Ethylation of 2-Alkenyltetrahydrofurans and 2-Alkenyltetrahydropyrans Catalyzed by Titaniun(IV) Isoprpopoxide. Supplement to the Synthesis of Pheromones of Lesser Plum Worm and Tea Leaf Roller Moth

Article abstract of DOI:10.1023/A:1026047515568

Reaction of 2-vinyltetrahydrofuran and 2-vinyltetrahydropyran with ethylmagnesium bromude in the presence ot titanium(IV) isopropoxide afforded in moderate selectivity trans-4-octen-1-ol and trans-5-nonen-1-ol respectively. Best yields and high stereochemical purity of products were obtained in ethylation under these conditions of 2-(cis-1-propenyl)tetrahydrofuran, 2-(cis-1-proprnyl)- and 2-(trans-1-propenyl)-tetrahydropyran. It is assumed that the key organometallic intermediate formed was diisopropoxytitanacycloprpopane, and direction of its addition to the doubel bond governed the streochemistry of the resulting product. The obtained trans-4-octen-1-ol and trans-7-methyl-5-nonen-1-ol were applied as initial products in the synthesis of sex pheromones of lesser plum worm (Grafolita funebrana) and tea leaf roller moth (Adoxophyes sp).

Full text of DOI:10.1023/A:1026047515568

Russian Journal of Organic Chemistry, Vol. 39, No. 4, 2003, pp. 478 485. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 4, 2003,
pp. 514 521.
Original Russian Text Copyright
2003 by Matyushenkov, Churikov, Sokolov, Kulinkovich.
Dedicated to Full Member of the Russian Academy of Sciences
I. P. Beletskaya on occasion of her jubilee
Ethylation of 2-Alkenyltetrahydrofurans
and 2-Alkenyltetrahydropyrans Catalyzed by Titaniun(IV)
Isoprpopoxide. Supplement to the Synthesis of Pheromones
of Lesser Plum Worm and Tea Leaf Roller Moth
E. A. Matyushenkov, D. G. Churikov, N. A. Sokolov, and O. G. Kulinkovich
Belorussian State University, Minsk, 220050 Belarus
Received December 4, 2002
Abstract Reaction of 2-vinyltetrahydrofuran and 2-vinyltetrahydropyran with ethylmagnesium bromude in
the presence ot titanium(IV) isopropoxide afforded in moderate selectivity trans-4-octen-1-ol and trans-5-
nonen-1-ol respectively. Best yields and high stereochemical purity of products were obtained in ethylation
under these conditions of 2-(cis-1-propenyl)tetrahydrofuran, 2-(cis-1-proprnyl)- and 2-(trans-1-propenyl)-
tetrahydropyran. It is assumed that the key organometallic intermediate formed was diisopropoxy-
titanacycloprpopane, and direction of its addition to the doubel bond governed the streochemistry of
the resulting product. The obtained trans-4-octen-1-ol and trans-7-methyl-5-nonen-1-ol were applied
as initial products in the synthesis of sex pheromones of lesser plum worm (Grafolita funebrana) and
tea leaf roller moth (Adoxophyes sp).
Several years ago our research team developed an
efficient and experimentally simple cyclopropanation
method for carboxylic acids esters by treating them
with ethylmagnesium bromide in the presence of
titanium(IV) isopropoxide [1, 2]. It was assumed that
the reaction proceeded via formation of thermally
unstable diethyltitanium intermediate A which suf-
fered -elimination giving ethane and diisopropoxy-
titanacyclopropane B (Scheme 1). The latter acted in
reactions with esters as an equivalent of 1,2-ethylene
dicarbanion affording the corresponding cyclo-
propanols.
and carboxilic acids nitriles [6] furnishing the cor-
responding aminocyclopropanes, and also effected
some other synthetically useful reactions [2, 7, 8]. In
particular, we recently found that reaction of EtMgBr
with magnesium alcoholates of allyl alcohols in the
presence of Ti(i-PrO)4 afforded products of formal
SN2 substitution of a hydroxy group by ethyl [9].
Similarly react also ethers of allyl alcohols; therewith
the corresponding olefins with the best trans-, cis-
selectivity form from tetrahydropyranyl ethers [9].
In this study we investigated titanium-catalyzed
ethylation of allyl ethers whose oxygen atom is
located in a saturated heteroring. The process is a
convenient way to unsaturated alcohols. A reaction
of 2-vinyltetrahydrofuran (Ia) with 2.5 equiv of
EtMgBr in the presence of 0.1 equiv of Ti(i-PrO)4
afforded in a moderate yield cis- and trans-isomeric
octanols IIa in 1: 3 ratio (Scheme 2, table, run
no. 1). At the use of twice less relative amount of
Scheme 1.
EtMgBr
2-vinyltetrahydrofuran
(Ia)
reacted
incompletely, and also the yield of compound IIa
decreased in about the same proportion (table, run
no. 2). The increased stereoselectivity [up to 90% of
the trans-4-octen-1-ol (IIa)] was achieved at lower
temperature, but in this case the complete conversion
of substrate was reached at the use of 3 equiv of
EtMgBr per 1 equiv of Ti(i-PrO)4 (table, run no. 3).
It was established later that the dialkoxytitanacyclo-
propane reagent B took part in ligand exchange with
olefins [3, 4], in alkylation of N,N-dialkylamides [5]
1070-4280/03/3904-0478$25.00 2003 MAIK Nauka/Interperiodica

ETHYLATION OF 2-ALKENYLTETRAHYDROFURANS
479
Reactions of alkenyltetrahydrofurans Ia, c and alkenyltetrahydropyrans Ib, d with ethylmagnesium bromide in the
presence of titanium(IV) isopropoxide
Run Substrate EtMgBr (equiv) Ti(i-PrO)4 (equiv)
no.
T, C
Reaction
product
trans-/cis-ratio
Yield, %a
1
2
3
4
5
6
7
8
9
Ia
Ia
Ia
Ib
Ib
2.5
1.3
3.0
2.5
3.0
2.5
2.5
2.5
3.0
0.1
0.1
1.0
0.1
1.0
0.1
0.2
0.2
1.0
20
20
65 20
20
65 20
20
20
IIa
IIa
IIa
IIb
IIb
IIc
IId
IId
IId
75/25
Not determined
90/10
55
35
50
63
57
55
67
85
81
70/30
80/20
95/5
95/5
95/5
98/2
cis-Ic
cis-Id
trans-Id
trans-Id
20
65 20
a
Yield of isolated product.
Reactions with vinyltetrahydropyran (Ib) under the
same conditions gave similar results (Scheme 2,
table, runs nos. 4, 5). In reaction of compounds Ia
and Ib with EtMgBr in the presence of Ti(i-PrO)4
formed about 20 30% of side products arising from
reductive elimination of the hydroxy group [8]; these
were mixtures of hexenols IIIa and heptenols IIIb
respectively. We did not determine the isomeric
composition of compounds IIIa and IIIb and
separated them from the main products IIa, b by
fractional distillation in a vacuum.
The ethylation mechanism of compounds Ia d
similar to previously assumed ethylation mechanism
of allyl alcohols [9] is presented in Scheme 3. The
coordination of initial compounds Ia d to the titana-
cyclopropane imtermediate B results in complex C.
Therewith the approach of bulky reagent B to the
double bond of substrate Ia d located in syn-position
to oxygen [10] becomes less sterically hindered and
occurs from the less sterically loaded exo-side. The
addition of ethylmagnesium bromide to the arising
complex C furnishes titancyclopentane at-complex D
[7] followed by intramolecular anti-elimination of the
titanium alkoxide, and formation of a trans double
carbon carbon bond. Thus formed dialkylated
titanium derivatives E undergo disproportionation
into titanacyclopropane B and magnesium alcoholates
of unsaturated alcohols (IIa d). Therewith the highest
stereoselectivity of the reaction with substrate Id
originates apparently from lesser tendency of trans-
disubstituted double bond to -complexing with metal
atoms; thus increases the directing influence of the
oxygen atom on the stereochemistry of titanacyclo=
propane complex B addition to the double bond
resulting in complex C formation.
The ethylation 2-(cis-1-propenyl)tetrahydrofuran
(Ic) and 2-(cis-1-propenyl)tetrahydropyran (Id) also
furnished the target products in a moderate yield, but
the stereoselectivity of the reaction was considerably
higher, and the cis-isomer content in the arising
trans-alkenols IIc, d did not exceed 5% (tanle,
runs nos. 6, 7). Here also formed unsaturated
alcohols IIIc, d as side products (about 15%). The
most cleanly occurred the ethylation with ethyl-
magnesium bromide in the presence of catalytic
amounts of Ti(i-PrO)4 when 2-(trans-1-propenyl)-
tetrahydropyran (Id) was used as substrate. The
resulting trans-7-methyl-5-nonen-1-ol (IId) was
obtained in over 80% yield and of stereochemical
purity up to 98(table, runs nos. 7, 8).
The appearance of side products resulting from
reductive elimination of hydroxy group IIIa d is due
Scheme 2.
Ia IIIa, R = H, n = 1; Ib IIIb, R = H, n = 2; Ic IIIc, R = CH3, n = 1; Id IIId, R = CH3, n = 2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

480
MATYUSHENKOV et al.
Scheme 3.
R = H, CH3; n = 1, 2.
Scheme 4.
to ejection of ethylene from C intermediate giving
rise to tetrahydrofuryl- and tetrahydropyranyl-sub-
stituted titanacyclopropane intermediates F. The
subsequent intramolecular 1,2-elimination of titanium
alkoxide affords allyltitanium alcoholates G which on
hydrolysis furnish linear unsaturated alcohols IIIa d.
Therewith the contribution of this side reaction to the
overall ethylation product falls in the series Ia Ib >
Ic > Id in compliance with decrease in the double
carbon carbon bond ability to form complexes with
titanium in the series CH2=CH > cis-CH3CH=CH >
trans-CH3CH=CH.
Compound IV, a strong inhibitor of the attractive
effect of codlemone (sex pheromone of lesser apple
worm Laspeyresia pomonella L [17]) was synthesized
from trans-4-octen-1-ol (IIa), prepared in its turn by
ethylating tetrahydrofuran Ia with ethylmagnesium
bromide at low temperature (see the table, run no. 3).
The unsaturated alcohol IIa containing no more than
10% of cis-isomer was converted into the cor-
responding bromide VI via methylsulfonate. The
building-up of the carbon carbon backbone was
carried out by cross-coupling of alkylmagnesium
bromide obtained from bromide VI with 4-iodobutyl
acetate in the presence of copper(I) iodide [18]. Thus
in a moderate yield was obtained trans-8-dodecen-
1-yl acetate (VII) which in its turn was a component
of a pheromone composition of a false lesser apple
worm (Cryptophlebia leucotreta) [19]. The method
of configuration change applied to this compound was
described earlier [20]. It consists in alternating
bromochlorination stages effected by N-bromosuc-
cinimide in the presence of hydrogen chloride with
dehalogenation of the product obtained with sodium
We applied the ethylation of 2-alkenyl-substituted
oxygen-containing heterocycles to the synthesis of
cis-8-dodecen-1-yl acetate (IV) [11] (Scheme 4) that
constituted the main component of pheromone
compositions of lesser plum worm (Grafolita fune-
brana) [12, 13] and some other insects from order of
Lepidoptera [12, 14, 15], and also to preparation of
racemic form of 12-methyltetradecan-1-yl acetate (V)
(Scheme 5), a component of pheromone of tea leaf
roller moth (Adoxophyes sp) [16].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

ETHYLATION OF 2-ALKENYLTETRAHYDROFURANS
481
Scheme 5.
iodide in dimethylformamide. The content of the
trans-isomer in the target cis-8-dodecen-1-yl acetate
(IV) was about 15%, close to the amount of the
minor isomer in the ethylation product obtained from
vinyltetrahydrofuran Ia.
Ethyl ether and tetrahydrofuran were dried and
distilled over sodium.
Ethylation of 2-alkenyltetrahydrofurans Ia, c
and 2-alkenyltetrahydropyrans Ib, d. (a) Reaction
at room temperature (see the table, runs nos. 1, 2, 4,
6 8). To a stirred solution of 100 mmol of com-
pounds Ia d [21] and 3 6 ml (10 20 mmol) of
Ti(i-PrO)4 in anhydrous ether (60 ml) was added
dropwise 2 M solution of ethylmagnesium bromide in
ether (125 ml) within 2 h at room temperature. After
stirring fot 3 h the black reaction mixture was
cautiously poured into a mixture of 30 ml of concn.
sulfuric acid and 300 g of ice. The organic layer was
separated, the water layer was extracted with ether
(3 30 ml). The combined organic solutions were
washed in succession with saturated solutions of
NaHCO3 and NaCl. The resulting organic phase was
dried on Na2SO4, the solvent was distilled off at the
atmospheric pressure, and the unsaturated alcohols
IIa d were distilled in a vacuum.
12-Methyltetradecan-1-yl acetate (V) was syn-
hesized from unsaturated alcohol IId (see the table,
run no. 7) that by a common procedure was converted
into the corresponding iodide VIII. Cross-coupling
of the latter in the presence of copper(I) iodide with a
Grignard reagent IX prepared from 2-(5-bromopent-
yloxy)tetrahydro-2H-pyran afforded after removing
the tetrahydropyranyl protection unsaturated alcohol
X. The catalytic hydrogenation of compound X fol-
lowed by acetylation furnished the target pheromone
V in 28% overall yield (Scheme 5).
Thus in the present paper we have reported on a
useful application of titanium-catalyzed alkylation of
allyl ethers with ethylmagnesium bromide to prepara-
tion of 4- and 5-alken-1-ols. The latter were used in
syntheses of pheromones of lesser plum worm and tea
leaf roller moth.
(b) Reaction at low temperature (see the table, runs
nos. 3, 5, 9). To a stirred solution of 50 mmol of
compounds Ia, b, d [21] and 14.9 ml (50 mmol) of
Ti(i-PrO)4 in anhydrous ether (30 ml) at cooling to
75 C was added dropwise 2 M solution of ethyl-
magnesium bromide in ether (75 ml) at a rate per-
mitting to maintain the temperature of the reaction
mixture below 65 C. After completing the addition
the reaction mixture was stirred for 3 h while gradual-
ly warming to room temperature, and the stirring at
room temperature was continued for another 2 h.
Then the work-up was performed as described above.
Unsaturated alcohols IIa, b, d were distilled in a
vacuum.
EXPERIMENTAL
1H NMR spectra were registered on spectrometers
Bruker AC-200 (operating frequency 200 MHz) and
Bruker Avance 400 (operating frequency 400 MHz)
from 4% solutions of compounds in CDCl3 (as
internal reference served residual protons of the
solvent). 13C NMR spectra were measured on the
same instruments at operating frequencies 50 and
100.6 MHz respectively from solutions in CDCl3.
IR spectra were recorded on spectrophotometer
Specord 75IR from solutions in CCl4. Chromato-
graphic analysis and measurement of mass spectra
was performed on a Hewlett Packard GC-MS
5890/5972 instrument, ionizing electrons energy
70 eV.
trans-4-Octen-1-ol (IIa). Bp 85 90 C (12 mm Hg)
1
{86 88 C (11 mm Hg) [22]}. IR spectrum, cm :
3613 ( OH). 1H NMR spectrum (200 MHz) (identical
to publ. [22]), , ppm: 0.90 t, (3H, J 7 Hz), 1.28
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

482
MATYUSHENKOV et al.
1.46 m (2H), 1.56 1.70 m (2H), 1.86 s (1H), 1.90
2.16 m (4H), 3.64 t (2H, J 7 Hz), 5.36 5.50 m (2H).
13C NMR spectrum (50 MHz), , ppm: 13.6, 22.6,
28.8, 32.4, 34.6, 62.4, 129.5, 130.9. Mass spectrum,
m/z: 29, 41, 55, 67, 81, 95, 110, 128 [M]+ . Found,
%: C 73.51; H 12.01. C8H16O. Calculated, %:
C 74.94; H 12.58.
was dried over Na2SO4, and the solvent was distilled
off in a vacuum. The trans-4-octen-1-yl methane-
sulfonate was used further without additional purifica-
tion. Yield 6.93 g (99%). 1H NMR spectrum
(400 MHz), , ppm: 0.87 t (3H, J 7.4 Hz), 1.36
sextet (2H, J 7.4 Hz), 1.80 quintet (2H, J 6.8 Hz),
1.95 q.d (2H, J 6.8, 1.2 Hz), 2.11 q.d (2H, J 6.8,
1.2 Hz), 2.98 s (3H), 4.21 t (2H, J 6.8 Hz),
5.35 d.t.t (1H, J 15.6, 6.8, 1.2 Hz), 5.46 d.t.t
(1H, J 15.6, 6.8, 1.2 Hz). 13C NMR spectrum
(100.6 MHz), , ppm: 13.53, 22.51, 28.21, 28.89,
34.54, 37.30, 69.40, 127.92, 132.12.
trans-5-Nonen-1-ol
(IIb).
Bp
95 100 C
(12 mm Hg) {107 C (17.5 mm Hg) [23]}. IR spec-
1
trum, cm : 3615
(
OH). 1H NMR spectrum
(200 MHz), , ppm: 0.86 t (3H, J 7 Hz), 1.26
1.48 m (4H), 1.48 1.58 m (2H), 1.88 2.16 m (5H),
3.62 t (2H, J 6.5 Hz), 5.30 5.50 m (2H). Mass
spectrum, m/z: 29, 41, 55, 67, 81, 95, 109, 124, 142
[M]+ . Found, %: C 75.32; H 12.37. C9H18O. Cal-
culated, %: C 76.00; H 12.75.
trans-1-Bromo-4-octene (VI).
A solution of
6.80 g (33 mmol) of trans-4-octenyl methanesulfonate
and 5.65 g (65 mmol) of anhydrous LiBr in 100 ml
of anhydrous acetone was heated under reflux for 3 h.
On cooling the solvent was distilled off under reduced
pressure. To the residue was added 100 ml of water
and 50 ml of ethyl ether. The organic layer was
separated, the water layer was extracted with ether
(2 20 ml). The combined organic solutions were
washed with water (30 ml), with saturated NaCl
solution (50 ml), and dried with Na2SO4. On remov-
ing the solvent the residue was distilled in a vacuum.
Yield of bromide VI 5.55 g (88%), bp 74 80 C
trans-6-Methyl-4-octen-1-ol (IIc). Bp 55 60 C
(3 mm Hg) {94 95 C (10 mm Hg) [24]}. IR spec-
1
trum, cm : 3633
(
OH). 1H NMR spectrum
(200 MHz), , ppm: 0.85 t (3H, J 7 Hz), 0.95 d (3H,
J 6.5 Hz), 1.20 1.34 m (2H), 1.56 1.75 m (2H),
1.96 2.16 m (4H), 3.63 t (2H, J 6.5 Hz), 5.30
5.48 m (2H). 13C NMR spectrum (50 MHz), , ppm:
12.0, 20.9, 29.6, 30.5, 33.3, 39.2, 62.5, 128.4,
137.3. Mass spectrum, m/z: 29, 41, 55, 67, 81, 95,
109, 142 [M]+ . Found, %: C 74.73; H 11.92.
C9H18O. Calculated, %: C 75.99; H 12.75.
1
(12 mm Hg) {82 85 C (5 mm Hg) [26]}. H NMR
spectrum (400 MHz), , ppm: 0.88 t (3H, J 7.2 Hz),
1.32 1.43 m (2H), 1.87 2.01m (4H), 2.10 2.18m
(2H), 3.40t (2H, J 7.0 Hz), 5.30 5.41 m (1H),
5.43 5.53 m (1H). 13C NMR spectrum (100.6 MHz),
, ppm: 13.57, 22.58, 30.86, 30.50, 33.22, 34.62,
128.05, 131.98.
trans-7-Methyl-5-nonen-1-ol (IId). Bp 80 85 C
1
(3 mm Hg). IR spectrum, cm : 3633 ( OH).
1H NMR spectrum (200 MHz), , ppm: 0.84 t (3H,
J 7 Hz), 0.94 d (3H, J 6.5 Hz), 1.18 1.65 m (6H),
1.95 2.16 m (4H), 3.64 t (2H, 7 Hz), 4.88 5.44 m
(2H). 13C NMR spectrum (50 MHz), , ppm: 11.9,
20.4, 25.8, 27.3, 30.4, 32.1, 38.3, 62.4, 128.3,
136.8. Mass spectrum, m/z: 29, 41, 55, 67, 81, 95,
109, 123, 128, 138, 156 [M]+ . Found, %: C 75.40;
H 11.61. C10H20O. Calculated, %: C 76.86; H 12.90
(publ.: [25]).
trans-8-Dodecenyl acetate (VII). Into a three-neck
flask of 100 ml capacity equipped with a stirrer, low-
temperature thermometer, and flushed with dry argon
was charged 5.57 g (23 mmol) 4-iodobut-1-yl acetate,
0.28 g (1.47 mmol) of anhydrous CuI, and 5 ml of
tetrahydrofuran. The mixture was cooled to 80 C,
and thereto was gradually added under argon atmo-
sphere at stirring a solution of Grignard reagent
prepared from 5.54 g (29 mmol) of 1-bromo-4-octene
(VI) and 0.70 g (29 mmol) of magnesium turnings in
22 ml of THF. The rate of addition was so controlled
as to maintain the temperature of the reaction mixture
below 70 C. After completing the addition the reac-
tion mixture was stirred for 3 h while gradually
warming to room temperature, and then it was
slowly within 1.5 h heated to boiling. Then the mix-
ture was refluxed for 1.5 h and on cooling it was
treated with a saturated NH4Cl solution (30 ml). The
organic layer was separated, the water layer was
extracted with ether (3 5 ml). The combined organic
solutions were washed with water (2 30 ml), with
trans-4-Octenylmethanesulfonate. To a solution
of 4.35 g (34 mmol) of trans-4-octen-1-ol and 6.17 g
(61 mmol) of triethylamine in 50 ml of anhydrous
ethyl ether at cooling with an ice bath was added
dropwise while stirring 5.15 g (45 mmol) of methane-
sulfonyl chloride. After completing the addition the
reaction mixture was stirred for 1 h, then 50 ml of
water was added. The organic layer was separated,
the water layer was extracted with ether (2 20 ml).
The combined organic solutions were washed in
succession with 5% solution of HCl (30 ml), water
(30 ml), saturated solution of NaHCO3 (30 ml), and
saturated solution of NaCl (50 ml). The organic phase
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ETHYLATION OF 2-ALKENYLTETRAHYDROFURANS
483
saturated NaCl solution (40 ml), and dried with
Na2SO4. Then the solvent was distilled off, and the
residue was subjected to fractional distillation in a
vacuum collecting the fraction with bp 114 122 C
(3 mm Hg) {69 71 C (0.04 mm Hg) [27]}. The
substance obtained (3.72 g) was additionally purified
by column chromatography on silica gel (eluent cyclo-
hexane ethyl acetate, 20: 1) to get 2.98 g of acetate
VII as a mixture of geometric isomer [trans-/cis-,
88: 12 (GC-MS)]. Yield 57% (with respect to
129.66, 129.85, 171.03. Mass spectrum, m/z: 43, 55,
67, 82, 96, 109, 110, 166 (publ.: [11]).
trans-9-Iodo-3-methyl-4-nonene (VIII). To a
solution of 5.77 g (37 mmol) of trans-7-methyl-4-
nonen-1-ol and 6.78 g (67 mmol) of triethylamine in
50 ml of anhydrous ethyl ether was added dropwise
while stirring and cooling with ice bath 5.50 g
(48 mmol) of methanesulfonyl chloride. The reaction
mixture was stirred for 1 h, and then 50 ml of water
was added. The organic layer was separated, the
water layer was extracted with ether (2 20 ml). The
combined organic solutions were washed in
succession with 5% solution of HCl (30 ml), water
(30 ml), saturated solution of NaHCO3 (30 ml), and
saturated solution of NaCl (50 ml). The organic phase
was dried over Na2SO4, and the solvent was distilled
off in a vacuum. Then to the residue (8.64 g) was
added 11.10 g (74 mmol) of anhydrous NaI in 70 ml
of anhydrous acetone. The mixture was boiled for
2 h, the solvent was removed under reduced pressure,
and 120 ml of water and 60 ml of ethyl ether was
added to the residue. The organic layer was separated,
the water layer was extracted with ether (2 20 ml).
The combined organic solutions were washed with
water (30 ml), with saturated NaCl solution (50 ml),
and dried with Na2SO4. On distilling off the solvent
under reduced pressure we obtained 9.15 g (93%) of
1
4-iodobut-1-yl acetate). IR spectrum, cm : 1716
1
(
CO). H NMR spectrum (400 MHz), , ppm: 0.86 t
(3H, J 7.5 Hz), 1.29 1.37 m (10H), 1.56 1.61 m
(2H), 1.92 2.01 m (4H), 2.01 s (3H), 4.04 t (2H,
J 6.9 Hz), 5.35-5.39 m (2H). 13C NMR spectrum
(100.6 MHz), , ppm: 13.53, 20.86, 22.66, 25.81,
28.55, 28.90, 29.04, 29.46, 32.46, 34.63, 64.53,
130.16, 130.34, 171.08. Mass spectrum, m/z: 43, 55,
67, 82, 96, 109, 110, 166.
cis-8-Dodecenyl acetate (IV). Through a solution
of 1.10 g (4.9 mmol) of trans-8-dodecenyl acetate in
11 ml of anhydrous dichloromethane cooled to 70 C
was passed for 15 min a flow of dry hydrogen
chloride till saturation. Then at the same temperature
was added by portions at stirring 1.03 g (5.8 mmol)
of powdered N-bromosuccinimide. In 20 min after
completion of addition the reaction mixture was
cautiously poured into 20 ml of cooled 10% solution
of sodium sulfite, the organic layer was separated, the
water layer was extracted with dichloromethane (3
10 ml), the combined organic solutions were washed
with water (2 10 ml), with saturated solution of
NaHCO3 (20 ml), and dried over Na2SO4. On remov-
ing the solvent under reduced pressure we obtained
1.30 g of product that was added to a solution of
13.0 g (86.7 mmol) of anhydrous NaI in 65 ml of dry
DMF. The mixture was heated at stirring to 85 C for
20 h, then the hot reaction mixture was poured into
150 ml of water, sodium sulfite was added till the
color of iodine disappeared, and the reaction products
were extracted into cyclohexane (4 25 ml). The
combined organic solutions were washed with water
(2 20 ml), with saturated NaCl solution (40 ml),
and dried with Na2SO4. On removing the solvent
under reduced pressure we obtained 0.81 g (94%) of
compound IV as a mixture of isomers [trans- and
1
iodide VIII. H NMR spectrum (400 MHz), , ppm:
0.84 t (3H, J 7.2 Hz), 0.95 d (3H, J 6.4 Hz), 1.22
1.34 m (2H), 1.41 1.52 m (2H), 1.78 1.89 m (2H),
1.92 2.10 m (3H), 3.18 t (2H, J 7.2 Hz), 5.23
5.37 m (2H). 13C NMR spectrum (100.6 MHz), ,
ppm: 6.84, 11.72, 20.35, 29.79, 30.43, 31.41,
32.96, 38.32, 127.55, 137.01.
trans-12-Methyl-10-tetradecen-1-ol (X). A mix-
ture of 1.86 g (7 mmol) of trans-9-iodo-3-methyl-4-
nonene (VIII), 84 mg (0.44 mmol) of anhydrous CuI
and 4 ml of THF under argon atmosphere was cooled
to 90 C, and at stirring was slowly added a solution
of Grignard reagent prepared from 2.17 g (8.7 mmol)
of 2-(5-bromopentyloxy)tetrahydro-2H-pyran and
0.21 g (8.7 mmol) of magnesium turnings in 9 ml of
THF. The rate of addition was so controlled that the
temperature of the reaction mixture was below 70 C.
After addition the mixture within 2 h was warmed at
stirring to room temperature, and then it was gradual-
ly within 1.5 h heated to boiling. Then the mixture
was refluxed for 1 h. The solvent was removed at
reduced pressure, and to the residue was added a
saturated NH4Cl solution (15 ml) and ether (15 ml).
The organic layer was separated, the water layer was
extracted with ether (3 15 ml). The combined
1
cis-isomers, 15: 85 (GC-MS)]. IR spectrum, cm :
1
1716 ( CO). H NMR spectrum (400 MHz), , ppm:
0.88 t (3H, J 7.5 Hz), 1.30 1.42 m (10H), 1.60
1.70 m (2H), 1.97 2.04 m (4H), 2.02 s (3H), 4.03 t
(2H, J 6.6 Hz), 5.37 5.44 m (2H). 13C NMR spec-
trum (100.6 MHz), , ppm: 13.69, 20.87, 22.81,
25.82, 27.09, 28.55, 29.07, 29.22, 29.57, 64.53,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003

484
MATYUSHENKOV et al.
organic solutions were washed with water (2 15 ml),
with saturated NaCl solution (30 ml), and dried with
Na2SO4. Then the solvent was distilled off, to the
residue obtained (3.0 g) was added 25 ml of 96%
ethanol, 0.1 g of p-toluenesulfonic acid, and the mix-
ture was boiled for 1 h. On cooling to the reaction
mixture was added 4 ml of saturated NaHCO3 solu-
tion, the solvent was distilled off at reduced pressure,
and to the residue was added 15 ml of water and 15
ml of ether. The organic layer was separated, the
water layer was extracted with ether (3 15 ml).
The combined organic solutions were washed with
saturated NaCl solution and dried on Na2SO4. On
removing the solvent the product was purified by
column chromatography on silica gel (eluent ethyl
acetate cyclohexane, 1: 5). Yield of trans-12-methyl-
10-tetradecen-1-ol (X) 0.55 g (35%). IR spectrum,
cm : 3627 ( OH). H NMR spectrum (200 MHz), ,
ppm: 0.86 t (3H, J 7.0 Hz), 0.95 d (3H, J 6.5 Hz),
1.32 br.s (14H), 1.50 1.63 m (2H), 1.88 s (1H),
1.92-2.06 m (3H), 3.62 t (2H, J 7.0 Hz), 5.04
5.44 m (2H). Mass spectrum , m/z: 29, 41, 55, 70,
83, 95, 109, 123, 137, 151, 179, 197, 208, 226 [M]+
(publ.: [28]).
solution (10 ml), and dried over Na2SO4. On remov-
ing the solvent under reduced pressure the product
was purified by column chromatography on silica
gel (eluent ethyl acetate cyclohexane, 1: 10). Yield
1
95 mg (95%). IR spectrum, cm : 1722 ( CO).
1H NMR spectrum (400 MHz, CDCl3), , ppm:
0.82 0.95m (6H), 1.05 1.20m (2H), 1.26 br.s (19H),
1.58 1.70m (2H), 2.04s (3H), 4.05t (2H, J 7.0 Hz).
13C NMR spectrum (100.6 MHz), , ppm: 11.36,
19.19, 20.96, 25.90, 27.09, 28.60, 29.24, 29.49,
29.55, 29.62, 29.68, 30.00, 34.39, 36.63, 64.64,
171.00. Mass spectrum, m/z: 29, 43, 55, 70, 83, 97,
111, 125, 140, 153, 181, 199, 210, 255 (publ.: [16,
28]).
The study was carried out under financial support
of INTAS program (grant no. O-549) and Founda-
tion for Fundamental Research of Belarus’ Republic
(X01-165).
1
1
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