One-pot synthesis of borolanes by reaction of aluminacyclopentanes with BF3· Et2O

Article abstract of DOI:10.1134/S1070428012060012

A selective procedure was developed for the synthesis of substituted borolanes via transmetalation with BF₃ · Et₂O of 3-alkyl-1-ethylaluminacyclopentanes obtained from the corresponding terminal olefins and AlEt₃ in the presence of Cp₂ZrCl₂ as a catalyst. 3-Substituted 1-fluoroborolanes were isolated and identified as 1 : 1 complexes with EtBF₂.

Full text of DOI:10.1134/S1070428012060012

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 6, pp. 755–760. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © L.O. Khafizova, L.I. Khusainova, T.V. Tyumkina, U.M. Dzhemilev, 2012, published in Zhurnal Organicheskoi Khimii, 2012,
Vol. 48, No. 6, pp. 759–764.
One-Pot Synthesis of Borolanes by Reaction
of Aluminacyclopentanes with BF3·Et2O
L. O. Khafizova, L. I. Khusainova, T. V. Tyumkina, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received October 26, 2011
Abstract—A selective procedure was developed for the synthesis of substituted borolanes via transmetalation
with BF3·Et2O of 3-alkyl-1-ethylaluminacyclopentanes obtained from the corresponding terminal olefins and
AlEt3 in the presence of Cp2ZrCl2 as a catalyst. 3-Substituted 1-fluoroborolanes were isolated and identified as
1:1 complexes with EtBF2.
DOI: 10.1134/S1070428012060012
An efficient procedure for the synthesis of cyclic
organoboron compounds is based on the reaction of
cyclic or α,ω-bis-metalated organometallic compounds
containing both transition and non-transition metals
(Li, Mg, Sn, Hg, Zr, Ti) with an equimolar amount of
boron halide [1–11]. Prior to our studies we have
found no published data on the synthesis of boracyclo-
alkanes with the use of organoaluminum compounds.
On the other hand, successful exchange reactions
between trialkylalanes [AlEt3, Al(i-Bu)3] or alkylhalo-
alanes (AlEt2Cl, AlEtCl2) and BF3·Et2O or BCl3 were
reported [12, 13].
produce the corresponding 3-alkyl-1-fluoroborolanes
II (Scheme 1). As model reaction we selected the
reaction of 1-ethyl-3-hexylaluminacyclopentane (Ib)
generated in situ from oct-1-ene and AlEt3 in hexane
in the presence of 5 mol % of Cp2ZrCl2 [14] with
an equimolar amount (with respect to AlEt3) of BF3·
Et2O. After removal of the solvent from the reaction
mixture in a stream of argon, the residue was distilled
under reduced pressure to isolate a colorless liquid
fuming on exposure to air but stable in an inert atmos-
phere, bp 98°C (16 mm). The product was identified
1
by NMR spectroscopy. Comparison of the H and
13C NMR spectra of initial aluminacyclopentane Ib
[16] and compound IIb revealed considerable differ-
ences only in the chemical shifts of CH2 groups
directly linked to Al or B.
With a view to develop an efficient procedure for
the synthesis of borolanes (boracyclopentanes) and
elucidate the possibility for transmetalation of five-
membered cyclic organoaluminum compounds with
boron halides we examined reactions of 1,3-substituted
aluminacyclopentanes with BF3·Et2O as transmetalat-
ing agent [12]. We presumed that 3-substituted 1-ethyl-
aluminacyclopentanes I obtained by catalytic cyclo-
alumination of olefins with AlEt3 in the presence of
Cp2ZrCl2 [14, 15] could react in situ with BF3·Et2O to
Compound Ib characteristically showed in the
1H and 13C NMR spectra upfield signals from protons
and carbon atoms directly attached to Al: δC2 13.6 ppm,
δ(2-H) –0.98, 0.00 ppm; δC5 5.7 ppm, δ(5-H) –0.49,
0.20 ppm [4]. In the HSQC NMR spectrum of IIb
(Fig. 1) we observed signals from three couples of dia-
Scheme 1.
R
R
R
R
[Zr]
BF3·Et2O, THF
H2O2, OH–
+
AlEt3
+
R
OH
CH2
Al
Et
B
F
HO
Me
HO
Ia–Ic
IIa–IIc
IIIa–IIIc
IVa–IVc
R = Bu (a), C6H13 (b), C8H17 (c).
755

KHAFIZOVA et al.
756
δC, ppm
CH3CH2BF2
10
10
11
Me
8
9
6
C11
15
20
25
30
35
40
7
4
3
CH3CH2BF2
2
5
B
F
F
B
F
C10
Et
C5
C5
C7
C8
C9
C4
C4
C2
C6
C2
1.0
Fig. 1. HSQC spectrum of 1-ethyl-3-hexylborolane (IIb) in CDCl3.
C3
2.0
1.8
1.6
1.4
1.2
0.8
0.6 δ, ppm
stereotopic protons on C2, C4, and C5 in the boracyclo-
pentane ring: δC2 35.59 ppm, δ(2-H) 0.49, 1.63 ppm;
δC5 27.33 ppm, δ(5-H) 0.83, 1.49 ppm. In addition, we
observed signals at δC 9.48 and 17.83 ppm (the latter
was broadened) which displayed couplings with pro-
tons resonating at δ 1.05 and 1.30 ppm, respectively.
Signals in the 13C NMR spectrum of IIb were
broadened due to coupling with boron. The position of
the C3 signal (δC 43.10 ppm) was almost the same as in
the spectrum of Ib. Thus compound IIb was identified
as 1-fluoro-3-hexylborolane. The 11B NMR spectrum
of the isolated compound contained two signals, one of
which (δB 93.2 ppm) was assigned to the endocyclic
boron atom, while the second (δB 34.6 ppm) was
typical of EtBF2 [17]. Therefore, we presumed that the
product is a molecular complex of 1-fluoro-3-hexyl-
borolane (IIb) with EtBF2.
Presumably, EtBF2 is formed as a result of reaction
of EtAlF2 with BF3·Et2O, whereas EtAlF2 is the trans-
metalation product of aluminacyclopentane with BF3·
Et2O. Thus transmetalation of 1-ethyl-3-hexylalumina-
cyclopentane (IIb) to 1-fluoro-3-hexylboracyclo-
pentane by the action of BF3·Et2O is accompanied by
formation of an equimolar amount of EtBF2. Obvious-
ly, the above noted additional NMR signals at δ 1.05,
1.30 ppm, δC 9.48, 17.83 ppm, and δB 34.60 ppm
should be assigned to ethyldifluoroborane. The molec-
ular weight of the product, determined by cryoscopy,
was 259 (calcd. 248) which corresponds to IIb·BEtF2.
1
Thus the data of H, 13C, and 11B NMR spectroscopy,
including two-dimensional COSY, HMBC, and HSQC
experiments, as well as molecular weight determina-
tion, allowed us to conclude that the reaction of
1-ethyl-3-hexylaluminacyclopentane (Ib) with BF3·
Et2O yields a stable molecular complex of 1-fluoro-3-
hexylborolane (IIb) with EtBF2 (Scheme 2).
Quantum-chemical simulation (PBE/3z, PRIRODA
6.0 program [18]) of the potential energy surface for
complex IIb·BEtF2 revealed two energy minima. The
corresponding optimized structures are shown in
Fig. 2. The calculated distances between the boron and
fluorine atoms in complex A are about 3.0 Å, whereas
the bridging B···F bond length in structure B is almost
equal to covalent B–F bond length (1.6 Å), so that the
configuration of bonds at the boron atom approaches
tetrahedral. As a result, the energy of complex B is
higher by 20.6 kcal/mol than that of A. The energy
minima are related to each other through transition
state TS (Fig. 3), the energy barrier being 20.8 kcal/mol,
and the imaginary frequency 179i corresponds to
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

ONE-POT SYNTHESIS OF BOROLANES
757
Scheme 2.
C6H13
C6H13
BF3·Et2O, hexane
–10°C
AlEt3, Cp2ZrCl2, 0°C
–C2H6
+
EtAlF2
C6H13
CH2
Al
Et
B
F
Ib
IIb
C6H13
C6H13
BF3·Et2O
Distillation
+
EtBF2
B
F
B
F
F
B
F
Et
IIb·EtBF2
IIb
vibrations of just bridging B–F bonds. We believe that
the experimental NMR spectra of the complexes match
structure A as thermodynamically more favorable;
in addition, the chemical shifts of the boron atom
(δB ~93 ppm) imply trigonal bond configuration at the
boron atom [19]. On the other hand, the B···F distance
equal to ~3.0 Å and the calculated enthalpy of the re-
action IIb + EtBF2 → IIb·EBtF2 (ΔH = –1.65 kcal×
mol–1; ∆G298 = 5.3 kcal/mol) indicate that complex A
is fairly weak; therefore, it should be stable only in
nonpolar medium.
To conclude, we have found that substituted
aluminacyclopentanes undergo transmetalation by the
action of BF3·Et2O with formation of the correspond-
ing 1,3-substituted borolanes which are stabilized as
1:1 complexes with EtBF2. The proposed procedure
ensures a simple and efficient one-pot synthesis of
3.31
2.98
Analogous results were obtained by transmetalation
with BF3 ·Et2O of 3-butyl- and 3-octylaluminacyclo-
pentanes Ia and Ic which were prepared by cyclo-
alumination of hex-1-ene and dec-1-ene, respectively,
according to [14] (Scheme 1).
A
1.74
We made an attempt to extend the developed proce-
dure to other terminal olefins containing cyclic and
aromatic substituents. For this purpose, 1,3-substituted
aluminacyclopentanes prepared from 4-vinylcyclo-
hexene and allylbenzene were brought into reaction
with BF3·Et2O under analogous conditions. 3-(Cyclo-
hex-3-en-1-yl)-1-ethylaluminacyclopentane (V) and
3-benzyl-1-ethylaluminacyclopentane (IX) reacted
with BF3·Et2O to produce the corresponding borolanes
VI and X as 1:1 complexes with EtBF2 (Scheme 3).
1.71
TS
1.62
1.60
1.57
Oxidation of substituted borolanes IIa–IIc, VI, and
X with hydrogen peroxide in alkaline medium [12, 20,
21] gave mixtures of 1,4-diols IVa–IVc, VIII, and XII
and monools IIIa–IIIc, VII, and XI at a ratio of 3:1
(Schemes 1, 3). The formation of monools IIIa–IIIc,
VII, and XI may be rationalized in terms of specificity
of oxidation of fluorine-containing borolanes as com-
plexes with EtBF2. As might be expected, the 13C NMR
spectra of compounds VI−VIII having a cyclohexenyl
substituent displayed double sets of signals due to the
presence of a chiral center in the six-membered ring.
B
Fig. 2. Optimized structures A and B of complex IIb·EtBF2
at the energy minima and transition state TS according to
DFT–PBE/3z calculations (PRIRODA 06).*
* The geometric parameters of the 1:1 complex of 3-butyl-1-
fluoroborolane with ethyldifluoroborane, optimized at the DFT–
MP2 level of theory, were fairly similar.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

KHAFIZOVA et al.
758
Scheme 3.
B
AlEt3, [Zr]
BF3·Et2O
CH2
F
Al
F
–EtAlF2
Et
B
Et
F
V
VI
H2O2, OH–
*
*
+
OH
HO
Me
HO
VII
VIII
Ph
B
F
F
B
AlEt3, [Zr]
BF3·Et2O
–EtAlF2
Ph
Ph
Al
CH2
Et
Et
F
IX
X
Ph
Ph
H2O2, OH–
+
OH
HO
Me
HO
XI
XII
five-membered cyclic organoboron compounds start-
ing from olefins, AlEt3, and BF3·Et2O.
spectra were recorded on a Bruker Vertex 70 spectrom-
1
eter from liquid films. The H, 13C, and 11B NMR
spectra and two-dimensional homo- (COSY) and het-
eronuclear (HSQC, HMBC) correlation spectra were
recorded from solutions in CDCl3 on a Bruker Avance
400 spectrometer operating at 400.13 (1H), 100.62
(13C), or 128.33 MHz (11B). The chemical shifts were
determined relative to tetramethylsilane (1H, 13C;
internal reference) or BF3·Et2O (11B). The molecular
weights of organoboron compounds were determined
by cryoscopy in benzene under argon according to [22]
with the use of a three-necked glass cell equipped with
a Beckmann thermometer (accuracy ±0.005°C). The
elemental analyses were obtained using a Carlo Erba
1106 analyzer.
EXPERIMENTAL
All reactions with organometallic reagents were
carried out under argon. Commercially available 98%
AlEt3 and 48% BF3·Et2O were used without additional
purification. GC–MS analysis was performed on
a Shimadzu GCMS-QP2010 Plus instrument [SLB-
5ms glass capillary column, 60000 mm × 0.25 mm×
0.25 μm (Supelco, USA); carrier gas helium; oven
temperature programming from 40 to 280°C at a rate
of 5 deg/min; injector temperature 280°C; ion source
temperature 200°C; electron impact, 70 eV]. The IR
3-Substituted 1-fluoroborolanes IIa–IIc, VI,
and X (general procedure). A 50-ml glass reactor was
charged under dry argon at 0°C with 0.5 mmol of
Cp2ZrCl2; 10 mmol of the corresponding alkene and
12 mmol of AlEt3 were added in succession under stir-
ring, and the mixture was stirred for 8 h at 20–22°C.
Hexane, 10 ml, was then added, the mixture was
cooled to –10°C, 24 mmol of BF3 ·Et2O was added
dropwise, and the mixture was allowed to warm up to
room temperature and stirred for 0.5 h. The solvent
was evaporated, and the residue was distilled under
reduced pressure in a stream of argon.
TS
20.8 kcal/mol
20.6 kcal/mol
B
0.0 kcal/mol
A
Fig. 3. Calculated (DFT–PBE/3z; PRIRODA 06) relative
Gibbs energy diagram; TS is the transition state calculated
for model complex IIb·EtBF2 (gas phase).
3-Butyl-1-fluoroborolane–ethyldifluoroborane
(1/1) (IIa). Yield 1.01 g (46%), colorless liquid,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012

ONE-POT SYNTHESIS OF BOROLANES
759
bp 72°C (16 mm). IR spectrum, ν, cm−1: 2975, 2926,
2858, 1460, 1375, 1206, 1079, 774, 728. H NMR
3-(Cyclohex-3-en-1-yl)-1-fluoroborolane–ethyldi-
fluoroborane (1/1) (VI). Yield 1.12 g (46%), colorless
liquid, bp 99°C (16 mm). IR spectrum, ν, cm−1: 3022,
2921, 2661, 1653, 1619, 1457, 1372, 912, 773, 728,
1
spectrum, δ, ppm: 0.48 d.d (1H, 2-H, J = 17.6,
10.0 Hz), 0.82–0.98 m (4H, 5-H, CH3), 1.04 t (3H,
CH3CH2BF2, J = 7.6 Hz), 1.12 m (1H, 4-H), 1.22–
1.35 m (6H, CH2), 1.30** q (2H, CH3CH2BF2, J =
7.6 Hz), 1.47 br.d (1H, 5-H, J = 18.6 Hz), 1.61 br.d
(1H, 2-H, J = 18.0 Hz), 1.78 m (1H, 3-H), 1.94 m (1H,
4-H). 13C NMR spectrum, δC, ppm: 9.47 (CH3CH2-
BF2), 14.29, 17.39 (CH3CH2BF2), 23.17, 27.31 (C5),
31.04, 33.51 (C4), 35.52 (C2), 37.70, 41.58 (C3).
1
655. H NMR spectrum, δ, ppm: 0.47 m (1H, 2-H),
0.73–0.85 m (2H, 2-H, 5-H), 0.90–0.96 m (3H,
CH3CH2BF2), 1.20–1.40 m (2H, 5-H, 1′-H), 1.25 m
(2H, CH3CH2BF2), 1.50–1.78 m (5H, 2′-H, 4-H, 6′-H),
1.58 m (1H, 3-H), 2.00–2.18 m (3H, 4-H, 5′-H),
5.60 br.s (2H, 3′-H, 4′-H). 13C NMR spectrum, δC,
ppm: 8.00, 9.20 (CH3CH2BF2), 18.85, 19.50 (CH3CH2-
BF2), 25.68, 25.72, 26.75, 26.79 (C5′, C6′), 26.32, 26.40
(C5), 30.33, 30.44, 30.91, 30.98 (C4, C2′), 32.57, 33.10
(C2), 40.95, 41.09 (C1′), 47.25, 47.32 (C3), 127.07,
127.11 (C3′, C4′). 11B NMR spectrum, δB, ppm: 35.63
(EtBF2, W1/2 = 2.8 kHz), 87.10 (W1/2 = 1.8 kHz).
Found, %: C 58.90; H 8.55. M 258. C12H21B2F3. Cal-
culated, %: C 59.09; H 8.68. M 243.91.
11B NMR spectrum, δB, ppm: 34.6 (BEtF2, W1/2
=
1.6 kHz), 92.9 (W1/2 = 1.2 kHz). Found, %: C 54.39;
H 9.52. M 229. C10H21B2F3. Calculated, %: C 54.62;
H 9.63. M 219.89.
1-Fluoro-3-hexylborolane–ethyldifluoroborane
(1/1) (IIb). Yield 1.19 g (48%), colorless liquid,
bp 98°C (16 mm). IR spectrum, ν, cm−1: 2963, 2950,
2856, 1462, 1371, 1206, 1076, 769, 730. 1H NMR spec-
trum, δ, ppm: 0.49 d.d (1H, 2-H, J = 17.8, 10.4 Hz),
0.78–0.90 m (1H, 5-H), 0.92 t (3H, CH3, J = 7.2 Hz),
1.05 t (3H, CH3CH2BF2, J = 7.6 Hz), 1.11–1.18 m
(1H, 4-H), 1.27–1.40 m (10H, CH2), 1.30** q (2H,
CH3CH2BF2, J = 7.6 Hz), 1.49 d.d (1H, 5-H, J = 18.2,
6.8 Hz), 1.63 d.d (1H, 2-H, J = 18.0, 6.4 Hz), 1.79 m
(1H, 3-H), 1.95 m (1H, 4-H). 13C NMR spectrum, δC,
ppm: 9.48 (CH3CH2BF2), 14.25, 17.83 (CH3CH2BF2),
22.90, 27.33 (C5), 28.79, 29.81, 32.21, 33.54 (C4),
35.59 (C2), 38.07, 41.65 (C3). 11B NMR spectrum, δB,
3-Benzyl-1-fluoroborolane–ethyldifluoroborane
(1/1) (X). Yield 1.19 g (47%), colorless liquid,
bp 103°C (17 mm). IR spectrum, ν, cm−1: 3084, 3062,
3026, 2959, 2925, 2873, 1602, 1494, 1375, 1205,
1
1113, 742, 699. H NMR spectrum, δ, ppm: 0.73 d.d
(1H, 2-H, J = 17.7, 10.3 Hz), 0.99 m (1H, 5-H), 1.15 t
(3H, CH3CH2BF2, J = 7.5 Hz), 1.34 m (1H, 4-H),
1.40 q (2H, CH3CH2BF2, J = 7.6 Hz), 1.56–1.75 m
(2H, 5-H, 2-H), 2.02 m (1H, 4-H), 2.23 m (1H, 3-H),
2.77 d.d and 2.83 d.d (1H each, PhCH2, J = 12.8,
7.2 Hz), 7.10–7.50 m (5H, Harom). 13C NMR spectrum,
δC, ppm: 9.48 (CH3CH2BF2), 17.75 (CH3CH2BF2),
27.08 (C5), 33.71 (C4), 35.24 (C2), 43.41 (C3), 43.96
(C6), 125.58, 128.38, 129.06, 142.49. 11B NMR spec-
trum, δB, ppm: 36.06 (EtBF2, W1/2 = 2.4 kHz), 92.99
(W1/2 = 1.4 kHz). Found, %: C 61.28; H 7.42. M 252.
C13H19B2F3. Calculated, %: C 61.49; H 7.54. M 253.90.
ppm: 34.6 (EtBF2, W1/2 = 2.8 kHz), 93.2 (W1/2
=
1.6 kHz). Found, %: C 57.92; H 10.08. M 259.
C12H25B2F3. Calculated, %: C 58.13; H 10.16.
M 247.94.
1-Fluoro-3-octylborolane–ethyldifluoroborane
(1/1) (IIc). Yield 1.30 g (47%), colorless liquid,
bp 117°C (9 mm). IR spectrum, ν, cm−1: 2961, 2952,
2853, 1487, 1458, 1419, 1374, 1337, 1220, 1053, 765,
724. 1H NMR spectrum, δ, ppm: 0.49 d.d (1H, 2-H, J =
17.6, 10.4 Hz), 0.76 m (1H, 5-H), 0.89 t (3H, CH3, J =
7.2 Hz), 0.98 t (3H, CH3CH2BF2, J = 7.6 Hz), 1.10–
1.17 m (1H, 4-H), 1.18 q (2H, CH3CH2BF2, J =
7.6 Hz), 1.23–1.40 m (15H, 5-H, CH2), 1.48 d.d (1H,
2-H, J = 17.2, 6.0 Hz), 1.73 m (1H, 3-H), 1.89 m (1H,
4-H). 13C NMR spectrum, δC, ppm: 9.46 (CH3CH2-
BF2), 14.56, 17.80 (CH3CH2BF2), 23.61, 27.95 (C5),
29.73, 30.42, 30.77, 31.09, 32.98, 33.61 (C4), 35.48
(C2), 39.09, 41.70 (C3). 11B NMR spectrum, δB, ppm:
34.7 (EtBF2, W1/2 = 1.8 kHz), 93.1 (W1/2 = 1.6 kHz).
Found, %: C 60.69; H 10.47. M 267. C14H29B2F3.
Calculated, %: C 60.92; H 10.59. M 275.99.
Oxidation of borolanes IIa–IIc, VI, and X with
hydrogen peroxide in alkaline medium (general
procedure). A solution of 5 mmol of borolane IIa–IIc,
VI, or X in 10 ml of hexane was cooled to 0°C, 6 ml of
20% aqueous sodium hydroxide was added, and 2 ml
of 30% hydrogen peroxide was then slowly added
dropwise, and the mixture was stirred for 6 h. The
organic layer was separated, the aqueous layer was
extracted with diethyl ether (2×30 ml), the extracts
were combined with the organic phase, dried over
CaCl2, and concentrated under reduced pressure, and
the residue was separated by column chromatography
on silica gel (40–100 mesh, 30 cm× 12 mm; ethyl
acetate–hexane, 1:50). The spectral parameters and
physical constants of compounds IIIa, IIIc, IVa, IVb,
XI, and XII were reported previously [14, 15, 23–26].
** The signal was obscured by those of alkyl protons.
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KHAFIZOVA et al.
760
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1.71 m (13H, CH, CH2), 3.57−3.82 m (2H, CH2OH).
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7.0 Hz), 1.08–1.75 m (17H, CH, CH2), 3.25−3.75 m
(4H, CH2OH). 13C NMR spectrum, δC, ppm: 14.30,
22.84, 28.31, 28.63, 28.82, 29.61, 30.20, 32.51, 35.90,
36.72, 60.72, 65.91. Mass spectrum: m/z 202 [M]+.
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C 71.23; H 12.95. M 202.23.
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Compounds in Organic Synthesis, Chur, Switzerland:
Harwood Academic, 1984.
13. Ramakrishnan, S. and Chung, T.C., J. Organomet.
Chem., 1990, vol. 388, p. 1.
14. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P.,
Muslukhov, R.R., and Tolstikov, A.G., Bull. Acad. Sci.
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Chem., 2010, vol. 46, p. 474.
3-(Cyclohex-3-en-1-yl)butan-1-ol (VII). Yield
0.42 g (27%), oily substance, Rf 0.49 (ethyl acetate–
hexane, 1:1). 1H NMR spectrum, δ, ppm: 0.94−0.97 m
(3H, CH3), 1.32–2.07 m (10H, CH, CH2), 3.63−3.81 m
(2H, CH2OH), 5.68 m (2H, CH=CH). 13C NMR spec-
trum, δC, ppm: 14.08 (14.47), 20.51 (20.58), 26.03
(26.10), 26.15 (26.21), 28.69 (29.12), 34.13 (34.17),
47.00 (47.05), 62.94 (63.14), 126.89 (127.00), 127.07
(126.14). Mass spectrum: m/z 154 [M]+. Found, %:
C 77.73; H 11.69. C10H18O. Calculated, %: C 77.86;
H 11.76. M 154.25.
17. Nöth, H. and Vahrenkamp, H., Chem. Ber., 1966,
2-(Cyclohex-3-en-1-yl)butane-1,4-diol (VIII).
vol. 99, p. 1049.
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19. Hermanek, S., Chem. Rev., 1992, vol. 92, p. 325.
20. Brown, H.C. and Gupta, S.K., J. Am. Chem. Soc., 1972,
vol. 94, p. 4370.
21. Kulkarni, S.U., Lee, H.D., and Brown, H.C., Synthesis,
Yield 1.09 g (64%), oily substance, Rf 0.14 (ethyl
1
acetate–hexane, 1:1). H NMR spectrum, δ, ppm:
1.67–2.02 m (10H, CH, CH2), 3.49−3.73 m (4H,
CH2OH), 4.48 s (2H, OH), 5.62 m (2H, CH=CH).
13C NMR spectrum, δC, ppm: 25.84, 26.04 (26.09),
28.59 (28.99), 32.81 (33.02), 35.61 (35.51), 43.99
(44.05), 61.29 (61.36), 64.17 (64.38), 126.54 (126.62),
126.99. Mass spectrum: m/z 170 [M]+. Found, %:
C 69.45; H 10.58. C10H18O2. Calculated, %: C 70.55;
H 10.66. M 170.25.
1982, p. 193.
22. Rybak, B.M., Analiz nefti i nefteproduktov (Analysis of
Petroleum and Petrochemicals), Moscow: Gostoptekh-
izdat, 1962.
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Muslukhov, R.R., and Tolstikov, A.G., Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1990, vol. 39, p. 2570.
This study was performed under financial support
by the Presidium of the Russian Academy of Sciences
(program no. 18) and by the Russian Foundation for
Basic Research (project no. 12-03-97013).
24. Azerad, R. and Buisson, D., Tetrahedron, 1988, vol. 44,
p. 6407.
25. Millward, D.B., Cole, A.P., and Waymouth, R.M.,
Organometallics, 2000, vol. 19, p. 1870.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 6 2012