Reaction of 2-Bromo-2-phenyl-1,1-dichlorocyclopropane with phenols and alcohols

Full text of DOI:10.1134/S0012500812080022

ISSN 0012ꢀ5008, Doklady Chemistry, 2012, Vol. 445, Part 2, pp. 150–151. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.K. Kurbankulieva, A.N. Kazakova, S.S. Zlotskii, 2012, published in Doklady Akademii Nauk, 2012, Vol. 445, No. 4, pp. 419–420.
CHEMISTRY
Reaction of 2ꢀBromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocyclopropane
with Phenols and Alcohols
E. K. Kurbankulieva, A. N. Kazakova, and S. S. Zlotskii
Presented by Academician A.A. Berlin December 5, 2011
Received March 28, 2012
DOI: 10.1134/S0012500812080022
We showed recently that substituted gemꢀdichloroꢀ
cyclopropanes in the reactions with monohydric and
dihydric phenols convert at the first stage to comꢀ
pounds with exocyclic double bond. The latter, owing
to the presence of the reactive chloroallyl moiety,
readily react with hydroxy groups to form the correꢀ
sponding cyclopropanone ketals [1].
It was interesting to study the transformations under
these conditions of 2ꢀbromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocyꢀ
clopropane (
available ꢀbromostyrene with dichlorocarbene [2].
We have found that compound reacts with phenols
IIc under phase transfer catalysis conditions to yield
I), which readily forms via the reaction of
α
I
IIa–
acetals of phenylpropargyl aldehyde IIIa–IIIc.
Br
2
O R
2 3
1
3
+ ROH
1
O R
Cl Cl
I
IIa–IIc, IVa, IVb
IIIa–IIIc, Va, Vb
R = Ph (IIa, IIIa); 2ꢀCH3C6H4 (IIb, IIIb); 4ꢀClC6H4 (IIc, IIIc);
nꢀC4H9 (IVa, Va); CH2=CH–CH2 (IVb, Vb).
Endocyclic elimination of HBr is likely to lead to
intermediate cyclopropenes in which the chloroallyl
fragments react rapidly with phenols IIa IIc. The
reaction is accompanied by ring opening to form the
acetylene bond.
EXPERIMENTAL
Qualitative and quantitative analysis of the initial
compounds and reaction products were performed on
an LKhMꢀ8D chromatograph equipped with a cathaꢀ
rometer, helium as a carrier gas (column 2000 × 5 mm
–
Allyl alcohol (IVa) and butyl alcohol (IVb) do not
react under these conditions with compound I. We
managed to accomplish this reaction using as a cataꢀ
lyst sodium metal in excess of the initial alcohol. The
yields of resultant acetals in the reaction with alcohols
are much lower than in the reactions with phenols,
while conditions are more severe (table).
1
with 5% SEꢀ30). H and 13C NMR spectra were
recorded on a Bruker AMꢀ300 spectrometer (operatꢀ
ing at 300.13 and 75.47 MHz, respectively) in CDCl3
Reaction of phenols IIa–IIc and alcohols IVa and IVb with
2ꢀbromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocyclopropane
I
Reaction
conditions
Reaction product
(yield, %)
A nonselective formation of acetylene structures
was noted previously in the condensation of polysubꢀ
stituted gemꢀdibromocyclopropanes with alkanols [3].
We established for the first time that gemꢀdichlorocyꢀ
clopropanes containing bromine atom in the ring can
participate in similar transformations.
Reactant
IIa
IIb
IIc
A
IIIa (78)
IIIb (69)
IIIc (33)
IVa
IVb
B
Va (11)
Vb (30)
Note: System A: molar ratio NaOH : IIa–IIc : I = 0.02 : 0.007 : 0.003,
3.5 mL of DMF, 20 C, reaction time 4 h (2 h for phenol IIa).
System B: molar ratio Na : IVa, IVb : I = 0.1 : 0.012 : 0.005,
100 C, reaction time 8 h (12 h for alcohol IVb).
°
Ufa State Oil Technical University, ul. Kosmonavtov 1, Ufa,
450062 Russia
°
150

REACTION OF 2ꢀBROMOꢀ2ꢀPHENYLꢀ1,1ꢀDICHLOROCYCLOPROPANE
151
using Me4Si as an internal reference. GCꢀMS analysis
(1ꢀPhenylpropꢀ1ꢀynꢀ3,3ꢀdiyl)bis(hydroxyꢀ4ꢀchloꢀ
robenzene), IIIc. Rf 0.24.
was performed with the use of a Focus instrument with
a Finnigan DSQ II massꢀspectral detector (EI, 70 eV;
ionizing chamber temperature, 200°C; direct inlet
temperature, 50–270°C; heating rate, 10 K/min).
1H NMR (CDCl3,
δ
, ppm,
J, Hz): 6.90–7.48
(m, 13H, Ph; 1H, CH).
MS
m/z (I
rel, %): 368/370/372 [М]+• (<1),
Synthesis of compound I. A 50% solution of NaOH
(320 g) was added dropwise for 2 h to a vigorously stirred
175 (76), 158 (100), 144 (17), 131 (18), 116 (28), 102
(28), 91 (18), 77 (15), 63 (16), 51 (17).
mixture of 0.1 mol of
ylbenzylammonium chloride as the phase transfer cataꢀ
lyst in 300 mL of chloroform at 40 . After that, the mixꢀ
ture was stirred for another 1 h at 40 . Then, the reacꢀ
α
ꢀbromostyrene and 0.2 g of triethꢀ
Synthesis of compounds Va and Vb. Sodium metal
(0.012 mol) was gradually added to 0.1 mol of alcohol
°С
IVa
pane
,
IVb. 2ꢀBromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocycloproꢀ
(0.005 mol) was added to the prepared alcohoꢀ
°С
I
tion mixture was washed with water, the solvent was
evaporated, and the residue was distilled in a vacuum.
late and heated to 100°C for 8–12 h. The reaction
mixture was diluted with water, extracted with ether,
and washed with water, and the solvent was evapoꢀ
rated. TLC analysis was performed on Silufol plates
(Merk) using hexane–ethyl acetate, 9 : 1, as an eluent.
Preparative separation was accomplished by column
chromatography on silica gel (hexane with ethyl aceꢀ
tate gradient from 5 to 100% as an eluent).
2ꢀBromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocyclopropane I.
Bp 125–127°C (4 mmHg).
1H NMR (CDCl3
, δ, ppm, J, Hz): 2.06 (d, 1H,
C3Ha, 2J 9.0), 2.09 (d, 1H, С3Нb, 2J 9.0), 7.17–7.39
(m, 4H, Ph).
13С NMR (CDCl3
62.9 (CCl2), 128.7, 128.9, 129.3, 138.9 (Ph).
, δ, ppm): 35.4 (CH2), 43.0 (CBr),
(3,3ꢀDibutoxypropꢀ1ꢀynꢀ1ꢀyl)benzene, Va. Rf 0.27.
1H NMR (CDCl3,
δ
, ppm, J, Hz): 0.95–1.01
MS
rel, %): 264/266/268/270 [М]+• (1),
192/194 (5/5), 185/186/188 [М – Br•]+ (10/6/1)
149/151 (100/30), 115 (47), 89 (28), 75 (18), 63 (22).
Synthesis of compounds IIIa IIIc. A solution of
0.003 mol of 2ꢀbromoꢀ2ꢀphenylꢀ1,1ꢀdichlorocycloꢀ
propane ( ) in 1 mL of DMF was added dropwise to a
vigorously stirred mixture of 0.007 mol of phenol IIa
IIc, 0.02 mol of NaOH, and 2.5 mL of DMF. After 2–
4 h, the reaction mixture was diluted with water,
extracted with chloroform, and washed with water, the
solvent was removed, and the residue was chromatoꢀ
graphed on silica gel (hexane–ethyl acetate, 9 : 1, as an
eluent).
m/z (I
(m, 6H, C4'H3, C4''H3), 1.38–1.49 (m, 4H, C3'Ha,
C3'Hb, C3''Ha, C3''Hb), 1.72–1.81 (m, 4H, C2'Ha,
C2'Hb, C2''Ha, C2''Hb), 3.43–3.50 (m, 2H, C1'Ha,
C1'Hb), 3.66–3.72 C1''Ha, C1''Hb), 5.29 (с, 1H, C3H),
,
–
I
7
.25–7.48 (m, 5H, Ph).
–
MS m/z (I
rel, %): 260 [М]+• (<0.1), 203 [М –
C4H8]+• (1), 187 (17), 159 (3), 147 (6), 131 (100),
102 (36), 91 (6), 77 (22), 57 (36).
(3,3ꢀDiallyloxypropꢀ1ꢀynꢀ1ꢀyl)benzene], Vb. Rf 0.30.
1H NMR (CDCl3;
, ppm, J, Hz): 4.13–4.32 (m,
δ
4H, C1'Ha, C1'Hb, C1''Ha, C1''Hb), 5.21–5.39 (m, 4H,
C3'Ha, C3'Hb, C3''Ha, C3''Hb), 5.56 (с, 1H, C3H), 5.91–
6.04 (m, 2H, C2'H, C2''H), 7.27–7.50 (m, 5H, Ph).
(1ꢀPhenylpropꢀ1ꢀynꢀ3,3ꢀdiyl)bis(hydroxybenzene),
IIa. Rf 0.22.
1H NMR (CDCl3
,
δ
, ppm,
J, Hz): 7.05–7.40 (m,
13C NMR (CDCl3 , ppm): 66.29 (C1'Н2, C1''Н2),
,
δ
15H, Ph; 1H, CH).
83.97 (C2), 85.78 (C1), 91.02 (C3H), 117.50 (C3'Н2,
13C NMR (CDCl3
,
δ
, ppm): 85.32 (C2), 95.10 (C1),
C3''Н2), 121.82, 128.29, 128.89, 131.96 (Ph), 134.05
103.39 (C3), 126.58, 127.61, 128.10, 128.35, 129.00,
(C2'Н, C2''Н)
MS m/z (I
rel, %): 228 [М]+• (<0.1), 171 [М –
.
131.02, 158.37 (Ph).
MS
m/z (I
rel, %): 300 [М]+• (<1), 207 [М –
•OC3H5]+ (18), 142 (78), 128 (100), 115 (40), 102 (58),
91 (22), 77 (27), 63 (13), 51 (19).
•OC6H5]+ (2), 175 (100), 158 (91), 144 (13), 131 (15),
116 (28), 102 (19), 91 (12), 77 (10), 63 (11).
(1ꢀPhenylpropꢀ1ꢀynꢀ3,3ꢀdiyl)bis(hydroxyꢀ2ꢀmethꢀ
ylbenzene), IIIb. Rf 0.27.
REFERENCES
1H NMR (CDCl3
CH3), 6.7–7.5 (m, 13H, Ph; 1H, CH).
,
δ
, ppm, J, Hz): 2.2 (s, 6H,
1. Kazakova, A.N., Bogomazova, A.A., and Zlotskii, S.S.,
Dokl. Chem., 2011, vol. 441, part 2, pp. 371–373.
2. Newman, M.S., Dhawan, B., Hashem, M.M., et al.,
MS
rel, %): 328 [М]+• (<1), 175 (100), 158
m/z (I
Org. Chem., 1976, vol. 41, no. 24, p. 3925.
(87), 144 (12), 131 (15), 116 (29), 102 (21), 91 (12), 77
(10), 63 (12), 51 (4).
´
n
3. Fedory ski, M., Chem. Rev., 2003, vol. 103, no. 4,
pp. 1099–1132.
DOKLADY CHEMISTRY Vol. 445
Part 2
2012