New rearrangement of substituted chloromethyl-gem-dichlorocyclopropanes under Friedel-Crafts reaction conditions

Full text of DOI:10.1134/S0012500813070045

ISSN 0012ꢀ5008, Doklady Chemistry, 2013, Vol. 451, Part 1, pp. 189–190. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.K. Aminova, A.N. Kazakova, L.V. Spirikhin, S.S. Zlotskii, 2013, published in Doklady Akademii Nauk, 2013, Vol. 451, No. 3, pp. 288–290.
CHEMISTRY
New Rearrangement of Substituted
Chloromethylꢀgemꢀdichlorocyclopropanes
under Friedel–Crafts Reaction Conditions
E. K. Aminovaa, A. N. Kazakovaa, L. V. Spirikhinb, and S. S. Zlotskiia
Presented by Academician A.A. Berlin March 11, 2013
Received March 11, 2013
DOI: 10.1134/S0012500813070045
Alkylation of aromatic hydrocarbons with chloꢀ
romethylꢀgemꢀdichlorocyclopropanes in the presence chloromethylꢀgemꢀdichlorocyclopropane (III) with
of Lewis acids is known to result in gemꢀdichloroalkeꢀ benzene ( ) and toluene (II) leads to gemꢀdimethylꢀ
We revealed that the reaction of 2,2ꢀdimethylꢀ3ꢀ
I
nyl derivatives [1].
alkenearomatic hydrocarbons (IV, Va , Vb) with vicinal
arrangement of chlorine atoms.
Cl
CH3
CH3
R
CH3
R
AlCl3
Cl
+
CH3
Cl
Cl
Cl
I, II
III
IV; Va, b
[R = H (I, IV); R = CH3 (II, Va, b)]
Scheme 1.
Vb in We explain the formation of compounds IV, Va , and
The yields of reaction products IV and Va
the alkylation of substrates
+
Vb by the fact that dehydrochlorination is accompanied
by the opening of the cyclopropane ring at the C2–C3
bond with migration of chlorine atom and the reaction of
the nascent unstable diene with the aromatic substrate.
I
and II are close under
studied conditions (table). Toluene (II) produces
ortho and para isomers Va and Vb with the same selecꢀ
tivity.
Cl
5
CH3
2
1
2'
3
3
R
Cl
4
2
CH3
Cl
AlCl3
I, II
1'
CH3
CH3
CH3
–HCl
1
4'
CH3
Cl
Cl
Cl
6
Cl
III
IV; Va, b
Scheme 2.
Until now, no halogen shift was observed in the
cleavage of gemꢀdichlorocyclopropanes, and comꢀ
pounds with geminal arrangement of chlorine atoms
were the main reaction products [2].
EXPERIMENTAL
Qualitative and quantitative analysis of the initial
compounds and reaction products was performed on a
Kristallꢀ2000M chromatograph with a thermal conꢀ
ductivity detector, helium as a carrier gas (column
a Ufa State Oil Technical University,
ul. Kosmonavtov 1, Ufa, 450062 Russia
b Institute of Organic Chemistry, Ufa Research Center,
Russian Academy of Sciences,
2000 5 mm with 5% SEꢀ30 on Chromaton NꢀAW).
×
1H, and 13C NMR spectra were recorded on a
Bruker AMꢀ300 spectrometer operating at 300.13 and
75.47 MHz, respectively, in CDCl3 solutions with
pr. Oktyabrya 71, Ufa, 450054 Russia
189

190
AMINOVA et al.
Alkylation of benzene (I) and toluene (II) with 2,2ꢀdimeꢀ
thylꢀ3ꢀchloromethylꢀgemꢀdichlorocyclopropane III
2,3ꢀDichloroꢀ4ꢀmethylpentꢀ3ꢀenꢀ1ꢀylbenzene IV
bp 131–133°C (3 mmHg).
,
1H NMR (CDCl3,
, ppm,
δ
J
, Hz): 1.95 (s, 3H,
Aromatic hydrocarbon Reaction products (yield, %)
C5H3), 2.00 (s, 3H, С6Н3), 3.92 (dd, 1H, C1Hа, 2
J
10.6,
9.6), 4.42 (dd, 1H,
7.8), 7.24 (t, 1H, C3'H, C5'H, 3
7.8), 7.32 (t, 2H,
C3'H, C5'H, 3 7.8), 7.37 (d, 2H, C2'H, C6'H, 3
7.8).
13C NMR (CDCl3, , ppm): 20.91 (C5), 22.42 (С6),
I
II
IV (70)
Va Vb (65)*
3J 5.7), 4.12 (dd, 1H, С1Нb, 2
С4'Н, 3
J
10.6,3
J
+
Note: Molar ratio I (II) : III : AlCl = 10 : 1 : 0.3, 70–80°C, reaction
3
J
J
time 4 h. * A mixture of ortho and para isomers (Va : Vb = 1 : 1).
J
J
Me4Si as an internal reference. 2D NMR spectra were
obtained on a Bruker AVꢀ500 spectrometer.
δ
45.55 (C1), 50.10 (C2), 127.45 (C3), 127.70 (C3', C5'),
128.28 (C4'), 128.61 (C2', C6'), 131.38 (C4), 137.33 (C1').
MS (m/z (I
rel, %)): 228/230/232 [М]+• (12/7/1.2),
179 (86), 143 (100), 128 (65), 115 (22), 101 (13),
91 (6), 77 (20).
GCꢀmass spectrometric analysis was carried out on
a Shimadzu GCMSꢀQP2010 Plus instrument (EI, 70
eV, ionizing chamber temperature 200°C, direct inlet
temperature 40–290°C, heating rate 12 K/min).
(2,3ꢀDichloroꢀ4ꢀmethylpentꢀ3ꢀenꢀ1ꢀyl)ꢀ2ꢀmethylꢀ
benzene Va, bp 146–148°C (3 mmHg).
Procedure for the Synthesis of Compound III
A 50% NaOH solution (320 g) was added in 2 h to
a mixture of 1ꢀchloroꢀ3ꢀmethylbuteneꢀ1 (0.1 mol)
and Katamin AB (0.2 g) as the phase transfer catalyst
in 300 mL of chloroform on cooling to 10°C under
vigorous stirring. The mixture was stirred for addiꢀ
tional 1 h at 20°C. The reaction mixture was washed
with water, the solvent was evaporated, and the residue
was distilled in a vacuum.
1H NMR (CDCl3,
C5H3), 2.0 (s, 3H, С6Н3), 2.46 (s, 3H, C2'СH3), 3.92
(dd, 1H, С1На, 2 10.6, 3 5.8), 4.11 (dd, 1H, C1Hb, 2
10.6, 3 9.6), 4.43 (dd, 1H, С2Н, 3J 9.6, 3
5.8), 7.12
(t, 1H, C4'H 3 8.0), 7.18 (t, 1H, C5'H, 3
8.0), 7.22 (d,
2H, C2'H, C6'H, 3 8.0), 7.32 (d, 1H, C3'H, 3
8.0).
13C NMR (CDCl3, , ppm): 20.67 (C5), 21.59
(С2'СH3), 22.12 (C6), 43.06 (C1), 49.89 (C2), 123.09
δ
, ppm, J, Hz): 1.91 (s, 3H,
J
J
J
J
J
J
J
J
J
δ
2,2ꢀDimethylꢀ3ꢀchloromethylꢀgemꢀdichlorocycloꢀ
propane III, bp 58°C (3 mmHg).
1H NMR (CDCl3,
С1'H3), 1.42 (s, 3H, С2'H3), 1.66 (dd, 1H, C3H
3J 8.2), 3.55 (dd, 1H, C4Ha, 2 11.8, 3
8.2), 3.75 (dd,
1H, С4'Hb, 2 11.8, 3
7.4).
13C NMR (CDCl3, , ppm): 16.89 (C1'), 24.65 (C2'),
30.63 (C2), 39.31 (C3), 41.13 (C4), 70.28 (C1).
δ
, ppm,
J
, Hz): 1.29 (s, 3H, (C4'), 123.14 (C5'), 126.53 (C3), 127.46 (C3'), 128.90
(C6'), 131.12 (C4), 136.18 (C2'), 138.10 (C1')
MS (
rel, %)): 242/244/246 [М]+• (34/20/3),
.
, J 7.4,
J
J
m/z (I
J
J
229(65), 227 (95), 195 (31), 193 (100), 191 (25), 157
(70), 156 (45), 141(42), 128 (27), 115 (20), 77 (9).
δ
(2,3ꢀDichloroꢀ4ꢀmethylpentꢀ3ꢀenꢀ1ꢀyl)ꢀ2ꢀmethylꢀ
benzene Vb, bp 145–147°C (3 mmHg).
MS
m/z (I
rel, %): 186 (1) [М]+•, 151/153/155
1H NMR (CDCl3,
1.98 (s, 3H, С6Н3), 2.36 (s, 3H, C4'СH3), 3.92 (dd, 1Н,
С1На, 2 10.7, 3 5.8), 4.11 (dd, 1H, C1Hb, 2 10.7,3
9.6),
4.43 (dd, 1H, 1Н, С2Н, 3 9.6, 3 5.8), 7.18 (t, 2H, C3'H,
C5'H, 3 8.0), 7.22 (d, 2H, C2'H, C6'H, 3
8.0).
13C NMR (CDCl3, , ppm): 20.88 (C5), 21.59
С4'СH3), 22.42 (C6), 43.16 (C1), 49.82 (C2), 127.53
(C3), 128.23 (C2', C6'), 128.90 (C4'), 129.35 (C3', C5'),
131.10 (C4), 137.19 (C1')
MS (
rel, %)): 242/244/246 [М]+• (13/9/1),
δ
, ppm, J
, Hz): 1.92 (s, 3H, C5H3),
(20/14/2) [М–•Cl]+, 137 (100), 109 (22), 101 (11),
79 (30), 65 (29), 53 (10), 39 (32).
J
J
J
J
Procedure for the Synthesis of Compounds IV
A solution of 2,2ꢀdimethylꢀ3ꢀchloromethylꢀgem
dichlorocyclopropane III (0.002 mol) in arene or II
(0.004 mol) was added dropwise in 0.25 h to a mixture
of arene or II (0.0156 mol) and AlCl3 (0.0006 mol)
, Va , and Vb
J
J
ꢀ
J
J
I
δ
(
I
on heating to 75–80°C under vigorous stirring. The
mixture was stirred for additional 4 h at 75–80°C.
Then, the reaction mixture was poured into a beaker
with ice and 10% hydrochloric acid solution, extracted
with diethyl ether, washed with water, and the solvent
was removed. Individual compound Vb and a mixture
.
m/z (I
193 (100), 157 (79), 143 (15), 142 (27), 115 (17), 91
(8), 77 (6).
REFERENCES
of isomers Va
+ Vb were isolated by column chromaꢀ
1. Kazakova, A.N., Spirikhin, L.V., and Zlotskii, S.S.,
Neftekhimiya, 2012, vol. 52, no. 2, pp. 142–145.
2. Zyk, N.V., Bondarenko, O.B., Gavrilova, A.Yu.,
Chizhov, A.O., and Zefirov, N.S., Izv. Akad. Nauk, Ser.
Khim., 2011, no. 2, pp. 321–326.
tography from the reaction mixture of toluene alkylaꢀ
tion with reagent III. The spectral parameters of comꢀ
pound Va were determined in the enriched mixture
using 2D NMR spectroscopy based on HSQC and
HMBC spectra.
Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 451
Part 1
2013