro-1-methylcyclopropyl)methyl]-
malonate (IIIb). Yield 30%, bp 190°C (5 mmHg).
Physicochemical constants and parameters of NMR
and mass spectra correspond to the literature data [6].
7
h at 50°C, then washed with water and evaporated.
The residue was distilled in a vacuum.
Chromatographic analysis of the reaction products
was performed on a HRGS 5300 MegaSeries Carlo
Erba chromatograph equipped with a flame ionization
detector (carrier gas helium, flow rate 30 mL min ,
the column length 25 m, the temperature 50–280°C,
programmed heating at a rate 8 deg min , detector
temperature 250°C, evaporator temperature 300°C).
Gas chromatography-mass spectra (electron impact
ionization) were recorded on a Fisons (quartz capillary
column DB 560) and Focus instruments equipped with
mass spectrometric detector Finingan DSQ II (the ion
source temperature 200°C, the temperature of the
direct input 50–270°C, heating rate 10 K min ,
column Thermo TR-5MS, 50 × 2.5 × 10 m, helium
flow rate 0.7 mL min ). NMR spectra were registered
on a Bruker AVANCE-400 (400.13 MHz) spectro-
meter.
Diethyl 2-allylmalonate (IVa). Yield 87%, bp 85°C
1
–
1
(
5 mmHg). Н NMR spectrum (CDCl ), δ, ppm (J,
3
5
7
8
Hz): 0.85 m (6H, C H , C H ), 2.60 m (2H, C H ,
C H ), 3.30 m (1H, C H), 3.90 m (4H, C H , C H ,
C H , C H ), 4.89 d (1H, C H , J 1.6, J 17.1), 5.00
d.d (1H, C H , J 10.2), 5.71 m (1Н, C H). C NMR
3
3
a
8
2
4
4
–
1
b
a
b
6
6
10
2
3
a
b
a
1
0
3
9
13
b
5
7
spectrum (CDCl ), δ , ppm: 13.89 (C Н , C Н ), 32.21
3
С
3
3
8
2
4
6
(
(
C Н ), 51.34 (C Н), 61.08 (C Н , C Н ), 116.42
2 2 2
1
0
9
1
3
C Н ), 137.90 (C Н), 168.26 (C =О, C =О). Mass
2
spectrum, m/e (I , %): 200 (3), 169 (21), 141 (100),
rel
–
1
1
23 (72), 112 (28), 95 (78), 55 (42), 41 (18).
–4
–
1
Diethyl 2-(2-methylprop-2-en-1-yl)malonate (IVb).
1
Yield 82%, bp 89°C (5 mmHg). Н NMR spectrum
5
7
(
1
3
CDCl ), δ, ppm (J, Hz): 0.89 m (6H, C H , C H ),
3
3
3
1
1
8
8
3
.50 s (3H, C H ), 2.70 d (2H, C H , C H , J 7.6),
3 a b
2
4
4
6
.60 t (1H, C H), 3.88 m (4H, C H , C H , C H ,
a
b
a
ACKNOWLEDGMENTS
6
10
10
3
13
C H ), 4.74 d (2H, C H , C H , J 19.5). C NMR
b
a
b
5
7
spectrum (CDCl ), δ , ppm: 14.35 (C Н , C Н ), 22.56
3
С
3
3
This work was supported by the Ministry of
Education and Science of Russia in the frame of the
basic part of the governmental contract “Development
and creation of innovative highly effective methods of
obtaining heteroanalogs of alkanes, cycloalkanes and
syntheses based on them” and the Foundation for
1
1
8
2
4
(
C Н ), 37.23 (C Н ), 51.21 (C Н), 61.53 (C Н ,
3 2 2
6
10
9
1
C Н ), 112.76 (C Н ), 142.56 (C Н), 169.25 (C =О,
C =О). Mass spectrum, m/e (I , %): 214 (<1) [M] ,
2
2
3
•+
rel
1
69 (13), 141 (100), 123 (61), 112 (34), 95 (82), 55
(
15), 41 (10).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 1 2015