Alkylation of aromatic hydrocarbons with 2-bromo-2-phenyl-gem- dichlorocyclopropane

Article abstract of DOI:10.1134/S107036321306008X

The alkylation of aromatic hydrocarbons with 2-bromo-2-phenyl-gem- dichlorocyclopropane in the presence of catalytic quantities of aluminum chloride was found to afford the corresponding 2-aryl-3-phenyl-1,1-dichloroprop- 1-enes. It was shown that the yiel

Full text of DOI:10.1134/S107036321306008X

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 6, pp. 1060–1063. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.K. Kurbankulieva, A.N. Kazakova, L.V. Spirikhin, S.S. Zlotskii, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 6,
pp. 929–932.
Alkylation of Aromatic Hydrocarbons
with 2-Bromo-2-phenyl-gem-dichlorocyclopropane
E. K. Kurbankulievaa, A. N. Kazakovaa, L. V. Spirikhinb, and S. S. Zlotskiia
a Ufa State Oil Technical University, ul. Kosmonavtov 1, Ufa, 450062 Russia
e-mail: k.elmira.k@yandex.ru
b Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Russia
Received May 10, 2012
Abstract―The alkylation of aromatic hydrocarbons with 2-bromo-2-phenyl-gem-dichlorocyclopropane in the
presence of catalytic quantities of aluminum chloride was found to afford the corresponding 2-aryl-3-phenyl-
1,1-dichloroprop-1-enes. It was shown that the yield of the alkylation products depended on the nature of
substituents in the aromatic ring. Compared with the thermal heating, microwave irradiation allows reducing
the reaction time and increasing the yield of the corresponding 2-aryl-3-phenyl-1,1-di-chloroprop-1-enes,
wherein the ortho-/para-isomers ratio changes.
DOI: 10.1134/S107036321306008X
Substituted gem-dichlorocyclopropanes are widely
used in organic synthesis [1]. We previously showed
that the chloroalkyl-gem-dichlorocyclopropanes react
with toluene and benzene to form the corresponding
3,3-dichloroalkenyl derivatives [2]. In continuation of
this research we studied the alkylation of aromatic
hydrocarbons Ia–Id with 2-bromo-2-phenyl-gem-
dichlorocyclopropane II, which is readily formed from
the available α-bromostyrene [3].
the electronegative chlorine in Id has virtually no
effect on the yield of alkylation products (see table).
Note that the microwave irradiation reduces the
reaction time and increases almost two times the yield
of alkylation products IIIa–IIIf . The selectivity of o-
isomers formation increases in the case of compounds
Ib and Ic (see table).
The formation of products IIIa–IIIf is probably due
to the primary elimination of HBr molecule followed
by alkylation of aromatic ring of Ia–Id with unstable
cyclopropene that is accompanied by the ring opening
and the migration of a hydrogen atom.
In the presence of the Friedel–Crafts reaction
catalysts (AlCl3) the alkylation of aromatic compounds
Ia–Id with the bromo derivative II occurs through the
cyclopropane ring opening to give the corresponding
2-aryl-3-phenyl-1,1-dichlorprop-1-enes IIIa–IIIf.
Earlier the rearrangement of the gem-
dichlorocyclopropanes with the formation of 1,1-
dichloroalk-1-enes has been described in [2, 4].
Methyl substituents in the aromatic ring of Ib and
Ic reduce the activity of an aromatic compound; while
R1
R1
Br
AlCl3
R2
Cl
+
Cl
R2
Cl
Cl
IIIа−IIIf
Iа−Id
II
R1 = R2 = H (Iа, IIIа); R1 = H, R2 = 2-CH3 (Ib, IIIb); R1 = H, R2 = 4-CH3 (IIIc); R1 = R2 = 2,4-CH3 (Ic, IIId); R1 = H, R2 =
2-Cl (Id, IIIe); R1 = H, R2 = 4-Cl (Id, IIIf).
1060

ALKYLATION OF AROMATIC HYDROCARBONS
1061
R
R
AlCl3,
ArH
Ar
Br
H
Ph
Ph
Cl
Cl
IIIа−IIIf
Ph
Ph
Cl
H
−HBr
H
Cl
Cl
Cl
Cl
Cl
II
The products of the reaction of aromatic com-
pounds Ia–Id with reagent II were isolated by vacuum
distillation as individual compounds (IIIa, IIId) or as
mixtures of isomers (IIIb + IIIc, IIIe + IIIf). Their
structure and the ratio of ortho- and para-isomers in
on a Focus instrument equipped with a mass spec-
trometric detector Finingan DSQ II (ion source
temperature 200°C, temperature of the direct input 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–1).
GLC analysis was performed on a Crystal-2000M
chromatograph with a thermal conductivity detector,
carrier gas helium, flow rate 1.5 l h–1, the column
length 2 m, 5% SE-30 on Chromaton N-AW.
1
the mixture were determined by the H and 13C NMR
spectroscopy, GC-MS method.
A feature of the 13C NMR spectra of compounds
IIIa–IIIf, recorded in the modulation of the constant
of C–H coupling made (JMOD), is the presence of a
signal characteristic of the methylene carbon atoms
[42.20 (IIIa), 41.89 (IIIb), 39.52 (IIIc), 39.41 (IIId),
41.76 (IIIe), 39.61 ppm (IIIf)] and a signal of
quaternary carbon atom of CCl2-group [118.83 (IIIa),
118.76 (IIIb, IIIc), 118.82 (IIId), 119.93 (IIIe),
119.27 ppm (IIIf)]. The 13C NMR spectra of para-
isomers contain the mutually equivalent signals of the
carbon atoms of double intensity, whereas in the
spectra of ortho-isomers with different substituents all
the carbon atoms of the aromatic rings have different
chemical shifts [5]. On this basis the signals of the
aromatic carbons in the spectrum of mixtures (IIIb +
IIIc) and (IIIe + IIIf) were assigned to the
corresponding ortho- and para-isomers.
Dihalocarbenylation procedure. To a mixture of
0.1 mol of α-bromostyrene and 0.2 g of TEBAC in
300 ml of chloroform was added dropwise 320 g of a
50% solution of NaOH within 2 h under heating at 40°C
and vigorous stirring. Then the mixture was stirred for
1 h at 40°C, washed with water, concentrated, and
distilled in vacuum.
2-Bromo-2-phenyl-gem-dichlorocyclopropane (II).
Yield 95%, colorless liquid, bp 125–127°С (4 mm
1
Hg). H NMR spectrum, δ, ppm (J, Hz): 2.06 d (1H,
2
2
C3Ha, J 9.0), 2.09 d (1Н, С3Нb, J 9.0), 7.17–7.39 m
Alkylation of aromatic hydrocarbons with 2-bromo-2-phenyl-
gem-dichlorocyclopropane [(Iа–Id):II:AlCl3 = 7.8:1:0.3,
Т = 100°С]
In the mass spectra of compounds IIIa–IIIf there
are stable molecular ions (10–40%). The most
intensive are ions with m/z 191 (IIIa), 205 (IIIb, IIIc),
219 (IIId), 225/227 (IIId, IIIf) formed by successive
elimination of halogens. The main direction of
dissociation for ortho- and para-isomers (IIIb, IIIc,
IIIe, IIIf) is similar.
Comp.
Reaction products
Time, h
Yield, % (ortho:para)
no.
2
47
Ia
IIIа
0.5а
2
98
IIIb + IIIc
IIId
37 (1:1)
65 (2.5:1)
29
Ib
Ic
Id
Thus, 2-bromo-2-phenyl-gem-dichlorocyclopropane
can be advantageously used as an alkylating agent to
produce 2-aryl-3-phenyl-gem-dichloropropenes.
0.5а
2
0.5а
2
60
EXPERIMENTAL
1
The H and 13C NMR spectra (JMOD mode) were
48 (1:1)
97 (2:1)
IIIe + IIIf
recorded on a Bruker AM-300 spectrometer (300.13
and 75.47 MHz, respectively) in CDCl3, internal
reference TMS. The GC-MS spectra were registered
0.5а
a
Microwave irradiation, 420 W.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 6 2013

1062
KURBANKULIEVA et al.
(4H, Ph). 13С NMR spectrum, δС, ppm: 35.43 (C3H2),
43.01 (C2Br), 62.88 (C1Cl2), 128.71 (C2H, C6H, Ph),
129.01 (C4H, Ph), 129.28 (C3H, C5H, Ph), 138.87 (С1).
Mass spectrum, m/z (Irel, %): 264/266/268/270 (1) [М]+,
192/194 (5/5), 185/186/188 (10/6/1) [М – Br]+,
149/151 (100/30), 115 (47), 89 (28), 75 (18), 63 (22).
trum, δС, ppm: 19.48 (СН3), 41.89 (С1Н2, Bn), 118.76
(С2Cl2), 125.65 (C4H, Bn), 130.09 (C4H, C6H4), 126.58
(C3H, C5H, Bn), 128.53 (C3H, C6H4), 128.41 (C5H,
C6H4), 129.07 (C2H, C6H, Bn), 125.92 (C6H, C6H4),
136.86 (C2, C6H4), 135.09 (C1, C6H4), 136.02 (C1, Bn),
138.75 (С1). Mass spectrum, m/z (Irel, %): 276/278/281
(16/7/4) [М]+, 241/243 (54/16) [М – Cl]+, 205 (100),
191 (18), 178 (12), 163/165 (41/11), 149/151 (54/21),
136 (13), 128 (13), 105 (56), 101 (33), 89 (16), 77
(31), 65 (20), 63 (21), 53 (11), 51 (28). para-IIIc. 13С
NMR spectrum, δС, ppm: 20.97 (СН3), 39.52 (С1Н2,
Bn), 118.76 (С2Cl2), 125.65 (C4H, Bn), 126.58 (C3H,
C5H, Bn), 128.08 (C3H, C5H, C6H4), 127.66 (C2H,
C6H, C6H4), 128.29 (C2H, C6H, Bn), 137.54 (C4,
C6H4), 133.86 (C1, C6H4), 136.38 (C1, Bn), 140.06
(С1). Mass spectrum, m/z (Irel, %): 276/278/281
(22/12/2) [М]+, 241/243 (59/12) [М – Cl]+, 205 (83),
191 (12), 189 (17), 178 (12), 163/165 (66/31), 149/151
(41/17), 136 (21), 127 (15), 105 (100), 101 (36), 89
(17), 77 (39), 65 (19), 63 (21), 53 (9), 51 (33).
Alkylation of aromatic hydrocarbons Ia–Id with
2-bromo-2-phenyl-gem-dichlorocyclopropane (II)
(general procedure). To a mixture of 39 mmol of arene
Ia–Id and 1.4 mmol of AlCl3 under stirring and
heating to 90°C was added dropwise a solution of
5 mmol of 2-bromo-2-phenyl-gem-dichlorocyclopropane
II in 11 mmol of the corresponding aromatic com-
pound over 2 h. After the addition was completed, the
reaction mixture was heated with vigorous stirring for
further 15 min and then poured into a mixture of ice
and 10% hydrochloric acid solution, then extracted
with diethyl ether. The organic layer was washed with
water and dried over MgSO4. After evaporation of the
solvent the residue was distilled in vacuum.
2-(1-Benzyl-2,2-dichlorovinyl)-1,4-dimethyl-
benzene (IIId). Colorless liquid, bp 163°C (2 mm
Hg). 13С NMR spectrum, δС, ppm: 19.23, 21.18 (СН3),
39.64 (С1Н2, Bn), 118.82 (С2Cl2), 127.51 (C4H, Bn),
127.87 (C3H, C5H, Bn), 129.85 (C3H, C6H3), 130.09
(C5H, C6H3), 128.35 (C2H, C6H, Bn), 130.27 (C6H,
C6H3), 135.15 (C2, C6H3), 135.48 (C4, C6H3), 133.44
(C1, C6H3), 134.10 (C1, Bn), 138.95 (С1). Mass spec-
trum, m/z (Irel, %): 290/292/294 (16/10/2) [М]+,
255/257 (69/22) [М – Cl•]+, 219 (100), 203(23),
177/179 (45/17), 149/151 (51/18), 119 (86), 101 (32),
91 (59), 77 (36), 65 (12), 51 (19).
Alkylation of aromatic hydrocarbons Ia–Id with
2-bromo-2-phenyl-gem-dichlorocyclopropane
II
under microwave irradiation (general procedure). A
mixture of 50 mmol of arene Ia–Id, 1.4 mmol of AlCl3
and 5 mmol of 2-bromo-2-phenyl-gem-dichlorocyclo-
propane II was stirred under irradiation in a domestic
microwave oven Sanyo EM-S1073W at 420 W for
30 min. Then the reaction mixture was poured into a
mixture of ice and 10% hydrochloric acid solution and
extracted with diethyl ether. The organic layer was
washed with water and dried over MgSO4. After
evaporation of the solvent the residue was distilled in a
vacuum.
A mixture of 1-(1-benzyl-2,2-dichlorovinyl)-2-
chlorobenzene (IIIe) and 1-(1-benzyl-2,2-dichloro-
vinyl)-4-chlorobenzene (IIIf). Colorless liquid, bp
165–167°С (2mm Hg). ortho-IIIe. 13С NMR spec-
trum, δС, ppm: 41.76 (С1Н2, Bn), 119.93 (С2Cl2),
126.79 (C4H, Bn), 129.52 (C4H, C6H4), 127.93, 128.44
(C3H, C5H, C6H4), 128.02 (C3H, C5H, Bn), 128.29
(C2H, C6H, Bn), 128.38 (C6H, C6H4), 138.74 (C2,
C6H4), 132.51 (C1, C6H4), 137.46 (C1, Bn), 134.76
(С1). Mass spectrum, m/z (Irel, %): 296/298/300/302
(45/36/12/2) [М]+•, 261/263/265 (44/23/4) [М – Cl•]+,
225/227 (100/35), 183/185/187 (57/31/13), 149/151
(43/15), 136/138 (28/9), 125/127 (53/17), 95 (59), 90
(33), 75 (15), 63 (21), 51 (17). para-IIIf. 13С NMR
spectrum, δС, ppm: 39.61 (С1Н2, Bn), 119.27 (С2Cl2),
126.79 (C4H, Bn), 128.02 (C3H, C5H, Bn), 130.12
(C3H, C5H, C6H4), 128.29 (C2H, C6H, Bn), 128.65
(C2H, C6H, C6H4), 138.42 (C4, C6H4), 134.28 (C1,
1,1'-(1,1-Dichloroprop-1-ene-2,3-diyl)biphenyl
1
(IIIa). Colorless liquid, bp 142°C (2 mm Hg). Н
NMR spectrum, δ, ppm: 3.95 s (2H, C3H2), 7.05–7.30
m (10H, Ph). 13С NMR spectrum, δС, ppm: 42.30
(С3Н2), 118.83 (С1Cl2), 126.58 (C4H, Ph), 127.73
(C4'H, Ph), 128.18 (C3H, C5H, Ph), 128.38, (C3'H,
C5'H, Ph), 128.27 (C2'H, C6'H, Ph), 128.67 (C2H, C6H,
Ph), 136.99 (C1', Ph), 138.63 (C1, Ph), 139.05 (С2).
Mass spectrum, m/z (Irel, %): 262/264/266 (16/10/2)
[М]+, 227/229 (24/7) [М – Cl]+, 191 (74), 165 (17),
149/151 (100/30), 136 (14), 115 (12), 91 (74), 65 (47),
51 (25).
A mixture of 1-(1-benzyl-2,2-dichlorovinyl)-2-
methylbenzene (IIIb) and 1-(1-benzyl-2,2-dichloro-
vinyl)-4-methylbenzene (IIIb). Colorless liquid, bp
152–154°С (2 mm Hg). ortho-IIIb. 13С NMR spec-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 6 2013

ALKYLATION OF AROMATIC HYDROCARBONS
REFERENCES
1063
C6H4), 135.63 (C1, Bn), 138.24 (С1). Mass spectrum,
m/z (Irel, %): 296/298/300/302 (45/36/12/2) [М]+•,
261/263/265 (44/23/4) [М – Cl•]+, 225/227 (100/35),
183/185/187 (57/31/13), 149/151 (43/15), 136/138
(28/9), 125/127 (53/17), 95 (59), 90 (33), 75 (15), 63
(21), 51 (17).
1. Fedoryсski, M., Chem. Rev., 2003, vol. 103, no. 4,
p. 1099.
2. Kazakov, A.N., Spirikhin, L.V., and Zlotskii, S.S.,
Neftekhimiya , 2012, vol. 52, no. 2, p. 142.
3. Newman, M.S., Dhawan, B., Hashem, M.M., Khan-
na, V.K., and Springer, J.M., J. Org. Chem., 1976,
vol. 41, no. 24, p. 3925.
ACKNOWLEDGMENTS
4. Zyk, N.V., Bondarenko, O.B., Gavrilova, A.Yu., Chi-
zhov A.O., and Zefirov, N.S., Izv. Akad. Nauk., Ser.
Khim., 2011, no. 2, p. 321.
5. Gunther, H., Introduction to the Course of NMR Spec-
troscopy, Springer-Verlag, 1984.
This work was carried out within the Federal Target
Program “Research and scientific-pedagogical
personnel of innovative Russia” for 2009–2013, (state
contract no. 14.740.11.0910 from 29.04.2011).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 6 2013