Hypohalogenation of vinyl- and allylacetylenes and some chemical transformations of the products

Article abstract of DOI:10.1134/S1070428007110036

Hypohalogenation of 2-methylhex-5-en-3-yn-2-ol, 2-methylhept-6-en-3-yn-2- ol, and their methyl ethers at 303-328 K with hydrochloric or hydrobromic acid in the presence of hydrogen peroxide involves only the double bond to produce the corresponding halohydrins in fairly high yields. Kinetic parameters of these reactions were determined, and the allylacetylenic alcohol and its methyl ether were found to be more reactive than their vinylacetylenic analogs. Acetylenic halohydrins and oxiranes derived therefrom were shown to be quite reactive compounds which may be used as building blocks in organic synthesis.

Full text of DOI:10.1134/S1070428007110036

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1604–1611. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © M.G. Veliev, O.A. Sadygov, Kh.M. Alimardanov, M.I. Shatirova, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43,
No. 11, pp. 1609–1616.
Hypohalogenation of Vinyl- and Allylacetylenes and Some
Chemical Transformations of the Products
M. G. Velieva, O. A. Sadygovb, Kh. M. Alimardanovb, and M. I. Shatirovaa
a Institute of Polymeric Materials, National Academy of Sciences of Azerbaidjan,
ul. S. Vurguna 124, Sumgait, 5004 Azerbaidjan
b Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaidjan,
Baku, Azerbaidjan
Received July 12, 2006
Abstract—Hypohalogenation of 2-methylhex-5-en-3-yn-2-ol, 2-methylhept-6-en-3-yn-2-ol, and their methyl
ethers at 303−328 K with hydrochloric or hydrobromic acid in the presence of hydrogen peroxide involves only
the double bond to produce the corresponding halohydrins in fairly high yields. Kinetic parameters of these
reactions were determined, and the allylacetylenic alcohol and its methyl ether were found to be more reactive
than their vinylacetylenic analogs. Acetylenic halohydrins and oxiranes derived therefrom were shown to be
quite reactive compounds which may be used as building blocks in organic synthesis.
DOI: 10.1134/S1070428007110036
and nonconjugated enyne systems in various trans-
formations [14−16, 21, 22], in the present work we
examined hypohalogenation of vinyl- and allylacety-
lenic alcohols, as well as chemical transformations of
the halohydrins thus obtained, with a view to synthe-
size new functionally substituted derivatives, specif-
ically oxiranes having an alkynyl group.
Functionally substituted enynes are important
building blocks in the synthesis of a series of biologi-
cally active compounds and analogs of natural prod-
ucts [1−3] such as pheromones, hormones, and prosta-
glandins [4−6]. In the recent years, enynes were
generally synthesized by reactions of terminal alkynes
with alkenyl halides in the presence of transition metal
complexes [7−9]. Cross-coupling reactions of halo-
enyne ethers, including those containing heteroele-
ments, with various terminal alkynes were studied in
[10−13]. Analysis of published data shows that allyl-
acetylene derivatives have been studied to a much
lesser extent than their vinylacetylene analogs. In
particular, only a few data are available on the relative
reactivities of vinyl- and allylacetylenic systems
toward nucleophilic and electrophilic reagents (except
for [2+1]- and [4+2]-cycloadditions) [14−16]. Un-
doubtedly, such studies would be important from both
theoretical and practical viewpoints [17−20]. In con-
tinuation of our studies on the reactivity of conjugated
We found that 2-methylhex-5-en-3-yn-2-ol,
2-methylhept-6-en-3-yn-2-ol, and their methyl ethers
smoothly react at 303−328 K with HOCl and HOBr
generated in situ from hydrochloric or hydrobromic
acid and hydrogen peroxide (Scheme 1). The resulting
acetylenic chloro- and bromohydrins I−VIII were
characterized by elemental analyses, physical con-
1
stants, and IR and H NMR spectra. Apart from
absorption bands due to stretching vibrations of C–H
bonds and molecular backbone, the IR spectra of
I−VIII contained bands in the regions 3360−3400,
2230−2250, 1120−1150, and 750−600 cm−1, which
were assigned to stretching vibrations of O–H, C≡C,
Scheme 1.
Me
Me
OH
Me
OR
Me
OR
HX, H2O2, Δ
X
H2C
( )n
( )n
I–VIII
I–IV, n = 0; V–VIII, n = 1; I, V, X = Cl, R = H; II, VI, X = Cl, R = Me; III, VII, X = Br, R = H; IV, VIII, X = Br, R = Me.
1604

HYPOHALOGENATION OF VINYL- AND ALLYLACETYLENES
1605
Table 1. Temperature effect on the yield of halohydrins I–
VIII; substrate–HX–H2O2 ratio 1:1.2:1.2; HCl concentra-
tion 10%, HBr concentration 6%; reaction time 7.5 h; rate of
addition of H2O2 10 g/h
C–O–C, and C–Br (C–Cl) bonds, respectively. No
absorption typical of double C=C bond (1630−
1650 cm−1) and C−H bonds in terminal =CH2 group
(3095, 1420, 915 cm−1) were present [23, 24]. In the
1H NMR spectra of compounds I−VIII, protons in
the geminal methyl groups resonated as a singlet at
δ 1.30 ppm, signal from the hydroxy proton appeared
as δ 3.85 ppm, and methoxy protons gave rise to
a signal at δ 3.20 ppm. Protons in the halohydrin frag-
ment CH2−CH appeared as multiplets at δ 3.35−3.55
(CH2Hlg) and δ 3.75−4.00 ppm (CH) [24, 25].
Yield, %
Tempera-
ture, K
I
II
III IV
V
VI VII VIII
303
313
318
328
72.3 77.6 68.8 71.2 76.8 81.4 74.5 77.7
88.5 90.3 85.7 89.3 92.5 93.5 90.6 91.6
92.6 92.8 90.6 90.8 95.4 94.3 92.5 92.8
94.3 93.4 92.8 92.5 96.3 95.2 94.3 94.1
In order to estimate the relative reactivities of
vinyl- and allylacetylenic alcohols and their methyl
ethers in the hypohalogenation reaction and find
optimal conditions for the preparation of acetylenic
halohydrins, we examined the effects of different
parameters on the yields of compounds I–VIII. It
turned out that their yields depend on the temperature
and hydrohalic acid concentration (Tables 1, 2). It is
seen that raising the temperature from 303 to 328 K
increases the yield of I–VIII by 13−16%. The reaction
direction and product yield essentially depend on the
hydrohalic acid (HCl, HBr) concentration (Table 2).
Fairly high yields (up to 94%) are attained with the use
of 6−10% hydrochloric acid. Further increase in the
acid concentration in the range from 15 to 35 wt %
leads to reduced yield (39.6% for compound II).
Analogous results were obtained in experiments with
hydrobromic acid. High yields of bromohydrins were
obtained with 6% hydrobromic acid. In more concen-
trated hydrobromic acid, the yield of bromohydrins
decreases to 43.5%, presumably due to increased con-
tribution of the process leading to formation of
molecular halogens (Scheme 2). Electrophilic addition
of the latter at the vinyl or allyl double bond gives the
corresponding dichloro or dibromo derivatives. In fact,
the formation of dihalogen derivatives IX–XVI was
detected in the reactions performed with 36% hydro-
chloric acid and 43% hydrobromic acid.
Table 2. Effect of hydrochloric acid concentration on the
yield of chlorohydrins I–IV; substrate–HCl–H2O2 ratio
0.2:0.22:0.24, temperature 313 K, rate of addition of H2O2
10 g/h, reaction time 8 h
Yield, %
Concentration
of HCl, %
I
II
III
VI
06.0
10.0
15.0
25.0
36.0
78.6
89.6
67.5
50.6
44.3
75.2
90.3
64.6
48.2
39.6
80.5
85.7
72.8
65.7
50.5
77.4
89.3
68.7
52.6
46.7
to estimate the contribution of electronic factors to the
reactivity of conjugated and nonconjugated enynes in
the addition of HOCl and HOBr at the double bond.
The rate constants were calculated using kinetic equa-
tions for bimolecular reactions [26]. All the examined
enynes showed linear dependences between the loga-
rithms of the rate constants and reciprocal temperature
(see figure). On the basis of these dependences we
determined the thermodynamic parameters of the reac-
tions under study (Table 3). The rate constants for the
formation of acetylenic chlorohydrins increase as the
temperature rises from 303 to 328 K. The energies of
activation for hypohalogenation of 2-methylhex-5-en-
3-yn-2-ol and 2-methylhept-6-en-3-yn-2-ol were esti-
mated at 62.0 and 59.3 kJ/mol, and the corresponding
We also studied the kinetics of the above reactions
and determined their activation parameters with a view
Scheme 2.
2HX
Me
+
H2O2
X2
–2H2O
Me
X
Me
Me
OR
X2, Δ
X
H2C
( )n
( )n
IX–XVI
OR
IX–XII, n = 0; XIII–XVI, n = 1; IX, XIII, X = Cl, R = H; X, XIV, X = Cl, R = Me; XI, XV, X = Br, R = H;
XII, XVI, X = Br, R = Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

VELIEV et al.
1606
Table 3. Rate constants and activation parameters for hypohalogenation of enynes
k×103, l mol–1 min–1
Comp.
no.
−ΔS≠,
E, kJ/mol
ΔH≠, kJ/mol
ΔG≠, kJ/mol
J mol–1 K−1
303 K
313 K
318 K
328 K
1.594
1.968
1.168
1.693
3.513
4.527
1.967
2.910
4.878
6.114
3.323
5.784
09.297
12.020
06.036
08.440
62.0
59.3
53.5
54.3
185.3
188.1
183.9
182.6
61.4
58.6
52.8
53.7
117.5
115.6
108.5
109.0
I
II
V
VI
values for their methyl ethers were 53.5 and 54.3 kJ×
mol–1, respectively. The entropies of activation suggest
that the transition state in the reaction with alcohols is
more ordered (σ 1.39) than in the reaction with methyl
ethers (σ 1.79). Reduction of the energy of activation
in going from the enyne alcohols to their methyl ethers
is compensated by reduction in the entropy of ac-
tivation. Thus comparison of the rate constants and
thermodynamic parameters shows that 2-methylhept-6-
en-3-yn-2-ol and its methyl ether are more reactive
than their their vinylacetylenic analogs.
Development of a convenient method for the syn-
thesis of acetylenic mono- and diepoxy derivatives is
an important problem from the practical viewpoint, for
such compounds are widely used as monomers for
epoxy resins and intermediate products in organic syn-
thesis and synthesis of polymers [27−29]. As shown in
[30], alkynyl-substituted oxiranes can be synthesized
in two steps, the first of which is condensation of
a chloro ketone with an acetylenic alcohol, and the
second is alkaline treatment of the condensation prod-
uct (the corresponding chlorohydrin). The most widely
used method for the preparation of mono- and diepoxy
derivatives is based on oxidation of appropriate unsat-
urated substrates with peroxy acids [31]. However,
introduction of a second or third epoxy group into
a molecule having a triple C≡C bond is often accom-
panied by side processes, and the target product is
formed in a very poor yield [31, 32].
logk
–3.0
–3.2
–3.4
We found that both chloro and bromo alcohols
I−VIII readily undergo dehydrohalogenation by the
action of powdered potassium hydroxide to give the
corresponding oxiranes XVII–XX in 85.5−96.7%
yield (Scheme 3). The yield increases with rise in tem-
perature from 303 to 318 K and attains 91.3 (XVII), 95
(XVIII), 96.3 (XIX), and 97.4% (XX) (Table 4).
Raising the temperature above 318 K is not advisable,
for the dehydrohalogenation process is accompanied
by opening of the oxirane ring with formation of tars,
and the yield of compounds XVII–XX decreases.
–3.6
2
The structure of oxirane derivatives XVII−XX was
confirmed by their IR and H NMR spectra. The
1
–3.8
1
oxirane ring in compounds XVII−XX is characterized
3
4
Scheme 3.
Me
O
Me
OR
1/T×103
KOH, 303–328 K
3.0
3.2
I–VIII
( )n
XVII–XX
Plots of the logarithms of rate constants versus reciprocal
temperature for hypohalogenation of (1) 2-methylhex-5-en-
3-yn-2-ol, (2) 2-methylhept-6-en-3-yn-2-ol, (3) 5-methoxy-
5-methylhex-1-en-3-yne, and (4) 6-methoxy-6-methylhept-1-
en-4-yne.
XVII, XVIII, n = 0; XIX, XX, n = 1; XVII, XIX, R = H;
XVIII, XX, R = Me.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

HYPOHALOGENATION OF VINYL- AND ALLYLACETYLENES
1607
Table 4. Temperature effect on the yield of epoxy deriva-
tives XVII–XX
by IR absorption bands at 915, 3060, and 1260−
1235 cm−1, belonging to vibrations of C−H bonds at
the oxirane ring. According to the procedure described
in [24] we determined the epoxide number for each
compound: 12.2 (XVII), 12.0 (XVIII), 11.0 (XIX),
Yield, wt %
Temperature,
K
XVII
XVIII
XIX
XX
1
and 10.9 (XX). In the H NMR spectra of XVII−XX,
303
313
318
328
70.0
90.1
91.3
82.2
68.5
96.7
95.0
84.3
72.5
85.5
96.3
85.6
71.8
89.8
97.4
88.5
protons of the CH2 group in the oxirane ring gave
two signals: a doublet at δ 2.5 ppm and a triplet at
δ 2.65 ppm. The upfield signal was split due to cou-
pling with the OCH proton (δ 3.0 ppm) with a constant
J of 2.5 Hz, and the corresponding coupling constant
for the downfield signal was J = 5.0 Hz. The geminal
coupling constant for the CH2 protons coincided with
the larger vicinal constant (2J = 5.0 Hz).
XXIII and XXIV contained no hydroxy group absorp-
tion, but strong bands typical of terminal triple C≡C
bond were present (2125 and 3310 cm−1). In the
1H NMR spectra of these compounds we observed no
signals assignable to geminal methyl groups and
hydroxy proton; instead, the ≡C–H signal appeared as
a triplet at δ 2.21−2.24 ppm.
Chemical transformations of epoxy acetylenic com-
pounds XVII−XX attract interest from both synthetic
and practical viewpoints. We tried to synthesize acet-
ylenic compounds having two oxirane rings via reac-
tion of XVII and XIX with halomethyloxiranes. The
reactions were carried out in one step: epoxy acetylen-
ic alcohols were used without isolation from the reac-
tion mixture. Dehydrohalogenation was accomplished
by the action of potassium hydroxide in anhydrous di-
ethyl ether, and the corresponding diepoxy derivatives
XXI and XXII were obtained in 60−70% yield
(Scheme 4).
Scheme 5.
H
O
KOH, 100–110°C
–Me2CO
XVII, XIX
( )n
XXIII, XXIV
XXIII, n = 0; XXIV, n = 1.
By reactions of epoxyalkynyl methyl ethers XVIII
and XX with nucleophilic reagents we obtained vari-
ous functional derivatives of the acetylene series.
Treatment of XVIII and XX with acetone in the
presence of boron trifluoride–ether complex resulted in
formation of 2,2-dimethyl-1,3-dioxolanes XXV and
XXVI, respectively. Compounds XVIII and XX
readily reacted with acetic anhydride in the presence of
sulfuric or sulfonic acid to produce diacetates XXVII
and XXVIII. Alkaline hydrolysis of XVIII and XX, as
well as of XXVII and XXVIII, gave diols XXIX and
XXX (Scheme 6). The structure of compounds XXV–
Scheme 4.
X
XVII, XIX
+
Me Me
O
KOH, Et2O, Δ
–KCl (KBr)
O
O
( )n
XXI, XXII
X = Cl, Br; XXI, n = 0; XXII, n = 1.
Compounds XXI and XXII displayed in the IR
spectra absorption bands typical of oxirane rings
(3065, 1248, 915 cm−1) and disubstituted acetylenic
bond (2230−2250 cm−1), whereas no absorption as-
signable to hydroxy group was present. Their 1H NMR
spectra lacked signal at δ 3.85 ppm, typical of hydroxy
proton. The epoxide numbers of compounds XXI and
XXII were 17.1 and 16.0, respectively.
1
XXX was confirmed by the IR and H NMR spectra.
The absence in their IR spectra of absorption bands at
3065 and 915 cm−1, which are typical of vibrations of
CH2 group in oxirane ring and asymmetric stretching
vibrations of oxirane ring, respectively, indicated that
the above reactions involved opening of the oxirane
ring. On the other hand, strong absorption bands at
1250 and 1745 cm−1 were observed due to acetoxy
groups. Absorption bands at 3400 and 1000−1170 cm−1
in the IR spectra of XXIX and XXX were assigned to
stretching vibrations of associated OH groups and
stretching C–O and bending O–H vibrations.
Epoxyalkynols XVII and XIX readily underwent
the reverse Favorskii reaction in the presence of
powdered potassium hydroxide at 100–110°C. Elimi-
nation of acetone molecule gave terminal epoxyal-
kynes XXIII and XXIV (Scheme 5). The IR spectra of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

VELIEV et al.
1608
Scheme 6.
Me
O
Me
Me
Me2CO, BF3 ·Et2O
Me
O
AcO
HO
( )n
XXV, XXVI
OMe
Me
OAc
Me
Ac2O, H+
XVIII, XX
( )n
XXVII, XXVIII
OMe
Me
OH
Me
NaOH, H2O
( )n
XXIX, XXX
OMe
XXV, XXVII, XXIX, n = 0; XXVI, XXVIII, XXX, n = 1.
Hydrolysis of terminal epoxyalkynes XXIII and
NaCl; oven temperature 140°C; carrier gas nitrogen,
flow rate 60 ml/min]. The rate constants and activation
parameters were calculated using kinetic equations for
bimolecular reactions [23] on the basis of the kinetic
data measured by GLC. Kinetic experiments were
carried out in the temperature range from 303 to 328 K
with equimolar amounts of the components, which
ruled out side processes.
XXIV in aqueous sodium hydroxide gave 85−89% of
diols XXXI and XXXII (Scheme 7). The IR and
1H NMR spectra of XXXI and XXXII showed the
absence of oxirane ring and the presence of terminal
acetylenic bond and hydroxy group in their molecules.
Scheme 7.
OH
H
NaOH, H2O
Acetylenic halohydrins I−VIII (general proce-
dure). The reactions were performed maintaining the
temperature with an accuracy of ± 0.2°C. A flask was
charged at a specified temperature with 0.2−0.4 mol of
6% hydrobromic acid or 6−10% hydrochloric acid and
0.2 mol of 2-methylhex-5-en-3-yn-2-ol, 2-methylhept-
6-en-3-yn-2-ol, or the corresponding methyl ether. The
mixture was stirred, and 0.22 mol of a 26−30% aque-
ous solution of hydrogen peroxide was added from
a dropping funnel at a rate of 10 g/h. The mixture was
stirred for 6.5−8.5 h until complete disappearance of
H2O2 and HOCl or HOBr (according to the permanga-
natometric or iodometric titration data). The resulting
chloro- and bromohydrins were converted without
isolation into the corresponding epoxy derivatives by
adding potassium hydroxide to the reaction mixture.
Individual compounds I−VIII were isolated as fol-
lows. The organic phase was separated, the aqueous
phase was extracted with diethyl ether (2×50 ml),
the extracts were combined with the organic phase,
neutralized by treatment with a 10% solution of
sodium carbonate, and dried over magnesium sulfate,
the solvent was removed, and the residue was distilled
under reduced pressure.
XXIII, XXIV
HO
( )n
XXXI, XXXII
XXXI, n = 0; XXXII, n = 1.
Thus the results of our study demonstrate that
acetylenic chloro- and bromohydrins I−VIII can be
used as starting compounds in the synthesis of new
epoxy and other functionalized acetylene derivatives.
EXPERIMENTAL
The IR spectra were recorded in the range from
400−3600 cm−1 on a UR-20 spectrometer from neat
1
substances (films). The H NMR spectra were meas-
ured on Tesla BS-487B (80 MHz) and Tesla BS-467
instruments (60 MHz) from solutions in carbon tetra-
chloride using hexamethyldisiloxane as internal refer-
ence. The purity of the products was checked by TLC
(Silufol UV-254 plates; benzene–diethyl ether, 3:1 to
5:1; development with iodine vapor) and by GLC
using an LKhM-8 MD-5 chromatograph equipped with
a thermal conductivity detector [200×0.4-cm column
packed with 0.5 wt % of poly(dimethylsiloxane) on
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

HYPOHALOGENATION OF VINYL- AND ALLYLACETYLENES
1609
1-Chloro-5-methylhex-3-yne-2,5-diol (I). Yield
72%, bp 109−110°C (5 mm), nD20 = 1.4895, d420
5,6-Dibromo-2-methylhex-3-yn-2-ol (XI). Yield
82%, bp 116−117°C (2 mm), nD20 = 1.5637, d420
=
=
1.1326. Found, %: C 51.60; H 6.71; Cl 21.96.
C7H11ClO2. Calculated, %: C 51.70; H 6.82; Cl 21.80.
1.7857. Found, %: C 31.26; H 3.61; Br 59.36.
C7H10Br2O. Calculated, %: C 31.14; H 3.73; Br 59.20.
1-Chloro-5-methoxy-5-methylhex-3-yn-2-ol (II).
Yield 78%, bp 82−83°C (5 mm), nD20 = 1.4670, d420 =
1.0885. Found, %: C 54.53; H 7.45; Cl 20.01.
C8H13ClO2. Calculated, %: C 54.39; H 7.41; Cl 20.07.
1,2-Dibromo-5-methoxy-5-methylhex-3-yne
(XII). Yield 84%, bp 95−96°C (2.5 mm), nD20 = 1.5412,
d420 = 1.6582. Found, %: C 33.95; H 4.12; Br 56.20.
C8H12Br2O. Calculated, %: C 33.83; H 4.26; Br 56.28.
1-Bromo-5-methylhex-3-yne-2,5-diol (III). Yield
6,7-Dichloro-2-methylhept-3-yn-2-ol (XIII).
Yield 80%, bp 117−118°C (2 mm), nD20 = 1.5174, d420 =
1.2285. Found, %: C 49.18; H 6.27; Cl 36.47.
C8H12Cl2O. Calculated, %: C 49.25; H 6.20; Cl 36.35.
69%, bp 114−115°C (2.5 mm), nD20 = 1.5221, d420
=
1.4714. Found, %: C 40.52; H 5.45; Br 38.52.
C7H11BrO2. Calculated, %: C 40.60; H 5.36; Br 38.60.
1-Bromo-5-methoxy-5-methylhex-3-yn-2-ol (IV).
Yield 71%, bp 89−90°C (2 mm), nD20 = 1.4990, d420 =
1.3685. Found, %: C 43.53; H 5.81; Br 36.20.
C7H11BrO2. Calculated, %: C 43.46; H 5.93; Br 36.14.
6,7-Dichloro-2-methoxy-2-methylhept-3-yne
(XIV). Yield 82%, bp 94−95°C (2 mm), nD20 = 1.4950,
d420 = 1.1518. Found, %: C 51.76; H 6.65; Cl 33.83.
C9H14Cl2O. Calculated, %: C 51.69; H 6.75; Cl 33.91.
7-Chloro-2-methylhept-3-yne-2,6-diol (V). Yield
6,7-Dibromo-2-methylhept-3-yn-2-ol (XV). Yield
77%, bp 121−122°C (5 mm), nD20 = 1.4755, d420
=
83%, bp 125−126°C (2 mm), nD20 = 1.5510, d420
=
1.1462. Found, %: C 54.31; H 7.32; Cl 20.22.
C8H13ClO2. Calculated, %: C 54.39; H 7.41; Cl 20.07.
1.6810. Found, %: C 33.74; H 4.18; Br 56.36.
C8H12Br2O. Calculated, %: C 33.83; H 4.26; Br 56.27.
1-Chloro-6-methoxy-6-methylhept-4-yn-2-ol
(VI). Yield 81%, bp 95−96°C (5 mm), nD20 = 1.4540,
d420 = 1.0994. Found, %: C 56.59; H 7.95; Cl 18.79.
C9H15ClO2. Calculated, %: C 56.69; H 7.92; Cl 18.59.
6,7-Dibromo-2-methoxy-2-methylhept-3-yne
(XVI). Yield 86%, bp 104−105°C (2 mm), nD20
=
1.5270, d420 = 1.5646. Found, %: C 3616; H 4.86;
Br 53.75. C9H14Br2O. Calculated, %: C 33.83; H 4.26;
Br 56.27.
7-Bromo-2-methylhept-3-yne-2,6-diol (VII).
Yield 75%, bp 126−127°C (2 mm), nD20 = 1.5075, d420 =
1.3834. Found, %: C 43.32; H 5.85; Br 36.26.
C8H13BrO2. Calculated, %: C 43.46; H 5.93; Br 36.14.
Epoxy derivatives XVII−XX (general procedure).
Compound I−VIII, 0.05 mol, was dissolved in 60 ml
of diethyl ether, and powdered potassium hydroxide,
8.4 g (0.15 mol), was added under stirring and cooling
(281−283 K). The mixture was stirred for 2 h at
285−287 K and subjected to appropriate treatment.
Compounds XVII−XX were isolated by vacuum dis-
tillation.
1-Bromo-6-methoxy-6-methylhept-4-yn-2-ol
(VIII). Yield 78%, bp 99−100°C (2 mm), nD20 = 1.4870,
d420 = 1.2906. Found, %: C 45.85; H 6.52; Br 33.83.
C9H15BrO2. Calculated, %: C 45.97; H 6.43; Br 33.98.
Dichloro and dibromo derivatives IX−XVI
(general procedure). Hydrogen peroxide was added at
a rate of 10g/h to a mixture of 0.1 mol of compound I–
VIII and 0.22 mol of 43% hydrobromic acid or 36%
hydrochloric acid. The mixture was stirred for 4 h at
313 K, the heavy organic layer was separated from the
aqueous layer, and compounds IX−XVI were isolated
by vacuum distillation.
2-Methyl-4-(oxiran-2-yl)but-3-yn-2-ol (XVII).
Yield 90%, bp 94−95°C (5 mm), nD20 = 1.4650, d420 =
1.0745. Found, %: C 66.50; H 8.01. C7H10O2. Calcu-
lated, %: C 66.64; H 7.98.
2-(3-Methyl-3-methoxybut-1-yn-1-yl)oxirane
(XVIII). Yield 97%, bp 66−67°C (5 mm), nD20
=
1.4520, d420 = 0.9638. Found, %: C 68.52; H 8.62.
5,6-Dichloro-2-methylhex-3-yn-2-ol (IX). Yield
78%, bp 112.5−113.5°C (4 mm), nD20 = 1.5312, d420 =
1.2888. Found, %: C 46.56; H 5.42; Cl 39.23.
C7H10Cl2O. Calculated, %: C 46.43; H 5.57; Cl 39.16.
C8H12O2. Calculated, %: C 68.57; H 8.57.
2-Methyl-5-(oxiran-2-yl)pent-3-yn-2-ol (XIX).
Yield 86%, bp 100−101°C (5 mm), nD20 = 1.4610, d420 =
1.0016. Found, %: C 68.62; H 8.42. C8H12O2. Calculat-
ed, %: C 68.57; H 8.57.
1,2-Dichloro-5-methoxy-5-methylhex-3-yne (X).
Yield 80%, bp 86−87°C (4 mm), nD20 = 1.5087, d420
=
2-(4-Methyl-4-methoxypent-2-yn-1-yl)oxirane
1.2071. Found, %: C 49.38; H 6.11; Cl 36.24.
C8H12Cl2O. Calculated, %: C 49.25; H 6.20; Cl 36.35.
(XX). Yield 90%, bp 75−76°C (5 mm), nD20 = 1.4484,
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VELIEV et al.
1610
d420 = 0.9608. Found, %: C 70.06; H 9.20. C9H14O2.
Calculated, %: C 70.10; H 9.25.
Found, %: C 67.71; H 9.66. C12H20O3. Calculated, %:
C 67.89; H 9.50.
5-Methoxy-5-methylhex-3-yne-1,2-diyl diacetate
(XXVII). Acetic anhydride, 4.5 g (0.056 mol), was
slowly added under stirring at 283 K to a mixture of
20 g of benzene, 7.0 g (0.05 mol) of compound XVIII,
and 1.5 g of KU-2 cation exchanger (H-form). The
addition was accompanied by slight heat evolution.
The mixture was stirred for 2.5 h at 285−287 K, the
catalyst was filtered off through a Schott filter, the sol-
vent was distilled off from the filtrate, and the residue
was distilled under reduced pressure. Yield 77%,
bp 104−105°C (1 mm), nD20 = 1.4840, d420 = 1.1188.
Found, %: C 59.30; H 9.25. C12H18O5. Calculated, %:
C 59.49; H 7.49.
2-[3-Methyl-3-(oxiran-2-ylmethoxy)but-1-yn-1-
yl]oxirane (XXI). Diethyl ether, 30 ml, and chloro-
methyloxirane, 4 g (0.042 mol), or bromomethyl-
oxirane, 5.8 g (0.042 mol), were added under stirring
and cooling (281−283 K) to 0.1 mol of compound
XVII. Powdered potassium hydroxide, 4.7 g, was then
added, and the mixture was stirred for 2 h at 285−
287 K. After appropriate treatment, compound XXI
was isolated by vacuum distillation. Yield 61%,
bp 97−98°C (1 mm), nD20 = 1.4912, d420 = 1.2109.
Found, %: C 65.75; H 7.88. C10H14O3. Calculated, %:
C 65.91; H 7.74.
2-[4-Methyl-4-(oxiran-2-ylmethoxy)pent-2-yn-1-
yl]oxirane (XXII) was synthesized in a similar way
from compound XIX. Yield 71%, bp 112−113°C
(1 mm), nD20 = 1.4753, d420 = 1.0616. Found, %: C 67.26;
H 8.14. C11H16O3. Calculated, %: C 67.32; H 8.22.
6-Methoxy-6-methylhept-4-yne-1,2-diyl diace-
tate (XXVIII) was synthesized in a similar way from
compound XX. Yield 81%, bp 112−113°C (1 mm),
nD20 = 1.0933, d420 = 1.0933. Found, %: C 60.83; H 7.80.
C13H20O5. Calculated, %: C 60.92; H 7.87.
2-Ethynyloxirane (XXIII). A mixture of 6.5 g
(0.05 mol) of compound XVII and 0.1 g of powdered
potassium hydroxide was distilled in a stream of
nitrogen at 333−338 K. The mixture was heated in
such a way that the products gradually condensed in
a pipe coil receiver. We thus obtained an equimolar
mixture of acetone and compound XXIII. Yield 87%,
bp 86−87.5°C, nD20 = 1.4265, d420 = 0.8935. Found, %:
C 70.65; H 5.80. C4H4O. Calculated, %: C 70.57;
H 5.92.
Acetylenic diols XXIX−XXXII (general proce-
dure). Compound XVIII, XX, XXIII, or XXIV,
0.1 mol, was added to a solution of 2 g of sodium
hydroxide in 15 g of water, and the mixture was stirred
for 4 h at 323−333 K. The mixture was then saturated
with potassium carbonate and extracted with diethyl
ether, the extract was dried over calcined potassium
carbonate, the solvent was removed, and the residue
was distilled under reduced pressure. The product
crystallized in the receiver.
2-(Prop-2-yn-1-yl)oxirane (XXIV) was obtained
in a similar way from epoxy alcohol XIX. Yield 89%,
bp 102−103°C, nD20 = 1.4207, d420 = 0.8610. Found, %:
C 73.28; H 7.30. C5H6O. Calculated, %: C 73.14;
H 7.37.
5-Methoxy-5-methylhex-3-yne-1,2-diol (XXIX).
Yield 82%, mp 43−44°C. Found, %: C 60.63; H 8.97.
C8H14O3. Calculated, %: C 60.74; H 8.92.
6-Methoxy-6-methylhept-4-yne-1,2-diol (XXX).
Yield 87%, mp 48−49°C. Found, %: C 62.89; H 9.28.
C9H16O3. Calculated, %: C 62.76; H 9.37.
4-(3-Methoxy-3-methylbut-1-yn-1-yl)-2,2-di-
methyl-1,3-dioxolane (XXV). Compound XVIII,
4.6 g (0.032 mol), was added in portions to a mixture
of 25 g of acetone and 0.2 ml of boron trifluoride–
ether complex. The mixture slightly warmed up. It was
left overnight and treated with a saturated solution of
potassium carbonate, and the organic phase was sepa-
rated, dried over magnesium sulfate, and distilled
under reduced pressure. Yield 70%, bp 69−70°C
(5 mm), nD20 = 1.4335, d420 = 0.9674. Found, %: C 66.58;
H 9.25. C11H18O3. Calculated, %: C 66.64; H 9.15.
But-3-yne-1,2-diol (XXXI). Yield 85%, mp 39−
40°C. Found, %: C 55.99; H 7.16. C4H6O2. Calculated,
%: C 55.80; H 7.03.
Pent-4-yne-1,2-diol (XXXII). Yield 90%, mp 44−
45°C. Found, %: C 59.82; H 8.20. C5H8O2. Calculated,
%: C 59.98; H 8.05.
REFERENCES
4-(4-Methoxy-4-methylpent-2-yn-1-yl)-2,2-di-
methyl-1,3-dioxolane (XXVI) was synthesized in
a similar way from compound XX. Yield 76%,
bp 77−78°C (4 mm), nD20 = 1.4195, d420 = 0.9173.
1. Trakarpuk, W., Rheingold, A., Haggerty, B.S., and
Ernst, R.D., Organometallics, 1994, vol. 13, p. 3914.
2. Wong, T., Romero, F., and Fallis, A.G., J. Org. Chem.,
1994, vol. 59, p. 5527.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

HYPOHALOGENATION OF VINYL- AND ALLYLACETYLENES
1611
3. Salmanov, M.A., Veliev, M.G., and Muradov, P.Z. Izv.
Nats. Akad. Nauk Azerb., Ser. Biol. 2004, p. 159.
4. Grigor’eva, N.Ya. and Pinsker, O.A., Usp. Khim., 1994,
vol. 63, p. 177.
5. Tolstikov, A.G. and Tolstikov, G.A., Usp. Khim., 1996,
vol. 65, p. 474.
20. Kurts, A.L., Matveeva, E.D., Erin, A.S., and Kva-
sha, M.P., Vestn. Mosk. Gos. Univ., Ser. Khim., 1996,
vol. 37, p. 151.
21. Veliev, M.G., Shatirova, M.I., Chalabiev, Ch.A., Mame-
dov, I.M., and Mustafaev, A.M., Russ. J. Org. Chem.,
1995, vol. 31, p. 52.
22. Veliev, M.G., Akperova, E.G., Shatirova, M.I., Aske-
rov, O.V., and Mamedov, El.Sh., Azerb. Khim. Zh.,
2003, no. 3, p. 41.
6. Brunel, Y. and Rousseau, G., J. Org. Chem., 1996,
vol. 61, p. 5793.
7. Sonogachira, R., Tohda, Y., and Hagihara, N., Tetra-
hedron Lett., 1975, vol. 16, p. 4467.
8. Rossi, R., Carpita, A., Quirici, M.G., and Gauden-
zi, M.Z., Tetrahedron, 1982, vol. 38, p. 631.
9. Alami, L. and Linstrumelle, G., Tetrahedron Lett., 1991,
vol. 32, p. 6109.
23. Bellamy, L.J., The Infra-red Spectra of Complex
Molecules, London: Methuen, 1958. Translated under
the title Infrakrasnye spektry slozhnykh molekul,
Moscow: Inostrannaya Literatura, 1963, p. 474.
24. Silverstein, R.M., Bassler, G.C., and Morrill, T.C., Spec-
trometric Identification of Organic Compounds, New
York: Wiley, 1974, 3rd ed.
10. Bumagin, N.A., Ponomarev, A.B., and Beletskaya, I.P.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1987, p. 1565.
25. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion, New York: Wiley, 1972.
11. Efimova, I.V., Golyavin, A.A., Kazankova, M.A., and
Beletskaya, I.P., Russ. J. Org. Chem., 1995, vol. 31,
p. 296.
26. Denisov, E.T., Kinetika gomogennykh reaktsii (Kinetics
of Homogeneous Reactions), Moscow: Khimiya, 1978.
12. Trostyanskaya, I.G., Shevtsov, A.S., Efimova, I.V.,
Kazankova, M.A., and Beletskaya, I.P., Russ. J. Org.
Chem., 1996, vol. 32, p. 946.
13. Kazankova, M.A., Trostyanskaya, I.G., Lutsenko, S.V.,
Efimova, I.V., and Beletskaya, I.P., Russ. J. Org. Chem.,
1999, vol. 35, p. 1273.
27. Sorokin, M.F. and Lyalyushko, K.A., Praktikum po
khimii i tekhnologii plenkoobrazuyushchikh veshchestv
(Laboratory Course on the Chemistry and Technology
of Film-Forming Substances), Moscow: Khimiya, 1972.
28. Korshak, V.V., Termostoikie polimery (Heat-Resistant
14. Veliev, M.G., Chalabieva, A.Z., Gakhramanov, R.F., and
Polymers), Moscow: Nauka, 1969.
Mustafaev, A.M., Zh. Org. Khim., 1994, vol. 30, p. 40.
29. Paken, A.M., Epoksidnye soedineniya i epoksidnye
smoly (Epoxy Compounds and Epoxy Resins), Moscow:
Goskhimizdat, 1962.
30. Zubkovits, I.Yu., Martynova, V.F., Tatarchuk, V.V., and
Shchelkunov, A.V., Khimiya atsetilena (Acetylene
Chemistry), Moscow: Nauka, 1972.
31. Prilezhaeva, E.N., Reaktsiya Prilezhaeva. Elektrofil’noe
okislenie (Prilezhaev Reaction. Electrophilic Oxidation),
Moscow: Nauka, 1974.
32. Malinovskii, M.S., Okisi olefinov i ikh proizvodnye
(Olefin Oxides and Their Derivatives), Moscow:
Goskhimizdat, 1964.
15. Veliev, M.G., Chalabieva, A.Z., Shatirova, M.I., and
Gakhramanov, R.F., Russ. J. Org. Chem., 2000, vol. 36,
p. 960.
16. Veliev, M.G., Chalabieva, A.Z., Shatirova, M.I., and
Akperova, E.G., Russ. J. Org. Chem., 2003, vol. 39,
p. 825.
17. Veliev, M.G., Guseinov, M.M., Yanovskaya, L.A., and
Burstein, K.Ya., Tetrahedron, 1985, vol. 41, p. 749.
18. Zhang, M. and Buchwald, S.L., J. Org. Chem., 1996,
vol. 61, p. 4498.
19. Jeffery, T., Tetrahedron Lett., 1989, vol. 30, p. 2225.
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