Alkylation of benzene and toluene with chloromethyl-gem- dichlorocyclopropanes

Article abstract of DOI:10.1134/S0965544112020090

By alkylation of benzene and toluene with chloromethyl-gem- dichlorocyclopropanes in the presence of AlCl₃, the corresponding 3,3-dichloroalkenyl derivatives have been obtained. It has been shown that methylation of the ring reduces the reactiv

Full text of DOI:10.1134/S0965544112020090

ISSN 0965ꢀ5441, Petroleum Chemistry, 2012, Vol. 52, No. 2, pp. 123–125. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.N. Kazakova, L.V. Spirikhin, S.S. Zlotskii, 2012, published in Neftekhimiya, 2012, Vol. 52, No. 2, pp. 142–145.
Alkylation of Benzene and Toluene
with Chloromethylꢀgemꢀdichlorocyclopropanes
A. N. Kazakovaa, L. V. Spirikhinb, and S. S. Zlotskiia
a Ufa State Petroleum Technical University, ul. Kosmonavtov 1, Ufa, 450062 Bashkortostan, Russia
b Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
eꢀmail: aꢀkazakova@inbox.ru
Received May 23, 2011
Abstract—By alkylation of benzene and toluene with chloromethylꢀgemꢀdichlorocyclopropanes in the presꢀ
ence of AlCl3, the corresponding 3,3ꢀdichloroalkenyl derivatives have been obtained. It has been shown that
methylation of the ring reduces the reactivity of substituted gemꢀdichlorocyclopropanes.
DOI: 10.1134/S0965544112020090
Dichlorocarbenation of commercial dienes and acid and extracted with diethyl ether. The organic
chloroalkenes quantitatively yields the corresponding layer was washed with water and dried over anhydrous
alkenylꢀ and chloroalkylꢀgemꢀdichlorocyclopropanes,
which are of particular interest as semiproducts in
organic synthesis [1–3].
MgSO4. After solvent evaporation, the resulting resiꢀ
due was distilled in vacuum.
The reaction products were analyzed on an
LKhMꢀ8MD chromatograph equipped with a therꢀ
mal conductivity detector and 2ꢀm column with 5%
SEꢀ30 on a Chromaton NꢀAW support. The starting
The use of vinylꢀgemꢀdichlorocyclopropane in the
alkylation of aromatic compounds was reported earlier
[4, 5]. The resulting substituted benzenes and phenols
are of considerable interest as additives for fuels, lubriꢀ
cating oils, and polymers [6]. It was also of interest to
explore the possibility of their preparation by alkylaꢀ
tion of aromatic hydrocarbons with chloromethylꢀ
gemꢀdichlorocyclopropanes.
column temperature was 100
300 , the programming rate was 20
rier gas (helium) flow rate was 30 mL/min, and the
evaporator temperature was 250 . The calculations
°
С
, and the final one was
°
С
°
C/min, the carꢀ
°
С
were performed using the method of internal normaꢀ
lization, which is based on the reduction of a total area
of peaks to 100%.
The present paper presents the results on alkylation
of benzene and toluene with 2ꢀchloromethylꢀgem
ꢀ
dichlorocyclopropane (Ia) and 2ꢀ(chloromethyl)ꢀ2ꢀ
methylꢀgemꢀdichlorocyclopropane (Ib) in the preꢀ
sence of an aluminum chloride catalyst.
1H and 13C NMR spectra were recorded on a
Bruker AMꢀ300 spectrometer (300.13 and
75.47 MHz, respectively) in CDCl3, using Me4Si as an
internal standard. Mass chromatograms were recorded
on a SHIMADZU GCMSꢀQP2010 Plus instrument
EXPERIMENTAL
(EI, 70 eV, ion source temperature of 200
lumn injection temperature of 40–290 , heating rate
of 12 C/min).
°
С, onꢀcoꢀ
The reagents 1,1ꢀdichloroꢀ2ꢀchloromethylcycloꢀ
propane (Ia) and 1,1ꢀdichloroꢀ2ꢀ(chloromethyl)ꢀ2ꢀ
methylcyclopropane (Ib) were synthesized according
to the procedure described in [7]. A general procedure
for the alkylation with chloromethylꢀgemꢀdichlorocyꢀ
clopropanes (Ia, Ib): to a stirred mixture of 0.05 mol
(3.9 g) of benzene (or 4.6 g of toluene) and 0.0007 mol
(0.09 g) of AlCl3, 0.005 mol of gemꢀdichlorocycloproꢀ
pane (0.8 g of Ia or 0.87 g of Ib)) was slowly added
°
С
°
RESULTS AND DISCUSSION
The data obtained in this study (table) show that in
the case of alkylation of benzene and toluene with
reagents Ia and Ib in the presence of catalytic amounts
of AlCl3, the reaction is accompanied by opening of
dropwise with stirring and heating to 70°С for 2 (in the
case of Ia) or 3 h (in the case of Ib). After completion
of the addition, the reaction mixture was further the cyclopropane ring and leads to the formation of
heated for 15 min with vigorous stirring and then the corresponding 3,3ꢀdichloroalkenylderivatives IIa,
poured into a beaker with ice and 10% hydrochloric IIb, and IIIa–IIId.
123

124
KAZAKOVA et al.
Alkylation of benzene and toluene by gemꢀdichlorocyclopropanes Ia and Ib
Reactants
Time, h
2
Products
Yield, %
75
CH3
Cl
Cl
Cl
Ia
Ib
IIa
IIb
Cl
Cl
CH3
CH3
CH3
Cl
Cl
Cl
Cl
2
3
3
21
Cl
Cl
CH3
Cl
Cl
70*
Ia
IIIa, b
IIIc, d
Cl
Cl
CH3
CH3
CH3
CH3
CH3
Cl
Cl
H3C
Cl
43**
Ib
Cl
Cl
* Mixture of
oꢀ and
pꢀisomers (IIIa : IIIb = 1 : 7.5). **Mixture of oꢀ and pꢀisomers (IIIc : IIId = 1 : 9).
R1
CH3
Cl
CH3
R1
Cl
R2
R2
R1
Cl
Cl
AlCl
–HCl
3
R2
ArH
Cl
.
Cl
AlCl
Cl
3
R1
Cl
+
R1
Cl
Cl
Cl
Iа, b
Cl
This type of ring opening in substituted gem
dichlorocyclopropanes mediated by acid catalysts was
described earlier in [8].
The relative activity of Ia and Ib toward benzene
was estimated by means of competitive kinetics and it
was found that the presence of methyl group in the
cyclopropane moiety reduces the activity of comꢀ
pound Ib by a factor of 3, which is in a good agreement
with our data (see table).
ꢀ
IIа, b, IIIa–d
R1 = H(Ia);
R1 = H, R2 = H(IIa);
R1 = H, R2 = orthoꢀCH3(IIIa);
R1 = H, R2 = paraꢀCH3(IIIb);
R1 = CH3(Ib);
R1 = СH3, R2 = H(IIb);
R1 = СH3, R2 = orthoꢀCH3(IIIc);
R1 = СH3, R2 = paraꢀCH3(IIId).
Individual substances IIa and IIb and a mixture of
IIIa,b and IIIc,d isomers were isolated by vacuum disꢀ
tillation from the reaction mass of the interaction of
the aromatic compounds with reagents Ia and Ib.
In the case of chloromethyl derivative Ia, the yields
of alkylation products are considerably higher than
those with the use of chloride IIb. At the same time, in
the reaction of Ia and IIb with toluene (table) yields
Their structure and the oꢀ to pꢀisomer ratio in the mixꢀ
tures of IIIa,b and IIIc,d were determined by 1H NMR
and mass spectrometry.
(3,3ꢀDichloroꢀ1ꢀmethylpropeneꢀ2ꢀylꢀ1)benzene
(IIa). Yield 75%, colorless liquid. Bp 96 С (5 mmHg).
°
the oꢀ and pꢀisomers in approximately the same ratio
1H NMR (CDCl3,
7.2 Hz), 3.75–3.86 (qu.d, 1H, СН3–СН, 3
9.6 Hz), 5.93–5.96 (d, 1H, =CH, 3J 9.6 Hz), 7.11–
7.29 (m, 5H, Ar). 13C NMR (CDCl3,
, ppm): 20.74
(СН3), 40.31 (СН3–СН), 120.03 (СCl2), 126.86
Ar), 126.93 ( ꢀAr), 128.84 ( ꢀAr), 134.41 (=CH),
143.54 (Ph). Mass spectrum m/e Irel %):
δ
, ppm): 1.36 (d, 3H, СН3, 3J 7.2
(IIIa : IIIb = 1 : 7.5, IIIc : IIId = 1 : 9).
J
7.2 Hz, 3J
The formation of IIa, IIb, and IIIa–IIId is presumꢀ
ably due to the elimination of HCl molecule, involving
cyclopropane ring opening by the С1–С2 bond and the
formation of intermediate unstable diene which reacts
with the aromatic substrate
δ
(mꢀ
o
p
,
(
,
PETROLEUM CHEMISTRY Vol. 52
No. 2
2012

ALKYLATION OF BENZENE AND TOLUENE
125
CH3), 47.02 (CH3–C–CH3), 123.07 (
о
ꢀAr), 125.43
200/202/204
М+
(5/3/0.8), 165/167 [М–Cl•]+ (18/6),
(10/6/1.3),
185/187/189
[М⎯ ]
CH•3
(
(
p
ꢀAr), 126.49, 128.28 (mꢀAr), 134.43 (CCl2), 135.73
+
oꢀAr–CH3), 142.90 (=CH), 145.52 (Ar). Mass specꢀ
149/145 (60/20), 129 (100), 115 (23), 105 (12), 91 (4),
77 (30), 63 (20), 51 (37).
trum m/e, (
I
rel, %): 228/230/232 М+ (7/5/0.8),
213/215/217 [М– CH3•
]
(1), 193/196 [М–Cl•]+
+
Mixture of 1ꢀ(3,3ꢀdichloroꢀ1ꢀmethylpropeneꢀ2ꢀylꢀ
1)ꢀ2ꢀmethylbenzene (IIIa) and 1ꢀ(3,3ꢀdichloroꢀ1ꢀ
methylpropeneꢀ2ꢀylꢀ1)ꢀ4ꢀmethylbenzene (IIIb) (ratio
of isomers IIIa : IIIb = 1 : 7.5). Yield 70%, colorless
(50/18), 177/179 (22/7), 157 (100), 142 (60), 128 (20),
115 (27), 105 (11), 91 (18), 77 (17), 65 (18), 51 (12).
ꢀIsomer (IIId). 1H NMR (CDCl3,
, ppm): 1.53
p
δ
liquid. Bp 112–114 С (5 mm Hg).
°
(s, 6Н, СН3–С–СН3), 2.35 (s., 3Н, СН3–Ar), 6.23
o
ꢀIsomer (IIIa). 1H NMR (CDCl3,
δ
, ppm): 1.40
6.9 Hz), 2.38 (s, 3Н, СН3–Ar), 3.97–
6.9 Hz, 3J 9.3 Hz), 5.95–
(s, 1H, CH=), 7.01–7.26 (m, 4H, Ar). 13C NMR
(d, 3H,СН3, 3
J
(CDCl3,
CH3), 49.13 (CH3–C–CH3), 125.86 (
ꢀAr), 134.43 (CCl2), 135.42 ( ꢀAr–CH3), 138.75
, ppm): 20.34 (СН3–Ar), 21.59 (=CH), 144.71 (Ar). Mass spectrum m/e, (
δ
, ppm): 21.04 (СН3–Ar), 29.60 (CH3–C–
4.07 (qu.d, 1H, СН3–СН, 3
J
о
ꢀAr), 129.07
5.98 (d., 1H, =CH, 3J 9.3 Hz), 7.10–7.21 (m, 4H, Ar).
13C NMR (CDCl3,
(CH3), 31.98 (СН3–СН), 123.15 (СCl2), 123.89
Ar), 125.60, 127.55 ( ꢀAr), 130.64 ( ꢀAr), 135.02 (
(
m
p
δ
Irel, %):
228/230/232 М+ (8/5/0.8), 213/215/217 [М– CH3•
]
(
p
o
ꢀ
ꢀ
+
m
o
(1), 193/196 [М–Cl•]+ (55/18), 177/179 (29/10), 157
(100), 142 (64), 128 (23), 115 (28), 105 (11), 91 (18),
77 (18), 65 (17), 51 (12).
Ar–CH3), 137.02 (=CH), 139.42 (Ar). Mass spectrum
m/e
,
(Irel
,
%): 214/216/218 М+ (28/18/3),
H3•
]
(30/20/3.5), 179/181
+
1
199/201/203 [М
[М
(96), 119 (11), 115 (40), 91 (35), 77 (25), 63 (28), 51 (34).
ꢀIsomer (IIIa). 1H NMR (CDCl3,
, ppm): 1.41
(d, 3H, СН3, 3
7.2 Hz), 2.35 (s, 3Н, СН3–Ar), 3.77ꢀ
3.88 (qu.d, 1H, СН3–СН, 3 7.2 Hz, 3J 9.6 Hz), 5.97–
6.0 (d, 1H, =CH, 3J 9.6 Hz), 7.10–7.21 (m, 4H, Ar).
13C NMR (CDCl3,
, ppm): 20.73 (СН3–Ar), 21.10
(CH3), 39.86 (СН3–СН), 123.15 (СCl2), 126.75
Ar), 129.45 ( ꢀAr), 134.55 (=CH), 136.20 ( ꢀAr),
%):
⎯
C
In H NMR spectrum of IIa, IIb, and IIIa–IIId,
⎯
Cl•]+ (25/8), 163/165 (98/30), 143 (100), 128
the signals of cyclopropane ring protons in the region
of 1.2–1.8 ppm disappear and new signals due to СН3
protons and double bond protons appear at 1.4–1.5
and 5.9–6.5 ppm, respectively.
p
δ
J
In the mass spectra of IIa, IIb and IIIc, IIId, the
J
molecular ions have a low intensity to make 2 to 10%,
whereas compounds IIIa and IIIb form stable moleꢀ
cular ions (m/z = 28–31%). The most abundant ions
δ
are those with m/z = 129 (for IIa), m/z = 143 (for IIb
IIIa IIIb), and m/z= 157 (for IIIc IIId) formed as a
result of successive elimination of halogens. The main
route of dissociation is almost the same for the oꢀ and
ꢀisomers of IIIa IIId
Thus, chloromethylꢀgemꢀdichlorocyclopropanes
,
(mꢀ
,
,
o
p
140.54 (Ar). Mass spectrum m/e
, (Irel,
214/216/218 М+ (31/21/3), 199/201/203 [М–
p
⎯
.
+
C
H3•
]
(40/25/4.5), 179/181 [М–Cl•]+ (35/12),
163/165 (95/30), 143 (100), 128 (97), 119 (18), 115
(28), 91 (30), 77 (23), 63 (22), 51 (28).
can be successfully used as alkylation agents for preꢀ
paration of substituted benzenes containing the
dichloroalkenyl moiety.
(3,3ꢀDichloroꢀ1,1ꢀdimethylpropeneꢀ2ꢀylꢀ1)benꢀ
zene (IIa). Yield 21%, colorless liquid. Bp 109 С
°
1
REFERENCES
(5 mmHg). H NMR (CDCl3,
СН3–С–СН3), 6.25 (s, 1H, =CH), 7.18–7.33 (m,
5H, Ar). 13C NMR (CDCl3,
, ppm): 29.53 (CH3–C–
CH3), 54.66 (CH3–C–CH3), 126.25 ꢀAr), 128.36
ꢀAr), 128.51 ( ꢀAr), 134.26 (СCl2), 138.57 (=CH),
140.85 (Ar). Mass spectrum m/e Irel %):
δ
, ppm): 1.55 (s, 6Н,
1. R. R. Kostikov, A. P. Molchanov, and A. Ya. Bespalov,
Zh. Org. Khim. 10, 10 (1974).
δ
2. N. S. Zefirov, I. V. Kazimirchik, and K. L. Lukin,
Cycloaddition of Dichlorocarbene to Olefins (Nauka,
Moscow, 1985) [in Russian].
3. T. V. Arbuzova, A. R. Khamidullina, and S. S. Zlotskii,
Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 50
(6), 15 (2007).
4. A. R. Khamidullina, E. A. Brusentsova, and
S. S. Zlotskii, Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol. 51 (9), 106 (2008).
(
p
(
o
m
,
(
,
214/216/218 М+ (2), 199/201/203 [М– CH•3 ]+ (1),
179/181 [М–Cl•]+ (45/15), 163/165 (18/6), 143
(100), 128 (68), 115 (11), 91 (15), 77 (17), 63 (12), 51 (20).
Mixture of 1ꢀ(3,3ꢀdichloroꢀ1,1ꢀdimethylpropeneꢀ
2ꢀylꢀ1)ꢀ2ꢀmethylbenzene (IIIc) and 1ꢀ(3,3ꢀdichloroꢀ
1,1ꢀdimethylpropeneꢀ2ꢀylꢀ1)ꢀ4ꢀmethylbenzene (IIId)
(ratio of isomers IIIc : IIId = 1 : 9). Yield 43%, colorꢀ
less liquid. Bp 122–124°C (5 mmHg).
5. E. A. Kletter, Yu. P. Kozyreva, D. I. Kutukov, and
S. S. Zlotskii, Pet. Chem. 50, 65 (2010).
6. E. A. Brusentsova, S. V. Kolesov, A. I. Vorob’eva, et al.,
Zh. Org. Khim. 78, 783 (2008).
oꢀIsomer (IIIc). 1H NMR (CDCl3,
, ppm): 1.54
δ
7. A. R. Shiriazdanova, A. N. Kazakova, and
(s, 6Н, СН3–С–СН3), 2.37 (s, 3Н, СН3ꢀAr), 6.23(s,
S. S. Zlotskii, Bashkir. Khim. Zh. 16, 142 (2009).
1H, CH=), 7.01–7.26 (m, 4H, Ar). 13C NMR
8. N. V. Zyk, O. B. Bondarenko, A. Yu. Gavrilova, et al.,
Izv. Akad. Nauk, Ser. Khim., No. 2, 321 (2011).
(CDCl3, δ, ppm): 21.14 (СН3–Ar), 29.60 (CH3–C–
PETROLEUM CHEMISTRY Vol. 52
No. 2
2012