Hypohalogenation of functionally substituted acetylenic norbornenes

Article abstract of DOI:10.1134/S1070428008090066

Hypohalogenation of norbornenes containing a triple bond and various functional groups in the side chain was performed using mixtures of aqueous solutions of hydrochloric or hydrobromic acid (or sodium or potassium bromide) and hydrogen peroxide. The reaction was found to involve addition of electrophilic reagent generated in situ (HOBr or HOCl) at the endocyclic double bond with formation of the corresponding halohydrins. The latter underwent dehydrohalogenation by the action of alklai to give exo-5,6-epoxybicyclo[2.2.1]- heptane derivatives in high yields. Kinetic relations holding in the hypobromination process were established, and the initial rates and activation parameters were calculated.

Full text of DOI:10.1134/S1070428008090066

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 9, pp. 1282–1290. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © M.G. Veliev, O.A. Sadygov, M.I. Shatirova, Kh.M. Alimardanov, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44,
No. 9, pp. 1298–1307.
Hypohalogenation of Functionally Substituted
Acetylenic Norbornenes
M. G. Velieva, O. A. Sadygovb, M. I. Shatirovaa, and Kh. M. Alimardanovb
a Institute of Polymeric Materials, National Academy of Sciences of Azerbaidjan,
ul. S. Vurguna 124, Sumgaiyt, Az5004 Azerbaidjan;
e-mail: mveliyev@mail.ru
b Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaidjan, Baku, Azerbaidjan
Received July 12, 2007
Abstract—Hypohalogenation of norbornenes containing a triple bond and various functional groups in the side
chain was performed using mixtures of aqueous solutions of hydrochloric or hydrobromic acid (or sodium or
potassium bromide) and hydrogen peroxide. The reaction was found to involve addition of electrophilic reagent
generated in situ (HOBr or HOCl) at the endocyclic double bond with formation of the corresponding halo-
hydrins. The latter underwent dehydrohalogenation by the action of alklai to give exo-5,6-epoxybicyclo[2.2.1]-
heptane derivatives in high yields. Kinetic relations holding in the hypobromination process were established,
and the initial rates and activation parameters were calculated.
DOI: 10.1134/S1070428008090066
The chemistry of norbornene and its derivatives is
now rapidly developing, thus opening new prospects
for use of these compounds in organic synthesis [1–3].
It is known that norbornene derivatives are used in
perfumery, food industry, and medicine, as well as
monomers in the manufacture of valuable polymeric
materials and insecticides and pesticides for agriculture
[4–6]. However, the synthesis and chemical trans-
formations of bicyclic unsaturated compounds contain-
ing a triple bond and various functional groups in the
side chain have been reported only in a few publica-
tions [7–9]. Due to the presence of double and triple
bonds and reactive functional groups such compounds
could be brought into diverse chemical transformations
[10–13]. In this work we studied hypohalogenation of
bicyclo[2.2.1]hept-2-enes having a triple bond in the
side chain, kinetic parameters of the process, and trans-
formations of the resulting halohydrins.
We found that acetylenic norbornenes Ia–If and
IIa–IIf react with hypochlorous and hypobromous
acids in statu nascendi (HOCl and HOBr were generat-
ed in the system HCl or HBr/H2O2 or MBr/H2O2/H+) at
10–40°C to give the corresponding halohydrins IIIa–
IIIf, IVa–IVf, Va–Vf, and VIa–VIf (Scheme 1). The
yields, physical constants, and elemental analyses of
compounds III–VI are given in Experimental. Their
structure was proved by IR and 1H NMR spectroscopy.
The IR spectra of IIIa–VI contained strong absorption
bands in the regions of 3450, 3300, 2270, 2230, 2140,
1720, 1155, 805, 750, and 630 cm–1 due to stretching
and bending vibrations of the O–H, ≡C–H, C≡C, C≡N,
C=O, C–O–C, C–Br, and C–Cl bonds [14, 15]. In the
1
upfield region of the H NMR spectra of compounds
III–VI we observed a multiplet at δ 1.32 ppm, corre-
sponding to the endo-6-H proton, while the exo-6-H
signal appeared as a triplet in a weaker field
Scheme 1.
X
( )n
( )n
+ HX (or MBr) + H2O2
R
R
HO
Ia–If, IIa–IIf
IIIa–IIIf, IVa–IVf, Va–Vf, VIa–VIf
III, V, X = Cl; IV, VI; X = Br; R = H (a), HOCMe2 (b), MeOCMe2 (c), NCCH2CH2OCMe2 (d), HOCH2CH2OCMe2 (e),
MeCOOCMe2 (f); I, III, IV, n = 0; II, V, VI, n = 1; M = Na, K.
1282

HYPOHALOGENATION OF FUNCTIONALLY SUBSTITUTED ACETYLENIC ...
1283
Table 1. Yields of halohydrins III–VI in the hypohalogenation of compounds Ia–If and IIa–IIf at different temperatures
Yield, wt %
Compound
10°C
20°C
30°C
40°C
no.
X = Cl
X = Br
X = Cl
X = Br
X = Cl
X = Br
X = Cl
X = Br
IIIa, IVa
IIIb, IVb
IIIc, IVc
IIId, IVd
IIIe, IVe
IIIf, IVf
Va, VIa
Vb, VIb
Vc, VIc
Vd, VId
Ve, VIe
70.5
72.6
74.2
71.5
76.3
74.6
72.6
74.3
75.6
73.8
77.5
75.8
72.3
74.5
76.6
73.4
77.8
76.0
74.6
76.3
77.4
76.5
78.6
78.2
75.3
76.5
78.3
75.1
80.3
78.6
76.5
81.6
83.0
77.6
86.2
84.5
78.5
81.6
84.5
80.2
85.3
83.0
78.0
80.0
85.0
79.0
87.3
86.0
80.6
82.6
85.7
80.6
86.6
84.7
85.3
88.4
87.4
82.4
89.8
89.3
86.5
88.3
89.5
85.3
90.5
86.6
87.5
89.0
90.7
84.0
92.7
91.6
83.6
87.5
92.6
90.5
91.5
89.4
92.8
94.0
91.5
87.5
93.7
92.6
91.8
93.2
94.3
90.4
95.3
92.1
94.0
95.0
94.6
89.0
96.0
95.0
Vf, VIf
(δ 2.09 ppm). The exo-5-H proton resonated as a multi-
plet centered at δ 2.75 ppm. The coupling constants
J6,6′ = 12.2–12.5, J5,endo-6 = 5.0–5.3, and J5,exo-6 = 9.5–
9.7 Hz suggest endo configuration of the substituent on
C5 (large value of J5,exo-6 and small value of J5,endo-6).
The anti-7-H and syn-7-H protons gave signals in the
upfield region (δ 1.70 ppm). Signals at δ 3.65 and
3.88 ppm were assigned to protons on C2 and C3,
respectively; the vicinal coupling constant J2,3 is 4.5–
4.7 Hz. The other proton signals were located at δ,
ppm: 2.12 d (1-H), 2.31 m (4-H), 1.95 m (8-H), 2.42 t
(9-H) [14, 15].
The data in Table 1 show that the yields of chloro-
and bromohydrins III and IV (n = 0) are lower by 2–
4% than those of their analogs V and VI with a longer
side chain (n = 1). The reaction selectivity and the
yield of III–VI strongly depended on the hydrohalic
acid concentration. At low concentration of HCl (10–
15%) and HBr (6–10%) the corresponding halohydrins
were formed in almost quantitative yield, whereas
higher concentration of hydrohalic acids favored
formation of dichloro- and dibromobicycloheptane
derivatives as by-products. Presumably, increased con-
centration of HCl and HBr promotes their oxidation to
molecular halogens which add at the double bond of
the substrate with formation of dihalo derivatives (they
will be the subject of our further studies).
With a view to find optimal conditions for the syn-
thesis of acetylenic chloro- and bromohydrins of the
bicycloheptene series we examined influence of differ-
ent parameters on the product yields. Such factors as
temperature, concentration of hydrohalic acid, and in-
tensity of stirring of the reaction mixture were found to
be important. Insofar as acetylenic bicycloheptenes are
almost insoluble in water, the reactions were hetero-
geneous, i.e., HOCl and HOBr were generated in the
aqueous phase, while their addition occurred in the
organic phase or at the phase boundary. Therefore, all
reactions should be performed under vigorous stirring
(the rate of stirring was 600–700 rpm). Raising the
temperature from 10 to 40°C increased the yield of
chlorohydrins IIIa–IIIf and Va–Vf from 71 do 92%;
the yield of bromohydrins IVa–IVf and VIa–VIf also
increased from 72 to 96% (Table 1).
We also tried to estimate the reactivity of the
bicycloheptene fragment toward HOCl and HOBr,
depending on the position and structure of the side-
chain acetylenic fragment. For this purpose, we meas-
ured the kinetic parameters of the hypobromination
process. The initial rates of addition of HOBr at the
double bond were calculated from the GLC data on
accumulation of the corresponding bromohydrins. The
reaction rates were determined by graphical differen-
tiation of the kinetic curves plotted in the coordinates
product yield–time using the formula given in [16].
The relation between the logarithm of the initial
rate and reciprocal temperature for the examined
bicycloheptene series fits the Arrhenius equation
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

VELIEV et al.
1284
Table 2. Kinetic parameters of hypobromination of compounds Ia–If and IIa–IIf
Initial reaction rates w0 ×103, l mol–1 min–1
Activation parameters
E, kJ/mol ΔH≠, kJ/mol ΔS≠, J mol–1 K–1 ΔG≠, kJ/mol
Compound
no.
10°C
20°C
30°C
40°C
Ia
03.52
08.43
05.25
8.2
06.86
11.50
08.42
12.10
11.67
19.20
10.30
16.80
08.57
12.50
08.48
14.30
10.67
17.83
13.83
18.70
18.20
31.10
16.80
36.20
15.30
19.80
11.76
20.30
16.73
24.83
17.82
38.30
30.10
47.70
23.50
67.80
23.70
28.60
18.20
50.40
28.6
33.9
23.1
30.0
30.3
24.6
25.2
34.7
23.3
30.3
21.5
34.3
28.0
33.2
23.0
29.4
29.6
24.0
24.6
34.1
22.6
29.4
20.6
33.4
65.3
75.5
68.5
72.0
72.0
66.4
66.9
76.3
69.4
71.9
61.5
77.8
47.8
56.1
43.8
51.2
51.4
44.1
44.9
57.2
43.6
51.2
39.2
57.0
IIa
Ib
IIb
Ic
07.63
11.90
06.53
10.30
06.83
08.21
5.9
IIc
Id
IId
Ie
IIe
If
IIf
08.43
(Table 2). The initial rates and energies of activation
for the formation of bromohydrins having acetylenic
bonds in the β-position with respect to the bicyclic
fragment are greater than those found for their analogs
with a triple bond in the α-position. In the first case,
the transition state is more ordered, as follows from
the entropy values. Comparison of the initial reaction
rates and activation parameters shows that α-acetylenic
norbornenes are less reactive than their β-acetylenic
analogs.
signal was located in a weaker field, as a multiplet at
δ 1.46–1.72 ppm. The 5-H signal was a multiplet at
δ 2.15 ppm. The coupling constants for the 5-H and
6-H protons were as follows: J6,6′ = 12.2–12.4, J5,6
=
10.3–10.5, J5,6′ = 4.5–4.8 Hz; these findings unambigu-
ously indicate endo orientation of the prop-2-yn-1-yl
substituent on C5. The syn-7-H (δ 1.32 ppm, m) and
anti-7-H protons (δ 0.65 ppm, d) together with 1-H and
4-H give rise to an ABX spin system. The 1-H and 4-H
signals appeared as an unresolved multiplet centered at
δ 2.37 ppm. The 2-H and 3-H protons resonated as
a doublet of doublets at δ 2.86 ppm, J2,3 = 3.7–3.8 Hz,
indicating exo orientation of the epoxy group. Com-
pounds VIIa, VIIb, VIId, VIIIa, VIIIb, and VIIId
were also synthesized by direct epoxidation of the
corresponding norbornenes Ia, Ib, Id, IIa, IIb, and IId
with peroxyacetic acid (Scheme 3); in this case, the
yield was 78–80%. Samples of VII and VIII obtained
by the two methods were identical in physical prop-
erties and spectral parameters.
Both chloro- and bromo-substituted hydroxynor-
bornanes III–VI readily underwent dehydrohalogena-
tion by the action of powdered potassium hydroxide.
As a result, the corresponding epoxy derivatives VIIa–
VIIe and VIIIa–VIIIe were obtained in 85–90% yield
(Scheme 2). The structure of compounds VIIa–VIIe
and VIIIa–VIIIe was confirmed by the IR and
1H NMR data. The IR spectra of VII and VIII lacked
absorption at 1635 and 3095 cm–1, which is typical
of HC=CH bond, but bands at 850, 910, 1245, and
3060 cm–1 were present due to vibrations of bonds in
the oxirane ring. In the 1H NMR spectra of these com-
pounds, the endo-6-H proton resonated as a multiplet
in a strong field, at δ 0.80 ppm, while the exo-6-H
Hydrolysis of chloro- and bromohydrins IIIa–VIa
in aqueous methanol in the presence of catalytic
amounts of HgSO4 and H2SO4 gave the corresponding
acetyl- and acetonyl-substituted norbornanes IX–XII
Scheme 2.
X
( )n
( )n
KOH
O
R
R
HO
IIIa–IIIe, IVa–IVe, Va–Ve, VIa–VIe
VIIa–VIIe, VIIIa–VIIIe
VII, n = 0; VIII, n = 1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

HYPOHALOGENATION OF FUNCTIONALLY SUBSTITUTED ACETYLENIC ...
1285
Scheme 3.
( )n
( )n
MeCO3H
O
R
R
Ia, Ib, Id, IIa, IIb, IId
VIIa, VIIb, VIId, VIIIa, VIIIb, VIIId
in almost quantitative yield. The subsequent dehydro-
halogenation of IX–XII by the action of powdered
potassium hydroxide led to the formation of epoxy
ketones XIII and XIV (Scheme 4) whose structure was
confirmed by the IR and 1H NMR spectra.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spec-
trometer. The H NMR spectra were measured on
1
a Tesla BS-487B instrument (80 MHz) from solutions
in carbon tetrachloride using hexamethyldisiloxane as
internal reference. Gas–liquid chromatography was per-
formed on an LKhM-8MD-5 chromatograph equipped
with a thermal conductivity detector and a 200×0.4-cm
column packed with 0.5 wt % of poly(dimethylsilox-
ane) on NaCl; oven temperature 140°C; carrier gas
helium, flow rate 60 ml/min. The initial rates and
thermodynamic parameters were determined following
accumulation of the corresponding bromohydrins; the
calculations were performed by known equations [16].
Compounds VIIa and VIIIa having a terminal
triple bond can be obtained in high yield by treatment
of halohydrins IIIb–VIb with alkali in toluene at 40–
50°C, followed by heating at 90–100°C (Scheme 5).
Here, elimination of hydrogen halide was accompanied
by the reverse Favorsky reaction. It should be noted
that raising the temperature to 110–120°C leads to
reduced yield of final products VIIa and VIIIa
because of appreciable tarring, while lowering the tem-
perature to 80–90°C also reduces the yield to 50–60%
due to deceleration of the reverse Favorsky reaction.
Hydrolysis of epoxides VIIa and VIIIa in 10% sul-
furic acid gave acetylenic dihydroxynorbornanes XV
and XVI.
Initial compounds Ia–If and IIa–IIf were synthe-
sized by the Diels–Alder reactions of cyclopentadiene
with the corresponding enynes [9]; their physical con-
stants were consistent with those given in [7–12].
Thus the results of our study showed that hypo-
halogenation of norbornenes having a triple bond and
various functional groups in the side chain involves the
endocyclic double bond in the substrate to produce the
corresponding halohydrins. These compounds, as well
as epoxides and diols derived therefrom, attract interest
as intermediate products for the preparation of various
polyfunctionalized compounds with practically useful
properties.
Halohydrins III–VIa (general procedure). A 26–
30% aqueous solution of hydrogen peroxide, 0.22 mol,
was added from a dropping funnel at a rate of 10 g/h
under stirring to a mixture of 0.2 mol of 6% aqueous
HBr (or NaBr + HCl) or 10% hydrochloric acid and
0.2 mol of alkynylnorbornene Ia–If or IIa–IIf. The
mixture was stirred for 5.5–6.5 h, the organic phase
was separated, neutralized, and dried, and the products
were isolated by vacuum distillation.
Scheme 4.
X
X
Me
Me
( )n
( )n
( )n
H2O, HgSO4, H+
KOH
CH
O
–KX
–H2O
O
O
HO
HO
IIIa–VIa
IX–XII
XIII, XIV
IX, XI, X = Cl; X, XII, X = Br; IX, X, XIII, n = 0; XI, XII, XIV, n = 1.
Scheme 5.
X
HO
( )n
( )n
( )n
KOH
H2O, H+
OH
Me
O
CH
CH
–Me2CO, –KX
–H2O
HO
HO
Me
IIIb–VIb
VIIa, VIIIa
XV, XVI
VIIa, XV, n = 0; VIIIa, XVI, n = 1; X = Cl, Br.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

VELIEV et al.
1286
3-Chloro-5-ethynylbicyclo[2.2.1]heptan-2-ol
4-(6-Chloro-5-hydroxybicyclo[2.2.1]hept-2-yl)-2-
methylbut-3-yn-2-yl acetate (IIIf). Yield 19 g (71%),
bp 108–109°C (1 mm), d420 = 1.1983, nD20 = 1.5213. IR
spectrum, ν, cm–1: 3500 (O–H); 2230 (C≡C); 1720,
(IIIa). Yield 13.2 g (75%), bp 85–86°C (10 mm), d420 =
1.1456, nD20 = 1.5172. IR spectrum, ν, cm–1: 3525
(O–H); 3290, 2140 (C≡CH); 850 (C–Cl), 745. 1H NMR
spectrum, δ, ppm: 1.53 t (1H, 1-H), 1.81 t (1H, 4-H),
1.82 d (1H, HC≡), 2.48 d (1H, 5-H), 3.47 d (1H, 2-H),
3.49 d (1H, 3-H), 4.81 br.s (1H, OH). Found, %:
C 63.48; H 6.39; Cl 20.64. C9H11ClO. Calculated, %:
C 63.35; H 6.50; Cl 20.77.
1
1080 (COO); 850, 745 (C–Cl). H NMR spectrum, δ,
ppm: 1.67 s (6H, CH3), 2.02 s (3H, COCH3), 2.48 d
(1H, 5-H), 3.47–3.49 d.d (2H, 2-H, 3-H). Found, %:
C 62.28; H 6.90; Cl 13.18. C14H19ClO3. Calculated, %:
C 62.10; H 7.07; Cl 13.09.
3-Bromo-5-ethynylbicyclo[2.2.1]heptan-2-ol
(IVa). Yield 16.9 g (79%), bp 94–95°C (10 mm), d420 =
1.1335, nD20 = 1.5130. IR spectrum, ν, cm–1: 3625, 1100
(O–H); 3300, 2130 (C≡CH); 750, 680 (C–Br).
1H NMR spectrum, δ, ppm: 1.83 d (1H, HC≡C),
2.48 m (1H, 5-H), 3.46 t (1H, 3-H), 3.56 t (1H, 2-H).
Found, %: C 50.38; H 5.01; Br 37.30. C9H11BrO. Cal-
culated, %: C 50.25; H 5.16; Br 37.15.
3-Chloro-5-(3-hydroxy-3-methylbut-1-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (IIIb). Yield 17.5 g (77%),
bp 103–104°C (1 mm), d420 = 12.005, nD20 = 1.5317. IR
spectrum, ν, cm–1: 3200–3550 (O–H); 2200 (C≡C);
1
850, 745 (C–Cl). H NMR spectrum, δ, ppm: 1.48 s
(6H, CH3), 1.52 t (1H, 1-H), 2.47 m (1H, 5-H), 3.47 d
(1H, 2-H), 3.49 d (1H, 3-H), 4.81 br.s (1H, OH),
5.46 br.s (1H, OH). Found, %: C 63.18; H 7.32;
Cl 15.65. C12H17ClO2. Calculated, %: C 63.01; H 7.49;
Cl 15.50.
3-Bromo-5-(3-hydroxy-3-methylbut-1-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (IVb). Yield 22.3 g (81%),
bp 108–109°C (1 mm), d420 = 1.1616, nD20 = 1.5213. IR
spectrum, ν, cm–1: 3620, 3500–3200 (O–H); 2225
3-Chloro-5-(3-methoxy-3-methylbut-1-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (IIIc). Yield 18.9 g (78%),
bp 109–110°C (1 mm), d420 = 1.1576, nD20 = 1.5208. IR
spectrum, ν, cm–1: 3480 (O–H); 2245 (C≡C); 1125
1
(C≡C); 750, 680 (C–Br). H NMR spectrum, δ, ppm:
1.48 s (6H, CH3), 2.48 d (1H, 5-H), 3.46 t (1H, 3-H),
3.57 t (1H, 3-H), 4.81 br.s (1H, OH), 5.46 br.s
(1H, OH). Found, %: C 52.61; H 6.18; Br 29.40.
C12H17BrO2. Calculated, %: C 52.76; H 6.27; Br 29.75.
1
(C–O–C); 850, 745 (C–Cl). H NMR spectrum, δ,
ppm: 1.48 s (6H, CH3), 2.47 m (1H, 5-H), 3.25 s (3H,
OCH3), 3.47 d (1H, 2-H), 3.49 d (1H, 3-H). Found, %:
C 64.29; H 7.80; Cl 14.79. C13H12ClO2. Calculated, %:
C 64.32; H 7.89; Cl 14.60.
3-Bromo-5-(3-methoxy-3-methylbut-1-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (IVc). Yield 24.3 g (85%),
bp 113–114°C (1 mm), d420 = 1.1316, nD20 = 1.9164. IR
spectrum, ν, cm–1: 3460 (O–H); 2245 (C≡C); 1150
(C–O–C); 750, 680 (CBr). 1H NMR spectrum, δ, ppm:
1.48 s (6H, CH3), 3.25 s (3H, OCH3), 3.45 t (1H, 3-H),
3.57 t (1H, 2-H), 4.81 br.s (1H, OH). Found, %:
C 54.21; H 6.79; Br 27.64. C13H19BrO2. Calculated, %:
C 54.36; H 6.67; Br 27.82.
3-[4-(6-Chloro-5-hydroxybicyclo[2.2.1]hept-2-
yl)-2-methylbut-3-yn-2-yloxy]propanenitrile (IIId).
Yield 21 g (75%), bp 137–138°C (1 mm), d420
=
1.1852, nD20 = 1.5250. IR spectrum, ν, cm–1: 3360
(O–H); 2235 (C≡C); 2160 (C≡N); 1140 (C–O–C); 850,
1
745 (C–Cl). H NMR spectrum, δ, ppm: 1.48 s (6H,
CH3), 1.53 t (1H, 1-H), 2.48 d (1H, 5-H), 2.59 d (2H,
CH2CN), 3.46 d (1H, 3-H), 3.58 d (1H, 2-H), 3.75 d
(2H, OCH2), 4.81 br.s (1H, OH). Found, %: C 63.79;
H 7.28; Cl 12.42; N 4.83. C15H20ClNO2. Calculated,
%: C 63.94; H 7.15; Cl 12.58; N 4.97.
3-[4-(6-Bromo-5-hydroxybicyclo[2.2.1]hept-2-
yl)-2-methylbut-3-yn-2-yloxy]propanenitrile (IVd).
Yield 26.1 g (80%), bp 143–144°C (1 mm), d420
=
1.1590, nD20 = 1.5204. IR spectrum, ν, cm–1: 2245
(C≡C); 2170 (C≡N); 1100 (C–O–C); 750, 680 (CBr).
1H NMR spectrum, δ, ppm: 1.48 s (6H, CH3), 2.48 t
(1H, 5-H), 2.58 d (2H, CH2CN), 3.46 t (1H, 3-H),
3.58 t (1H, 2-H), 3.74 d (2H, OCH2), 4.81 br.s (1H,
OH). Found, %: C 55.08; H 6.30; Br 24.32; N 4.21.
C15H20BrNO2. Calculated, %: C 55.22; H 6.18;
Br 24.49; N 4.29.
3-Chloro-5-[3-(2-hydroxyethoxy)-3-methylbut-1-
yn-1-yl]bicyclo[2.2.1]heptan-2-ol (IIIe). Yield 21.8 g
(80%), bp 144–145°C (1 mm), d420 = 1.2116, nD20
=
1.5346. IR spectrum, ν, cm–1: 3600, 3350 (O–H); 850,
1
745 (C–Cl). H NMR spectrum, δ, ppm: 1.48 s (6H,
CH3), 2.48 d (1H, 5-H), 3.47–3.49 d.d. (2H, 2-H, 3-H),
3.66 d (2H, OCH2), 3.71 d.d (2H, CH2O), 4.79 br.s
(1H, OH), 4.81 br.s (1H, 2-OH). Found, %: C 61.78;
H 7.91; Cl 13.09. C14H21ClO3. Calculated, %: C 61.65;
H 7.71; Cl 13.03.
3-Bromo-5-[3-(2-hydroxyethoxy)-3-methylbut-1-
yn-1-yl]bicyclo[2.2.1]heptan-2-ol (IVe). Yield 27 g
(85%), bp 151–152°C (1 mm), d420 = 1.1830, nD20
=
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

HYPOHALOGENATION OF FUNCTIONALLY SUBSTITUTED ACETYLENIC ...
1287
1.5280. IR spectrum, ν, cm–1: 3360 (O–H); 2210
(C≡C); 750, 680 (C–Br). H NMR spectrum, δ, ppm:
1.48 s (6H, CH3), 3.46 t (1H, 3-H), 3.57 t (1H, 2-OH),
3.57 d (2H, OCH2), 3.71 d (2H, CH2O), 4.81 br.s
(1H, OH). Found, %: C 53.18; H 6.51; Br 25.05.
C14H21BrO2. Calculated, %: C 53.0; H 6.67; Br 25.19.
CH2O). Found, %: C 64.80; H 7.71; Cl 11.81; N 4.62.
C16H22ClNO2. Calculated, %: C 64.96; H 7.50;
Cl 11.98; N 4.74.
1
3-Chloro-5-[4-(2-hydroxyethoxy)-4-methylpent-
2-yn-1-yl]bicyclo[2.2.1]heptan-2-ol (Ve). Yield 24.6 g
(86%), bp 153–154°C (1 mm), d420 = 1.4204, nD20
=
1.5667. IR spectrum, ν, cm–1: 3370 (O–H); 850, 745
4-(6-Bromo-5-hydroxybicyclo[2.2.1]hept-2-yl)-2-
methylbut-3-yn-2-yl acetate (IVf). Yield 23.6 g
1
(C–Cl). H NMR spectrum, δ, ppm: 1.48 s (6H, CH3),
(75%), bp 114–115°C (1 mm), d420 = 1.1716, nD20
=
1.82–2.07 d.d (2H, CH2C≡), 3.56 d.d (2H, OCH2),
3.71 d.d (2H, CH2O), 3.78–3.49 d.d (2H, 2-H, 3-H),
4.81 br.s (1H, 2-OH). Found, %: C 62.69; H 8.20;
Cl 12.49. C15H23ClO3. Calculated, %: C 62.83; H 8.03;
Cl 12.38.
1.5113. IR spectrum, ν, cm–1: 3550 (O–H); 2260
(C≡C); 1740, 1135 (COO); 750, 680 (C–Br). 1H NMR
spectrum, δ, ppm: 1.67 s (6H, CH3), 2.02 s (3H,
OCH3), 3.45 t (1H, 3-H), 3.57 t (1H, 2-H), 4.81 br.s
(1H, OH). Found, %: C 53.20; H 6.17; Br 25.46.
C14H19BrO3. Calculated, %: C 53.34; H 6.08; Br 25.35.
5-(6-Chloro-5-hydroxybicyclo[2.2.1]hept-2-yl)-2-
methylpent-3-yn-2-yl acetate (Vf). Yield 20.9 g
(74%), bp 123–124°C (1 mm), d420 = 1.4112, nD20
=
3-Chloro-5-(prop-2-yn-1-yl)bicyclo[2.2.1]heptan-
2-ol (Va). Yield 14 g (77%), bp 96–97°C (5 mm), d240 =
1.4330, nD20 = 1.5498. IR spectrum, ν, cm–1: 3600
(O–H); 3290, 2120 (C≡CH); 850, 745 (C–Cl). 1H NMR
spectrum, δ, ppm: 1.41 t (1H, 5-H), 1.82 s (1H, HC≡),
1.87–2.12 d.d (2H, CH2C≡), 3.48 d (1H, 2-H), 3.49 d
(1H, 3-H). Found, %: C 65.19; H 7.22; Cl 19.01.
C10H13ClO. Calculated, %: C 65.04; H 7.09; Cl 19.20.
1.5544. IR spectrum, ν, cm–1: 3600 (O–H); 2230
(C≡C); 1720, 1080 (COO); 850, 745 (C–Cl). 1H NMR
spectrum, δ, ppm: 1.67 s (6H, CH3), 1.86–2.07 d.d
(2H, CH2C≡), 2.02 s (3H, CH3CO), 3.47–3.49 d.d (2H,
2-H, 3-H). Found, %: C 63.12; H 7.58; Cl 12.30.
C15H21ClO3. Calculated, %: C 63.26; H 7.43; Cl 12.45.
3-Bromo-5-(prop-2-yn-1-yl)bicyclo[2.2.1]heptan-
2-ol (VIa). Yield 17.8 g (78%), bp 104–105°C (5 mm),
d240 = 1.3744, nD20 = 1.5389. IR spectrum, ν, cm–1: 3540
(O–H); 3300, 2135 (C≡CH); 750, 680 (C–Br). 1H NMR
spectrum, δ, ppm: 1.82 d (1H, HC≡), 1.87–2.13 d.d
(2H, CH2C≡), 3.45 d (1H, 3-H), 3.58 d (1H, OH).
Found, %: C 52.31; H 5.89; Br 34.74. C10H13BrO. Cal-
culated, %: C 54.36; H 6.67; Br 27.82.
3-Chloro-5-(4-hydroxy-4-methylpent-2-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (Vb). Yield 19.7 g (82%),
bp 118–119°C (1 mm), d420 = 1.4391, nD20 = 1.5642. IR
spectrum, ν, cm–1: 3540 (O–H); 2225 (C≡C); 850, 745
1
(C–Cl). H NMR spectrum, δ, ppm: 1.48 s (6H, CH3),
1.52 t (1H, 1-H), 2.07–1.82 d.d (2H, CH2C≡), 3.47 d
(1H, 2-H), 3.49 d (1H, 3-H), 4.81 br.s (1H, OH),
5.46 br.s (1H, OH). Found, %: C 64.21; H 7.78;
Cl 14.76. C10H13ClO. Calculated, %: C 65.04; H 7.09;
Cl 19.20.
3-Bromo-5-(4-hydroxy-4-methylpent-2-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (VIb). Yield 23 g (80%),
bp 123–124°C (1 mm), d420 = 1.3913, nD20 = 1.5576. IR
spectrum, ν, cm–1: 3600, 3360 (O–H); 2235 (C≡C);
3-Chloro-5-(4-methoxy-3-methylpent-2-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (Vc). Yield 21.2 g (83%),
bp 122–123°C (1 mm), d420 = 1.3603, nD20 = 1.5534. IR
spectrum, ν, cm–1: 3495 (O–H); 2245 (C≡C); 1150
1
750, 680 (C–Br). H NMR spectrum, δ, ppm: 1.48 s
(6H, CH3), 1.83–2.06 d.d (2H, CH2C≡), 3.45 d (1H,
3-H), 3.57 d (1H, 2-OH), 4.81 br.s (1H, OH). Found,
%: C 54.22; H 6.55; Br 27.99. C13H19BrO2. Calculated,
%: C 54.36; H 6.67; Br 27.82.
1
(C–O–C); 850, 745 (C–Cl). H NMR spectrum, δ,
ppm: 1.48 s (6H, CH3), 1.82–2.08 d.d (2H, CH2C≡),
3.25 s (3H, OCH3), 3.47 d (1H, 2-H), 3.49 d (1H, 3-H).
Found, %: C 65.35; H 8.39; Cl 13.70. C14H21ClO2.
Calculated, %: C 65.49; H 8.25; Cl 13.81.
3-Bromo-5-(4-methoxy-4-methylpent-2-yn-1-yl)-
bicyclo[2.2.1]heptan-2-ol (VIc). Yield 25.6 g (85%),
bp 129–130°C (1 mm), d420 = 1.3179, nD20 = 1.5372. IR
spectrum, ν, cm–1: 3500 (O–H); 1140 (C–O–C); 750,
3-[5-(6-Chloro-5-hydroxybicyclo[2.2.1]hept-2-
yl)-2-methylpent-3-yn-2-yloxy]propanenitrile (Vd).
1
680 (C–Br). H NMR spectrum, δ, ppm: 1.48 s (6H,
Yield 22.2 g (78%), bp 148–149°C (1 mm), d420
=
CH3), 1.82–2.08 d.d (2H, CH2C≡), 3.25 s (3H, CH3O),
3.45 t (1H, 3-H), 3.57 d (1H, OH). Found, %: C 55.73;
H 7.19; Br 26.36. C14H21BrO2. Calculated, %: C 55.82;
H 7.03; Br 26.53.
1.3750, nD20 = 1.5523. IR spectrum, ν, cm–1: 3470
(O–H); 2250 (C≡C); 2165 (C≡N); 1130 (C–O–C); 850,
1
745 (C–Cl). H NMR spectrum, δ, ppm: 1.48 s (6H,
CH3), 1.81–2.08 d.d (2H, CH2C≡), 2.58 d (2H,
H2CCN), 3.47–3.49 d.d (2H, 2-H, 3-H), 3.74 d.d (2H,
3-[5-(6-Bromo-5-hydroxybicyclo[2.2.1]hept-2-
yl)-2-methylpent-3-yn-2-yloxy]propanenitrile (VId).
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VELIEV et al.
1288
Yield 26.9 g (79%), bp 154–155°C (1 mm), d420
=
2.48 t (1H, 5-H), 2.86 d.d (2H, 2-H, 3-H), 5.46 br.s
(1H, OH). Found, %: C 74.82; H 8.48. C12H16O2. Cal-
culated, %: C 74.96; H 8.39.
1.3376, nD20 = 1.5460. IR spectrum, ν, cm–1: 3600
(O–H); 2250 (C≡C); 2185 (C≡N); 1150 (C–O–C); 750,
1
680 (C–Br). H NMR spectrum, δ, ppm: 1.41 t (1H,
2,3-Epoxy-5-(3-methoxy-3-methylbut-1-yn-1-yl)-
bicyclo[2.2.1]heptane (VIIc). Yield 18.3 g (89%),
bp 100–101°C (2 mm), d420 = 1.0454, nD20 = 1.5046. IR
spectrum, ν, cm–1: 3060, 1260, 910, 850 (oxirane);
2-H), 1.48 s (6H, CH3), 1.87–2.08 d.d (2H, CH2C≡),
2.58 d (2H, H2CCN), 3.45 t (1H, 3-H), 3.56 t (1H,
OH), 3.75 d (2H, OCH2), 4.81 br.s (1H, OH). Found,
%: C 56.34; H 6.69; Br 23.30. C16H22BrNO2. Calculat-
ed, %: C 56.47; H 6.72; Br 23.48.
1
2215 (C≡C); 1090 (C–O–C). H NMR spectrum, δ,
ppm: 1.48 s (6H, CH3), 2.47 t (1H, 5-H), 2.86 d.d (2H,
2-H, 3-H), 3.25 s (3H, CH3O). Found, %: C 75.80;
H 8.63. C13H18O2. Calculated, %: C 75.69; H 8.79.
3-Bromo-5-[4-(2-hydroxyethoxy)-4-methylpent-
2-yn-1-yl]bicyclo[2.2.1]heptan-2-ol (VIe). Yield
28.9 g (87%), bp 158–159°C (1 mm), d420 = 1.3785,
nD20 = 1.5592. IR spectrum, ν, cm–1: 3520 (O–H); 3410
3-[4-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
but-3-yn-2-yloxy]propanenitrile (VIId). Yield 21.5 g
1
(O–H); 2200 (C≡C); 750, 680 (C–Br). H NMR spec-
(87.5%), bp 129–130°C (1 mm), d420 = 1.0724, nD20
=
trum, δ, ppm: 1.41 t (1H, 2-H), 1.67 s (6H, CH3), 1.83–
3.57 d (2H, OCH2), 2.08 d.d (2H, CH2C≡), 3.45 t (1H,
3-H), 3.56 t (1H, 2-OH), 3.71 d (2H, CH2O), 4.81 br.s
(1H, OH). Found, %: C 54.50; H 7.15; Br 24.01.
C15H23BrO3. Calculated, %: C 54.39; H 7.0; Br 24.12.
1.5031. IR spectrum, ν, cm–1: 3060, 1260, 910, 850
(oxirane); 2240 (C≡N); 1080 (C–O–C). 1H NMR spec-
trum, δ, ppm: 1.48 s (6H, CH3), 2.47 t (1H, 5-H),
2.59 d (2H, CH2CN), 2.86 d.d (2H, 2-H, 3-H), 3.75 d
(2H, CH2O). Found, %: C 73.30; H 7.97; N 5.64.
C15H20NO2. Calculated, %: C 73.17; H 8.13; N 5.69.
5-(6-Bromo-5-hydroxybicyclo[2.2.1]hept-2-yl)-2-
methylpent-3-yn-2-yl acetate (VIf). Yield 25.5 g
(77%), bp 128–129°C (1 mm), d420 = 1.3704, nD20
=
2-[4-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
but-3-yn-2-yloxy]ethanol (VIIe). Yield 20.4 g (87%),
bp 136–137°C (2 mm), d420 = 1.0159, nD20 = 1.5178. IR
spectrum, ν, cm–1: 3470 (O–H); 3060, 1260, 910, 850
1.5474. IR spectrum, ν, cm–1: 3600 (O–H); 2225
(C≡C); 1720, 1080 (COO); 750, 680 (C–Br). 1H NMR
spectrum, δ, ppm: 1.67 s (6H, CH3), 1.82–2.08 d.d
(2H, CH2C≡), 2.02 s (3H, CH3CO), 2.48 t (1H, 5-H),
3.45 t (1H, 3-H), 3.57 t (1H, OH), 4.81 br.s (1H, OH).
Found, %: C 54.63; H 6.59; Br 24.11. C15H21BrO3.
Calculated, %: C 54.72; H 6.43; Br 24.27.
1
(oxirane); 1145 (C–O–C). H NMR spectrum, δ, ppm:
1.48 s (6H, CH3), 1.77 t (1H, 1-H), 2.48 t (1H, 5-H),
2.81 t (1H, 4-H), 2.86 d.d (2H, 2-H, 3-H), 3.56 d (2H,
OCH2), 3.71 d (2H, CH2O), 4.78 br.s (1H, OH). Found,
%: C 75.78; H 9.66. C14H21O2. Calculated, %: C 75.97;
H 9.57.
Acetylenic 2,3-epoxynorbornanes VIIa–VIIe and
VIIIa–VIIIe (general procedure). Powdered potas-
sium hydroxide, 8.4 g (0.15 mol), was added under
stirring to a solution of 0.05 mol of compound IIIa–
IIIe or VIa–VIe in 60 ml of anhydrous diethyl ether,
maintaining the temperature at 8–10°C. The mixture
was then stirred for 2 h at 12–14°C, the solvent was
distilled off, and the residue was distilled under
reduced pressure.
2,3-Epoxy-5-(prop-2-yn-1-yl)bicyclo[2.2.1]hep-
tane (VIIIa). Yield 13.5 g (85%), bp 82–83°C
(10 mm), d420 = 0.9959, nD20 = 1.4876. IR spectrum, ν,
cm–1: 3060, 1245, 910, 850 (oxirane); 3300, 2125
1
(C≡CH). H NMR spectrum, δ, ppm: 1.76 d.d (2H,
1-H, 4-H), 1.83 s (1H, HC≡C), 1.87–2.12 d.d (2H,
CH2C≡), 2.86 d.d (2H, 2-H, 3-H). Found, %: C 81.21;
H 8.02. C10H22O. Calculated, %: C 81.04; H 8.16.
2,3-Epoxy-5-ethynylbicyclo[2.2.1]heptane (VIIa).
Yield 11.4 g (85%), bp 75–76°C (10 mm), d420
=
5-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
pent-3-yn-2-ol (VIIIb). Yield 17.7 g (86%), bp 99.5–
100.5°C (1 mm), d420 = 1.0413, nD20 = 1.5101. IR spec-
trum, ν, cm–1: 3400 (O–H); 3060, 1260, 910, 850
1.0356, nD20 = 1.5018. IR spectrum, ν, cm–1: 3290, 2125
1
(C≡CH); 3060, 1245, 910, 850 (oxirane). H NMR
spectrum, δ, ppm: 1.82 d (1H, HC≡C), 2.86 d.d (2H,
2-H, 3-H). Found, %: C 81.21; H 8.02. C10H22O. Cal-
culated, %: C 81.04; H 8.16.
1
(oxirane); 2200 (C≡C). H NMR spectrum, δ, ppm:
1.48 s (6H, CH3), 1.76 d.d (2H, 1-H, 4-H), 1.83–
2.08 d.d (2H, CH2C≡), 2.86 d.d (2H, 2-H, 3-H),
4.45 br.s (1H, OH), Found, %: C 75.58; H 8.70.
C13H18O2. Calculated, %: C 75.69; H 8.79.
4-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
but-3-yn-2-ol (VIIb). Yield 16.4 g (86%), bp 95–96°C
(1 mm), d420 = 1.0825, nD20 = 1.5152. IR spectrum, ν,
cm–1: 3060 (C–H, oxirane), 2200 (C≡C), 1260, 910,
2,3-Epoxy-5-(4-methoxy-4-methylpent-2-yn-1-
yl)bicyclo[2.2.1]heptane (VIIIc). Yield 19.8 g (90%),
1
850. H NMR spectrum, δ, ppm: 1.48 s (6H, CH3),
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HYPOHALOGENATION OF FUNCTIONALLY SUBSTITUTED ACETYLENIC ...
1289
bp 105–106°C (2 mm), d420 = 1.0114, nD20 = 1.4896. IR
spectrum, ν, cm–1: 3060, 1260, 910, 850 (oxirane);
1150 (C–O–C). 1H NMR spectrum, δ, ppm: 1.48 s (6H,
CH3), 1.76 d.d (2H, 1-H, 4-H), 1.82–2.08 d.d (2H,
CH2C≡), 2.86 d.d (2H, 2-H, 3-H), 3.24 s (3H, CH3O).
Found, %: C 76.48; H 9.30. C14H20O2. Calculated, %:
C 76.32; H 9.15.
separated, dried over sodium sulfate, and distilled un-
der reduced pressure in the presence of hydroquinone.
2,3-Epoxy-5-ethynylbicyclo[2.2.1]heptane (VIIa).
Yield 12.1 g (86%), bp 75–76°C (10 mm), d420
1.0360, nD20 = 1.5015.
=
2,3-Epoxy-5-(prop-2-yn-1-yl)bicyclo[2.2.1]hep-
tane (VIIIa). Yield 14.8 g (89%), bp 82–83°C
(10 mm), d420 = 0.9964, nD20 = 1.4870.
3-[5-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
pent-3-yn-2-yloxy]propanenitrile (VIIId). Yield
22.9 g (88%), bp 137–138°C (1 mm), d420 = 1.0524,
nD20 = 1.4883. IR spectrum, ν, cm–1: 3060, 1260, 910,
850 (oxirane); 2250 (C≡N); 2200 (C≡C); 1095
Hydrolysis of compounds IIIa–VIa (general
procedure). Halohydrin IIIa–VIa, 0.05 mol, was
added dropwise to a solution of 0.5 g of mercury(II)
sulfate in 21 ml of 7% aqueous sulfuric acid, main-
taining the temperature at 26–30°C. The mixture was
stirred for 0.5 h, kept for 4–5 h at 55–60°C, cooled,
and extracted with diethyl ether. The extract was
washed with water, dried over anhydrous magnesium
sulfate, and evaporated, and the residue was distilled
under reduced pressure to isolate ketones IX–XII.
1
(C–O–C). H NMR spectrum, δ, ppm: 1.48 s (6H,
CH3), 1.76 d.d (2H, 1-H, 4-H), 1.83–2.08 d.d (2H,
CH2C≡), 2.58 d (2H, CH2CN), 2.86 d.d (2H, 2-H,
3-H), 3.75 d (2H, CH2O). Found, %: C 74.24; H 8.0;
N 5.28. C16H21NO2. Calculated, %: C 74.10; H 8.11;
N 5.41.
2-[5-(5,6-Epoxybicyclo[2.2.1]hept-2-yl)-2-methyl-
1-(6-Chloro-5-hydroxybicyclo[2.2.1]heptan-2-
yl)ethanone (IX). Yield 14 g (75%), bp 95–96°C
(10 mm), d420 = 1.2091, nD20 = 1.5098. IR spectrum, ν,
cm–1: 3520 (O–H); 1725 (C=O); 850, 745 (C–Cl).
1H NMR spectrum, δ, ppm: 2.1 s (3H, CH3CO), 3.45 d
(1H, 3-H), 3.58 d (1H, OH), 4.81 br.s (1H, OH).
Found, %: C 57.21; H 6.82; Cl 18.90. C9H13ClO2. Cal-
culated, %: C 57.30; H 6.95; Cl 18.79.
pent-3-yn-2-yloxy]ethanol (VIIIe). Yield 21.5 g
(88%), bp 140–141°C (1 mm), d420 = 1.4116, nD20
=
1.5032. IR spectrum, ν, cm–1: 3400 (O–H); 3060, 1260,
910, 850 (oxirane); 1150 (C–O–C). 1H NMR spectrum,
δ, ppm: 1.41 d (1H, 5-H), 1.48 s (6H, CH3), 1.76 d.d
(2H, 1-H, 4-H), 1.83–2.08 d.d (2H, CH2C≡), 2.86 d.d
(2H, 2-H, 3-H), 3.57 d.d (2H, OCH2), 3.71 d.d (2H,
CH2OH). Found, %: C 72.40; H 8.30. C15H21O3. Cal-
culated, %: C 72.26; H 8.49.
1-(6-Bromo-5-hydroxybicyclo[2.2.1]heptan-2-yl)-
ethanone (X). Yield 17 g (73%), bp 102–103°C
(5 mm), d420 = 1.5243, nD20 = 1.5422. IR spectrum, ν,
cm–1: 3600 (O–H); 1730 (C=O); 750, 680 (C–Br).
1H NMR spectrum, δ, ppm: 2.08 d (1H, 1-H), 2.1 s
(3H, CH3CO), 2.49 t (1H, 2-H), 3.58 d (1H, 5-H),
4.81 br.s (1H, OH). Found, %: C 46.28; H 5.79;
Br 17.32. C10H15BrO2. Calculated, %: C 59.86; H 7.46;
Br 17.49.
Epoxidation of bicycloheptenes Ia, Ib, Id, IIa,
IIb, and IId (general procedure). Bicycloheptene Ia,
Ib, Id, IIa, IIb, or IId, 0.27 mol, was dissolved in
50 ml of anhydrous diethyl ether, 43.5 ml of 45% per-
oxyacetic acid was added at 15–20°C, the mixture was
kept for 4 h and treated with 100 ml of 5% aqueous
sodium hydrogen carbonate, the organic phase was
separated and dried over sodium sulfate, and the
solvent was distilled off. Vacuum distillation of the
residue gave compounds VIIa, VIIb, VIId, VIIIa,
VIIIb, and VIIId. The products were identical in
physical properties to samples obtained as described
above.
1-(6-Chloro-5-hydroxybicyclo[2.2.1]heptan-2-
yl)propan-2-one (XI). Yield 15.9 g (79%), bp 108–
109°C (10 mm), d420 = 1.1857, nD20 = 1.4956. IR spec-
trum, ν, cm–1: 3490 (O–H); 1720 (C=O); 850, 745
1
(C–Cl). H NMR spectrum, δ, ppm: 1.84 t (1H, 1-H),
2.1 s (3H, CH3CO), 2.29–2.54 d.d (2H, CH2CO),
4.81 br.s (1H, OH). Found, %: C 59.40; H 7.37;
Cl 17.32. C10H15ClO2. Calculated, %: C 59.26; H 7.46;
Cl 17.49.
Independent synthesis of compounds VIIa and
VIIIa (general procedure). Powdered potassium hy-
droxide, 20 g, was added in five portions under stirring
to a mixture of 0.1 mol of compound IIIb–VIb and
50 ml of toluene, maintaining the temperature in the
range from 40 to 50°C. The mixture was then heated to
95–100°C and was kept for 8 h at that temperature.
The mixture was cooled, and the organic phase was
1-(6-Bromo-5-hydroxybicyclo[2.2.1]heptan-2-yl)-
propan-2-one (XII). Yield 18.9 g (76%), bp 107–
108°C (5 mm), d420 = 1.4431, nD20 = 1.5273. IR spec-
trum, ν, cm–1: 3500 (O–H); 1720 (C=O); 750, 680
1
(C–Br). H NMR spectrum, δ, ppm: 1.53 t (1H, 4-H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

VELIEV et al.
1290
1.84 t (1H, 1-H), 2.1 s (3H, CH3CO), 2.29–2.55 d.d
(2H, CH2CO), 3.46 d (1H, 3-H), 3.57 d (1H, 5-H),
4.81 br.s (1H, OH). Found, %: C 48.78; H 6.03;
Br 32.42. C10H15BrO2. Calculated, %: C 48.6; H 6.19;
Br 32.34.
REFERENCES
1. Fel’dblyum, V.Sh., Sintez i primenenie nepredel’nykh
tsiklicheskikh uglevodorodov (Synthesis and Applica-
tions of Unsaturated Cyclic Hydrocarbons), Moscow:
Khimiya, 1982, pp. 17, 134.
Compounds IX–XII, 0.05 mol, were subjected to
dehydrohalogenation using 0.15 mol of powdered
potassium hydroxide according to the procedure de-
scribed above for the synthesis of VIIa. As a result,
epoxy ketones XIII and XIV were obtained.
2. Zyk, N.V., Beloglazkina, E.K., Tyurin, V.S., and Gri-
shin, Yu.K., Izv. Ross. Akad. Nauk, Ser. Khim., 1998,
p. 2290.
3. Osokin, Yu.G., Neftekhimiya, 2007, vol. 47, p. 3.
4. Grigor’ev, A.A., Ioffe, A.E., Sadovskaya, T.P., and
1-(5,6-Epoxybicyclo[2.2.1]heptan-2-yl)ethanone
(XIII). Yield 5.4 g (70%), bp 82–83°C (10 mm), d420 =
1.1105, nD20 = 1.4948. IR spectrum, ν, cm–1: 3060,
1245, 910, 850 (oxirane); 1740 (C=O). 1H NMR spec-
trum, δ, ppm: 1.85 t (1H, 4-H), 2.09 s (3H, CH3CO),
3.45 d (1H, 3-H), 3.57 d (1H, 2-H). Found, %: C 71.20;
H 7.81. C9H12O2. Calculated, %: C 71.02; H 7.95.
Dolgaya, K.N., Khim. Promst., 1983, p. 393.
5. Makovetskii, K.L., Vysokomol. Soedin. B, 1999, vol. 41,
p. 1525.
6. Artem’eva, V.I., Kudryavtsev, V.V., Kukarkina, A.V.,
and Yakimanskii, A.V., Zh. Prikl. Khim., 2000, vol. 73,
p. 117.
7. Nazarov, I.N. and Nagibina, T.D., Izv. Akad. Nauk SSSR,
Otd. Khim. Nauk, 1946, p. 83.
1-(5,6-Epoxybicyclo[2.2.1]heptan-2-yl)propan-2-
one (XIV). Yield 6.1 g (74%), bp 95–96°C (10 mm),
d240 = 1.0640, nD20 = 1.4801. IR spectrum, ν, cm–1: 3060,
1245, 910, 850 (oxirane); 1715 (C=O). 1H NMR spec-
trum, δ, ppm: 2.1 s (3H, CH3CO), 2.29–2.54 d.d (2H,
CH2CO), 3.46 d (1H, 3-H), 3.58 d (1H, 2-H). Found,
%: C 72.49; H 8.32. C10H14O2. Calculated, %: C 72.26;
H 8.49.
8. Nazarov, I.N., Izbrannye trudy (Selected Papers),
Moscow: Akad. Nauk SSSR, 1961, p. 690.
9. Veliev, M.G. and Guseinov, M.M., Tetrahedron, 1985,
vol. 41, p. 749.
10. Veliev, M.G., Guseinov, M.M., Yanovskaya, L.A., and
Gakhramanov, R.F., Izv. Akad. Nauk SSSR, Ser. Khim.,
1981, p. 144.
11. Veliev, M.G., Chalabieva, A.Z., Shatirova, M.I., and
Akperova, E.G., Russ. J. Org. Chem., 2003, vol. 39,
p. 825.
Hydrolysis of compounds VIIa and VIIIa gave
diols XV and XVI, respectively.
5-Ethynylbicyclo[2.2.1]heptane-2,3-diol (XV).
Yield 6.5 g (86%), mp 43–44°C, Rf 0.68 (hexane–
EtOAc, 7:3). IR spectrum, ν, cm–1: 3520 (O–H); 3295,
2125 (C≡CH). 1H NMR spectrum, δ, ppm: 1.51–1.53 d
(2H, 1-H, 4-H), 1.83 d (2H, HC≡C), 3.24 d.d (2H, 2-H,
3-H), 4.81 br.s (2H, OH). Found, %: C 71.19; H 7.80.
C9H12O2. Calculated, %: C 71.02; H 7.95.
12. Veliev, M.G., Guseinov, M.M., and Mamedov, S.A.,
USSR Inventor’s Certificate no. 793973, 1980; Byull.
Izobret., 1981, no. 1.
13. Veliev, M.G., Guseinov, M.M., and Mamedov, S.A.,
Synthesis, 1981, p. 400.
14. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spec-
trometric Identification of Organic Compounds, New
York: Wiley, 1974, 3rd ed. Translated under the title
Spektrometricheskaya identifikatsiya organicheskikh
soedinenii, Moscow: Mir, 1977, p. 590.
5-(Prop-2-yn-1-yl)bicyclo[2.2.1]heptane-2,3-diol
(XVI). Yield 7.3 g (88%), mp 49–50°C, Rf 0.69
(hexane–EtOAc, 7:3). IR spectrum, ν, cm–1: 3510
1
(O–H); 3300, 2130 (C≡CH). H NMR spectrum, δ,
15. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion, New York: Wiley, 1972.
ppm: 1.51–1.53 d (2H, 1-H, 4-H), 1.82 s (1H, HC≡C),
1.87–1.12 d.d (2H, CH2C≡), 4.81 br.s (2H, OH).
Found, %: C 72.08; H 8.37. C10H14O2. Calculated, %:
C 72.26; H 8.49.
16. Emanuel’ N.M. and Knorre, D.G., Kurs khimicheskoi
kinetiki (Lectures on Chemical Kinetics), Moscow:
Vysshaya Shkola, 1974, p. 400.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008