Reactions of substituted gem-dichlorocyclopropanes with mono-and dihydroxybenzenes

Full text of DOI:10.1134/S0012500811110036

ISSN 0012ꢀ5008, Doklady Chemistry, 2011, Vol. 441, Part 2, pp. 371–373. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.N. Kazakova, A.A. Bogomazova, S.S. Zlotskii, 2011, published in Doklady Akademii Nauk, 2011, Vol. 441, No. 6, pp. 759–761.
CHEMISTRY
Reactions of Substituted gemꢀDichlorocyclopropanes
with Monoꢀ and Dihydroxybenzenes
A. N. Kazakova, A. A. Bogomazova, and S. S. Zlotskii
Presented by Academician M.G. Voronkov June 20, 2011
Received June 20, 2011
DOI: 10.1134/S0012500811110036
The reaction of gemꢀdibromocyclopropanes with
Ketals Va –Vc are the main products of thermal proꢀ
phenols and alcohols is known to result in correspondꢀ cess, whereas the use of microwave radiation (MWR)
ing 1,1ꢀdiphenoxyꢀ and dialkoxycyclopropanes [1]. It sharply accelerates the substitution for the exocyclic
seems important to involve abundant and available (on chlorine atom, and ethers IVa
the basis of commercial monoꢀ and dichloropropenes) selectivity (Table 1).
substituted gemꢀdichlorocyclopropanes in this reacꢀ
–IVc form with high
Catechols VIa and VIb react with compound
I to
tion [2].
give 2'ꢀmethylenespiro[1,3ꢀbenzodioxolaneꢀ2,1'ꢀcycloꢀ
We have found conditions for the substitution for
propanes] (VIIa
,
VIIb) and ethers VIIIa
,
VIIIb.
exocyclic and endocyclic chlorine atoms in 2ꢀchloꢀ
romethylꢀgemꢀdichlorocyclopropane ( ) and in cis
and transꢀ1,1,2ꢀtrichloroꢀ3ꢀchloromethylcycloproꢀ
3
I
ꢀ
O
1'
2'
2
panes (cisꢀII, transꢀII) and accomplished this reacꢀ
tion.
R
O
1
OH
+
VIIа, VIIb
Cl
Compound
I reacts with phenols (IIIa–IIIc)
Cl
Cl
under conditions of phase transfer catalysis to give
R
OH
VIа, VIb
OH
competitively ethers (IVa
–
IVc) and ketals (Va –Vc ).
I
R1
R
O
VIIIа, VIIIb
O
Cl
VIIIb).
Cl
OH
Cl
Cl
R1
R = H (VIа
,
VIIа
,
VIIIа); tertꢀC4H9 (VIb, VIIb,
R2
R1
IVа–IVc
Cl
Scheme 2.
+
Cl
Cl
Exposure to microwave radiation sharply accelerꢀ
ates the displacement of chlorine atom in the CH2Cl
O
O
R2
IIIа–IIIc
I
R1
group of compound
this case (Table 2).
I and no ketals VIIa, VIIb form in
R1 = R2 = H (III
R1 = CH3, R2 = H (III
R1 = H, R2 = Cl (III
а
,
IV
а
b
,
V
а
);
b
R2
Vа–Vc
R2
,
IV
,
V
b
);
Table 1. Reaction of phenols IIIa
thylꢀgemꢀdichlorocyclopropane
–IIIc with 2ꢀchloromeꢀ
c
IV
c
,
V
c
).
I
Scheme 1.
Phenol
Reaction products (yield, %)
It is likely that only allyl chlorine atoms undergo
substitution, therefore, ethers IVa–IVc do not react
IIIa
IIIb
IIIc
IVa (5), (90)*
Va (86), (–)*
Vb (61), (–)*
Vc (59), (–)*
IVb (20), (73)*
IVc (38), (77)*
with phenols.
Note: Molar ratio NaOH : IIIa–IIIc : I : TEBAC = 6 : 3 : 1 : 0.02
(TEBAC, triethylbenzylammonium chloride) in 6.3 mL of
DMSO, 60°C, 5 h. * MWR, 230 W, 1 h.
Ufa State Oil Technical University, ul. Kosmonavtov 1,
Ufa, 450062 Bashkortostan, Russia
371

372
KAZAKOVA et al.
Phenols IIIa
–
IIIc react with cisꢀ and trans
ꢀ
transꢀII) to give stereoisomeric chloromethylene
1,1,2ꢀtrichloroꢀ3ꢀchloromethylcyclopropanes (cis
ꢀ
II,
(
IXa
–
IXc
,
Xa–Xc) and methylene ketals (XIa–XIc).
H
Cl
H
Cl
2
1
O
O
O
O
R1
R1 R1
+
R1
R2
R2
R2
Xа–Xc
R2
OH
R2
R1
IXа–IXc
Cl
Cl
+
Cl
2
3
Cl
II
Cl
trans II
1
O
O
R1
R1
cis
ꢀ
,
ꢀ
IIIа–IIIc
R2
R2
XIа–XIc
R1 = R2 = H (III
R1 = CH3, R2 = H (III
R1 = H, R2 = Cl (III
а
,
IX
а
b
,
X
а
,
b
X
,
Iа);
,
IX
Xb
,
X
Ib);
c
,
IX
c
,
Xc
,
XIc).
Scheme 3.
The preferable reaction route is endocyclic dehyꢀ NMR spectra were recorded on a Bruker AMꢀ300
drochlorination, which leads, on account of migraꢀ
tion of the double bond, to chloromethylene ketals
spectrometer (operating at 300.13 and 75.47 MHz,
respectively) in CDCl3 using Me4Si as an internal refꢀ
erence. GC–MS analysis was carried out with a Focus
(
IXa
–IXc, Xa–Xc) dominating in reaction mixture
(Table 3).
Let us note that the use of microwave radiation in
this reaction did not produce phenyl ethers.
Table 3. Reaction of cis and transꢀ1,1,2ꢀtrichloroꢀ3ꢀchloꢀ
romethylcyclopropanes (cis
IIIa IIIc
ꢀII, transꢀII) with phenols
–
EXPERIMENTAL
Yield of reaction products, %
(isomer ratio)
Initial compounds
cisꢀII IIIa
transꢀII
Initial
2ꢀchloromethylꢀgemꢀdichlorocycloproꢀ
pane and cis and transꢀ1,1,2ꢀtrichloroꢀ3ꢀchloromethꢀ
ylcyclopropanes were obtained by the known proceꢀ
dure [2, 3]. Qualitative and quantitative analysis of the
initial compounds and reaction products was perꢀ
formed with an LKhMꢀ8MD chromatograph with
thermal conductivity detection, helium as a carrier gas
+
IXa Xa XIa
80 (10 : 1 : 2)
IXa Xa XIa
90 (25 : 1 : 8)
IXb Xb XIb
79 (11 : 2 : 1)
IXb Xb XIb
87 (25 : 1 : 2)
IXc Xc XIc
89 (16 : 1 : 4)
IXc Xc XIc
94 (30 : 1 : 5)
,
,
+
IIIa
,
,
cisꢀII
transꢀII
cisꢀII
transꢀII
+
IIIb
,
,
(column 2000 ×
5 mm with 5% of SEꢀ30). 1H and 13C
+
IIIb
,
,
Table 2. Reaction of catechols VIa
thylꢀgemꢀdichlorocyclopropane
, VIb with 2ꢀchloromeꢀ
I
+
IIIc
,
,
Catechol
Reaction products (yield, %)
VIa
VIb
VIIa (41), (–)*
VIIb (5), (–)*
VIIIa (52), (62)*
VIIIb (45), (46)*
+
IIIc
,
,
Note: Molar ratio NaOH : VIa, VIb : I : TEBAC = 4 : 2 : 1 : 0.02 in
3.8 mL of DMSO, 65–70°C, 2 h. * MWR, 230 W, 0.1 h.
Note: Molar ratio NaOH : IIIa–IIIc : cisꢀII, transꢀII = 6 : 3 : 1 in
6.3 mL of DMSO, 0–5°C, 0.2 h.
DOKLADY CHEMISTRY Vol. 441
Part 2
2011

REACTIONS OF SUBSTITUTED
373
instrument interfaced with a Finnigan DSQ II massꢀ (19), 115 (100), 94 (17), 91 (56), 77 (78), 65 (21), 51
spectral detector (EI, 70 eV, ionizing chamber temꢀ (51).
perature of 200
°C, direct inlet temperature of 50–
1,1ꢀ[(2E)ꢀ2ꢀ(Chloromethylenecyclopropaneꢀ1,1ꢀ
diyl)bis(oxydibenzene)] Xa. Rf 0.21 (hexane–AcOEt,
270 C, heating rate of 10 K/min).
°
General procedure for the synthesis of adducts IVa–
IVc, Va–Vc, VIIa, VIIb, VIIIa, VIIIb, IXa–IXc, Xa–
Xc, XIa–XIc.
60 : 1, as eluent).
1H NMR (СDCl3
,
δ
, ppm): 2.13 (d, 2H, cycloꢀ
CH2, 2.47), 6.37 (t, 1H, CHCl,
J
J
2.6), 7.05–7.37
A solution of 0.005 mol of substituted gemꢀdichloꢀ
(m, 10H, Ph).
13C NMR (СDCl3
84.61 (cycloꢀC), 115.34 (=CHCl), 117.1 (oꢀPh),
rocyclopropane (
DMSO was added dropwise to a mixture of 0.015 mol
of phenol IIIa IIIc (or catechol VIa VIc), 0.03 mol
of NaOH (0.02 mol in the case of VIa VIc), 0.0001 mol
of TEBAC (in the case of compound ), 5.3 mL of
DMSO (2.8 mL in the case of VIa VIc) at 55–60
(on cooling to 0–5 C in the case of compounds cis
trans II) under vigorous stirring. After 2–5 h (0.2 h in
the case of compounds cis and trans ), the reaction
I, cisꢀII, or transꢀII) in 1 mL of
, δ, ppm): 20.49 (cycloꢀCH2),
–
–
122.9 (
(Ph).
pꢀPh), 125.99 (cycloꢀC=), 129.5 (
mꢀPh), 156.0
–
I
MS (m/z (Irel, %)): 271/273 M–1 (1), 235 (2),
–
°C
°
ꢀII,
179/181 M–OPh (42/13), 151/153 (32/10), 143 (19),
115 (100), 94 (15), 91 (45), 77 (75), 65 (17), 51 (39).
ꢀ
ꢀI
ꢀI
1,1ꢀ[2ꢀChloroꢀ3ꢀmethylenecyclopropaneꢀ1,1ꢀ
diyl)bis(oxydibenzene)] XIa. Rf 0.26 (hexane–AcOEt,
60 : 1, as eluent).
mixture was diluted with water, extracted with chloroꢀ
form, the organic layer was washed with 40 mL of
20% NaOH solution, then with water until neutral
reaction, dried with freshly calcined MgSO4, the chloꢀ
roform was removed under a slight vacuum, and the
residue was chromatographed on silica gel (hexane
(cyclohexane) with ethyl acetate gradient from 5 to
100% as an eluent).
1H NMR (СDCl3
CHCl, 2.07), 5.95 (d, 1H, =CH2,
1H, =CH2, 1.03), 7.11–7.38 (m, 10H, Ph).
13C NMR (СDCl3
, ppm): 36.20 (cycloꢀCHCl),
82.69 (cycloꢀC–(O–)2), 113.32 (=CH2), 116.92,
117.29 (oꢀPh), 122.95, 123.10 ( ꢀPh), 129.52, 129.72
ꢀPh), 132.30 (cycloꢀC), 155.13, 156.11 (Ph).
MS (
rel, %)): 272/274 [M]+ (<0.1), 236 (<1),
,
δ
, ppm): 4.03 (t, 1H, cycloꢀ
J
J
1.55), 6.07 (d,
J
,
δ
2'ꢀMethylenespiro[1,3ꢀbenzodioxolaneꢀ2,1'cycloꢀ
p
propane] VIIa. Bp 79–81
1H NMR (СDCl3
°
C (4 mmHg).
(
m
,
δ
, ppm): 2.14 (t, 2H, С11Н2),
5.05 (s, 1H, С12Н2), 5.33 (s, 1H, С12Н2), 6.63–6.91
m/z (I
207 (1), 179/181 [M–OPh]+ (1/0.3), 161 (100), 131
(1), 121 (5), 94 (5), 77 (28), 65 (14), 51 (8).
(m, 4H, C6H4).
MS (EI, 70 eV,
m/z (I
rel, %)): 160 M+ (81), 145
(37), 134 (100), 121 (3), 103 (4), 92 (7), 76 (6), 67
(18), 51 (14).
ACKNOWLEDGMENTS
This work was supported by the Ministry of Educaꢀ
tion and Science of the Russian Federation and the
Academy of Sciences of the Republic of Bashkorꢀ
tostan (grant no. B.4–11).
1,1ꢀ[(2Z)ꢀ2ꢀ(Chloromethylenecyclopropaneꢀ1,1ꢀ
diyl)bis(oxydibenzene)] IXa. Rf 0.30 (hexane–AcOEt,
60 : 1, as eluent).
1H NMR (СDCl3
,
δ
, ppm, J, Hz): 2.21 (d, 2H,
cycloꢀCH2, 3.23), 6.93 (t, 1H, CHCl,
7.37 (m, 10H, Ph).
J
J
3.23), 7.05–
REFERENCES
´
1. Fedory ski, M., Chem. Rev., 2003, vol. 103, no. 4,
n
13C NMR (СDCl3
, δ, ppm): 21.34 (cycloꢀCH2),
pp. 1099–1132.
2. Levashova, V.I., Neftepererab. Neftekhim., 2001, no. 10,
85.3 (cycloꢀC), 113.73 (=CHCl), 117.1 (oꢀPh), 122.9
ꢀPh), 126.2 (cycloꢀC=), 129.5 ( ꢀPh), 156.0 (Ph).
MS (
rel, %)): 271/273 [M–1]+ (1), 235 (2),
179/181 [M–OPh]+ (39/14), 151/153 (34/11), 143
pp. 25–29.
(
p
m
3. Mandel’shtam, T.V., Kharicheva, E.M., Labeish, N.N.,
and Kostikov, R.R., Zh. Org. Khim., 1980, vol. 16,
no. 12, pp. 2513–2518.
m/z (I
DOKLADY CHEMISTRY Vol. 441
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2011