Intermolecular cycloalumination of cyclic and acyclic alkynes with Et nAlCl3-n in the presence of Cp2ZrCl2

Article abstract of DOI:10.1134/S1070428008090078

Intramolecular cycloalumination of cyclic and acyclic alkynes with Et _nAlCl_3-n (n = 0, 1) in the presence of Cp ₂ZrCl₂ gave previously unknown unsaturated bi-and tricyclic organoaluminum compounds in up to 80% y

Full text of DOI:10.1134/S1070428008090078

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 9, pp. 1291–1295. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.A. D’yakonov, L.F. Galimova, A.G. Ibragimov, U.M. Dzhemilev, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 9, pp. 1308–1312.
Intermolecular Cycloalumination of Cyclic and Acyclic Alkynes
with EtnAlCl3–n in the Presence of Cp2ZrCl2
V. A. D’yakonov, L. F. Galimova, A. G. Ibragimov, and U. M. Dzhemilev
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
February 13, 2008
Abstract—Intramolecular cycloalumination of cyclic and acyclic alkynes with EtnAlCl3–n (n = 0, 1) in the
presence of Cp2ZrCl2 gave previously unknown unsaturated bi- and tricyclic organoaluminum compounds in up
to 80% yield.
DOI: 10.1134/S1070428008090078
It is known [1], that internal alkynes react with
EtAlCl2 in the presence of Cp2ZrCl2 as catalyst to give
the corresponding cycloalumination products. From
1,2-diaryl-, 1-alkyl-2-aryl-, and 1-aryl-2-allylacety-
lenes we thus synthesized 2,3,4,5-tetrasubstituted
aluminacyclopenta-2,4-dienes. However, the behavior
of cyclic alkynes under catalytic cycloalumination con-
ditions remained unclear. With a view to elucidate
whether cyclic alkynes can be involved in cycloalu-
mination and obtain new organoaluminum compounds,
di- and tricyclic aluminacyclopenta-2,4-dienes, we
examined reactions of cyclic alkynes with EtnAlCl3–n
(n = 0, 1) in the presence of Cp2ZrCl2 which is widely
used as catalyst in cycloalumination of unsaturated
compounds (Dzhemilev reaction) [2–10]. As substrates
we used cyclooctyne, cyclododecyne, and acyclic
internal alkynes. The reactions were carried out with
commercially available AlCl3, EtAlCl2, and Cp2ZrCl2.
Cyclooctyne reacted with EtAlCl2 in the presence
of Cp2ZrCl2 and magnesium powder (molar ratio cy-
clooctyne–EtAlCl2–Mg–Cp2ZrCl2 10:7.5:7.5:1) under
the conditions developed previously [1] (THF, 20°C,
6 h) to give tricyclic organoaluminum compound Ia in
~78% yield. The structure of Ia was determined by
analysis of the 13C NMR spectra of its hydrolysis and
deuterolysis products IIa and IIIa (Scheme 1). The 13C
NMR spectrum of IIa contained two downfield signals
at δC 126.33 and 140.23 ppm, which were assigned to
double-bonded carbon atoms, and six signals in the
region δC 25–31 ppm due to sp3-hybridized carbon
atoms in the cyclic fragments. These data indicated
symmetric structure of molecule IIa. In the 13C NMR
spectrum of IIIa, the signal from the double-bonded
carbon atom was split into a triplet due to coupling
with deuterium (JCD = 23.4 Hz), and the upfield
α-isotope shift of the triplet center was ∆δC = 0.31 ppm
Scheme 1.
H+, H2O
EtnAlCl3–n
Cp2ZrCl2, Mg
( )m
( )m
IIa, IIb
( )m
( )m
( )m
Al
R
D+, D2O
Ia, Ib, Ia', Ib'
( )m
( )m
D D
IIIa, IIIb
n = 0, 1; m = 1 (a), 5 (b); I, R = Et; I′, R = Cl.
1291

D’YAKONOV et al.
1292
(relative to the corresponding signal of IIa). The
signals were assigned using the additivity scheme and
increments for cyclooctene given in [11]. The molec-
ular weights of IIa and IIIa (218 and 220, respec-
tively) were determined by mass spectrometry.
ucts, 2,2′-diiodo-1,1′-bi(cyclooctene) (IVa), 2,2′-di-
methyl-1,1′-bi(cyclooctene) (V), and 2,2′-diallyl-1,1′-
bi(cyclooctene) (VI) were isolated in 70–85% yield
(Scheme 2).
We also made an attempt to perform joint cyclo-
alumination of cycloalkynes with linear terminal al-
kynes with a view to synthesize new organoaluminum
compounds, bicyclic aluminacyclopenta-2,4-dienes.
By reaction of equimolar amounts of cyclooctyne and
hex-3-yne as model compounds we obtained a mixture
of aluminacyclopenta-2,4-dienes VII, I, and VIII at
a ratio of 1.5:1:1 (according to the GLC data for the
hydrolysis products) in an overall yield of ~91%
(Scheme 3). The reaction conditions were optimized so
that to maximize the yield of bicyclic compound VII.
Variation of the reactant ratio, solvent nature, tempera-
ture, and reaction time allowed us to find conditions
ensuring formation of VII in 75% yield (ratio cyclo-
octyne–hex-3-yne–EtAlCl2–Mg–Cp2ZrCl2 10:12:16.5:
16.5:2.2, THF, 20°C, 6 h); in this case, the ratio of
aluminacyclopenta-2,4-dienes VII, I, and VIII was
8:1:2, and the overall yield reached 94%. In the reac-
tion with AlCl3, other conditions being equal, the prod-
uct ratio and the overall yield were almost the same as
in the reaction with EtAlCl2. Minor products VIIIa–
VIIIc were identified by comparing physical prop-
erties and spectral data of the corresponding hydrol-
ysis products XIa–XIc with those of authentic samples
[1]. Bicyclic compound VII was assigned the structure
of 9,10,11-triethyl-9-aluminabicyclo[6.3.0]undeca-
On the basis of the H and 13C NMR and mass
1
spectra, the hydrolysis and deuterolysis products were
identified as 1,1′-bi(cyclooctene) (IIa) and 2,2′-di-
deutero-1,1′-bi(cyclooctene) (IIIa). The formation of
1,4-dideutero derivative IIIa from compound Ia
suggests that the aluminum atom in the latter is linked
to C9 and C11. Therefore, compound Ia was assigned
the structure of 10-ethyl-10-aluminatricyclo[6.9.0.02,9]-
heptadeca-1(11),2(9)-diene.
Like cyclooctyne, the Cp2ZrCl2-catalyzed reaction
of cyclododecyne with EtAlCl2 under analogous condi-
tions led to the formation of 14-ethyl-14-alyuminatri-
cyclo[10.13.0.02,13]pentacosa-1(15),2(13)-diene (Ib) in
64% yield. No appreciable effect on the product yield
was observed when AlCl3 was used instead of EtAlCl2
in the intermolecular cycloalumination of cycloal-
kynes. After acid hydrolysis of organoaluminum com-
pounds Ia′ and Ib′, hydrocarbons IIa and IIb were
isolated from the reaction mixtures in 76 and 65%
yield, respectively.
Aluminacyclopenta-2,4-diene Ia was brought into
reactions with iodine, methyl iodide, and allyl chloride
in the presence of a catalytic amount of copper(I)
chloride (10 mol %). Compound Ia showed high reac-
tivity in these processes, and the corresponding prod-
1
1(8),10-diene on the basis of the H and 13C NMR and
Scheme 2.
MeI, CuCl
Me Me
IVa
I2, CuCl
Al
R
I
I
Va
Ia
CH2=CHCH2Cl
CuCl
H2C
CH2
VIa
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

INTERMOLECULAR CYCLOALUMINATION OF CYCLIC AND ACYCLIC ALKYNES
1293
Scheme 3.
R
EtnAlCl3–n
Cp2ZrCl2, Mg
R
R
R
+
+
+
( )m
R
R
( )m
( )m
R
R
( )m
Al
Et(Cl)
Al
Al
Et(Cl)
VIII
R
Et(Cl)
VII
R
R
D+, D2O
+
+
R
R
R
( )m
( )m
( )m
R' R'
R'
R'
R'
R'
IXa–IXc, Xa–Xc, XIa, XIIa
II, III
XIIIa–XIIIc, XIVa–XIVc
n = 0, 1; IX, X, m = 1; XI, XII, m = 5; IX, XI, R′ = H; X, XII, R′ = D; R = Et (a), Pr (b), Bu (c).
mass spectra of hydrolysis and deuterolysis products
IX and X.
spectra were measured from solutions in CDCl3 on
a JEOL FX-90Q spectrometer at 89.55 (1H) and
22.5 MHz (13C). The yields of organoaluminum com-
pounds were determined by GLC analysis of the
hydrolysis products using n-hexadecane as internal
standard. The complex Cp2ZrCl2 was synthesized from
ZrCl4 according to the procedure described in [12].
Initial cycloalkynes were prepared as reported in [13].
Compounds XIIIa–XIIIc and XIVa–XIVc were iden-
tified by comparison with authentic samples [1].
Our subsequent experiments showed that analogous
pattern is typical of reactions of cyclooctyne with oct-
4-yne and dec-5-yne, as well as of reactions of cyclo-
dodecyne with hex-3-yne. However, the overall yield
decreased from 94 to 67% in going from hex-3-yne to
acetylenes with longer alkyl groups (oct-4-yne and
dec-5-yne) and from cyclooctyne to cyclododecyne
having a larger ring.
Reaction of cycloalkynes with EtnAlCl3–n in the
presence of Cp2ZrCl2 (general procedure). A glass
reactor was filled with dry argon and charged at ~0°C
under stirring with 1.0 mmol of Cp2ZrCl2, 7.5 mmol of
magnesium powder, 10 mmol of cyclooctyne or cyclo-
dodecyne, 10 ml of THF, and 7.5 mmol of EtAlCl2 or
AlCl3. The mixture was allowed to warm up to room
temperature (20–22°C), stirred for 6 h, treated with 7–
10% hydrochloric acid (or a 7–10% solution of DCl in
D2O), and extracted with hexane. The extract was
dried over MgSO4, and the products were isolated by
vacuum distillation.
Thus we were the first to perform Cp2ZrCl2-cata-
lyzed intermolecular cycloalumination of cycloalkynes
and joint cycloalumination of cycloalkynes and linear
internal alkynes with EtnAlCl3–n and obtain new bi-
and tricyclic unsaturated organoaluminum compounds.
The products possess a broad synthetic potential and
attract interest as new co-catalysts for Ziegler–Natta
systems and promising organoaluminum reagents for
organic and organometallic synthesis.
EXPERIMENTAL
All reactions with organometallic compounds were
carried out in a stream of dry argon. Tetrahydrofuran
and diethyl ether were dehydrated by boiling over
metallic sodium. Dichloroethylaluminum (86%) and
trichloroaluminum (99.8%) were commercial products.
Gas–liquid chromatography was performed on
a Chrom-5 instrument (1200×3-mm column packed
with 5% of SE-30 or 15% of PEG-6000 on Chromaton
N-AW; carrier gas helium). The elemental composi-
tions were determined on a Carlo Erba Model 1106
analyzer. The mass spectra (electron impact, 70 eV)
were recorded on an MKh-1306 spectrometer (ion
1,1′-Bi(cyclooctene) (IIa). Yield 78%, bp 121–
1
123°C (1 mm). H NMR spectrum, δ, ppm: 1.10–
1.55 m (16H, CH2), 2.16–2.38 m (8H, CH2CH=),
5.29–5.38 m (2H, CH=). 13C NMR spectrum, δC, ppm:
25.32, 26.17, 27.41, 27.54, 29.36, 30.60, 126.33,
140.23. Found, %: C 87.79; H 11.92. M 218. C16H26.
Calculated, %: C 88.00; H 12.00.
1
(2,2′-2H2)-1,1′-Bi(cyclooctene) (IIIa). H NMR
spectrum, δ, ppm: 1.12–1.58 m (16H, CH2), 2.14–
2.36 m (8H, CH2C=). 13C NMR spectrum, δC, ppm:
25.34, 26.12, 27.45, 27.61, 29.45, 30.63, 126.02 t
(JCD = 23.4 Hz), 140.24. Found, %: C 87.05;
1
source temperature 200°C). The H and 13C NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

D’YAKONOV et al.
1294
H+D 12.76. M 220. C16H24D2. Calculated, %: C 87.20;
H 10.98; D 1.82.
warm up to room temperature, stirred for 6 h, treated
with 5% hydrochloric acid, and extracted with diethyl
ether. The solvent was distilled off, and the residue was
subjected to vacuum distillation.
1,1′-Bi(cyclododecene) (IIb). Yield 64%, bp 210–
1
212°C (1 mm). H NMR spectrum, δ, ppm: 1.05–
1.49 m (32H, CH2), 2.11–2.36 m (8H, –CH2CH=),
5.31–5.41 m (2H, CH=). 13C NMR spectrum, δC, ppm:
26.07, 26.37, 26.56, 26.82, 27.05, 28.09, 28.61, 29.82,
31.38, 32.13, 121.64, 136.72. Found, %: C 87.12;
H 12.75. M 330. C24H42. Calculated, %: C 87.19;
H 12.81.
2,2′-Dimethyl-1,1′-bi(cyclooctene) (Va). Yield
61%, bp 132–133°C (1 mm). H NMR spectrum, δ,
1
ppm: 1.11–1.52 m (16H, CH2), 1.63 s (6H, CH3), 2.17–
2.34 m (8H, CH2C=). 13C NMR spectrum, δC, ppm:
20.14, 25.12, 26.67, 27.51, 28.24, 29.45, 31.67,
136.33, 143.15. Found, %: C 87.42; H 12.01. M 246.
C18H30. Calculated, %: C 87.73; H 12.27.
(2,2′-2H2)-1,1′-Bi(cyclododecene) (IIIb). H NMR
1
spectrum, δ, ppm: 1.08–1.51 m (32H, CH2), 2.14–
2.39 m (8H, CH2C=). 13C NMR spectrum, δC, ppm:
26.08, 26.37, 26.54, 26.86, 27.11, 28.21, 28.68, 29.81,
31.39, 32.23, 121.34 t (JCD = 23.5 Hz), 137.15. Found,
%: C 86.55; H+D 13.21. M 332. C24H40D2. Calculated,
%: C 86.67; H 12.12; D 1.21.
2,2′-Diallyl-1,1′-bi(cyclooctene) (VIa). Yield 55%,
bp 171–173°C (1 mm). H NMR spectrum, δ, ppm:
1
1.08–1.54 m (16H, CH2), 2.15–2.32 m (8H, CH2C=),
2.52–2.74 d (4H, CH2CH=), 4.81–4.89 m (4H, H2C=),
5.57–5.84 m (2H, H2C=CH). 13C NMR spectrum, δC,
ppm: 25.12, 26.31, 26.79, 27.28, 29.37, 32.23, 42.86,
114.35, 136.62, 137.50, 140.72. Found, %: C 87.34;
H 11.27. M 298. C22H34. Calculated, %: C 88.52;
H 11.48.
2,2′-Diiodo-1,1′-bi(cyclooctene) (IVa). A glass
reactor was filled with dry argon and charged at ~0°C
under stirring with 1.0 mmol of Cp2ZrCl2, 7.5 mmol of
magnesium powder, 10 mmol of cyclooctyne or cyclo-
dodecyne, 10 ml of THF, and 7.5 mmol of EtAlCl2 or
AlCl3. The mixture was allowed to warm up to room
temperature (20–22°C), stirred for 6 h, and cooled to
–20°C, 1 mmol of CuCl–2 Ph3P was added, and
a solution of 12.5 mmol of iodine in 8 ml of THF was
slowly added dropwise. The mixture was allowed to
warm up to room temperature, stirred for 3 h, treated
with 5% hydrochloric acid, and extracted with diethyl
ether. The extract was dried over MgSO4, and the
product was isolated by column chromatography on
silica gel L (180–250 μm) using hexane–ethyl acetate
Joint cycloalumination of cycloalkynes and
linear internal alkynes with EtnAlCl3–n in the pres-
ence of Cp2ZrCl2. A glass reactor was filled with dry
argon and charged at ~0°C uner stirring with 2.2 mmol
of Cp2ZrCl2, 16.5 mmol of magnesium powder,
10 mmol of cyclooctyne or cyclododecyne, 12 mmol
of hex-3-yne, oct-4-yne, or dec-5-yne, 15 ml of THF,
and 16.5 mmol of EtAlCl2 or AlCl3. The mixture was
allowed to warm up to room temperature (20–22°C),
stirred for 6 h, treated with 7–10% hydrochloric acid or
a 7–10% solution of DCl in D2O, and extracted with
hexane. The extract was dried over MgSO4, and the
products were isolated by vacuum distillation.
1
(10:1) as eluent. Yield 67%, Rf 0.42. H NMR spec-
trum, δ, ppm: 1.10–1.55 m (16H, CH2), 2.36–2.98 m
(8H, CH2CH=). 13C NMR spectrum, δC, ppm: 25.42,
26.82, 28.09, 31.38, 33.69, 40.34, 101.72, 152.77.
Found, %: C 40.48; H 5.09. C16H24I2. Calculated, %:
C 40.87; H 5.15.
1-[(1E)-1-Ethylbut-1-en-1-yl]cyclooctene (IXa).
Yield 75%, bp 116–117°C (5 mm). 1H NMR spectrum,
δ, ppm: 0.85–0.98 m (6H, CH3), 1.20–1.54 m (8H,
CH2), 1.68–2.31 m (8H, CH2C=), 5.34–5.68 m (2H,
CH=). 13C NMR spectrum, δC, ppm: 14.06, 14.17,
20.96, 23.31, 23.36, 25.32, 26.23, 27.41, 27.54, 30.61,
125.32, 126.98, 140.24, 144.73. Found, %: C 87.35;
H 12.49. M 192. C14H24. Calculated, %: C 87.42;
H 12.58.
Reactions of 10-ethyl-10-aluminatricyclo-
[6.9.0.02,9]heptadeca-1(11),2(9)-diene with methyl
iodide and allyl chloride (general procedure). A glass
reactor was filled with dry argon and charged at ~0°C
under stirring with 1.0 mmol of Cp2ZrCl2, 7.5 mmol of
magnesium powder, 10 mmol of cyclooctyne or cyclo-
dodecyne, 10 ml of THF, and 7.5 mmol of EtAlCl2 or
AlCl3. The mixture was allowed to warm up to room
temperature (20–22°C), stirred for 6 h, and cooled to
–20°C, 1 mmol of CuCl–2 Ph3P was added, and
12.5 mmol of methyl iodide or allyl chloride was
slowly added dropwise. The mixture was allowed to
1-[(1E)-1-Ethyl(2-2H)but-1-en-1-yl](2-2H)cyclo-
1
octene (Xa). H NMR spectrum, δ, ppm: 0.84–0.99 m
(6H, CH3), 1.21–1.53 m (8H, CH2), 1.68–2.30 m (8H,
CH2C=). 13C NMR spectrum, δC, ppm: 14.07, 14.17,
20.94, 23.28, 23.46, 25.34, 26.24, 27.42, 27.57, 30.63,
125.03 t (JCD = 23.4 Hz), 126.67 t (JCD = 24.0 Hz),
140.26, 144.70. Found, %: C 86.45; H+D 13.29.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

INTERMOLECULAR CYCLOALUMINATION OF CYCLIC AND ACYCLIC ALKYNES
1295
M 194. C14H22D2. Calculated, %: C 86.52; H 11.41;
D 2.07.
1-[(1E)-1-Ethyl(2-2H)but-1-en-1-yl](2-2H)cyclo-
dodecene (XIIa). H NMR spectrum, δ, ppm: 0.78–
1
0.95 m (6H, CH3), 1.11–1.53 m (16H, CH2), 1.67–
2.14 m (8H, CH2C=). 13C NMR spectrum, δC, ppm:
13.72, 13.85, 21.78, 22.43, 22.64, 23.15, 24.16, 24.37,
24.41, 24.83, 24.89, 27.44, 30.12, 32.13, 126.28 t
(JCD = 23.4 Hz), 126.37 t (JCD = 23.4 Hz), 141.78,
141.87. Found, %: C 86.27; H+D 13.49. M 250.
C18H30D2. Calculated, %: C 86.32; H 12.07; D 1.61.
1-[(1E)-1-Propylpent-1-en-1-yl]cyclooctene (IXb).
Yield 70%, bp 128–130°C (2 mm). 1H NMR spectrum,
δ, ppm: 0.83–0.96 m (6H, CH3), 1.21–1.56 m (12H,
CH2), 1.67–2.32 m (8H, CH2C=), 5.31–5.66 m (2H,
CH=). 13C NMR spectrum, δC, ppm: 13.87, 14.62,
22.03, 23.28, 23.35, 25.32, 26.21, 27.35, 27.54, 29.94,
30.31, 30.62, 125.21, 126.65, 140.32, 144.68. Found,
%: C 87.05; H 12.76. M 220. C16H28. Calculated, %:
C 87.19; H 12.81.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 05-03-32 367), by the President of the Russian
Federation (project nos. MK-1039.2007.3, NSh-2349.-
2008.3) and by the Foundation for Support of Russian
Science.
1-[(1E)-1-Propyl(2-2H)pent-1-en-1-yl](2-2H)-
1
cyclooctene (Xb). H NMR spectrum, δ, ppm: 0.83–
0.95 m (6H, CH3), 1.22–1.58 m (12H, CH2), 1.67–
2.31 m (8H, CH2C=). 13C NMR spectrum, δC, ppm:
13.79, 14.05, 22.06, 23.19, 23.35, 25.31, 26.24, 27.36,
27.51, 29.98, 30.28, 30.61, 124.91 t (JCD = 23.5 Hz),
126.31 t (JCD = 24.0 Hz), 141.02, 143.89. Found, %:
C 86.37; H+D 13.48. M 222. C16H26D2. Calculated, %:
C 86.41; H 11.78; D 1.81.
REFERENCES
1. Dzhemilev, U.M., Ibragimov, A.G., Khafizova, L.O.,
Yakupova, L.R., and Khalilov, L.M., Russ. J. Org.
Chem., 2005, vol. 41, p. 673.
2. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P.,
Muslukhov, R.R., and Tolstikov, G.A., Izv. Akad. Nauk
SSSR, Ser. Khim., 1989, p. 207.
1-[(1E)-1-Butylhex-1-en-1-yl]cyclooctene (IXc).
Yield 58%, bp 135–137°C (1 mm). 1H NMR spectrum,
δ, ppm: 0.82–0.97 m (6H, CH3), 1.22–1.56 m (16H,
CH2), 1.65–2.31 m (8H, CH2C=), 5.32–5.64 m (2H,
CH=). 13C NMR spectrum, δC, ppm: 14.05, 14.32,
22.05, 23.26, 23.31, 25.38, 26.25, 27.34, 27.55, 27.64,
27.83, 29.98, 30.32, 30.61, 125.42, 126.64, 140.30,
144.69. Found, %: C 86.95; H 12.86. M 248. C18H32.
Calculated, %: C 87.02; H 12.98.
3. Dzhemilev, U.M. and Ibragimov, A.G., Usp. Khim.,
2000, vol. 69, p. 134.
4. Dzhemilev, U.M. and Ibragimov, A.G., Izv. Ross. Akad.
Nauk, Ser. Khim., 1998, p. 816.
5. Dzhemilev, U.M., Tetrahedron, 1995, vol. 51, p. 4333.
6. Dzhemilev, U.M. and Ibragimov, A.G., J. Organomet.
Chem., 1994, vol. 466, p. 1.
1-[(1E)-1-Butyl(2-2H)hex-1-en-1-yl](2-2H)cyclo-
7. Kondakov, D.Y. and Negishi, E., J. Am. Chem. Soc.,
1
octene (Xc). H NMR spectrum, δ, ppm: 0.82–0.95 m
1996, vol. 118, p. 1577.
(6H, CH3), 1.22–1.57 m (16H, CH2), 1.65–2.32 m (8H,
CH2C=). 13C NMR spectrum, δC, ppm: 14.02, 14.28,
22.07, 23.18, 23.35, 25.32, 26.26, 27.36, 27.52, 27.59,
27.82, 29.91, 30.21, 30.66, 125.12 t (JCD = 23.5 Hz),
126.38 t (JCD = 24.5 Hz), 141.02, 144.89. Found, %:
C 86.27; H+D 13.46. M 250. C18H30D2. Calculated, %:
C 86.32; H 12.07; D 1.61.
8. Negishi, E. and Kondakov, D.Y., Chem. Soc. Rev., 1996,
vol. 26, p. 417.
9. Negishi, E., Kondakov, D.Y., Choueiry, D., Kasai, K.,
and Takahashi, T., J. Am. Chem. Soc., 1996, vol. 118,
p. 9577.
10. Lewis, D.P., Whitby, R.J., and Jones, R.V.H., Tetra-
hedron, 1995, vol. 51, p. 4541.
11. Dorman, D.E., Jautelat, M., and Roberts, J.D., J. Org.
Chem., 1971, vol. 36, p. 2757.
1-[(1E)-1-Ethylbut-1-en-1-yl]cyclododecene
1
(XIa). Yield 68%, bp 156–158°C (10 mm). H NMR
12. Ioffe, S.T. and Nesmeyanov, A.M., Metody elemento-
organicheskoi khimii. Podgruppa magniya, berilliya,
kal’tsiya, strontsiya, bariya (Methods of Organometallic
Chemistry. Magnesium, Beryllium, Calcium, Strontium,
and Barium Subgroup), Moscow: Akad. Nauk SSSR,
1963.
spectrum, δ, ppm: 0.79–0.95 m (6H, CH3), 1.13–
1.52 m (16H, CH2), 1.68–2.16 m (8H, CH2C=), 5.24–
5.36 m (2H, CH=). 13C NMR spectrum, δC, ppm:
13.70, 13.86, 21.77, 22.43, 22.62, 23.11, 24.05, 24.38,
24.48, 24.83, 24.93, 27.44, 30.11, 32.13, 126.59,
126.95, 141.79, 141.99. Found, %: C 86.94; H 12.86.
M 248. C18H32. Calculated, %: C 87.02; H 12.98.
13. Brandsma, L. and Verkruijsse, H.D., Synthesis, 1978,
p. 290.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008