Catalytic Isomerization of Substituted Vinylcyclopropanes

Article abstract of DOI:10.1134/S0012500819070115

Abstract: The catalytic isomerization of substituted vinyl-gem-dichlorocyclopropanes in the presence of a series of zeolite catalysts has been studied. It has been shown that substituted gem-dichlorocyclopentenes are the sole reaction products. The influence of a number of factors (the type of catalyst, temperature, and reaction time) on the yield of isomerization products has been investigated.

Full text of DOI:10.1134/S0012500819070115

ISSN 0012-5008, Doklady Chemistry, 2019, Vol. 487, Part 1, pp. 192–194. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Doklady Akademii Nauk, 2019, Vol. 487, No. 3.
CHEMISTRY
Catalytic Isomerization of Substituted Vinylcyclopropanes
a,
a
b
a
G. Z. Raskil’dina *, Yu. G. Borisova , A. R. Davletshin , and S. S. Zlotskii
Presented by Academician A.A. Berlin April 12, 2019
Received February 19, 2019
Abstract—The catalytic isomerization of substituted vinyl-gem-dichlorocyclopropanes in the presence of a
series of zeolite catalysts has been studied. It has been shown that substituted gem-dichlorocyclopentenes are
the sole reaction products. The influence of a number of factors (the type of catalyst, temperature, and reac-
tion time) on the yield of isomerization products has been investigated.
DOI: 10.1134/S0012500819070115
The reaction of dichlorocarbene with industrial
Judge by the yield of compounds 2a–2d, 2,2-
dienes results in vinyl-gem-dichlorocyclopropanes in disubstituted olefins 1b and 1c are close in activity to
high yields; these compounds are widely used in the each other and superior to 2-mono derivatives 1a and
synthesis of reagents, oligomers, and polymers [1–5]. 1d (Fig. 1).
In this work, we accomplished for the first time the
By the example of olefin 1c, we found that high
catalytic isomerization of mono-dichlorocarbenylated yield (≥90%) is achieved at 280°C for 1 h and at 230°C
olefins 1a–1d into the corresponding gem-dichlorocy- for 1.5 h (Table 1).
clopropentenes 2a–2d.
We revealed that other industrial zeolite reforming
Vinyl-gem-dichlorocyclopropanes are known to catalysts HY [8] and Tseokar-600 [9] also catalyze
undergo partial or complete dehydrochlorination at isomerization of olefins 1a–1d at 280°C, with zeolite
high temperatures (450–550°C), reaction products HY being equal to SAPO-34, while the yields of com-
contain small amounts (≤ 20%) of gem-dichlorocyclo- pounds 2a–2d in the presence of Tseokar-600 are by
propentenes, which are isomeric to the initial com- factor 1.2–1.5 lower (Fig. 2).
pounds [6].
The low efficiency of Tseokar-600 catalyst is likely
2
To accomplish the isomerization of vinyl-gem- to be due to its low specific surface (320 m /g) as com-
dichlorocyclopropanes 1a–1d, we employed well-
known domestic zeolite SAPO-34 [7], which is used in
industry for alkane and alkene reforming.
2
2
pared with SAPO-34 (630 m /g) and HY (600 m /g).
The presence of Pt atoms on the surface of Tseokar-
6
00 has no effect on the isomerization process.
It was found that the catalytic isomerization of
compounds 1a–1d at 180–280°C for 1 h leads to the
target cyclopentenes 2a–2d in 10–95% yield (selectiv-
ity ≥95%) (Scheme 1).
No transformation of compounds 1a–1d was
observed even at T = 280°C in the presence of silicon
oxide inert under these conditions.
Thus, the heterogeneous catalytic isomerization of
vinyl-gem-dichlorocyclopropanes
is
convenient
method for the selective preparation of gem-dichloro-
cyclopropentenes.
EXPERIMENTAL
Catalysts used in the work were zeolites SAPO-34
Reaction products contain no 5,5-dichloro deriva-
(
produced at the Topchiev Institute of Petrochemical
tives isomeric to cyclopentenes 2a–2d. We explain this
3
Synthesis, Russian Academy of Sciences), HY, and
Tseokar-600 (manufactured in the Salavat Catalyst
fact by the lower strength of the R C–CCl bond (42–
2
3
1
2
4
3 kcal/mol) as compared to the R C–CR R bond
49–50 kcal/mol) in the cyclopropane moiety.
1
(
Table 1. Effect of reaction time on the yield of cyclopentene
c in the presence of SAPO-34 catalyst
2
1
Bond strength was calculated by the M06-2X/MG3S method
[
Zhao, Y. and Truhlar, D.G., J. Chem. Phys. 2006, vol. 125, no. 19,
Yield (%)
p. 194101. https://doi.org/10.1063/1.2370993].
Contact time, h
180°C
230°C
280°C
a
Ufa State Petroleum Technological University,
ul. Kosmonavtov 1, Ufa, 450062 Russia
0
1
1.5
.5
22
38
70
45
65
90
80
95
99
b
Institute of Oil Chemical Processing, Ufa, 450062 Russia
*
e-mail: graskildina444@mail.ru
192

CATALYTIC ISOMERIZATION OF SUBSTITUTED VINYLCYCLOPROPANES
193
Yield, %
00
Yield, %
1
100
90
80
70
60
50
2 3
2
3
2
3
9
8
0
0
1ꢁ 2a
ꢁ 2b
3 ꢁ 2c
ꢁ 2d
1
2
3
− 2a
− 2b
− 2c
2
2
7
6
0
0
3
3
4
2
4 − 2d
5
0
3
4
4
4
3
2
0
0
0
4
3
0
0
2
1
1
1
1
4
4
1
1
4
20
1
10
1
0
4
0
0
80
230
Temperature, ꢀC
2
80
SAPO-34
H–Y
Tseokar-600
Fig. 1. Catalytic isomerization of substituted vinylcyclo-
propanes 1a–1d in the presence of SAPO-34 catalyst,
contact time 1 h.
Fig. 2. Catalytic isomerization of substituted vinylcyclo-
propanes 1a–1d in the presence of different catalysts, con-
tact time 1 h, t = 280°C.
Factory, Ltd.). Prior to use, all zeolites were calcined using chloroform, 50% alkali solution, and Katamin
in nitrogen flow at 550°C for 5 h.
AB phase transfer catalyst [11].
H and C NMR spectra were recorded on a
the work were obtained by the known procedures Bruker AM-500 spectrometer operating at 500 and
1
13
Vinyl-gem-dichlorocyclopropanes 1a–1d used in
Table 2. Characteristics of used catalysts [7, 9, 10]
SiO /Al O ,
Unit cell
Acidity,
Pore
diameter, Å
Pore volume, Specific surface
2
2
3
Catalysts
Na O, %
2
+
3
2
zeolite modulus size, nm meq, H /g
cm /g
area m /g
SAPO-34 [7]
H–Y [9]
Tseokar-600
22
6
5
10
24
50
0.06
2.1
0.54
0.05
0.60
0.1
3.8
0.74
–
0.27
0.56
0.5
630
600
320
(contains Pt) [10]
Table 3. Physical characteristics of compounds 2a–2d
Compound (yield,
1H NMR, ppm
13C NMR, ppm
123.39 (CH=CH), 53.29 (2
Bp
m/e, (I , %)
rel
%)
2
a (30)
100°C
5.39 (s, 2H, CH=CH,
(
138/140/142)/35/16/5M+,
(115/117)/(100/32),
(77/79)/(44/12), (51)/(39)
(
760 mmHg) J = 8.8). 2.53 (d, 2H, CH , CH ), 139.51 (C=)
2 2
J = 3.2)
Cl Cl
b (95)
H C
2
42°C
1.35 (s, 3H, CH ), 2.53 (d, 17.37 (CH ), 53.22 (CH ), (152/154/156)/35/16/5
3 3 2
+
(
60 mmHg) (2H, CH J = 3.9), 2.85 (d, 61.68 (CH ), 81.16 (C),
M , (115/117)/(100/34) ,
3
2,
2
2
1
H, CH , J = 3.9), 5.67 (s, 124.92 (CH=), 140.06 (C=) (77/79)/(87/26), (51)/(25)
H, CH)
2
Cl Cl
c (95)
2
83°C
1.29 (s, 3H, CH ), 1.52 (s, 16.26 (CH ), 18.43 (CH ), (164/166/168)/20/14/3
3
3
3
+
(
20 mmHg) 3H, CH ), 3.10 (s, 2H,
54.88 (CH ), 59.70 (CH ),
H C
3
2
2
M , (129/131)/(100/30) ,
3
CH3
CH ), 3.18 (s, 2H,CH )
82.01 (C), 138.52 (C=)
93/97, (77/79)/(70/15),
2
2
(51)/(20)
Cl Cl
d (36)
(194/196/198)/11/9/2 M+,
157/159)/(100/5), 82/14,
(77/79)/(50/9), (41)/(16)
2
76°C
10 mmHg) (s, 2H, CH=CH, J = 8.9) 86.37 (C), 137.23
CH=CH)
1.25 (s, 12H, 4 CH ), 5.39 28.19 (4 CH ), 52.60 (C),
3 3
(
(
H C
3
CH3
CH3
(
H C
3
Cl Cl
DOKLADY CHEMISTRY Vol. 487 Part 1 2019

1
94
RASKIL’DINA et al.
(except for 2a). Table 3 shows the physical constants of
R4
R3
R2
1
R4
R3
R2
R1
Cl
compounds 2a–2d.
R5
R6
5
R
R
6
R
FUNDING
Cl
Cl
2a−2d
Cl
This study was supported through a grant from Republic
of Bashkortostan for young scientists (of February 8, 2019).
1
a−1d
R3
R4
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3
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Translated by I. Kudryavtsev
DOKLADY CHEMISTRY
Vol. 487
Part 1
2019