Relative activity of alkenyl-gem-dichlorocyclopropanes in the reactions of hydrogenation and alkylation

Article abstract of DOI:10.1134/S1070427209060196

Relative activity of alkenyl-gem-dichlorocyclopropanes in reactions of hydrogenation and acidcatalyzed alkylation of benzene and toluene was studied.

Full text of DOI:10.1134/S1070427209060196

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 6, pp. 1029–1032. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.A. Brusentsova, S.S. Zlotskii, B.I. Kutepov, A.N. Khazipova, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 6,
pp. 972–975.
ORGANIC SYNTHESIS AND INDUSTRIAL
ORGANIC CHEMISTRY
Relative Activity of Alkenyl-gem-Dichlorocyclopropanes
in the Reactions of Hydrogenation and Alkylation
E. A. Brusentsova, S. S. Zlotskii, B. I. Kutepov, and A. N. Khazipova
Ufa State Petroleum Technical University, Ufa, Russia
Institute of Petrochemistry and Catalysis, Russian Academy of Science, Ufa, Russia
Received November 6, 2008
Abstract—Relative activity of alkenyl-gem-dichlorocyclopropanes in reactions of hydrogenation and acid-
catalyzed alkylation of benzene and toluene was studied.
DOI: 10.1134/S1070427209060196
Alkenyl-gem-dichlorocyclopropanes are formed in
high yield and selectivity at the addition of dichlorocar-
bene to industrial dienes, and they can be regarded as
accessible intermediates for the organic synthesis [1–3].
The competitive hydrogenation of a mixture of
compounds Ia and Ic at the conversion less than 30%
showed that according to the yield of products IIa and
IIc the vinyl derivative Ia is 3 times more active than
the isopropenyl analog Ic.
Various pathways of functionalization of a double
bond proceeding with the retention of the gem-
dichloro-cyclopropane fragment have been described
[4, 5]. A significant interest presents the behavior of
these compounds in practically important processes of
hydrogenation and alkylation.
In the presence of acid catalysts, olefin Ib is added
to benzene [8]. It is shown that sulfuric acid alkylation
(Table 2) of benzene (IIIa) and toluene (IIIb) by
vinyl derivatives Ia and Ib proceeds with low yield
(16–35%) of the corresponding substituted aromatic
compounds IVa, IVb and Va, Vb, respectively:
The heterogeneous catalysts Pd/Al2O3 and Ni/TiO2
widely used in the industry for the reduction of
vegetable fats and oils [6, 7] were found to be
applicable to a selectively hydrogenation of double
bonds in alkenylcyclopropanes Ia–Ic without destruc-
tion of carbocycle and substitution of halogen:
R1
H3C
R3
R3
R3
C−C−CH2
H2SO4
+
Ia−Ic +
R2
Cl
Cl
C
R1
IIIa, IIIb
R1
R1
VIa−VIc
H3C−C−C−CH2
R2
H2, catalyst
C
Cl
Cl
R2
R2
Cl Cl
Ia−Ic
Cl Cl
IVa−IVc
IIa−IIc
R1 = R2 = H (Ia, IVa, Va); R1 = CH3, R2 = H (Ib, IVb, Vb,
VIb); R1 = R2 = CH3 (Ic, IVc, Vc, VIc); R3 = H (IIIa, IVa–
IVc); CH3 (IIIb, Va–Vc, Via–VIc).
R1 = R2 = H (Ia, IIa); R1 = CH3, R2 = H (Ib, IIb); R1 = R2 =
CH3 (Ic, IIc).
Compounds with vinyl group Ia and Ib are close by
the activity and are reduced both on Pd/Al2O3 and on
Ni/TiO2 practically completely in less than 3 h.
Analogous result in the case of compound with iso-
propenyl group Ic is achieved in 4 h (Table 1).
The yield of compounds IVc–VIc, the derivatives
of olefin Ic is considerably higher (70–80%) that is
characteristic for acid-catalyzed alkylation of aromatic
compounds by isoalkenes [9].
1029

1030
BRUSENTSOVA et al.
Table 1. Hydrogenation of gem-dichlorocyclopropanes Ia–Ic.
P = 6 atm, solvent octane, 60°C, olefin–catalyst ratio 10:1 (wt)
Competitive alkylation of benzene by a mixture
containing Ib and heptene-1 (Id) (2 h, the degree of
conversion of olefins less than 30%) showed (Table 3),
that according to the yield of compounds IVb and IVd,
heptene-1 is 2.5 times more active than vinyl-gem-
dichlorocyclopropane Ib. At the competitive alkylation
of benzene by olefins Ib and Ic (2 h, conversion of
olefins less than 30%) from the yields of products IVb
and IVc follows that isopropenyl-gem-dichloro-
cyclopropane Ic is 4 times more active than the vinyl
analog Ia. In all cases the formation of the products of
alkylation was not accompanied by evolution of HCl
and splitting of the cyclopropane fragment.
Reaction
product
Compound
Catalyst
τ, h Yield, %
Pd/Al2O3
30
60
30
50
93
32
53
95
30
48
92
10
25
70
90
Ia
IIa
150
30
Ni/TiO2
Pd/Al2O3
Pd/Al2O3
Ib
IIb
60
150
30
EXPERIMENTAL
60
150
30
The reaction products were analyzed on a Tsvet
50M chromatograph with the flame-ionization detec-
tor, carrier gas helium, flow rate 20 ml min–1, column
1 m length, 3 mm diameter. As the stationary phase
was used 5% SE-30 on Chromaton N-AW. The 1H and
13C NMR spectra were registered on a Tesla-BS-567
spectrometer (100 MHz), solvent CDCl3, relative to
TMS. Chromatomass-spectrometric analysis was
carried out on a chromatomass-spectrometer HP-5859
coupled with a computer with mass-selective detector
NR-5972a, the glass capillary column of 30 m length,
5% of phenylmethylsilicone on HP-5.
Ic
IIc
60
150
240
Table 2. Alkylation of benzene IIIa and toluene IIIb by
gem-dichlorocyclopropanes Ia–Ic. Benzene, toluene 0.073 mol,
conc. H2SO4 0.0146 mol, olefin Ia–Ic 0.0146 mol, T = 40–45°C
Reaction
product
Yield, % (p/o
isomers ratio)
Reagent
τ, h
Alkenyl-gem-dichlorocyclopropanes Ia–Ic are
synthesized employing a known procedure [2]. In the
work were used unsaturated compounds of no less than
99% purity.
IIIa + Ia
IIIa + Ib
IIIa + Ic
IIIb + Ia
IIIb + Ib
IIIb + Ic
14
17
9
10
30
IVa
IVb
73
IVc
General procedure of hydrogenation of gem-di-
chlorocyclopropanes Ia–Ic. A metall 80 cm3 reactor
was charged with 0.01 mole of an appropriate olefin
Ia–Ic and 0.2 g of catalyst (Pd/Al2O3 or Ni/TiO2). The
ratio olefin : catalyst = 10:1 (wt). As a solvent was
used octane (40 ml). The reactor was closed
hermetically and filled with hydrogen to the pressure 6
atm, the temperature in the reaction zone was 60°C.
The regime of ideal mixing was reached by the
automatic intensive shaking the reactor. To the end of
experiment the reaction mass was filtered from the
catalyst, the filtrate was dried over calcium chloride,
the solvent was distilled off, and the product was
isolated at the atmospheric pressure. The physico-
chemical characteristics of the synthesized compounds
are presented in Table 4.
Va + VIa
Vb + VIb
Vc + VIc
7
12 (4:1)
34 (4:1)
82 (4:1)
9
4
Table 3. Relative activity of olefins Ib–Id in the reaction of
benzene alkylation. Mole ratio olefin : C6H6 : H2SO4 = 1:5:1,
T = 40–45°C, τ = 2 h
Reagent
Reaction product Relative activity
IIIa + Ib + Ic
IIIa + Ib + Id
IVb + IVc
IVb + IVd
IVc/IVb = 3
IVd/IVb = 2.5
Note that under the studied conditions regardless
the structure of alkenyl-gem-dichlorocyclopropane Ia–
Ic the ratio of ortho- and para-isomers at the alkyla-
tion of toluene is constant and equals to 1:4.
Alkylation by alkenyl-gem-dichlorocyclopropanes
(Ia–Ic). To a mixture of 0.073 mol (5.7 g) of benzene
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 6 2009

RELATIVE ACTIVITY OF ALKENYL-gem-DICHLOROCYCLOPROPANES
1031
(or 6.7 g of toluene) and 0.0146 mole (1.43 g) of con-
centrated sulfuric acid at stirring and heating to 40–45°C
was slowly added dropwise 0.0146 mol of the cor-
responding olefin (Ia 2.0 g, Ib 2.2 g, Ic 2.4 g). After
the completion of addition the reaction mixture was
heated for 4 to 17 h with vigorous stirring, then it was
cooled and extracted with an appropriate solvent.
Organic layer was washed with water, then with the
solution of NaHSO3, dried over MgSO4, and the
solvent was evaporated. The reaction products were
separated by vacuum distillation.
The physicochemical characteristics of the syn-
thesized compounds are listed in Table 4.
CONCLUSIONS
(1) Alkenyl-gem-dichlorocyclopropanes can be
used successfully in the reactions of hydrogenation and
alkylation.
(2) In the reactions of hydrogenation, vinyl-gem-
dichlorocyclopropane is 3 times more active than
Table 4. Physicochemical characteristics of obtained products
bp, °C
(p, mm Hg)
Compound
1H NMR spectrum, δ, ppm
Mass-spectrum, m/z (Irel, %)
1.07–1.11 (t, 3Н, Н3С); 138, 140 (5) [M+]; 123 (100); 110 (22);
1.41–1.58 (m, 2Н, Н2С); 75 (12); 87 (65); 51 (20); 39 (15)
1.69–1.82 (d.t, 2Н,
1,1-Dichloro-2-ethylcyclopropane (IIa)
146
СН2СCl2)
0.84–0.88 (t, 3Н, Н3С); 152, 154 (6) [M+]; 123 (100); 110 (20);
1.21–1.30 (кв, 2Н, Н2С); 75 (15); 87 (65); 51 (20); 39 (12)
1.24 (s, 2Н, СН2СCl2);
1,1-Dichloro-2-methyl-2-ethylcyclo-
propane (IIb)
154
170
1.33 (t, 3Н, Н3С)
0.92–0.95 (d, 3Н, Н3С); 166, 168 (5) [M+]; 151 (3); 137 (18);
1.04–1.06 (d, 3H, H3C); 123 (100); 110 (22); 75 (12); 87 (65); 51
1.07 (s, 3Н, Н3С); 1.13– (20); 39 (15)
1,1-Dichloro-2-methyl-2-isopropyl-
cyclopropane (IIc)
1.14 (d, 2Н, СН2СCl2);
1.87–1.89 (m, 1Н, НС)
0.85–1.55 (m, 2Н, 216, 218 (1) [M+]; 214 (14); 185 (53);
СН2СCl2); 1.38 ) (d, 3Н, 149 (100); 143 (10); 115 (30); 105 (6);
Н3С); 1.70–1.84 (m, 1Н, 77 (7)
[1-(2,2-Dichlorocyclopropyl)ethyl]-
benzene (IVa)
102 (2)
НС); 2.18–2.40 (m, 1Н,
НС); 7.18–7.39 (m, 5Н,
Ph)
0.80–1.35 (m, 2Н, 228, 230 (1) [M+]; 199 (13); 163 (46);
СН2СCl2); 1.45 ) (d, 3Н, 157 (10); 129 (10); 115 (10); 105
Н3С); 1.78 (s, 3Н, СН3); (100); 91 (17); 77 (16)
1.75–2.52 (m, 1Н, НС);
[1-(2,2-Dichloro-1-methylcyclopropyl]-
benzene (IVb)
106 (2)
117 (2)
7.00–7.18 (m, 5Н, Ph)
1.21–1.23 (d, 3Н, Н3С); 242, 244 (22) [M+]; 207 (5); 191 (98);
1.31 (s, 3Н, Н3С); 1.37– 155 (1); 129 (9); 105 (100); 91 (4); 77
1.57 (d, 2Н, СН2СCl2); (27)
[1-(2,2-dichloro-1-methylcyclopropyl)-
isopropyl]benzene (IVc)
1.41 (s, 3Н, Н3С); 7.23–
7.43 (m, 5Н, Ph)
p-Isomer Va: 1.32–1.34 p-Isomer Va: 228, 230 (5) [M+]; 213
(d, 3Н, Н3С); 1.40–1.44 (4); 199 (55); 163 (100); 157 (10); 129
(m, 2Н, СН2СCl2); 1.42– (20); 117 (5); 91 (5); 77 (10)
1.56 (m, 1Н, СНСCl2);
2.26 (s, 3Н, Н3С–Ph);
7.06–7.10 (m, 4Н, Ph)
Mixture of p- and o-isomers (4:1):
[1-(2,2-Dichlorocyclopropyl)ethyl]-4-
methylbenzene (Va)
[1-(2,2-Dichlorocyclopropyl)ethyl]-2-
methylbenzene (VIa)
118–119 (2)
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 6 2009

1032
BRUSENTSOVA et al.
Table 4. (Contd.)
bp, °C
(p, mm Hg)
Compound
1H NMR spectrum, δ, ppm
Mass-spectrum, m/z (Irel, %)
o-Isomer VIa: 1.30–1.32 o-Isomer VIa: 228, 230 (5) [M+]; 213
(d, 3Н, Н3С); 1.38–1.42 (4); 199 (23); 163 (75); 157 (6); 129
(m, 2Н, СН2СCl2); 1.40– (8); 117 (1); 91 (2); 77 (4)
1.55 (m, 1Н, СНСCl2);
2.19 (s, 3Н, Н3С–Ph);
6.77–7.65 (m, 4Н, Ph)
Mixture of p- and o-isomers (4:1):
1-[1-(2,2-dichloro-1-methylcyclo-
propyl)ethyl]-4-methylbenzene (Vb)
1-[1-(2,2-dichloro-1-methylcyclo-
propyl)ethyl]-2-methylbenzene (VIb)
p-Isomer Vb: 0.90–1.30 p-Isomer Vb: 242, 244 (12) [M+]; 227
(m, 2Н, -
СН2СCl2); (1); 213 (43); 179 (37); 177 (100); 157
121–122 1.39–1.40 (d, 3Н, Н3С); (8); 141 (19); 119 (55); 105 (13); 91
(2)
1.14 (s, 3Н, Н3С); 2.25 (100); 77 (10)
(s, 3Н, Н3С–Ph); 7.01–
7.08 (m, 4Н, Ph)
o-Isomer VIb: 0.90–31.30 o-Isomer VIb: 242, 244 (7) [M+]; 227
(m, 2Н, СН2СCl2); 1.35– (1); 213 (20); 179 (25); 177 (77); 157
1.37 (d, 3Н, Н3С); 1.14 (s, (6); 141 (13); 119 (20); 105 (9); 91 (35);
3Н, Н3С); 2.20 (s, 3Н, 77 (10)
Н3С–Ph); 6.84–7.62 (m,
4Н, Ph)
Mixture of p- and o-isomers (4:1):
1-[1-(2,2-dichloro-1-methylcyclo-
propyl)isopropyl]-4- methylbenzene
(Vc)
1-[1-(2,2-dichloro-1-methylcyclo-
propyl)isopropyl]-2- methylbenzene
(VIc)
p-Isomer Vc: 0.88–1.40 p-Isomer Vc 256, 258 (3) [M+]; 241
(m, 2Н, СН2СCl2); 1.22 (23); 213 (2); 207 (4); 191 (98); 155
129–131 (s, 3Н, Н3С); 1.29 (s, 3Н, (2); 129 (10); 105 (100); 91 (5); 77 (25)
(2)
Н3С); 1.40 (s, 3Н, Н3С);
2.27 (s, 3Н, Н3С–Ph);
6.89–6.91 (m, 4Н, Ph)
o-Isomer VIc: 0.87–1.40 o-Isomer VIc 256, 258 (3) [M+]; 241
(m, 2Н, )
СН2СCl2); (13); 213 (1); 207 (2); 191 (43); 155 (2);
1.21 (s, 3Н, Н3С); 1.26 (s, 129 (6); 105 (100); 91 (5); 77 (20)
3Н, Н3С); 1.38 (s, 3Н,
Н3С); 2.71 (s, 3Н, Н3С–
Ph); 6.81–7.53 (m, 4Н,
Ph)
4. Arbuzova, T.V., Khamidullina, A.R., and Zlotskii, C.C.,
Izv. Vuzov. Khimiya i Khim. Tekhnol., 2007, vol. 50,
no. 6, p. 15.
related isopropenyl derivative, while in acid-catalyzed
alkylation of benzene and toluene isopropenyl-gem-
dichlorocyclopropane is 4 times more active than vinyl
analog.
5. Kopsov, C.V. and Zlotskii, C.C., Zh. Prikl. Khim., 2008,
vol. 81, no. 3, p. 490.
REFERENCES
6. Minachev, Kh.M., Khodakov, Yu.C., and Hakhshu-
nov, V.C., Usp. Khim., 1976, vol. 45, no. 2, p. 280.
1. Kostikov, R.R., Molchanov, A.P., and Bespalov, A.Ya.,
7. Tsuji, J., Palladium Reagents and Catalysts–Innova-
tions in Organic Syntheses, Chichester: Wiley, 1995.
Zh. Obshch. Khim., 1974, vol. 10, p. 10
2. Arbuzova, T.V., Zlotskii, C.C., and Rakhmankulov, D.L.,
8. Khamidullina, A.R., Brusentsova, E.A., and Zlotskii, C.C.,
Izv. Vuzov. Khimiya i Khim. Tekhnol., 2008, vol. 51,
no. 9, p. 106.
Bashkir. Khim. Zh., 2005, vol. 12 no. 2, p. 19.
3. Zefirov, H.C., Kazimirchik, I.V., and Lukin, K.A.,
Tsikloprisoedinenie dichlorokarbena k olefinam (Cyclo-
addition of Dichlorocarbene to Olefins), Moscow:
Nauka, 1985.
9. Korenev, D.K., Zavorotnyi, V.A., and Kelarev V.I.,
KhTTM, 2003, no. 2, p. 61.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 82 No. 6 2009