Condensation of СН-acids with cis-1,4-dichlorobut-2-ene

Article abstract of DOI:10.1134/S1070363217010248

Synthesis of tri- and five-membered carboxylates are discussed. Microwave irradiation has been shown to stimulate the condensation of СН-acids with allyl chlorides. The selectivity of formation of target products was depending on the CH-acid structure. St

Full text of DOI:10.1134/S1070363217010248

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 1, pp. 151–153. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © G.Z. Raskildina, Yu.G. Borisova, E.A. Yakovenko, L.V. Spirikhin, S.S. Zlotskii, 2017, published in Zhurnal Obshchei Khimii, 2017,
Vol. 87, No. 1, pp. 157–159.
LETTERS
TO THE EDITOR
Condensation of СН-Acids with cis-1,4-Dichlorobut-2-ene
G. Z. Raskildina*, Yu. G. Borisova, E. A. Yakovenko, L. V. Spirikhin, and S. S. Zlotskii
Ufa State Petroleum Technological University, ul. Kosmonavtov 1, Ufa, 450062 Russia
*e-mail: graskildina444@mail.ru
Received September 8, 2016
Abstract—Synthesis of tri- and five-membered carboxylates are discussed. Microwave irradiation has been
shown to stimulate the condensation of СН-acids with allyl chlorides. The selectivity of formation of target
products was depending on the CH-acid structure. Structures of the isolated compounds have been confirmed
by 1Н and 13С NMR spectroscopy and chromato–mass spectrometry data.
Keywords: СН-acid, allyl chloride, microwave irradiation, gem-disubstituted vinylcyclopropane, cyclopentene-
carboxylate, С-alkylation
DOI: 10.1134/S1070363217010248
We have lately studied the alkylation of СН-acids
with allyl chlorides and chloromethyl-gem-dichloro-
cyclopropanes, followed by the reduction of obtained
malonates into polychlorinated cyclopropanecar-
boxylic acids [1, 2]. Extending these studies, we have
shown [3] that diethyl malonate interacts with cis-1,4-
dichlorobutene-2 in alkaline medium under the phase-
transfer catalysis conditions to form mono- and gem-
disubstituted malonates.
microwave irradiation (Scheme 1). The reactions
afforded the target products 3a–3c as well as their
derivatives of the cyclopentane series 4a–4c and gem-
disubstituted vinylcyclopropanes 5a–5c.
The microwave irradiation favored likely the elimina-
tion of chloride anion from compounds 3a–3c giving
the primary cation A that underwent reversible allyl
rearrangement to afford the secondary cation B. The
intramolecular attack of cations A and B at the polar
C–H bonds resulted in the formation of cyclopentenes
4a–4c and vinyl-gem-disubstituted cyclopropanes 5a–
5c, respectively (Scheme 2).
It is known that microwave irradiation can
stimulate the reactions occurring under conditions of
phase-transfer catalysis and affect the products
structure [4]. We performed the reactions of pentane-
2,4-dione 1a, acetoacetic ester 1b, and diethyl
malonate 1c with cis-1,4-dichlorobut-2-ene 2 under
Compounds 5a–5c were detected in the products of
alkylation of СН-acids 1a–1c with 2,3-dichlorobut-1-
Scheme 1.
O
O
O
O
O
O
O
O
MBU
+
+
Cl
Cl
R1
R2
R1
R2
R1
R2
R1
R2
2
4a−4c
5a−5c
1a−1c
Cl
3a−3c
O
O
+ Cl
R1
R2
Cl
6
1a−1c
R1 = R2 = CH3 (1a); R1 = C2H5O, R2 = CH3 (1b); R1 = R2 = C2H5O (1c).
151

152
RASKILDINA et al.
Selectivity of formation of compounds 4a–4c and 5a–5ca
1–2 h. After the reaction was complete the mixture was
poured into water, extracted with methylene chloride,
dried over Na2SO4, and evaporated. The residue was
distilled in a vacuum or purified by chromatography of
silica gel (1c, eluent: benzene–ethyl acetate, 8 : 2).
Conversion,
CH-Acid
Yield of the products, %
%
1а
1b
1c
65
4а (12%)
4b (25%)
4c (49%)
5а (37%)
5bb (25%)
5c (21%)
75
90
3-[(2Z)]-4-Chlorobut-2-enylpentane-2,4-dione
1
(3a). Yield 2.2 g (12%), bp 132°С (5 mmHg). Н
a
NMR spectrum, δ, ppm (J, Hz): 2.25 s (6Н, СН3СО),
2.40–2.45 m (2Н, СН2СН), 4.10–4.15 m (1Н, СНСН2),
4.60 d.d (2Н, СН2Cl, 2J = 10.0, 3J = 7.0), 5.30–5.60 m
(2Н, СН=СН). 13C NMR spectra, δС, ppm: 26.37
(СНСН2), 26.39 (СН3СО), 37.68 (С), 73.16 (СНСН2),
127.92 (СН=СН), 205.06 (С=О). Mass spectrum, m/e
(Irel, %): 188 (1) [M]+, 109 (10), 91 (5), 67 (7), 43 (100).
Molar ratio of 1 : 2 : K2CO3 = 0.1 : 0.15 : 0.1, acetonitrile as
solvent, 10 wt % of e catalyst, microwave irradiation.
Mixture of cis and trans isomers.
b
enes 6 by means of chromato–mass spectrometry
which gave another confirmation of the suggested
scheme of the three-membered ring formation.
Ethyl (4Z)-2-acetyl-6-chlorohex-4-enoate (3b).
Yield 5.5 g (25%), bp 151°C (5 mmHg). Н NMR
It should be noted that dichloride 2 reacts with
malonic acid dinitrile in the presence of alkali metals
alcoholates with exclusive formation of 2-vinyl-gem-
dicyanocyclopropane [5], whereas the cyclopentane 4c
was the major product of the alkylation of diethyl
malonate 1c under similar conditions.
1
spectrum, δ, ppm (J, Hz): 1.20 s (3Н, СН3СО), 1.95 s
3
(3Н, СН3CH2), 2.60 d.d (1Н, СН2СН, 2J = 12.6, J =
2.6), 2.90 d.d. (1Н, СН2СН, 2J = 12.6, 3J = 2.6), 3.45–
3.50 m (1Н, СНСН2), 4.30 m (2Н, СНСН2), 4.40 d
2
(2Н, СН2Сl, J = 8.5), 5.40–5.50 m (1Н, СН=СН),
5.80–5.90 m (1Н, СН=СН). 13C NMR spectrum, δС,
ppm: 13.96 (СН3СО), 23.05 (СН2СН), 29.67
(СН3CH2), 38.43 (СН2Сl), 59.41 (СНСН2), 61.43
(СН3CH2), 129.55 (СН=СН), 170.37 (С=О), 202.73
(С=О). Mass spectrum, m/e (Irel, %): 218 (1) [M]+·, 139
(100), 121 (5), 111 (35), 109 (25), 93 (35), 83 (5), 67
(55), 55 (5), 41 (100).
The selectivity of formation of three- (5a–5c) and
five-membered (4a–4c) compounds was determined by
the CH-acid structure (see table). The decrease in the
CH-acid activity resulted in the increased region-
selectivity of the formation of the cyclopropane
fragment. Evidently, the slower interaction of cations
A with СН-acid favored complete equilibration of the
allyl rearrangement yielding cations B.
Cyclopent-3-enepentane-2,4-dione (4a). Yield 5.6 g
1
Physicochemical parameters of compounds 3c and
4c coincided with the reference data [3].
(37%), bp 105°С (10 mmHg). Н NMR spectrum, δ,
ppm (J, Hz): 2.15 s (6Н, СН3СО), 2.90 s (4Н, СН2СН),
2
3
13
5.30 d.d (СН=СН, J = 3.4, J = 2.3). C NMR spec-
trum, δС, ppm: 26.37 (СН3СО), 32.46 (СН2СН), 37.68
(С), 127.90 (СН=СН), 206.06 (С=О). Mass spectrum,
m/e (Irel, %): 152/0 (1) [M]+·, 109 (35), 67 (20), 43
(100), 39 (10).
Synthesis of substituted carboxylates (general proce-
dure). A mixture of 0.1 mol of СН-acid 1, 0.15 mol of
1,4-dichlorobut-2-ene 2 or 3,4-dichlorobut-1-ene 6,
0.1 mol of K2CO3, 80 mL of anhydrous acetonitrile,
and 10 wt% of triethylbenzylammonium chloride was
stirred at 60°С during 6 h. In the case of microwave-
assisted synthesis, the reaction duration was reduced to
Ethyl 1-acetylcyclopent-3-ene-1-carboxylate (4b).
1
Yield 4.5 g (25%), bp 101°C (5 mmHg). Н NMR
spectrum, δ, ppm (J, Hz): 1.25 s (3Н, СН3СО), 2.30 s
(3Н, СН3CH2), 2.90 s (4Н, СН2СН), 4.10–4.15 m (2Н,
Scheme 2.
2
3
СН2CO), 5.80 d.d (2Н, СН=СН, J = 3.5, J = 1.6).
13C NMR spectrum, δС, ppm: 14.07 (СН3СО), 26.92
(СН3CH2), 33.47 (СН2СН), 62.28 (СН2CO), 63.38
(С), 132.79 (СН=СН), 202.49 (С=О). Mass spectrum,
m/e (Irel, %): 182 (1) [M]+·, 139 (35), 121 (35), 109 (9),
94 (25), 67 (55), 66 (33), 55 (5), 43 (100).
O
O
O
O
MBU
_Cl−
3a_3c
R1
R2
R1
R2
H
H
+
+
A
B
2-Vinylcyclopropylpentane-2,4-dione (5a). Yield
7.4 g (49%), bp 98°С (10 mmHg). 1Н NMR spectrum,
δ, ppm (J, Hz): 1.50 d.d (1Н, СН2СН, J = 8.8, J =
_H+
_H+
2
3
4a−4c
5a−5c
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153
CONDENSATION OF СН-ACIDS WITH cis-1,4-DICHLOROBUT-2-ENE
2
3
7.3), 1.80 d.d (1Н, СН2СН, J = 8.8, J = 7.3), 2.10 s
(6Н, СН3СО), 2.60–2.65 m (1Н, СН2СН), 5.12–5.15
m (1Н, СН=СН2), 5.27 m (2Н, СН=СН2). 13C NMR
spectrum, δС, ppm: 20.27 (СН2СН), 26.92 (СН3СО),
30.84 (СН2СН), 37.69 (С), 118.90 (СН=СН2), 132.82
(СН=СН2), 202.49 (С=О). Mass spectrum, m/e (Irel,
%): 152 (1) [M]+·, 137 (5), 109 (20), 43 (100), 39 (10).
column, temperature 50–280°С with a heating rate of
8 deg/min, detector temperature 250°С, evaporator
temperature 300°С). Chromato–mass spectra were
recorded using Fisons (quartz capillary column DB
560 50 m) and Focus instruments with a Finingan
DSQII mass spectrometric detector (ion source tem-
perature 200°С, injector temperature 50–270°С, heating
at a rate 10 deg/min, a ThermoTR-5MS 50×2.5×
10–4 m column, 0.7 mL/min of helium flow). Mass
spectra were recorded under EI conditions. NMR
spectra were recorded using a Bruker AVANCE-400
spectrometer (solutions in CDCl3).
Ethyl 1-acetyl-2-vinylcyclopropanecarboxylate (5b).
Yield 8.7 g (48%), bp 90°C (5 mmHg). Н NMR
spectrum, δ, ppm (J, Hz): 1.25 s (3Н, СН3СО), 1.50
1
2
3
d.d (1Н, СН2СН, J = 4.6, J = 1.1), 1.82 d.d (1Н,
СН2СН, 2J = 4.6, 3J = 1.1), 2.15 s (3Н, СН3CH2), 2.55–
2
2.62 m (1Н, СН2СН), 4.10 d (2Н, СН3CH2, J = 1.0),
ACKNOWLEDGMENTS
5.10 m (1Н, СН=СН2), 5.25 m (2Н, СН=СН2). 13C
NMR spectrum, δС, ppm: 14.20 (СН3CH2), 20.09
(СН2СН), 25.90 (СН3CH2), 30.53 (СН), 37.91 (С),
61.66 (СН3СО), 118.33 (СН=СН2), 132.79 (СН=СН2),
172.91 (С=О), 201.04 (С=О). Mass spectrum, m/e (Irel,
%): 182 (1) [M]+·, 139 (30), 121 (40), 109 (10), 94
(30), 66 (35), 43 (100), 39 (4).
This work was financially supported by the Grant
Council of the President of the Russian Federation
(project SP-1960.2015.4 for 2015–2017) and Ministry
of Education and Science of the Russian Federation in
the scope of basic part of the governmental contract.
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