Synthesis of halohydrines of 5-alkylbicyclo[2.2.1]heptene series using the systems inducing electrophilic reagents

Article abstract of DOI:10.1134/S1070363209080192

The reactions of induced hydroxyhalogenation of alkylnorbornenes with the use of a mixture of aqueous solutions of hydrochloric or hydrobromic acids (or sodium, potassium and cobalt bromides) and hydrogen peroxide or sodium hypochloriteare are studied. The reaction are established to proceed through the addition at the double bond of the ring of the electrophilic reagent HOBr or HOCl formed in situ yielding of cis-vicinal halohydrines. By dehydrohalogenation of the latter in the presence of alkali are obtained endo-6-alkyl-endo-3- oxatricyclo[3.2.1^1.5.0^2.4]octanes and by their oxidation are synthesized respective haloketones in a high yield.

Full text of DOI:10.1134/S1070363209080192

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1698–1703. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © O.A. Sadygov, Kh.M. Alimardanov, M.F. Abbasov, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 8, pp. 1338–
1343.
Synthesis of Halohydrines of 5-Alkylbicyclo[2.2.1]heptene Series
Using the Systems Inducing Electrophilic Reagents
O. A. Sadygov, Kh. M. Alimardanov, and M. F. Abbasov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
pr. Khodzhaly 30, Baku, Az1025, Azerbaijan
e-mail: omar.sadiqov@gmail.ru
Received March 18, 2009
Abstract—The reactions of induced hydroxyhalogenation of alkylnorbornenes with the use of a mixture of
aqueous solutions of hydrochloric or hydrobromic acids (or sodium, potassium and cobalt bromides) and
hydrogen peroxide or sodium hypochloriteare are studied. The reaction are established to proceed through the
addition at the double bond of the ring of the electrophilic reagent НОВr or НОCl formed in situ yielding of
cis-vicinal halohydrines. By dehydrohalogenation of the latter in the presence of alkali are obtained endo-6-
alkyl-endo-3-oxatricyclo[3.2.11.5.0 2.4]octanes and by their oxidation are synthesized respective haloketones in a
high yield.
DOI: 10.1134/S1070363209080192
In recent years increased interest to the bicyclic
unsaturated hydrocarbons and their derivatives caused
by high reactivity of the strained multiple bond of the
ring, stereoselectivity of the occurring reactions,
stability and biological activity of the compounds
synthesized on their basis. The direct halogenation of
norbornene with molecular chlorine, bromine, iodine
or mixed halides has been considered in detail [1–4].
The synthesized halo-substituted norbornenes were
proposed as initial compounds for obtaining α-
diketones [5] or cyclic halo-substituted ketones, easily
converted further into the phenol trihalo-derivatives [6,
7]. It is established that at the bromination of
norbornene and its alkyl derivatives depending on the
reaction conditions are formed either bromides or
bromohydrines, with the rearrangement of the initial
hydrocarbon [6, 7]. However, the reaction of the
induced halogenation or hydroxyhalogenation of the
norbornene alkyl derivatives which proceeds without a
change in the structure of initial hydrocarbon has not
been described so far. Meanwhile the realization of the
reaction of 1,2-addition to these hydrocarbons of the
elements of hypohalogenous acids induced in a special
system makes it possible to obtain vicinal
hydroxyhalides appropriate for the synthesis of endo-
oxiranes or halo-substituted ketones of bicyclic series
[9–11]. The halogenation of norbornene derivatives by
chloro(bromo)succinimide in a water–ether medium
and the subsequent epimerization of the obtained
products with sodium methylate is known to lead to
the formation of exo-chloro(bromo)hydrines. The by-
products of the reaction are nortricyclene derivatives [9].
The purpose of this work is to study the addition
reaction of the elements of hypohalogenous acids to 5-
R-bicyclo[2.2.1]hept-2-enes under the conditions that
induce formation of electrophilic reagent HOCl, HOBr
and transformation of the obtained compounds into
appropriate haloketones. As the inducing system we
used a mixture HX–H2O2 or (HX–MXn)–H2O2, M =
Na, K, Co (Scheme 1).
It is established that 5-alkylbicyclo[2.2.1]hept-2-
enes at 20–40ºC smoothly react with HOCl and HOBr
at the moment of their formation (in situ). In the IR
spectra of the compounds Ia–Ie and IIa–IIe the
absorption bands in the region of 745, 780 cm–1 (C–Cl
bond); 623, 640 cm–1 (C–Br bond), and 1100–1170,
3615 cm–1 (OH group) are common, and the bands at
1378, 1420, 1443 cm–1 correspond to the deformation
vibrations of CH2 and CH3 groups of the ring and alkyl
radical [12].
1
In the H NMR spectra of compounds Ia–Ie there
are doublets at δ 1.53–1.75 ppm with J = 5 Hz
corresponding to two bridgehead protons at C1 and C4.
The signal of one of them is split into a doublet with
J = 5 Hz and overlaps the signal of the other. The
1698

SYNTHESIS OF HALOHYDRINES OF 5-ALKYLBICYCLO[2.2.1]HEPTENE SERIES
1699
Scheme 1.
HX + H2O2 (or HX + MXn)
H
H
+
OH
R
X
R
Ia−Ie, IIa−IIe
М = Na, K, Co; n = 1, 2. X = Cl (I); Br (II); R = CH3 (а); С2Н5 (b); С3Н7 (c); С4Н9 (d); С5Н11 (e).
protons at C1 and C4 of compounds IIa – IIe also give
doublet signals, in the region of δ 1.53–1.85 ppm. The
doublet signals at δ 3.46–3.48 ppm and δ 3.36–3.58
ppm can be assigned to the protons at C2 and C3 of
compounds Ia–Ie and IIa–IIe, respectively. The
proton at the C5 carbon atom of compounds Ia and IIa
gives rise to the triplet at δ 1.61 ppm, and of
compounds Ic–Ie and IIc–IIe, at δ 1.42 ppm. The
signals of protons of OH group of compounds I and II
are observed in the region of δ 4.81 ppm as broad
singlets [13, 14].
The structure of the obtained epoxies IIIa–IIIe is
confirmed by the data of IR and 1H NMR spectroscopy
and by independent oxidation of alkylnorbornenes with
30% dioxane solution of H2O2 and CH3COOH in the
presence of the chlorine-bearing acidic cation-
excahnger KU-2×8 [15].
In the IR spectra of endo-6-alkyl-endo-3-oxa-
tricyclo[3. 2.11.5.02,4 ]octanes III the bands at 853 cm–1
related to C–O bond and the bands of stretching
vibrations of C–H bonds at 3028–3010 cm–1 in the
1
epoxy fragments are common. In the H NMR spectra
It is established that in the case of dehydro-
halogenation of halohydrines I and II with alkali
solution in alcohol the main reaction products are
endo-6-alkyl-endo-3-oxatricyclo[3.2.11.5.02,4]octanes,
with cis-vicinal arrangement of OH groups and atoms
Cl (Br) in the halohydrides:
appear a triplet at δ 1.77 ppm of the protons at C1 and
C5, a doublet at δ 2.87 ppm (C2 and C4), multiplets at δ
1.25–1.56 ppm related to CH2 groups of norbornane
and alkyl fragments. The doublets at δ 1.07 ppm in the
spectrum of epoxyde IIIa belongs to the CH3 protons
of alkyl fragment. With an increase in the length of
alkyl fragment these signals are shifted upfield and
appear as a triplet at δ 0.97 ppm. [13,14].
Scheme 2.
For the optimization of conditions of synthesis of
chloro(bromo)hydroxyhalides we studied the influence
of different parameters on the yield of the reaction
products. It was found that the yield of the final
product depended mainly on the temperature and
concentration of the hydrohalic acid (Tables 1 and 2).
As can be seen from the data in Table 1, at increase in
H
KOHT, anhydrous EtOH
Iа−Ie
IIа−IIe
+
O
R
IIIа−IIIe
R = CH3 (а); С2Н5 (b);С3Н7 (c); С4Н9 (d); С5Н11 (e).
Table 1. Influence of temperature on the yield of halohydrines. Ratio 5-R-bicyclo [2.2.1] hept-2-ene : НХ : Н2О2 = 0.1 :
0.14 : 0.14, acid solutions concentration 10% (HCl) and 6% (HBr), reaction duration 6.5 h, Н2О2 feeding rate 10 g h–1
Yield of halohydrines, %
Temperature,
I
II
°С
а
b
c
d
e
а
b
c
d
e
20
30
40
50
72.5
80.6
86.4
92.5
71.8
79.7
86.8
90.6
70.6
78.5
85.4
89.5
70.3
78.2
84.3
88.7
71.5
77.6
84.6
88.2
72.6
79.5
85.5
88.4
73.6
79.2
85.6
87.2
69.4
78.8
86.3
88.7
71.6
78.3
84.7
86.5
70.3
77.8
83.8
85.6
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SADYGOV et al.
Table 2. Dependence of halohydrine yield on the concentration of hydrochloric (hydrobromic) acid. Ratio 5-R-bicyclo[2.2.1]
jept-2-ene : НХ : Н2О2 = 0.2 : 0.22 : 0.24, temperature 30°C, Н2О2 feeding rate 10 g h–1, reaction duration 7.0 h
Yield of hydroxychloride I
Yield of hydroxybromide II
HBr
HCl
concentration,
concentration, %
а
b
c
d
e
а
b
c
d
e
%
6.0
10
74.3
80.6
72.6
63.4
40.6
72.5
79.7
70.4
65.6
39.6
70.6
78.5
69.4
53.2
39.5
71.0
78.2
67.5
50.6
38.7
69.5
77.6
64.8
51.5
40.7
68.6
79.5
69.2
53.4
39.5
70.3
79.2
68.5
50.6
40.4
67.6
78.8
67.2
48.5
41.6
68.5
78.3
66.4
46.8
39.0
69.2
77.8
65.3
47.6
39.2
6.0
10
20
30
45
15
25
35
Scheme 3.
temperature from 20 to 50°C the chloro- and
bromohydrines yield increases approximately by 10–
15%. The highest yields of chlorohydrines (81%) and
bromhydrines (79%) are reached at the temperature
30–40°C at the use of 6–10% aqueous solution of
hydrohalic acids (Table 2). An increase in the acid
concentration in the range of 15–35% (HCl) or 20–
46% (HBr) leads to decrease in the yield of chloro
(bromo)hydrines to 40%, which evidently is connected
with the intensification of the formation of molecular
halogen (Cl2 or Br2). The electrophilic addition of the
formed halides to the multiple bond of norbornene
fragment leads to the formation of certain amount of
dichloro- or dibromo-derivatives (38–40%), whose
structure we did not establish. It should be noted that
addition to the solutions of HCl or HBr up to 3–7 wt %
of MXn, M=Na, K, Co, also contributes to an increase
in the yield of chloro(bromo)hydroxyhalides.
O
CrO3, C6H5N or
H
K2Cr2O7 + H2SO4
Iа−Ie
IIа−IIe
+
R
X
IVа−IVe, Vа−Ve
X = Cl (IV); Br (V); R = CH3 (а); С2Н5 (b); С3Н7 (c);
С4Н9 (d); С5Н11 (e).
EXPERIMENTAL
The IR spectra of the synthesized compounds were
taken on a UR-20 spectrometer in the range 400–
3600 cm–1 from thin films. The H NMR spectra were
1
registered on a Bruker spectrometer with operating
frequency 300 MHz from the solutions in
deuterochloroform, internal reference HMDS. The
TLC data were otained with the use of Silufol UV-254
plates, the eluent ether, developing in iodine vapors.
In the literature there is practically no information
on the synthesis of chlorine(bromine)-containing
ketones of bicyclo[2.2.1]heptane series. An exception
is [9], where the reaction is examined of oxidation of
bromohydrin obtained by the epimerization of endo-
nitrile group in the molecule of anti-7-bromo-exo-2-
cyanobicyclo[2.2.1]heptane-5-one at the action of
sodium methoxide. At the oxidation of halohydrines
with the Brown mixture (or a mixture of CrO3 with
H2SO4) with a high selectivity are formed the cor-
responding haloketones according to Scheme 3.
The composition of the reaction products was
monitored by GLC on a chromatograph LKhM-8 MD-
5 with the detector on thermal conductivity, the
column 200×0.4 cm filled with 0.5 wt % of silicone
elastomer SE-30 on the carrier Chromoton-N-Super,
the carrier gas nitrogen (υ = 60 cm3 min–1), the column
temperature 140°C.
Initial cycloolefins were obtained by the known
procedure [16]. Their physicochemical constants
coincided with literature data [16, 17]. The
experiments were carried out in a glass reactor under
temperature control within ±0.2°C. To the reactor at a
given temperature was loaded 0.12–0.22 mol of 6%
aqueous solution of HBr or 6–10% solution of HCl (or
their mixture with MXn, M = Na, K, Co; X = Cl, Br,
n = 1; 2; 3–8 wt %) and 1 mol of norbornene alkyl
Thus, the use of the induction of electrophilic
reagents (HOCl or HOBr) in the highly acidic medium
makes it possible to synthesize cis-vicinal
halohydrines. Dehydrhalogenation and oxidation of the
latter leads to the formation of endo-6-alkyl-endo-3-
oxatricyclo[3. 2.11.5.02,4]octanes and 3-chloro(bromo)-
5-alkylbicyclo[2.2.1] heptan-2-ones with
selectivity.
a
high
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

SYNTHESIS OF HALOHYDRINES OF 5-ALKYLBICYCLO[2.2.1]HEPTENE SERIES
1701
derivative. To the reaction mixture at stirring through a
dropping funnel was introduced 0.24 mol of 26–30%
aqueous solution of hydrogen peroxide (feed rate 10 g h–1).
Stirring was continued for 6–7 h. The reaction was
completed after total consumption of H2O2, HOCl or
HOBr (tested by permanganometric and iodometric
methods). Organic layer was separated from the
aqueous layer. Aqueous layer was extracted with ether
(2×50 ml). The ether extracts were joined with the
organic layer, neutralized with 10% solution of
Na2CO3 and dried over magnesium sulfate.
Halohydrines Ia–Ie, IIa–IIe were separated by
distillation. The purity of the synthesized compounds
was estimated by GLC analysis.
Analogously were synthesized bromohydrines IIa–IIe.
3-Bromo-5-methylbicyclo[2.2.1]heptan-2-ol (IIa)
was obtained from 10.8 g of 5-methylbicyclo[2.2.1]
hept-2-ene. Yield 17.1 g (83.5%), mp 47–49°C. IR
spec-trum, ν, cm–1: 623, 640, 930 (CBr), 1380, 1410,
1
3320, (COH) [12]. H NMR spectrum, δ, ppm: 1.51 d
(1H, C1), 3.44–3.56 d.d (2H, C2, C3), 1.83 d (1H, C4),
1.61 d (1H, C5), 1.23–1.48 d. (2H, C6), 1.29–1.54 d.
(2H, C7), 1.07 d (3H, C8, alkyl) and 4.81 br.s (1H, OH)
[13, 14]. Found, %: C 47.08; H 6.58; Br 22.32.
C8H13BrO. Calculated, %: C 46.85; H 6.39; Br 38.96
[13,14]
3-Bromo-5-ethylbicyclo[2.2.1]heptan-2-ol (IIb) was
obtained from 12.2 g (0.1 mol) of 5-ethylbicyclo[2.2.1]
hept-2-ene. Yield 17.6 g (80.6%), mp 57–59.5°C. IR
spectrum, ν, cm–1: 623, 780, (CBr), 3320, 3615 (COH)
[12]. 1H NMR spectrum, δ, ppm: 1.53 d (1H, C1), 3.48
t (2H, C2, C3), 1.73 d (1H, C4), 1.41 so-called C5),
1.23–1.48 d.d (2H, C6), 1.29–1.54 d.d (2H, C7), 4.81
br.s. (1H, OH), 1.28 (2H, C8), 0.95 t (3H, C9, alkyl).
Found, %: C 62.12; H 8.92; Br21.08. C9H15BrO.
Calculated, %: C 61.89; H 8.66; Br 20.30 [13,14].
Identical spectral data were found for the compounds
IIc and IIe.
3-Chloro-5-methylbicyclo[2.2.1]heptan-2-ol (Ia)
was obtained from 10.8 g of 5-methylbicyclo[2.2.1]
hept-2-ene. Yield 13.8 g (86.4%), bp 94–95°C (3 mm
Hg) nD20 1.0983, d420 1.4763. IR spectrum, ν, cm–1: 745,
780, (CCl), 3320, 3615 (COH) [12]. 1H NMR
spectrum, δ, ppm: 1.53 d (1H, C1), 3.48 t (2H, C2, C3),
1.73 d (1H, C4), 1.61 t (1H, C5), 1.23–1.48 d.d (2H,
C6), 1.29–1.54 d.d (2H, C7), 1.07 d (3H, C8, alkyl) and
4.81 br.s (1H, OH). Found, %: C 60.08; H 8.35; Cl
22.32. C8H23ClO. Calculated, %: C 59.81; H 8.16; Br
22.07 [13,14].
3-Bromo-5-propylbicyclo[2.2.1]heptan-2-ol (IIc)
is obtained from 13.6 g (0.1 mol) of 5-propylbicyclo
[2.2.1]hept-2-ene. Yield 17.8 g (76.3%) mp 68–70°C.
Found, %: C 51.86; H 7.67; Br 34.46. C10H17BrO.
Calculated, %: C 51.52; H 7.35; Br 34.27.
3-Chloro-5-ethylbicyclo[2.2.1]heptan-2-ol (Ib) was
obtained from 12.2 g (0.1 mol) of 5-ethylbicyclo[2.2.1]-
hept-2-ene. Yield 6.4 g (85.2%), bp 101–103°C (3 mm
Hg) nD201.0988, d420 1.4783. IR spectrum, ν, cm–1: 745,
780, (CCl), 3320, 3615 (COH) [12]. 1H NMR
spectrum, δ, ppm: 1.53 d (1H, C1), 3.48 t (2H, C2, C3),
1.73 d (1H, C4), 1.41 so-called (C5), 1.23–1.48 d.d
(2H, C6), 1.29–1.54 d.d (2H, C7), 4.81 br.s. (1H, OH),
1.28 (2H, C8), 0.95 t (3H, C9, alkyl). Found, %: C
62.12; H 8.92; Cl 21.08. C9H815ClO. Calculated, %: C
61.89; H 8.66; Cl 20.30 [13,14]. Identical spectral
characteristics are obtained for the products Ic and Id.
3-Bromo-5-pentylbicyclo[2.2.1]heptane-2-ol (IIe)
was obtained from 16.4 g (0.1 mol) of 5-pentylbicyclo-
[2.2.1]hept-2-ene. Yield 17.8 g (68.2%), mp 91–94°C.
Found, %: C 55.62; H 8.44; Br 30.85. C12H21BrO.
Calculated, %: C 55.18; H 8.10; Br 30.59. At working
up the synthesized halohydrines with alcohol solution
of KOH are obtained respective endo-epoxies (yield
83.6–94.7%).
3-Chloro-5-propylbicyclo[2.2.1]heptan-2-ol (Ic)
was obtained from 15 g (0.1 mole) of 5-propylbicyclo
[2.2.1]hept-2-ene. Yield 15.4 g (81.4%), bp 113–114°
C (3 mm Hg), nD20 1.0998, d420 1.4875. Found, %: C
64.06; H 9.26; Cl 19.08. C10H17ClO. Calculated, %: C
63.65; H 9.08; Cl 18.797.
endo-6-Methyl-endo-3-oxatricyclo[3.2.11.5.02.4]oc-
tane (IIIa) was obtained from 16 g of Ia. Yield 11.5 g
(92.6%), bp 143°C, nD20 1.4657, d420 0.9724. IR
1
spectrum, ν, cm–1: 865, 873, 880 [12]. H NMR
spectrum, δ, ppm: 1.75 t (2H, C1, C5), 2.87 d (2H, C2,
C4), 1.59 d (1H, C6), 1.41 so-called C5), 1.23–1.48 d.
(2H, C7), 1.29–1.54 d. (2H, C8), 1.07 t (3H, C9).
[13,14]. Found, %: C 77.85; H of 10.03 Br21. C8H12O.
Calculated, %: C 77. 38; H 9.74.
3-Chloro-5-butylbicyclo[2.2.1]heptane-2-ol (Id)
was obtained from 15 g (0.1 mole) of 5-butylbicyclo
[2.2.1]hept-2-ene. Yield 15.2 g (70.2%), bp 134–136°
20
C (2 mm Hg), nD 1.1086, d420 1.4876. Found, %: C
endo-6-Ethyl-endo-3-oxatricyclo[3.2.11.5.02.4]octane
(IIIb) was obtained from 11 g (0.05 mol) of IIb. Yield
65.34; H 9.83; Cl 17.86. C11H21ClO. Calculated, %: C
65.17; H 9.45; Cl 17.49.
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SADYGOV et al.
6.2 g (90.5%), bp 166°C, nD20 1.4682, d420 0.9701. IR
3-Chloro-5-ethylbicyclo[2.2.1]heptane-2-one (IVb)
was obtained from 4.4 g (0.025 mol) of Ib. Yield 3.4 g
(79.3%), bp 94–95°C (3 mm Hg), d420 0.9932, nD20
1.4512. Found, %: C 62.07; H 8.93; Cl 20.76.
C9H13ClO. Calculated, %: C 61.89; H 8.66; Cl 20.30.
1
spectrum, ν, cm–1: 865, 873, 880 [12]. H NMR
spectrum, δ, ppm: 1.75 t (2H, C1, C5), 2.87 d (2H, C2,
C4), 1.59 d (1H, C6), 1.23–1.48 d (2H, C7), 1.29–1.54 d,
(2H, C8), 1.24 d (3H, C9), 0.97 t (3H, C10) [13,14].
Found, %: C 78.67; H 10.76. C9H14O. Calculated, %:
C 78. 21; H 10.21.
3-Chloro-5-propylbicyclo[2.2.1]heptane-2-one
(IVc) was obtained from 4.7 g (0.025 mol) of Ic. Yield
3.6 g (78.4%), mp 53–55°C. Found, %: C 64.67; H
8.43; Cl 19.12. C10H15ClO. Calculated, %: C 64.34; H
8.10; Cl 18.99.
Analogous spectral data were found for other
epoxies IIIc–IIIe.
endo-6-Propyl-endo-3-oxatricyclo[3.2.11.5.02.4]oc-
tane (IIIc) was obtained from 9.4 g (0.05 mol) of Ic.
Yield 6.7 g (88.6%), bp 71–73°C (14 mm Hg), nD20
1.4751, d420 0.9692. Found, %: C 79.08; H 10.83.
C10H16O. Calculated, %: C 78. 90; H 10.59.
endo-6-Butyl-endo-3-oxatricyclo[3.2.11.5.02.4]octane
(IIId) was obtained from 12.7 g (0.05 mol) of IId.
Yield 7.6 g (85.8%), bp 64–66°C (14 mm Hg), nD20
1.4826, d420 0.9823. Found, %: C 79.84; H 11.07.
C12H18O. Calculated, %: C 79. 46; H 10.91.
endo-6-Pentyl-endo-3-oxatricyclo[3.2.11.5.02.4]oc-
tane (IIIe) was obtained from 10.8 g (0.05 mol) of Ie.
Yield 7.5 g (83.7%), bp 83–75°C (3 mm Hg), nD20
1.4952, d420 0.9823. Found, %: C 80.06; H 11.26.
C10H20O. Calculated, %: C 79. 94; H 11.18.
3-Chloro-5-butylbicyclo[2.2.1]heptane-2-one (IVd)
was obtained from 5.1 g (0.025 mol) of Id. Yield 3.7 g
(75.6%), mp 63–65°C. Found, %: C 66.03; H 8.82; Cl
18.10. C11H17ClO. Calculated, %: C 65.83; H 8.54; Cl
17.66.
3-Chloro-5-pentylbicyclo[2.2.1]heptan-2-onet (IVe)
was obtained from 5.4 g (0.025 mole) of Ie. Yield 3.8 g
(70.8%), mp 74–76°C. Found, %: C 67.53; H 9.06; Cl
17.03. C12H19ClO. Calculated, %: C 67.12; H 8.92; Cl
16.51.
Bromoketones (Va–Ve) were obtained similarly to
the chloroketones. To 0.025 mole of 3-bromo-5-
alkylbicyclo[2.2.1]heptan-2-ol in 30 ml of pyridine
was added 9.8 g of chromium trioxide. The reaction
mixture was stirred at 30–45°C till completion
(according to the data of TLC), then pyridine was
removed in a vacuum. The residue was worked up with
water and the product was extracted with chloroform.
The organic layer was washed with diluted sulfuric
acid and water, then dried, the solvent was removed
and the ketone was isolated.
3-Chloro(bromo)-5-alkylbicyclo[2.2.1]heptan-2-
ones (I, II) (general procedure). To 0.025 mol of 3-
chloro-5-alkylbicyclo[2.2.1]heptan-2-ol in 40 ml of
ether was added dropwise 16 ml of Brown reagent
obtained by dissolving 20 g of potassium bichromate
in 20 ml of concentrated sulfuric acid with the
subsequent dilution by water to a volume of 55 ml.
The reaction proceeds at room temperature (18–20°C)
at stirring, for 20–30 min (according to the data of
GLC). The ether layer was separated, aqueous layer
was extracted with ether (2×50 ml), joined extracts
were dried, the solvent was removed, and the ketone
was separated.
3-Bromo-5-methylbicyclo[2.2.1]heptan-2-one (Va)
was obtained from 5.1 g (0.025 mol) of IIa. Yield 8.2 g
(80.7%), mp 58–60°C. IR spectrum, ν, cm–1: 1723,
1
1745 (C=O), 680, 750 (CBr) [12,14]. The H NMR
spectrum, δ, ppm: 2.06 d (1H, C1), 3.97 d (1H, C3),
2.42 d (1H, C4), 1.68 t (1H, C5), 1.60–1.85 d.d (2H,
C6), 1.81–2.06 d.d (2H, C7), 1.07 d (3H, CH3, alkyl)
[13,14]. Found, %: C 47.66; Н 5.83; Br 39.87.
C8Н11BrО. Calculated, %: C 47.32; Н 5.46; Br 39.35.
3-Chloro-5-methylbicyclo[2.2.1]heptan-2-one (IVa)
was obtained from 4 g of Ia. Yield 3.3 g (82%), bp 69–
71°C (3 mm Hg), d420 0.9962, nD20 1.4472. IR spectrum,
ν, cm–1: 1723, 1745 (C=O), 710, 745 (CCl4) [12,14].
Identical spectral data were obtained for the bromo-
ketones Vb–Ve.
1
The H NMR spectrum, δ, ppm: 2.06 d (1H, C1), 4.04
d (1H, C3), 2.32 d (1H, C4), 1.68 d (1H, C5), 1.60–1.85
d.d (2H, C6), 1.81–2.06 d.d (2H, C7), 1.07 d (3H, CH3,
alkyl) [13,14]. Found, %: C 60.75; H 7.12; Cl 22.74.
C8H11ClO. Calculated, %: C 60.57; H 6.99; Cl 22.35.
Analogously were obtained compounds IVb–IVe, the
chloroketones, with the same spectral characteristics.
3-Bromo-5-ethylbicyclo[2.2.1]heptan-2-one (Vb)
was obtained from 5.5 g (0.025 mol) of IIb. Yield 4.3 g
(79.3%), mp 69–71°C. Found, %: C 50.08; Н 6.35; Br
37.12. C9Н13BrО. Calculated, %: C 49.79; Н 6.04; Br
36.80.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

SYNTHESIS OF HALOHYDRINES OF 5-ALKYLBICYCLO[2.2.1]HEPTENE SERIES
1703
6. Khan, F.A., Dash, J., Jain, D., and Probydas, B., J. Chem.
Soc., Perkin Trans., 2001, p. 3132.
7. Mamedbeili (Mamedov), E.G., Klabunovskii, E.I., Ab-
diev, O.B., and Mamedova, I.M., Kataliz v pro-
myshlennosti, 2008, no. 5, p. 23.
3-Bromo-5-propylbicyclo[2.2.1]heptan-2-one (Vc)
was obtained from 5.8 g (0.025 mol) of IIc. Yield 4.5 g
(77.5%), mp 81–83°C. Found, %: C 52.10; Н 6.78; Br
35.08. C10Н15BrО. Calculated, %: C 51.97; Н 6.54; Br
34.57.
8. Dalton, D.R., Rodebugh, D.K., and Jefford, C.W.,
3-Bromo-5-butylbicyclo[2.2.1]heptan-2-one (Vd)
was obtained from 6.2 g (0.025 mol) of IId. Yield 4.6 g
(75.6%), mp 92–94°C. Found, %: C 54.06; Н 7.11; Br
33.11. C11Н17BrО. Calculated, %: C 53.89; Н 6.99; Br
32.59.
J. Org. Chem., 1973, vol. 37, p. 362.
9. Kas’yan, L.I., Zefirov, N.S., Khmelevskaya, N.D.,
Gnedenkov, L.Yu., et al., Zh. Org. Khim., 1978, vol. 14,
no. 11, p. 2297.
10. Plenat, F., Coste, J., and Cristol, H., Bull. Soc. Chem.,
1973, p. 1064.
11. Zefirov, N.S. and Filatova, R.S., Zh. Obshch. Khim.,
1967, vol. 37, p. 2240.
12. Bellami, L., Infrakrasnye spektry slozhnykh molekul (IR
Spectra of Complex Molecules), Moscow: Inostrannaya
Literatura, 1963.
3-Bromo-5-pentylbicyclo[2.2.1]heptan-2-one (Ve)
was obtained from 6.5 g (0.025 mol) of IIe. Yield 4.4 g
(68.3%), mp 102–104°C. Found, %: C 55.93; Н 7.76;
Br 31.12. C12Н19BrО. Calculated, %: C 55.61; Н 7.39;
Br 30.83.
13. Ionin, B.I. and Ershov, BA., YaMR spektroskopiya v
organicheskoi khimii (NMR Spectroscopy in Organic
Chemistry), Leningrad: Khimiya, 1967.
14. Gordon, A.J. and Ford, R.A., The Chemist’s Compa-
nion. A Handbook of Practical Data, Techniques and
References, New York: Wiley, 1972.
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