Synthesis of ethyl polychlorocyclopropanoates

Full text of DOI:10.1134/S1070363216080296

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 8, pp. 1954–1956. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © Yu.G. Borisova, G.Z. Raskildina, S.S. Zlotskii, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 8, pp. 1381–1383.
LETTERS
TO THE EDITOR
Synthesis of Ethyl Polychlorocyclopropanoates
Yu. G. Borisova, G. Z. Raskildina*, and S. S. Zlotskii
Ufa State Petroleum Technical University, ul. Kosmonavtov 1, Ufa, 450062 Russia
*e-mail: graskildina444@mail.ru
Received February 8, 2016
Keywords: gem-dichlorocyclopropylmalonate, polychlorocyclopropanoic acid, decarboxylation, carbenation
DOI: 10.1134/S1070363216080296
We have earlier shown [1] that alkylation of diethyl
malonate with chloromethyl-gem-dichlorocyclopropanes
affords cyclopropylmalonates 1a–1c with high selec-
tivity. Extending this study, we used compounds 1a–1c
to obtain ethyl polychlorocyclopropanoates 2a–2c which
are of interest for creation of bioactive materials [2].
containing malonates 1a–1c was advantageous for
obtaining esters 2a–2c.
Note that the studied conversion of trans-1,3-
dichloropropene derivatives 1c and 3c proceeded with
preservation of the trans-configuration. That was
indicated by the presence of a doublet signal of C3H
proton of cyclopropane ring at 3.20 ppm (3J = 6.2 Hz)
in the spectrum of compound 2c, whereas the same
proton signal of cis-isomer is observed in weak field
Decarboxylation of malonates 1a–1c was perf-
ormed via a known method [3] in the presence of
lithium chloride in DMSO medium at 140°C. The yield
of desired products 2a–2c was 80–90% (Scheme 1).
3
(3.57 ppm, J = 8.0 Hz) [5]. It is known [5] that the
C2H proton trans-positioned to electronegative substi-
tuent resonates in stronger field than that in cis-isomer.
Authentic synthesis of compounds 2a–2c was based
on dichlorocarbenation of ethyl esters 3a–3c obtained
via decarboxylation of the corresponding alkenyl-
malonates 4a–4c [4].
13
The C NMR spectrum of compound 2c contained
the signal of C3 carbon atom at 44.96 ppm, typical of
trans-substituted cyclopropanes, while in cis-isomer
this atom resonates in strong field (34.45 ppm) [5].
Comparison of two synthesis approaches showed
that the decarboxylation of polychlorocyclopropane-
Scheme 1.
O
O
O
R1
O
O
7
4
1
R2
5
3
R2
O
O
R2
8
2
R1
R1
Cl
Cl
Cl
O
Cl
1a_1c
2a_2c
3a_3c
O
O
O
R2
R1
4a_4c
O
R1 = H (1a, 1c, 2а, 2c, 3а, 3c, 4а, 4c), СН3 (1b, 2b, 3b, 4b); R2 = Н (1а, 1b, 2а, 2b, 3а, 3b, 4а, 4b), Cl (1c, 2c, 3c, 4c).
1954

1955
SYNTHESIS OF ETHYL POLYCHLOROCYCLOPROPANOATES
The starting cyclopropylmalonates 1a–1c were
prepared via C-alkylation of diethyl malonate with the
corresponding chloroalkenes as described in [1].
(5), 141(55), 143 (21), 145 (5), 125 (21), 115 (60), 117
(24), 119 (3), 99 (40), 101 (15), 103 (2).
Ethyl 3-(2,2,3-trichlorocyclopropyl)propanoate (2c).
Yield 45% (a), 35% (b), bp 130°C (4 mmHg), Rf 0.52.
1H NMR spectrum, δ, ppm (J, Hz): 1.30 t (3H, C8H3,
3J = 7.0), 1.75–1.80 m (1H, C3H), 1.85–1.95 m (2H,
C4Hа, C4Hb), 2.40–2.55 m (2H, C5Hа, C5Hb), 3.20 d
(1H, C3H, 3J = 6.2), 4.75 q (2H, C7Hа, C7Hb, 3J = 7.2).
13C NMR spectrum, δC, ppm: 14.21 (C8H3,), 24.42
(C4H2), 32.27 (C5H2), 39.01 (C3H), 44.96 (C1H), 60.79
(C7H2), 63.40 (C2Cl2), 172.22 (C3=О). Mass spectrum,
m/e (Irel, %): 245 (<1) [M]·+, 209 (78), 211 (45), 213
(8), 181 (40), 183 (15), 185 (3), 163 (9), 165 (6), 167
(1), 135 (100), 137 (30), 139 (11), 99 (31), 101 (9),
103 (4).
Synthesis of polychlorocyclopropanoic acids
esters (2a–2c). a. Decarboxylation of cyclopropyl-
malonates 1a–1c. A mixture of 0.01 mol of the
corresponding malonate 1, 0.03 mol (1.26 g) of lithium
chloride, 0.02 mol of (0.36 g) of water, and 10 mL of
DMSO was stirred at 140°C for 8 h. Upon completion
of the reaction (monitoring by GLC), the mixture was
cooled to room temperature, washed with water, and
extracted with chloroform. The organic layer was dried
over sodium sulfate and evaporated. The residue was
distilled in vacuum.
b. Dichlorocarbenation of compounds 3a–3c. A
mixture of 0.01 mol of the corresponding ester 3, 30 mL
of chloroform, 32 g of 50% NaOH solution, and
0.001 mol (0.23 g) of triethylbenzylammonium chloride
was stirred at 55°C for 4–11 h until the conversion of
the substrate was complete. After that, the mixture was
washed with water to neutral reaction. The organic
layer was dried over calcium chloride and evaporated.
The residue was subject to chromato-graphy on silica
gel eluting with a 9 : 1 hexane–diethyl ether mixture.
Synthesis of compounds 3a–3c. A mixture of
0.01 mol of the corresponding malonate 4, 0.03 mol
(1.26 g) of lithium chloride, 0.02 mol (0.36 g) of
water, and 10 mL of DMSO was stirred at 130 (3a) or
140°C for 4–8 h. After the reaction was complete
(monitoring by GC), the reaction mixture was cooled
to room temperature, washed with water, and extracted
with chloroform. The organic layer was dried over
sodium sulfate and evaporated. The residue was
distilled in vacuum.
Ethyl 3-(2,2-dichlorocyclopropyl)propanoate (2a).
Yield 80% (a) 59% (b), bp 120°C (9 mmHg), Rf 0.51.
1H NMR spectrum, δ, ppm (J, Hz): 1.15 t (1H, C8H3,
3J = 6.8), 1.30–1.35 m (1H, C3H), 1.60–1.65 m (2H,
C1Hа, C1Hb) 1.85–1.90 m (2H, C4Hа, C4Hb), 2.50–2.55
Ethyl pent-4-enoate (3а). Yield 90%, bp 120°C
(760 mmHg). 1H NMR spectrum, δ, ppm (J, Hz): 1.20
t (3H, C7H3, 3J = 7.1), 2.35 m (4H, C2H2, C3H2), 4.15 q
3
(2H, C6H2, J = 7.1) 5.05–5.10 m (2H, C5H2), 5.85–
m (2H, C5Hа, C5Hb), 4.00 q (2H, C7H2, J = 7.1). C
NMR spectrum, δC, ppm: 14.23 (C8H3), 25.77 (C4H2),
26.70 (C1H2), 29.88 (C5H2), 33.03 (C3H), 60.52
(C7H2), 60.98 (C2Cl2), 172.22 (C6=О). Mass spectrum,
m/e (Irel, %): 211 (<1) [M]·+, 164 (54), 166 (23), 168
(10), 136 (23), 138 (10), 140 (6), 122 (60), 124 (23),
126 (16), 111 (41), 113 (20), 115 (7), 88 (100), 90
(21), 92 (5).
5.90 m (1H, C4H). 13C NMR spectrum, δC, ppm: 14.35
(C7H3), 29.31 (C3H2), 34.64 (C2H2), 60.05 (C6H2),
115.39 (C5H2), 137.98 (C4H), 172.10 (C1=О). Mass
spectrum, m/e (Irel, %): 128 (10) [M]·+, 100 (5), 83
(30), 56 (27), 55 (100).
3
13
Ethyl 4-methylpent-4-enoate (3b). Yield 80%, bp
1
93°C (40 mmHg). H NMR spectrum, δ, ppm (J, Hz):
3
1.25 t (3H, C7H3, J = 7.1), 1.72 s (3H, C8H3), 2.30 d
3
Ethyl 3-(2,2-dichloro-1-methylcyclopropyl)pro-
panoate (2b). Yield 90% (a), 62% (b), bp 123°C
(9 mmHg), Rf 0.50. 1H NMR spectrum, δ, ppm (J, Hz):
(2H, C2H2, J = 8.6), 2.40 d (2H, C3H2, 3J = 8.6), 4.00
3
q (2H, C6H2, J = 7.2), 5.75–5.80 m (2H, C5H2). 13C
NMR spectrum, δC, ppm: 14.21 (C7H3), 22.47 (C8H3),
32.66 (C2H2, C3H2), 60.29 (C6H2), 110.31 (C5H2),
144.13 (C4), 173.28 (C1=О). Mass spectrum, m/e (Irel,
%): 143 (<2) [M]·+, 118 (34), 93 (100), 89 (39), 51
(31).
3
1.10 t (3H, C8H3, J = 6.9), 1.30 s (3H, C9H3), 1.95–
2.10 m (2H, C4Hа, C4Hb), 2.50–2.55 m (2H, C5Hа,
3
C5Hb), 4.10 q (2H, C7Hа, C7Hb, J = 7.2). 13C NMR
spectrum, δC, ppm: 14.20 (C8H3), 19.53 (C9H3), 29.35
(C5H2), 30.40 (C4H2), 31.92 (C1H2), 35.10 (C3), 60.50
(C7H2), 65.50 (C2Cl2), 172.64 (C6=О). Mass spectrum,
m/e (Irel, %): 225 (<1) [M]·+, 189 (36), 191 (13), (193)
Ethyl (2Е)-5-chloroprop-4-enoate (3c). Yield
82%, bp 81°C (40 mmHg). 1H NMR spectrum, δ, ppm
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

1956
BORISOVA et al.
3
(J, Hz): 1.25 t (3H, C7H3, J = 7.1), 2.35–2.60 m (4H,
C2H2, C3H2), 4.15 q (2H, C6H2, 3J = 7.2), 5.85–6.10 m
(2H, C5H, C4H). 13C NMR spectrum, δC, ppm: 14.24
(C7H3), 26.23 (C3H2), 33.51 (C2H2), 60.56 (C6H2),
118.43 (C5H), 131.81 (C4H), 172.41 (C1=О). Mass
spectrum, m/e (Irel, %): 127 (<2) [M]·+, 117 (34), 119
(12), 99 (100), 89 (39), 53 (31).
using a Bruker AVANCE-400 (400.13 MHz) spectro-
meter in CDCl3.
AKCNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (project no. 15-13-10034) and the
President of the Russian Federation in the framework
of the support program for young scientists and post-
graduate students (SP-1960.2015.4, 2015–2017).
Chromatographic analyzes were performed using a
HRGS 5300 Mega Series Carlo Erba chromatograph
equipped with a flame ionization detector (carrier gas
helium, flow rate 30 mL min–1, column length 25 m,
temperature range 50–280°C with a programmed
heating at 8 deg min–1, detector temperature 250°C,
and evaporator temperature 300°C). Chromatography–
mass spectra were recorded using a Fisons (capillary
column DB 560) and Focus instruments equipped with
a Finnigan DSQ II mass spectrometry detector (ion
source temperature 200°C, direct injection temperature
50–270°C, heating rate 10 deg min–1, column Thermo
TR-5MS, 50 × 2.5 × 10–4 m, helium flow rate –
0.7 mL/min). Mass spectra were registered in electron
impact ionization mode. NMR spectra were recorded
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