Hydrogen peroxide-or sodium hypochlorite-induced bromination of 1-arylbut-2-enes

Article abstract of DOI:10.1134/S1070428007110139

Bromination of 1-arylbut-2-enes in the system [HBr or NaBr (KBr)-HX]-H ₂O₂ (or NaOCl) under relatively mild conditions leads to electrophilic addition of bromine or hypobromous acid at the side-chain double bond. Under more severe conditions, the process is accompanied by bromination of the aromatic ring. Treatment of the title compounds with peroxy acids (RCOOH-H₂O₂) gives the corresponding epoxy derivatives which react with HBr and oxygen-containing nucleophiles to produce α-bromo alcohols, diols, and diol acetates.

Full text of DOI:10.1134/S1070428007110139

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 11, pp. 1661–1670. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © O.A. Sadygov, Kh.M. Alimardanov, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 11, pp. 1664–1672.
Hydrogen Peroxide- or Sodium Hypochlorite-Induced
Bromination of 1-Arylbut-2-enes
O. A. Sadygov and Kh. M. Alimardanov
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaidjan
pr. Khodzhaly 30, Baku, 1025 Azerbaidjan
e-mail: hafizalimardanov@yahoo.com
Received December 18, 2006; revised August 14, 2007
Abstract—Bromination of 1-arylbut-2-enes in the system [HBr or NaBr (KBr)–HX]–H2O2 (or NaOCl) under
relatively mild conditions leads to electrophilic addition of bromine or hypobromous acid at the side-chain
double bond. Under more severe conditions, the process is accompanied by bromination of the aromatic ring.
Treatment of the title compounds with peroxy acids (RCOOH–H2O2) gives the corresponding epoxy
derivatives which react with HBr and oxygen-containing nucleophiles to produce α-bromo alcohols, diols, and
diol acetates.
DOI: 10.1134/S1070428007110139
Halogen and hydroxy halogen derivatives of alkyl-
aromatic hydrocarbons are used as starting materials in
the synthesis of pharmacological agents [1], fragrant
substances [2, 3], and specialty composite materials
[4]. In the present article we report the results of our
study on the bromination of various 1-phenylbut-2-ene
derivatives and their heterophase epoxidation products
with alkali metal bromides or hydrobromic acid in
the presence of hydrogen peroxide or sodium hypo-
chlorite.
addition of halogens and hypohalous acids at a double
C=C bond was considered in detail in [6]. Later
publications on this topic were reviewed in [7–9].
However, bromination of unsaturated compounds of
the aromatic series in the presence of hydrogen per-
oxide or sodium hypochlorite has received much lesser
attention.
Initial 1-arylbut-2-enes were synthesized by alken-
ylation of benzene, toluene, chlorobenzene, anisole,
phenetole, and o-, m-, and p-xylenes with divinyl
according to the procedure described in [10, 11]. The
use of phosphoric acid instead of sulfuric acid favored
selective ortho-alkenylation (Scheme 1). The IR spec-
trum of 1-phenylbut-2-ene (Ia) contains strong absorp-
tion bands at 695 and 741 cm–1, which are typical of
monosubstituted benzene ring, and a band at 968 cm–1,
which was assigned to bending vibrations of the C–H
bonds at the trans-configured aliphatic double bond. In
the IR spectrum of butenyltoluene Ib, the most intense
band was that located at 980 cm–1; it characterizes
C=C bond with trans orientation of the alkyl groups.
This band is absent in the spectrum of the hydrogena-
Interest in conjugate electrophilic halogenation of
unsaturated hydrocarbons of the aromatic series stems
from convenience of these reactions as a one-step route
to aromatic compounds having various substituents in
the vicinal positions of the side chain, which opens the
way to their subsequent transformations. Addition of
hypohalous acids HOHlg across the multiple bond in
aliphatic unsaturated hydrocarbons has been studied in
detail. In particular, hypochlorination of ethylene and
propylene underlie large-scale technologies for manu-
facture of epoxyethane and 1,2-epoxypropane through
the corresponding chlorohydrins [5]. Electrophilic
Scheme 1.
Me
H3PO4
+
CH2=CHCH=CH2
R
R
Ia–Ih
R = H (a), Me (b), Cl (c), MeO (d), EtO (e), 1,2-Me2 (f), 1,3-Me2 (g), 1,4-Me2 (h).
1661

SADYGOV, ALIMARDANOV
1662
tion product of Ib. In addition, the weak band at
778 cm–1, which is likely to belong to the cis isomer,
disappears from the spectrum upon hydrogenation. The
presence of absorption bands at 742 and 809 cm–1 in-
dicates formation of a mixture of 1,2- and 1,4-substi-
tuted isomers (62% and 33%, respectively, according
to the GLC data). The IR spectrum of chlorophenyl
derivative Ic contains bands at 742 (C–Cl) and
996 cm–1 (trans-C=C). The GLC and spectral data
showed that the alkenylation products of anisole (Id)
and phenetole (Ie) are mixtures of 1,2- (54–57 wt %)
and 1,4-substituted isomers (37–40 wt %) [12, 13].
In fact, treatment of compounds Ia–Ih with MBr
(HBr)–H2O2 at a molar ratio of 1:2:1 at 0–20°C led
to the formation of vicinal dibromides IIa–IIh, while
in the presence of excess reagent [I–MBr (HBr)–H2O2
molar ratio 1:3:2] at 50–60°C bromination of the aro-
matic ring also occurred to give tribromo derivatives
IIIa–IIIh (Scheme 2).
The structure of compounds IIa–IIh and IIIa–IIIh
was confirmed by GLC, IR, and analytical data. Their
IR spectra contained absorption bands at 640 and 655–
680 cm–1 due to stretching vibrations of the C–Br
bonds, whereas absorption typical of C=C bond vibra-
tions (1600, 1608 cm–1) was absent [12, 13]. Apart
from products IIa–IIh and IIIa–IIIh, we detected in
the reaction mixtures the corresponding bromohydrins
Va–Vh (6–12.5 wt %) which were formed as a result
of electrophilic addition of HOBr at the side-chain
double bond. Compounds Va–Vh were synthesized by
independent method, bromination of the corresponding
1-aryl-2,3-epoxybutanes. The synthesis was performed
in two steps. In the first step, epoxidation of 1-arylbut-
2-enes in the presence of chlorine-containing acidic
cation exchanger KU-2×8 or KU-2×8n gave epoxy
derivatives IVa–IVh (Scheme 3). Their structure was
confirmed by elemental analysis and IR spectroscopy,
as well as by determination of epoxide numbers using
a solution of hydrogen chloride in acetone [15]. Com-
parison of the IR spectra of compounds Ia–Ih and
IVa–IVh showed disappearance of strong absorption
bands at 778, 968, 1600, and 1602 cm–1, typical of the
double bond in I, and appearance of new bands at 1260
and 1250 cm–1 due to C–O bond vibrations.
Isomer mixtures were also obtained by alkenylation
of individual o-, m-, and p-xylenes with buta-1,3-di-
ene. Products If–Ih displayed in the IR spectra a strong
band at 966 cm–1, which was assigned to the trans-
butenyl group. o-Xylene (If) gave rise to a mixture of
1,2,3- (up to 33%; 817–825 cm–1) and 1,2,4-substituted
isomers (63%; 780–790 cm–1). The major product of
alkenylation of m-xylene (Ig) was 1,3,4-substituted
isomer (up to 92%; 824 cm–1), while the fraction of
1,2,3-substituted derivative (766 cm–1) was as low
as 5%. 2-(But-2-en-1-yl)-1,4-dimethylbenzene was
formed as the only product in the reaction with
p-xylene (Ih).
The presence of a reactive double bond in the side
chain of compounds Ia–Ih provides the possibility for
using them in the synthesis of various functional deriv-
atives. We previously showed that alkylaromatic com-
pounds undergo bromination at the aromatic ring in
acid aqueous solutions of alkali metal bromides in the
presence of various oxidants [14]. Depending on the
conditions, compounds containing a double bond in the
side chain could give rise to bromination products both
at the side-chain double bond and at the aromatic ring.
Scheme 3.
Cl-KU-2× 8
R'COOH
+
H2O2
R'CO3H
Me
–H2O
Scheme 2.
Br
Ia–Ih
2NaBr (2HBr)–H2O2
0 to 20°C
O
Me
Me
R
Br
IIa–IIh
IVa–IVh
R
For R, see legend to Scheme 1; R′ = Me, Et.
Ia–Ih
Br
Br
The bromination of epoxy derivatives IVa, IVb,
and IVd–IVh under mild conditions [IV–NaBr (HBr)–
H2O2 molar ratio 1:1:1, 0–30°C] was accompanied by
opening of the oxirane ring with formation of the cor-
responding bromohydrins Va–Vh. Under more severe
conditions [IV–NaBr (HBr)–H2O2 molar ratio 1:2:2,
50–70°C] both hydrobromination of the epoxy group
3NaBr (3HBr)–2H2O2
50 to 60°C
Br
IIIa–IIIh
R
R = H (a), Me (b), Cl (c), MeO (d), EtO (e), 1,2-Me2 (f),
1,3-Me2 (g), 1,4-Me2 (h).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

HYDROGEN PEROXIDE- OR SODIUM HYPOCHLORITE-INDUCED BROMINATION
1663
Scheme 4.
OH
NaBr (HBr)–H2O2
0 to 30°C
Me
Br
R
Va, Vb, Vd–Vh
IVa, IVb, IVd–IVh
Br
Br
2NaBr (2HBr)–2H2O2
50 to 70°C
Me
OH
R
VIa, VIb, VId–VIh
R = H (a), Me (b), MeO (d), EtO (e), 1,2-Me2 (f), 1,3-Me2 (g), 1,4-Me2 (h).
Scheme 5.
OH
H2O, H+
Me
OH
R
VIIa, VIIb
H2O, H+
IVa, IVb
OAc
Ac2O, H+
Me
OAc
R
VIIIa, VIIIb
R = H (a), Me (b).
and electrophilic bromination of the benzene ring
EXPERIMENTAL
occurred as shown in Scheme 4. Determination of the
epoxide numbers [15] of the isolated products Va–Vh
and VIa–VIh showed that the conversion of the ox-
irane ring in compounds IVa–IVh by the action of HBr
was complete [16, 17]. Presumably, next followed
electrophilic bromination of the aromatic ring.
The IR spectra were obtained on a UR-20 spec-
trometer. The H NMR spectra were recorded on
1
a Tesla BS-484D instrument (80 MHz) from solutions
in carbon tetrachloride using hexamethyldisiloxane as
internal reference. The purity and isomeric composi-
tion of the initial compounds were checked by GLC.
Alkenylarenes, epoxy derivatives, and products of their
transformations were analyzed using a 0.3×200-cm
column packed with 12 wt % of Apiezon L on Celite
(oven temperature 210–250°C), and bromination prod-
ucts were analyzed using a 0.3 × 300-cm column
packed with 5% of XE-60 on Chromaton N-AW DMCS
(oven temperature 140°C); carrier gas helium, flow
rate 40 ml/min. The purity of compounds IIIa–IIIh
was checked by TLC on Silufol UV-254 plates using
benzene–dichloroethane–acetic acid (4:1.5:1 by vol-
ume) as eluent; spots were visualized under UV light.
The molecular weights of compounds IIIa–IIIh were
determined by cryoscopy in camphor.
By reactions of epoxides IVa and IVb with oxygen-
centered nucleophiles [18, 19] we synthesized some
their functional derivatives. Compounds IVa and IVb
readily reacted with water and acetic anhydride in the
presence of acid catalyst (RSO3H, KU-2) to give the
corresponding diols VIIa and VIIb and esters VIIIa
and VIIIb; acid hydrolysis of the latter also afforded
diols VIIa and VIIb (Scheme 5).
The results of the present study demonstrate that
alkenylaromatic hydrocarbons can be converted, de-
pending on the conditions, into various functionalized
alkylaromatic compounds which possess useful prop-
erties and attract interest from the viewpoint of their
subsequent transformations.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

SADYGOV, ALIMARDANOV
1664
diene, 27 g (0.5 mol), was passed at a flow rate of 6 l/h
through a mixture of 160 g (1.5 mol) of 1,2-dimethyl-
benzene and 18.5 g of 86% H3PO4. The mixture was
stirred for 3.5 h at 60°C and treated as described
above, and the residue was distilled under reduced
pressure. Yield 122.5 g (66%), bp 105–107°C
(15 mm), d420 = 0.8944, nD20 = 1.5170; iodine number
154. Found, %: C 89.75; H 10.13. C12H16. Calculated,
%: C 89.92; H 9.99. According to the GLC data, the
product contained 56% of 1,3,4-isomer and 40% of
1,2,3-isomer.
(But-2-en-1-yl)benzene (Ia). A mixture of 78 g
(1 mol) of benzene and 10.5 g of 86% H3PO4 was
heated to 60°C, and 27 g (0.5 mol) of buta-1,3-diene
was supplied at a rate of 6 l/h. The mixture was stirred
for 3.5 h at 60°C, washed with water until neutral
reaction, and dried over MgSO4. Unreacted benzene
was distilled off, and the residue was distilled under
reduced pressure. Yield 49 g (46%, calculated on the
initial benzene), bp 73–78°C (15 mm), d420 = 0.884,
nD20 = 1.5108; MRD = 44.75, calcd. 44.21; iodine num-
ber 188. Found, %: C 91.1; H 9.12. C10H12. Calculated,
%: C 90.84; H 9.08.
Compounds Ig and Ih were synthesized in a similar
way.
Compounds Ib–Ie were synthesized in a similar
way.
2-(But-2-en-1-yl)-1,3-dimethylbenzene and
1-(but-2-en-1-yl)-2,4-dimethylbenzene (Ig) were ob-
tained from 160 g (1.5 mol) of 1,3-dimethylbenzene.
1-(But-2-en-1-yl)-2-methylbenzene and 1-(but-2-
en-1-yl)-4-methylbenzene (Ib). Yield 65.5 g (58%,
calculated on the initial toluene), bp 192–194°C
(15 mm), d420 = 0.8859, nD20 = 1.5121; MRD = 49.49,
calcd. 49.47; iodine number 160. Found, %: C 90.48;
H 9.73. C11H14. Calculated, %: C 90.41; H 5.58.
According to the GLC data, the product contained 62%
of 1,2-isomer and 33% of 1,4-isomer.
Yield 133 g (71%), bp 102–105°C (15 mm), d420
=
0.8940, nD20 = 1.5140; MRD = 54.22, calcd. 54.65;
iodine number 154. Found, %: C 90.1; H 10.08.
C12H16. Calculated, %: C 89.92; H 9.9. According to
the GLC data, the product contained 10% of 1,2,3-
isomer and 90% of 1,2,4-isomer.
1-(But-2-en-1-yl)-2-chlorobenzene and 1-(but-2-
en-1-yl)-4-chlorobenzene (Ic) were obtained from
112.5 g (1 mol) of chlorobenzene. Yield 82 g (59%),
bp 80–82°C (15 mm), d420 = 1.1123, nD20 = 1.5685;
MRD = 49.04, calcd. 49.18; iodine number 150. Found,
%: C 72.15; H 6.8; Cl 21.62. C10N11Cl. Calculated, %:
C 72.03; H 6.6; Cl 21.31. According to the GLC data,
the product contained 51.6% of 1,2-isomer and 43.3%
of 1,4-isomer.
1-(But-2-en-1-yl)-1,4-dimethylbenzene (Ih) was
obtained from 160 g (1.5 mol) of 1,4-dimethylbenzene.
Yield 106 g (56%), bp 105–108°C (15 mm), d420
=
0.8955, nD20 = 1.5146; MRD = 56.6, calcd. 54.65; iodine
number 152. Found, %: C 90.07; H 10.1. C12H16. Cal-
culated, %: C 89.92; H 9.99.
2,3-Dibromo-1-phenylbutane (IIa). Sodium
bromide, 20.3 g (0.2 mol), or potassium bromide, 24 g
(0.2 mol), was dissolved in 25 ml of water, and 24 g
(0.2 mol) of 33% hydrochloric acid and 13.2 g
(0.1 mol) of (but-2-en-1-yl)benzene (Ia) were added
dropwise under stirring over a period of 30 min.
A 18.5% aqueous solution of sodium hypochlorite,
124.2 g (0.2 mol; 110 mol/l of active chlorine) was
then added over a period of 90 min, and the mixture
was heated to 30–40°C and stirred for 4 h at that tem-
perature. When the reaction was complete, the organic
phase was separated, washed, and dried over anhy-
drous calcium chloride. Vacuum distillation gave
28.5 g (98%) of IIa, bp 130°C (15 mm), d420 = 1.5901,
nD20 = 1.570; MRD = 60.2, calcd. 60.44. IR spectrum:
1-(But-2-en-1-yl)-2-methoxybenzene and 1-(but-
2-en-1-yl)-4-methoxybenzene (Id) were obtained
from 162 g (1.5 mol) of anisole. Yield 117.2 g (62%),
bp 109–114°C (14 mm), d420 = 0.9573, nD20 = 1.5112;
MRD = 50.72, calcd. 50.57; iodine number 143. Found,
%: C 81.65; H 8.76. C11H14O. Calculated, %: C 81.48;
H 8.64. According to the GLC data, the product con-
tained 40% of 1,2-isomer and 56% of 1,4-isomer.
1-(But-2-en-1-yl)-2-ethoxybenzene and 1-(but-2-
en-1-yl)-4-ethoxybenzene (Ie) were obtained from
183 g (1.5 mol) of phenetole. Yield 97.7 g (47%),
bp 118–120°C (15 mm), d420 = 0.9523, nD20 = 1.5120;
MRD = 55.44, calcd. 55.19; iodine number 139. Found,
%: C 81.63; H 8.98. C12H18O. Calculated, %: C 81.82;
H 8.69. According to the GLC data, the product con-
tained 42% of 1,2-isomer and 52% of 1,4-isomer.
1
ν 670 cm–1 (C–Br). H NMR spectrum, δ, ppm: 6.71–
7.01 m (5H, C6H5), 2.58–2.83 d (2H, CH2) 3.65–
3.68 m (3H, CH), 0.79 s (3H, CH3), 4.01–4.21 m (2H,
CHBr). Found, %: C 40.8; H 4.0; Br 54.66. C12H16Br2.
Calculated, %: C 41.1; H 4.1; Br 54.79. Analogous
results were obtained with the use of 30% hydrogen
1-(But-2-en-1-yl)-2,3-dimethylbenzene and
1-(but-2-en-1-yl)-3,4-dimethylbenzene (If). Buta-1,3-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

HYDROGEN PEROXIDE- OR SODIUM HYPOCHLORITE-INDUCED BROMINATION
1665
the GLC data, the product contained 42% of 1,2-iso-
mer and 52% of 1,4-isomer. Analogous results were
obtained with the use of 30% hydrogen peroxide and
46% hydrobromic acid (HBr–H2O2 molar ratio 2:1).
peroxide and 46% hydrobromic acid (HBr–H2O2 molar
ratio 2:1) as brominating agent.
1-(2,3-Dibromobutyl)-2-methylbenzene and
1-(2,3-dibromobutyl)-4-methylbenzene (IIb) were
obtained from 14.6 g (0.1 mol) of isomer mixture Ib.
Yield 28.2 g (92%), bp 150°C (15 mm), d420 = 1.5144,
nD20 = 1.5711; MRD = 65.34, calcd. 65.08. IR spectrum:
1-(2,3-Dibromobutyl)-2,3-dimethylbenzene and
1-(2,3-dibromobutyl)-3,4-dimethylbenzene (IIf)
were obtained from 16 g (0.1 mol) of isomer mixture
If. Yield 29 g (91%), bp 168°C (15 mm), d420 = 1.4946,
nD20 = 1.5745. IR spectrum: ν 676 cm–1 (C–Br). 1H NMR
spectrum, δ, ppm: 6.75−6.88 m (3H, C6H3), 2.34 s (6H,
CH3), 2.86–3.1 d (2H, CH2), 4.0–4.21 m (2H, CHBr),
1.78 s (3H, CH3). Found, %: C 45.15; H 5.12; Br 50.8.
C12H16Br2. Calculated, %: C 45.0; H 5.0; Br 50.0.
1
ν 676 cm–1 (C–Br). H NMR spectrum, δ, ppm: 7.0–
7.18 m (4H, C6H4), 0.89 s (3H, CH3), 2.58–2.83 d
(2H, CH2), 3.65–3.68 m (3H, CH), 0.87 s (3H, CH3),
4.0–4.22 m (2H, CHBr). Found, %: C 43.0; H 4.36;
Br 52.0. C11H14Br2. Calculated, %: C 43.13; H 4.57;
Br 52.3. Analogous results were obtained with the use
of 30% hydrogen peroxide and 46% hydrobromic acid
(HBr–H2O2 molar ratio 2:1) as brominating agent.
1-(2,3-Dibromobutyl)-2,4-dimethylbenzene and
2-(2,3-dibromobutyl)-1,3-dimethylbenzene (IIg)
were obtained from 16 g (0.1 mol) of isomer mixture
1-Chloro-2-(2,3-dibromobutyl)benzene and
1-chloro-4-(2,3-dibromobutyl)benzene (IIc) were
obtained from 16.8 g (0.1 mol) of isomer mixture Ic.
Yield 29.9 g (92%). IR spectrum, ν, cm–1: 1022
(C–Cl), 674 (C–Br). 1H NMR spectrum, δ, ppm: 6.69–
6.73 m (4H, C6H4), 2.59–2.84 d (2H, CH2), 4.0–4.21 m
(2H, CHBr), 1.79 s (3H, CH3). Found, %: C 36.58;
H 3.64; Br+Cl 59.65. C11H12ClBr2. Calculated, %:
C 36.64; H 3.66; Br+Cl 59.69.
Ig. Yield 29.6 g (92%), bp 163°C (15 mm), d420
=
1.4947, nD20 = 1.5712. IR spectrum: ν 674 cm–1 (C–Br).
1H NMR spectrum, δ, ppm: 6.81–6.87 m (3H, C6H3),
2.33 s (6H, CH3), 2.87–3.1 d (2H, CH2), 4.0–4.2 m
(2H, CHBr), 1.78 s (3H, CH3). Found, %: C 45.23;
H 5.18; Br 51.12. C12H16Br2. Calculated, %: C 45.0;
H 5.0; Br 50.0.
2-(2,3-Dibromobutyl)-1,4-dimethylbenzene (IIh)
was obtained from 16 g (0.1 mol) of compound Ih.
Yield 27.5 g (86%), bp 160°C (15 mm), d420 = 1.4943,
nD20 = 1.5734. IR spectrum: ν 678 cm–1 (C–Br). 1H NMR
spectrum, δ, ppm: 6.75–6.87 m (3H, C6H3), 2.34 s (6H,
CH3), 2.88–3.11 d (2H, CH2), 4.0–4.2 m (2H, CHBr),
1.78 s (3H, CH3). Found, %: C 45.17; H 5.2; Br 51.15.
C12H16Br2. Calculated, %: C 45.0; H 5.0; Br 50.0.
1-(2,3-Dibromobutyl)-2-methoxybenzene and
1-(2,3-dibromobutyl)-4-methoxybenzene (IId) were
obtained from 16.2 g (0.1 mol) of isomer mixture Id,
52 g (0.2 mol) of 46% hydrobromic acid, and 11.4 g
(0.1 mol) of 30% hydrogen peroxide. Yield 22.1 g
(69%), bp 155–160°C (15 mm), d420 = 1.5862, nD20
=
1.5775; MRD = 67.32, calcd. 66.72. IR spectrum:
1
ν 678 cm–1 (C–Br). H NMR spectrum, δ, ppm: 6.69–
1-Bromo-2-(2,3-dibromobutyl)benzene and
1-bromo-4-(2,3-dibromobutyl)benzenes (IIIa) were
obtained at a substrate–MBr (HBr)–H2O2 molar ratio
of 1:3:2 from 12.2 g (0.1 mol) of isomer mixture Ia at
50–60°C. Yield 32.2 g (87%), mp 75–76°C (from
7.2 m (4H, C6H4), 1.33 s (3H, CH3), 2.87–3.13 d (2H,
CH2), 4.0–4.22 m (2H, CHBr), 1.79 s (3H, CH3).
Found, %: C 39.78; H 4.18; Br 49.45. C11H14Br2O.
Calculated, %: C 41.0; H 4.35; Br 49.69. According to
the GLC data, the product contained 40% of 1,2-iso-
mer and 56% of 1,4-isomer. Analogous results were
obtained using a 26% solution of NaOCl (153 mol/l of
active chlorine) as oxidant.
1
benzene). IR spectrum: ν 678 cm–1 (C–Br). H NMR
spectrum, δ, ppm: 6.96–7.36 m (4H, C6H4), 2.86–
3.11 d (2H, CH2), 4.0–4.21 m (2H, CHBr), 1.78 s (3H,
CH3). Found, %: Br 49.45. M 370.2. C10H11Br3. Calcu-
lated, %: Br 49.69. M 371.
1-(2,3-Dibromobutyl)-2-ethoxybenzene and
1-(2,3-dibromobutyl)-4-ethoxybenzene (IIe) were
obtained from 17.6 g (0.1 mol) of isomer mixture Ie.
Compounds IIIb–IIIh were synthesized in a simi-
lar way.
Yield 22 g (65%), bp 165–170°C (15 mm), d420
=
1.5142, nD20 = 1.5674; MRD = 68.49, calcd. 69.33.
1H NMR spectrum, δ, ppm: 6.66–7.18 m (4H, C6H4),
3.89 m (2H, CH2), 1.33 s (3H, CH3), 2.87–3.12 d (2H,
CH2), 4.0–4.21 m (2H, CHBr), 0.86 s (3H, CH3).
Found %: C 42.58; H 4.65; Br 47.36. C12H16Br2O. Cal-
culated, %: C 42.86; H 4.76; Br 47.62. According to
1-Bromo-2-(2,3-dibromobutyl)-3-methylbenzene
and 1-bromo-2-(2,3-dibromobutyl)-4-methylben-
zene (IIIb) were obtained from 14.2 g (0.1 mol) of
isomer mixture Ib. Yield 34.8 g (91%), mp 70–71°C
(from benzene). IR spectrum: ν 676 cm–1 (C–Br).
1H NMR spectrum, δ, ppm: 6.64–6.96 m (3H, C6H3),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

SADYGOV, ALIMARDANOV
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1
benzene). IR spectrum: ν 678 cm–1 (C–Br). H NMR
spectrum, δ, ppm: 6.68–7.0 d (2H, C6H2), 2.34 s (6H,
CH3), 3.11–2.87 d (2H, CH2), 3.99–4.19 m (2H,
CHBr), 1.78 s (3H, CH3). Found, %: Br 59.68.
M 398.1. C12H15Br3. Calculated, %: Br 61.15. M 399.
2.32 s (3H, CH3), 2.87–3.12 d (2H, CH2), 4.0–4.21 m
(2H, CHBr), 1.78 s (3H, CH3). Found, %: Br 62.12.
M 383.5. C11H13Br3. Calculated, %: Br 62.34. M 385.
1-Bromo-3-chloro-2-(2,3-dibromobutyl)benzene
and 1-bromo-4-chloro-2-(2,3-dibromobutyl)benzene
(IIIc) were obtained from 16.6 g (0.1 mol) of isomer
mixture Ic. Yield 25.7 g (64%), mp 82–83°C (from
hexane). IR spectrum, ν, cm–1: 1065 (C–Cl), 674
(C–Br). Found, %: Br+Cl 67.68. M 403.8. C10H10Br3Cl.
Calculated, %: Br+Cl 67.94. M 405.5.
2-Benzyl-3-methyloxirane (IVa). A mixture of
12 g (0.2 mol) of acetic acid or 14.8 g (0.2 mol) of
propionic acid, 17 g (0.15 mol) of 30% hydrogen
peroxide (in water or dioxane), and 3.5 g of chlori-
nated KU-2×8n cation exchanger (9.5% of chlorine)
was heated to 50°C and stirred for 2 h at that tem-
perature, and a solution of 13.2 g (0.1 mol) of com-
pound Ia in 40 ml of toluene was added dropwise over
a period of 20 min. After consumption of the required
amount of H2O2, the mixture was filtered through
a Schott filter, the organic phase was separated and
washed with an aqueous solution of sodium carbonate
until neutral reaction, the aqueous phase was extracted
with toluene, the extract was combined with the
organic phase and dried over sodium sulfate, the
solvent was distilled off, and the residue was distilled
under reduced pressure. Yield 12.9 g (82%), bp 72–
73°C (2 mm), d420 = 0.9925, nD20 = 1.5113; MRD =
44.59, calcd. 44.5; epoxide number 10.2. IR spectrum,
ν, cm–1: 695 (C6H5); 1260, 1250 (C–O). Found, %:
C 81.04; H 8.28. C10H12O. Calculated, %: C 81.06;
H 8.16.
1-Bromo-2-(2,3-dibromobutyl)-3-methoxyben-
zene and 2-bromo-4-(2,3-dibromobutyl)-1-methoxy-
benzene (IIId) were obtained from 16.1 g (0.1 mol) of
isomer mixture Id. Yield 29.1 g (77%), mp 61–62°C
(from hexane). IR spectrum: ν 678 cm–1 (C–Br).
1H NMR spectrum, δ, ppm: 6.95–7.12 m (3H, C6H3),
2.86–3.112 d (2H, CH2), 4.0–4.21 s (2H, CH), 1.78 s
(3H, CH3). Found, %: Br 59.53. M 401.35. C11H13Br3O.
Calculated, %: Br 59.7. M 402.
1-Bromo-2-(2,3-dibromobutyl)-3-ethoxybenzene
and 2-bromo-4-(2,3-dibromobutyl)-1-ethoxyben-
zene (IIIe) were obtained from 17.5 g (0.1 mol)
of isomer mixture Ie. Yield 28.5 g (69%), mp 63–64°C
(from hexane). IR spectrum: ν 676 cm–1 (C–Br).
Found, %: Br 57.15. M 414.4. C12H15Br3O. Calculated,
%: Br 57.83. M 415.
Compounds IVb–IVh were synthesized in a similar
way.
1-Bromo-2-(2,3-dibromobutyl)-3,4-dimethylben-
zene and 1-bromo-2-(2,3-dibromobutyl)-4,5-di-
methylbenzene (IIIf) were obtained from 15.8 g
(0.1 mol) of isomer mixture If. Yield 34.1 g (86%),
mp 71–72°C (from benzene). IR spectrum: ν 678 cm–1
2-Methyl-3-(2-methylbenzyl)oxirane and
2-methyl-3-(4-methylbenzyl)oxirane (IVb) were ob-
tained from 14.6 g (0.1 mol) of isomer mixture Ib.
Yield 13.9 g (86%), bp 71–75°C (1 mm), d420 = 0.9856,
nD20 = 1.5136; MRD = 49.45, calcd. 49.15. Epoxide
number 9.4. IR spectrum, ν, cm–1: 746, 828 (δC6H4);
1260, 1250 (C–O). Found, %: C 81.39; H 9.05.
C11H14O. Calculated, %: C 81.43; H 8.7. According
to the GLC data, the product contained 62% of
1,2-isomer and 33% of 1,4-isomer.
1
(C–Br). H NMR spectrum, δ, ppm: 6.67–7.1 d (2H,
C6H2), 2.33 s (6H, CH3), 3.1–2.86 d (2H, CH2), 3.97–
4.2 m (2H, CHBr), 1.78 s (3H, CH3). Found, %:
Br 59.82. M 398.3. C12H15Br3. Calculated, %: Br 60.15.
M 399.
1-Bromo-3-(2,3-dibromobutyl)-2,3-dimethylben-
zene and 2-bromo-4-(2,3-dibromobutyl)-1,3-di-
methylbenzene (IIIg) were obtained from 15.8 g
(0.1 mol) of isomer mixture Ig. Yield 31.2 g (78%),
mp 68–69°C (from benzene). IR spectrum: ν 676 cm–1
2-(2-Chlorobenzyl)-3-methyloxirane and
2-(4-chlorobenzyl)-3-methyloxirane (IVc) were ob-
tained from 16.7 g (0.1 mol) of isomer mixture Ic.
Yield 16.4 g (90%), bp 81–83°C (15 mm), d420 = 1.131,
nD20 = 1.5284; MRD = 49.75, calcd. 50.92. Epoxide
number 8.5. IR spectrum, ν, cm–1: 752–826 (C–Cl);
748, 805, 810 (δC6H4); 1260, 1250 (C–O). Found, %:
C 64.56; H 6.01; Cl 18.58. C10H11OCl. Calculated, %:
C 65.75; H 6.03; Cl 19.45.
1
(C–Br). H NMR spectrum, δ, ppm: 6.70–6.80 d (2H,
C6H2), 2.34 s (6H, CH3), 3.11–2.87 d (2H, CH2), 3.99–
4.19 m (2H, CHBr), 1.78 s (3H, CH3). Found, %:
Br 59.75. M 398.1. C12H15Br3. Calculated, %: Br 60.15.
M 399.
1-Bromo-4-(2,3-dibromobutyl)-2,5-dimethylben-
zene (IIIh) was synthesized from 15.8 g (0.1 mol) of
compound Ih. Yield 32.1 g (71%), mp 70–71°C (from
2-(2-Methoxybenzyl)-3-methyloxirane and
2-(4-methoxybenzyl)-3-methyloxirane (IVd) were
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HYDROGEN PEROXIDE- OR SODIUM HYPOCHLORITE-INDUCED BROMINATION
1667
obtained from 16.1 g (0.1 mol) of isomer mixture Id.
C 81.53; H 9.27. C12H15O2. Calculated, %: C 81.89;
H 9.16.
Yield 17.2 g (90%), bp 94–96°C (15 mm), d420
=
1.0690, nD20 = 1.5264; MRD = 51.19, calcd. 50.92.
Epoxide number 8.5. IR spectrum, ν, cm–1: 1260, 1250
3-Bromo-1-(2-methylphenyl)butan-2-ol and
3-bromo-1-(4-methylphenyl)butan-2-ol (Vb). A 30%
solution of hydrogen peroxide, 11.3 g (0.1 mol), was
added at 20°C to 16.2 g (0.1 mol) of isomer mixture
IVb, 41 g of 20% hydrobromic acid was then added
over a period of 30 min, and the mixture was stirred
for 3 h. The organic phase was separated, washed with
water and 3% aqueous sodium hydrogen carbonate,
and dried over Na2SO4, the solvent was removed, and
the residue was distilled under reduced pressure. Yield
22.4 g (91%), bp 109–111°C (0.5 mm), d420 = 1.4162;
nD20 = 1.5972; MRD = 58.48, calcd. 58.63. IR spectrum,
ν, cm–1: 1100, 1755, 3625 (OH); 625, 640 (C–Br); 918,
974 (cis and trans); 770, 780, 840, 810 (δ C6H4).
1H NMR spectrum, δ, ppm: 6.98–7.2 m (4H, C6H4),
2.34 s (3H, CH3), 2.58–2.83 d (2H, CH2), 4.0 s (1H,
CHOH), 4.8 br.s (1H, OH), 3.67 m (1H, CHBr), 1.78 s
(3H, CH3). Found, %: C 54.10; H 5.98; Br 32.64.
C11H15BrO. Calculated, %: C 54.32; H 6.17; Br 32.82.
1
(C–O). H NMR spectrum, δ, ppm: 7.0–7.19 m (4H,
o-C6H4), 7.0 s (4H, p-C6H4), 2.34 s (3H, CH3), 2.34–
2.79 d (2H, CH2), 2.71–2.92 s (2H, CHO), 1.20 s (3H,
CH3). Found, %: C 73.89; H 7.95. C11H14O2. Calculat-
ed, %: C 74.15; H 7.85.
2-(2-Ethoxybenzyl)-3-methyloxirane and
2-(4-ethoxybenzyl)-3-methyloxirane (IVe) were ob-
tained from 17.5 g (0.1 mol) of isomer mixture Ie.
Yield 15.9 g (83%), bp 98–103°C (15 mm), d420
=
1.0568, nD20 = 1.5223. Epoxide number 8.3. IR spec-
1
trum, ν, cm–1: 1260, 1250 (C–O). H NMR spectrum,
δ, ppm: 6.72–7.02 m (4H, C6H4), 3.96 m (2H, CH2O),
1.31–1.33 s (3H, CH3), 2.70–2.90 s (2H, CHO), 1.20 s
(3H, CH3). Found, %: C 75.39; H 7.82. C12H15O2. Cal-
culated, %: C 75.69; H 7.85.
3-(2,3-Dimethylbenzyl)-3-methyloxirane and
2-(3,4-dimethylbenzyl)-3-methyloxirane (IVf) were
obtained from 16 g (0.1 mol) of isomer mixture If.
Yield 18.1 g (89%), bp 79–81°C (1 mm), d420 = 0.9778,
nD20 = 1.5178; MRD = 54.14, calcd. 53.8. Epoxide num-
ber 8.6. IR spectrum, ν, cm–1: 742, 772, 810, 883
3-Bromo-1-phenylbutan-2-ol (Va) was obtained
from 14.8 g (0.1 mol) of compound IVa. Yield 17.6 g
(77%), bp 105–106°C (0.5 mm), d420 = 1.4201, nD20
=
1.5856; MRD = 54.09, calcd. 54.04. IR spectrum, ν,
cm–1: 676 (C–Br); 1100, 3550 (CHOH). 1H NMR spec-
trum, δ, ppm: 7.11–7.26 m (5H, C6H5), 2.58–2.85 d
(2H, CH2), 4.0 m (1H, CHOH), 4.8 br.s (1H, OH),
3.68 m (1H, CHBr), 1.78 s (3H, CH3). Found, %:
C 52.34; H 6.98; Br 34.93. C10H13BrO. Calculated, %:
C 52.4; H 5.68; Br 34.93.
1
(δC6H3); 1260, 1250 (C–O). H NMR spectrum, δ,
ppm: 6.78–6.91 m (3H, C6H3), 2.35 s (3H, CH3), 2.56–
2.80 d (2H, CH2), 2.70–2.92 s (2H, CHO), 1.23 s (3H,
CH3). Found, %: C 82.74; H 9.04. C12H15O2. Calculat-
ed, %: C 81.89; H 9.16.
2-(2,4-Dimethylbenzyl)-3-methyloxirane and
2-(2,6-dimethylbenzyl)-3-methyloxirane (IVg) were
obtained from 16 g (0.1 mol) of isomer mixture Ig.
Yield 15.3 g (87%), bp 91–95°C (2 mm), d420 = 0.9754,
nD20 = 1.5168; MRD = 54.55, calcd. 53.8. Epoxide
number 8.8. IR spectrum, ν, cm–1: 1260, 1250 (C–O).
1H NMR spectrum, δ, ppm: 6.76–7.0 m (3H, C6H3),
2.35 s (3H, CH3), 2.87–3.12 d (2H, CH2), 3.62 m (1H,
CHOH), 4.80 m (1H, OH), 3.88 m (1H, CHBr), 2.70–
2.92 s (2H, CHO), 1.58 s (3H, CH3). Found, %:
C 82.62; H 9.6. C12H15O. Calculated, %: C 81.89;
H 9.16.
3-Bromo-1-(2-methoxyphenyl)butan-2-ol and
3-bromo-1-(4-methoxyphenyl)butan-2-ol (Vd) were
obtained from 17.8 g (0.1 mol) of isomer mixture IVd.
Yield 19.5 g (75%), bp 113–115°C (0.5 mm), d420
=
1.4287, nD20 = 1.5865; MRD = 60.87, calcd. 60.33. IR
spectrum, ν, cm–1: 678 (C–Br); 1100, 3580 (CHOH).
1H NMR spectrum, δ, ppm: 6.71–7.02 m (4H, C6H4),
3.72 s (3H, CH3O), 2.56–3.11 d (2H, CH2), 4.0 m
(1H, CHOH), 3.67 m (1H, CHBr), 4.81 br.s (1H, OH),
1.22 s (3H, CH3). Found, %: C 50.73; H 5.81; Br 30.25.
C11H15BrO2. Calculated, %: C 50.96; H 5.79; Br 30.89.
2-(2,5-Dimethylbenzyl)-3-methyloxirane (IVh)
was obtained from 16 g (0.1 mol) of compound Ih.
Yield 15.4 g (88%), bp 79–80°C (1 mm), d420 = 0.9727,
nD20 = 1.5160; MRD = 54.61, calcd. 53.8. Epoxide num-
ber 8.1. IR spectrum, ν, cm–1: 810, 883 (δC6H3); 1260,
3-Bromo-1-(2-bromo-6-ethoxyphenyl)butan-2-ol
and 3-bromo-1-(3-bromo-4-ethoxyphenyl)butan-2-
ol (Ve) were obtained from 19.2 g (0.1 mol) of isomer
mixture IVe. Yield 19.8 g (73%), bp 119–120°C
(0.5 mm), d420 = 1.4386, nD20 = 1.5736; MRD = 62.58,
1
1
1250 (C–O). H NMR spectrum, δ, ppm: 6.75–6.89 m
calcd. 62.1. H NMR spectrum, δ, ppm: 7.0–7.02 m
(3H, C6H3), 2.34 s (3H, CH3), 2.54–2.78 d (2H, CH2),
2.70–2.92 s (2H, CHO), 1.22 s (3H, CH3). Found, %:
(4H, C6H4), 3.98–4.01 d (2H, CH2O), 1.31 s (3H,
CH3), 2.58–2.83 d (2H, CH2), 4.01 m (1H, CHOH),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007

SADYGOV, ALIMARDANOV
1668
4.80 br.s (1H, OH), 3.68 m (1H, CHBr), 1.79 s (3H,
CH3). Found, %: C 53.0; H 6.10; Br 29.3. C12H18O2Br.
Calculated, %: C 52.75; H 6.23; Br 29.3.
Br 52.08. M 307.4. C10H12Br2O. Calculated, %:
C 38.96; H 3.89; Br 51.95. M 308.
Compounds VIb and VId–VIh were synthesized in
3-Bromo-1-(2,3-dimethylphenyl)butan-2-ol
and 3-bromo-1-(3,4-dimethylphenyl)butan-2-ol (Vf)
were obtained from 17.6 g (0.1 mol) of isomer mixture
IVf. Yield 21.9 g (85%), bp 114–115°C (0.5 mm),
d420 = 1.4686, nD20 = 1.5883; MRD = 58.92, calcd. 58.68.
IR spectrum, ν, cm–1: 655, 680 (C–Br); 1100, 3615
(CHOH); 918, 974 (cis and trans); 775, 810, 865
a similar way.
3-Bromo-1-(2-bromo-4-methylphenyl)butan-2-ol
and 3-bromo-1-(3-bromo-4-methylphenyl)butan-2-
ol (VIb) were obtained from 16.2 g (0.1 mol) of
isomer mixture IVb. Yield 27.1 g (84%), mp 58–59°C.
IR spectrum, ν, cm–1: 776, 810, 864 (δC6H3); 1100,
3625 (OH); 625, 655, 680 (C–Br); 918, 974 (cis and
1
(δC6H3). H NMR spectrum, δ, ppm: 6.80–6.90 m (3H,
1
trans). H NMR spectrum, δ, ppm: 6.87–7.23 m (3H,
C6H3), 2.35 s (6H, CH3), 2.58–2.83 d (2H, CH2),
3.62 m (1H, CHOH), 4.81 br.s (1H, OH), 3.67 m (1H,
CHBr), 1.58 s (3H, CH3). Found, %: C 56.14; H 6.48;
Br 31.23. C12H17BrO. Calculated, %: C 56.03; H 6.61;
Br 31.19.
C6H3), 2.34 s (3H, CH3), 2.57–2.82 d (2H, CH2), 3.89–
4.0 m (1H, CHOH), 4.81 br.s (1H, OH), 3.68 m (1H,
CHBr), 1.78 s (3H, CH3). Found, %: C 41.06; H 4.38;
Br 49.86. M 321.4. C11H14Br2O. Calculated, %: C 41.0;
H 4.35; Br 51.95. M 322.
3-Bromo-1-(2,4-dimethylphenyl)butan-2-ol and
3-bromo-1-(2,6-dimethylphenyl)butan-2-ol (Vg)
were obtained from 17.5 g (0.1 mol) of isomer mixture
IVg. Yield 21.5 g (84%), bp 111–113°C (0.5 mm),
d420 = 1.4628, nD20 = 1.5836; MRD = 58.71, calcd. 58.68.
IR spectrum, ν, cm–1: 655, 680 (C–Br); 1100, 3620
(CHOH). 1H NMR spectrum, δ, ppm: 6.76–7.0 m (3H,
C6H3), 2.34 s (6H, CH3), 2.86–3.10 d (2H, CH2),
4.01 m (1H, CHOH), 4.81 br.s (1H, OH), 3.68 m (1H,
CHBr), 1.59 s (3H, CH3). Found, %: C 56.0; H 6.58;
Br 31.2. C12H17BrO. Calculated, %: C 56.03; H 6.61;
Br 31.16.
3-Bromo-1-(2-bromo-6-methoxyphenyl)butan-2-
ol and 4-bromo-1-(3-bromo-4-methoxyphenyl)-
butan-2-ol (VId) were obtained from 17.8 g (0.1 mol)
of isomer mixture IVd. Yield 26.6 g (79%), mp 60–
61°C (from hexane). IR spectrum, ν, cm–1: 625, 655,
680 (C–Br); 776, 810, 840 (δC6H3); 1100, 3610 (OH);
1
918, 974 (cis and trans). H NMR spectrum, δ, ppm:
6.66–7.20 m (3H, C6H3), 2.73 s (1H, CH3O), 2.58–
2.83 d (2H, CH2), 3.80–3.83 m (1H, CHOH), 3.67 m
(1H, CHBr), 4.8 br.s (1H, OH), 1.78 s (3H, CH3).
Found, %: C 40.91; H 4.54; Br 45.45. M 336.2.
C11H14Br2O2. Calculated, %: C 40.93; H 4.58; Br 45.62.
M 338.
3-Bromo-1-(2,5-dimethylphenyl)butan-2-ol (Vh)
was obtained from 17.5 g (0.1 mol) of compound IVh.
Yield 22.2 g (86%), bp 113–116°C (0.5 mm), d420
=
3-Bromo-1-(2-bromo-6-ethoxyphenyl)butan-2-ol
and 3-bromo-1-(3-bromo-4-ethoxyphenyl)butan-2-
ol (VIe) were obtained from 19.2 g (0.1 mol) of isomer
mixture IVe. Yield 28.6 g (81%), mp 61–63°C (from
hexane). IR spectrum, ν, cm–1: 625, 655, 680 (C–Br);
1100, 3610 (OH); 730, 770, 810, 840 (δC6H3). 1H NMR
spectrum, δ, ppm: 6.70–7.10 m (3H, C6H3), 3.97 d
(2H, CH2O), 1.33 s (3H, CH3CH2O), 3.80 m (1H,
CHOH), 3.88 m (1H, CHBr), 4.8 m (1H, OH), 1.78 s
(3H, CH3). Found, %: C 40.98; H 4.58; Br 45.68.
M 351.2. C12H16Br2O2. Calculated, %: C 40.91; H 4.54;
Br 45.45. M 352.
1.4564, nD20 = 1.5778; MRD = 58.44, calcd. 58.67. IR
spectrum, ν, cm–1: 656, 680 (C–Br); 1100, 3618
1
(CHOH). H NMR spectrum, δ, ppm: 6.75–6.89 m
(3H, C6H3), 2.35 s (6H, CH3), 2.87–3.12 d (2H, CH2),
4.0 m (1H, CHOH), 4.81 br.s (1H, OH), 3.67 m (1H,
CHBr), 1.57 s (3H, CH3). Found, %: C 56.0; H 6.58;
Br 31.2. C12H17BrO. Calculated, %: C 56.03; H 6.61;
Br 31.19.
3-Bromo-1-(2-bromophenyl)butan-2-ol and
3-bromo-1-(4-bromophenyl)butan-2-ol (VIa) were
obtained from 14.8 g (0.1 mol) of compound IVa,
22.6 g (0.2 mol) of 30% hydrogen peroxide, and 40 g
of 46% hydrobromic acid. Yield 26.7 g (87%), mp 62–
64°C (from hexane). IR spectrum, ν, cm–1: 655, 680
(C–Br); 1100, 3625 (OH); 776, 810, 864 (δC6H3); 918,
3-Bromo-1-(4-bromo-2,3-dimethylphenyl)butan-
2-ol and 3-bromo-1-(3-bromo-4,5-dimethylphenyl)-
butan-2-ol (VIf) were obtained from 17.6 g (0.1 mol)
of isomer mixture IVf. Yield 30.7 g (92%), mp 68–
69°C (from hexane). IR spectrum, ν, cm–1: 650, 685
(C–Br); 1100, 3615 (OH); 918, 974 (cis and trans).
1H NMR spectrum, δ, ppm: 6.70–7.07 m (2H, C6H2),
2.35 s (6H, CH3), 2.88–3.12 d (2H, CH2), 3.80 m (1H,
1
974 (cis and trans). H NMR spectrum, δ, ppm: 6.69–
7.38 m (4H, C6H4), 2.59–2.84 d (2H, CH2), 3.89–
4.01 m (1H, CHOH), 4.8 br.s (1H, OH), 3.68 m (1H,
CHBr), 1.78 s (3H, CH3). Found, %: C 38.73; H 3.84;
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2 g of KU-2×8 cation exchanger (H form) in 25 g of
benzene was cooled to 10°C, and 4.5 g (0.056 mol) of
acetic anhydride was slowly added under stirring. The
reaction was accompanied by slight evolution of heat.
The mixture was stirred for 3 h and filtered through
a Schott filter, the solvent was distilled off from the
filtrate, and the residue was distilled under reduced
pressure. Yield 11.9 g (94%), bp 125–128°C (3 mm),
d420 = 1.083, nD20 = 1.4918; MRD = 67.01, calcd. 66.87.
1H NMR spectrum, δ, ppm: 7.1–7.24 m (5H, C6H5),
2.64–2.90 d (2H, CH2), 4.71–4.92 m (2H, CH), 1.38 s
(3H, CH3), 2.0 s (6H, CH3CO). Found, %: C 67.45;
H 7.38. C14H18O4. Calculated, %: C 67.2; H 7.2.
CHOH), 4.8 br.s (1H, OH), 3.89 m (1H, CHBr), 1.78 s
(3H, CH3). Found, %: C 42.86; H 4.76; Br 47.62.
M 335.4. C12H16Br2O. Calculated, %: C 42.82; H 4.74;
Br 47.86. M 336.
3-Bromo-1-(3-bromo-2,6-dimethylphenyl)butan-
2-ol and 3-bromo-1-(2-bromo-4,6-dimethylphenyl)-
butan-2-ol (VIg) were obtained from 17.6 g (0.1 mol)
of isomer mixture IVg. Yield 29.6 g (88%), mp 66–
67°C (from hexane). IR spectrum, ν, cm–1: 625, 655,
1
680 (C–Br); 1100, 3620 (OH). H NMR spectrum, δ,
ppm: 6.71–7.01 m (2H, C6H2), 2.35 s (6H, CH3), 2.57–
2.83 d (2H, CH2), 4.08 m (1H, CHOH), 4.81 br.s (1H,
OH), 3.67 m (1H, CHBr), 1.78 s (3H, CH3). Found, %:
C 42.83; H 4.73; Br 47.72. M 335. C12H12Br2O. Cal-
culated, %: C 42.86; H 4.76; Br 47.62. M 336.
1-(2-Methylphenyl)butane-2,3-diyl diacetate and
1-(3-methylphenyl)butane-2,3-diyl diacetate (VIIIb)
were obtained in a similar way from 8.0 g (0.05 mol)
of isomer mixture IVb and 4.5 g (0.056 mol) of acetic
anhydride. Yield 12.5 g (95%), bp 128–129°C
(1.5 mm), d4201 = 1.0701, nD20 = 1.4931; MRD = 71.57,
calcd. 71.52. H NMR spectrum, δ, ppm: 6.86–7.17 m
(4H, C6H4), 2.34 s (3H, CH3), 2.65–2.90 d (2H, CH2),
4.71–4.90 m (2H, CH), 1.39 s (3H, CH3), 2.0 s (6H,
CH3CO). Found, %: C 68.23; H 7.46. C15H20O4. Cal-
culated, %: C 68.18; H 7.58.
3-Bromo-1-(3-bromo-2,5-dimethylphenyl)butan-
2-ol (VIh) was obtained from 17.6 g (0.1 mol) of com-
pound IVh. Yield 31.1 g (93%), mp 69–70°C (from
hexane). IR spectrum, ν, cm–1: 625, 655, 680 (C–Br);
1
1100, 3620 (OH). H NMR spectrum, δ, ppm: 6.68–
7.06 m (2H, C6H2), 2.35 s (6H, CH3), 2.57–2.83 d (2H,
CH2), 4.0 m (1H, CHOH), 4.81 br.s (1H, OH), 3.67 m
(1H, CHBr), 1.76 s (3H, CH3). Found, %: C 42.8;
H 4.72; Br 48.06. M 335.2. C12H16Br2O. Calculated,
%: C 42.86; H 4.76; Br 47.62. M 336.
REFERENCES
1-Phenylbutane-2,3-diol (VIIa). A mixture of
14.8 g (0.1 mol) of compound IVa, 18 g (0.1 mol) of
water, and 3.5 g of KU-2×8 cation exchanger was
stirred for 4 h at 50–60°C. The product was recrystal-
lized according to the procedure described in [16].
Yield 15.4 g (93%), mp 54–55°C. IR spectrum, ν,
cm–1: 1100, 3625 (OH); 918, 974 (cis and trans).
1H NMR spectrum, δ, ppm: 7.12–7.26 m (5H, C6H5),
2.57–2.82 d (2H, CH2), 3.67–3.46 s (2H, CHOH),
4.81 br.s (1H, OH), 1.21 s (2H, CH3). Found, %:
C 72.18; H 8.26. C10H14O2. Calculated, %: C 72.29;
H 8.43.
1. Soldatenko, L.T., Kolyadina, I.M., and Shendrik, I.V.,
Osnovy organicheskoi khimii lekarstvennykh veshchestv
(Foundations of Organic Chemistry of Drugs), Moscow:
Mir, 2003.
2. Kheifits, L.A. and Dashunin, V.M., Dushistye veshche-
stva i drugie produkty dlya parfyumerii (Fragrant
Substances and Other Materials for Perfumery), Moscow:
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3. Shulov, L.M. and Kheifits, L.A., Dushistye veshchestva i
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1-(2-Methylphenyl)butane-2,3-diol and
1-(4-methylphenyl)butane-2,3-diol (VIIb) were ob-
tained in a similar way from 16 g (0.1 mol) of isomer
mixture IVb. Yield 16.8 g, mp 65–68°C. IR spectrum,
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1
ν, cm–1: 1100, 3625 (CHOH). H NMR spectrum, δ,
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ppm: 7.0–7.2 m (4H, o-C6H4), 7.0 s (4H, p-C6H4),
2.57–2.83 d (2H, CH2), 3.67–3.46 s (2H, CHOH),
4.81 br.s (2H, OH), 1.21 s (3H, CH3). Found, %:
C 73.02; H 8.68. C11H16O2. Calculated, %: C 73.33;
H 8.89.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 11 2007