Alkylation of phenols with alkenyl-gem-dichlorocyclopropanes

Article abstract of DOI:10.1134/S0965544110010093

The alkylation of phenol and 2,6-di-tert-butylphenol with alkenyl-gem-dichlorocyclopropanes in the presence of boron trifluoride etherate was studied. The products were obtained with a yield of 45-50% of the theoretical value. The structure of the products was determined by spectral methods.

Full text of DOI:10.1134/S0965544110010093

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 1, pp. 65–67. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.A. Kletter, Yu.P. Kozyreva, D.I. Kutukov, S.S. Zlotskii, 2010, published in Neftekhimiya, 2010, Vol. 50, No. 1, pp. 66–68.
Alkylation of Phenols with AlkenylꢀgemꢀDichlorocyclopropanes
E. A. Kletter, Yu. P. Kozyreva, D. I. Kutukov, and S. S. Zlotskii
Ufa State Technical University of Petroleum, Ufa, Russia
eꢀmail: el_brus82@bk.ru
Received April 17, 2009
Abstract—The alkylation of phenol and 2,6ꢀdiꢀtertꢀbutylphenol with alkenylꢀgemꢀdichlorocyclopropanes in
the presence of boron trifluoride etherate was studied. The products were obtained with a yield of 45–50% of
the theoretical value. The structure of the products was determined by spectral methods.
DOI: 10.1134/S0965544110010093
The dichlorocarbenylation of industrial diene
The procedure for the alkylation of phenols with
hydrocarbons leads to the formation of the correꢀ alkenylꢀgemꢀdichlorocyclopropanes Ia and Ib was as
sponding alkenylꢀgemꢀdihalocyclopropanes with follows: the corresponding gemꢀdichlorocycloproꢀ
quantitative yields, which are of interest as monomers pane (0.0146 mol) (of 2.0 g Ia or 2.2 g of Ib) was slowly
and intermediary petrochemicals [1–3]. In particular, added dropwise to a mixture of 0.073 mol (6.9 g) of
these olefins are successfully used for the production phenol (or 15 g of 2,6ꢀdiꢀtertꢀbutylphenol) and
of polyfunctional compounds containing a gemꢀdihaꢀ 0.01 mol (1.37 g) of the catalyst boron trifluoride
locyclopropyl fragment [4, 5]. Alkylꢀ and arylꢀgem
ꢀ
etherate with stirring at a temperature of 50–60°С.
dichlorocyclopropanes demonstrate herbicidal and The olefin : phenol : catalyst molar ratio was 1 : 5 : 1.
growthꢀstimulating activity and are of certain interest The resulting mixture was additionally heated for 9–
as promising plant protection chemicals [6].
17 h with vigorous stirring, then cooled, and extracted
by the corresponding solvent. The organic layer was
washed with water and a NаНСО3 solution and dried
over МgSО4. After the evaporation of the solvent, the
products were isolated chromatographically on a colꢀ
umn packed with silica gel (the eluent was a 19 : 5 hexꢀ
ane–ethyl acetate blend).
In this work, we report the results of phenol alkylaꢀ
tion with the products of butadiene (Ia) and isoprene
(
Ib) dichlorocarbenylation in the presence of boron
trifluoride etherate.
The GLC analysis was carried out on a Chromꢀ5
chromatograph with a flameꢀionization detector and a
2ꢀm column packed with Chromaton NꢀAWꢀDMC
coated with a 5% SEꢀ30 methylsiloxane elastomer
with temperature programming from 50 to 280°С at a
rate of 20°C/min; the carrier gas (helium) flow rate
was 30 ml/min. The evaporator temperature was
300°С. The calculations were carried out using the
method of internal normalization based on the reducꢀ
tion of the sum of peak areas to 100%.
The NMR spectra were recorded on a TeslaꢀBSꢀ
567 (100 Hz) spectrometer using tetramethylsiloxane
as a standard. Gas chromatographic–mass spectroꢀ
metric analysis was carried out on a computerized HPꢀ
5859 gas chromatograph–mass spectrometer
equipped with an HPꢀ5972A massꢀselective detector
and an HPꢀ5 30ꢀm glass capillary column coated with
5% phenyl methyl silicone.
EXPERIMENTAL
Alkenylꢀgemꢀdichlorocyclopropanes were syntheꢀ
sized by the following method: a fourꢀnecked flask
equipped with a mechanical stirrer, a reflux condenser,
a thermometer, and a dropping funnel was loaded with
0.1 mol of the corresponding olefin (butadiene or isoꢀ
prene), 300 ml of chloroform, and 0.1 g (0.0004 mol)
of the phaseꢀtransfer catalyst triethylbenzylammoꢀ
nium chloride. A solution of sodium hydroxide (320 g
of a 50% solution) was dropped into the resultant mixꢀ
ture for 2 h under agitating stirring at room temperaꢀ
ture or at –10°С in the case of isoprene and butadiene,
respectively. The resultant mixture was additionally
stirred for 1 h. The mixture was washed with water to
pH 7. The lower organic layer was separated, dried
with calcium chloride, and filtered off; after the evapꢀ
oration of chloroform, the products of dichlorocarbeꢀ
nylation were isolated by atmospheric distillation.
The unsaturated compounds used were of at least
99% purity, reagent grade phenol was freshly distilled
before the experiment, and 2,6ꢀdiꢀtertꢀbutylphenol
had a purity of 99.8%.
RESULTS AND DISCUSSION
The obtained results show that in the presence of
boron trifluoride etherate BF3O(C2H5)2, compounds
65

66
KLETTER et al.
Table 1. Alkylation of phenol and 2,6ꢀdiꢀtertꢀbutylphenol with gemꢀdichlorocyclopropanes Ia and Ib
Reactants
Ia
Products
Time (h)
17
Yield, % (pꢀ : oꢀisomers)
Phenol
p
ꢀ,
o
ꢀIsomer mixture
43
(1.2 : 1)
IIa + IIb
ꢀ, ꢀIsomer mixture
(1.2 : 1)
III + III
IVa*
IVb*
Ib
p
o
15
45
a
b
2,6ꢀDiꢀtertꢀbutylpheꢀ Ia
Ib
11
9
42
48
nol
* About 5% of oꢀtertꢀbutylphenol was found.
Ia and Ib alkylate phenol yielding a mixture of oꢀ and depends on the olefin structure (IIa
/IIb
≈
IIIa/IIIb ≈
p
ꢀisomers IIa
,
IIb and IIIa
,
IIIb in a ratio that slightly 1.3 : 1).
OH
Cl
Cl
OH
H3C
R
Cl
Cl
R
CH2
+
IIа, IIIа
Iа, Ib
HO
H3C
Cl
Cl
R
IIb, IIIb
where R = H for Ia
,
IIa, and IIb or R = CH3 for Ib
,
Similar values were obtained for the yields of prodꢀ
ucts IVa and IVb in the alkylation of 2,6ꢀdiꢀtert
ꢀ
IIIa, and IIIb
.
butylphenol with compounds Ia and Ib within 9–11 h
of the experiment:
Yields close to 50% were reached within 15–20 h of
the reaction (Table 1).
CH3
CH3
CH3 OH
CH3 OH
H3C
H3C
CH3
H3C
H3C
CH3
CH3
CH3
cat
Iа, Ib
+
Cl
Cl
H3C
IVа, IVb
R
where R = H (IVa) or CH3 (IVb).
It is obvious that the partial dealkylation of the iniꢀ
tial 2,6ꢀdiꢀtertꢀbutylphenol takes place under these
in agreement with the obtained results (Table 1). The
synthesized compounds were identified by proton
NMR spectroscopy, mass spectrometry (Table 2), and
elemental analysis.
Identification of the products by elemental analyꢀ
sis:
conditions, as indicated by the appearance of oꢀtertꢀ
butylphenol (about 5%) in the resultant mixture.
Using the method of concurrent kinetics, we evaluated
the relative activity of compounds Ia and Ib as comꢀ
A mixture of pꢀ and oꢀisomers (1.2 : 1): 4ꢀ[1ꢀ(2,2ꢀ
pared to 2,6ꢀdiꢀtertꢀbutylphenol and found that the (dichlorocyclopropyl)ethyl]phenol (IIa), 2ꢀ[1ꢀ(2,2ꢀ
isoprene derivative is 1.3–1.5 times more active; this is (dichlorocyclopropyl)ethyl]phenol (IIb):
PETROLEUM CHEMISTRY Vol. 50
No. 1
2010

ALKYLATION OF PHENOLS
Table 2. Physicochemical characteristics of the obtained compounds
67
Compound
1H NMR spectrum,
δ
, ppm
mass spectrum, m/z (Irel, %)*
p
:
o
ꢀisomer mixture(1.2 : 1)
p
ꢀisomer (IIa):
p
ꢀisomer (IIa):
4ꢀ[1ꢀ(2,2ꢀ(dichlorocycloproꢀ
pyl)ethyl]phenol (IIa
2ꢀ[1ꢀ(2,2ꢀ(dichlorocycloproꢀ
pyl)ethyl]phenol (IIb
1.76–1.81 (m, CHCCCl2);1.42–1.49 (dd,
CH2CCCl2); 2.02–2.07 (m, CH); 1.34–1.41 (d, 109 (15); 94 (15); 77 (10); 51 (5)
230 (5) [M+]; 150 (4); 121 (100);
)
CH3); 6.04 (s, OHꢀPh); 6.61–7.39 (4H, Ph)
ꢀisomer (IIb):
1.81–1.98 (m, CHCCCl2);1.41–1.47 (dd,
oꢀisomer (IIb):
)
o
230 (25) [M+]; 150 (25); 121
(100); 109 (20); 94 (50); 77 (25);
CH2CCCl2); 2.20–2.32 (m, CH); 1.42–1.43 (d, 51 (10)
CH3); 6.05 (s, OHꢀPh); 6.71–7.14 (4H, Ph)
p
:
o
ꢀisomer mixture(1.2 : 1)
p
ꢀisomer (IIIa):
1.32–1.39 (dd, CH2CCCl2); 1.90–1.95 (
1.39–1.40 (d, CH3); 1.15 (s, CH3); 6.04 (s, OHꢀ 121 (100); 109 (10); 94 (25);
Ph); 6.61–7.09 (4H, Ph) 77 (60); 51 (20)
ꢀisomer (IIIb): ꢀisomer (IIIb):
1.30–1.36 (dd, CH2CCCl2); 2.24–2.27 (
, CH); 244 (3) [M+]; 229 (25); 150 (25);
1.40–1.43 (d, CH3); 1.15 (s, CH3); 6.04 (s, OHꢀ 121 (100); 109 (20); 94 (45);
p
ꢀisomer (IIIa):
4ꢀ[1ꢀ(2,2ꢀ(dichloroꢀ1ꢀmethylꢀ
cyclopropyl)ethyl]phenol (IIIa
2ꢀ[1ꢀ(2,2ꢀ(dichloroꢀ1ꢀmethylꢀ
cyclopropyl)ethyl]phenol (IIIb
m
, CH); 244 (44) [M+]; 229 (85); 150 (25);
)
)
o
o
m
Ph); 6.61–7.09 (4H, Ph)
77 (30); 51 (20)
2,6ꢀDiꢀtertꢀbutylꢀ4ꢀ[1ꢀ(2,2ꢀ
1.78–1.83 (dd, CHCCCl2); 1.38–1.49 (m,
342 (5) [M+]; 233 (10); 191 (30);
(dichlorocyclopropyl)ethyl]pheꢀ CH2CCCl2); 1.78–1.79 (m, CH); 1.55–1.59 (d, 109 (20); 91 (20); 79 (30); 57 (100);
nol (IVa CH3); 5.37 (s, OHꢀPh); 1.40 (s, tꢀBuꢀCH3); 41 (10)
6.77–7.00 (dd, 2H, Ph)
)
2,6ꢀDiꢀtertꢀbutylꢀ4ꢀ[1ꢀ(2,2ꢀ
(dichloroꢀ1ꢀmethylcycloproꢀ
pyl)ethyl]phenol (IVb
1.36–1.39 (m, CH2CCCl2); 1.69–1.79 (m, CH); 356 (5) [M+]; 233 (30); 206 (10);
1.45–1.51 (d, CH3); 1.65 (s, CH3; 5.37 (s, OHꢀPh); 191 (100); 177 (10); 123 (8); 91 (5);
)
1.40 (s, tꢀBuꢀCH3); 6.77–7.00 (dd, 2H, Ph)
79 (10); 57 (25); 41 (10)
* The total intensity of isotope peaks is given counted on 35 amu of chlorine. The ratio of particles with masses differing by two atomic units
35
37
for chlorineꢀcontaining fragment peaks is 3 : 1, which corresponds to the natural content of Cl and Cl chlorine isotopes.
Found,%: C 57.12, H 5.22, Cl 30.70. Calculated ration of polyfunctional phenols containing the gem
ꢀ
for C22H24Cl4O2, %: C 57.16, H 5.23, Cl 30.68.
dichlorocyclopropyl moiety.
A mixture of pꢀ and ꢀisomers (1.2 : 1): 4ꢀ[1ꢀ(2,2ꢀ
o
(dichloroꢀ1ꢀmethylcyclopropyl)ethyl]phenol (IIIa),
2ꢀ[1ꢀ(2,2ꢀ(dichloroꢀ1ꢀmethylcyclopropyl)ethyl]pheꢀ
nol (IIIb):
Found,%: C 58.75, H 5.75, Cl 28.95. Calculated
for C24H28Cl4O2, %: C 58.79, H 5.76, Cl 28.92.
2,6ꢀdiꢀtertꢀbutylꢀ4ꢀ[1ꢀ(2,2ꢀ(dichlorocycloꢀ
propyl)ethyl]phenol (IVa):
Found,%: C 66.42, H 8.24, Cl 20.53. Calculated
for C19H28Cl2O, %: C 66.47, H 8.22, Cl 20.65.
2,6ꢀdiꢀtertꢀbutylꢀ4ꢀ[1ꢀ(2,2ꢀ(dichloroꢀ1ꢀmethylꢀ
cyclopropyl)ethyl]phenol (IVb):
Found,%: C 67.18, H 8.41, Cl 19.79. Calculated
for C20H30Cl2O, %: C 67.22, H 8.46, Cl 19.84.
REFERENCES
1. R. R. Kostikov, A. P. Molchanov, and A. Ya. Bespalov,
Zh. Org. Khim. 10, 10 (1974).
2. N. S. Zefirov, Kazimirchik, and K. A. Lukin, Cycloadꢀ
dition 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
15 (2007).
4. S. V. Kopsov and S. S. Zlotskii, Zh. Prikl. Khim.
(St. Petersburg) 81, 490 (2008)].
5. A. R. Khamidullina, E. A. Brusentsova, and
S. S. Zlotskii, Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol. 51, 106 (2008).
In summary, vinylꢀgemꢀdichlorocyclopropanes can
be successfully used as alkylating agents for the prepaꢀ
6. E. R. Ganiullina, B. I. Voronenko, V. M. Kuznetsov,
and S. S. Zlotskii, Bashkir. Khim. Zh. 15, 55 (2008).
PETROLEUM CHEMISTRY Vol. 50
No. 1
2010