Cycloaluminizing of acetylenes and 1,4-enynes in the presence of Zr-containing catalysts

Article abstract of DOI:10.1007/s11178-005-0224-9

Synthetic procedures were developed for preparation of substituted alumacyclopenta-2,4-dienes and 1-ethyl-2(3)-(1-ethyl-3-alumacyclopentylmethyl)- 3(2)-alkyl(phenyl)alumacyclopent-2-enes by cycloaluminizing acetylenes and 1,4-enynes using RAlCl₂

Full text of DOI:10.1007/s11178-005-0224-9

Russian Journal of Organic Chemistry, Vol. 41, No. 5, 2005, pp. 667-672. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005,
pp. 684-689.
Original Russian Text Copyright Ó 2005 by Dzhemilev, Ibragimov, Khafizova, Yakupova, Khalilov.
Cycloaluminizing of Acetylenes and 1,4-Enynes in the Presence
of Zr-containing Catalysts
U.M. Dzhemilev,A.G. Ibragimov, L.O. Khafizova, L.R. Yakupova, and L.M. Khalilov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075 Russia
e-mail: ink@anrb.ru
Received July 22, 2004
Abstract—Synthetic procedures were developed for preparation of substituted alumacyclopenta-2,4-dienes and
1-ethyl-2(3)-(1-ethyl-3-alumacyclopentylmethyl)-3(2)-alkyl(phenyl)alumacyclopent-2-enes by cycloaluminizing
acetylenes and 1,4-enynes using RAlCl2 (R = Et, BuO, Et2N) and Et3Al in the presence of Zr-containing catalysts
(Cp2ZrCl2, ZrCl4).
According to published data [1–3] the catalytic
cycloaluminizing of a-olefins, 1,2-dienes, and acetylenes
using trialkyl- and alkylhaloalanes afforded aluma-
cyclopropanes, alumacyclopropenes, alumacyclopentanes,
and alumacyclopentenes that in the course of a “one-
pot” process were converted into practically important
1,3-dienes [4], secondary and tertiary alcohols [5],
cyclopropanes [6], cyclobutanes [7], cyclopentanols [8],
and five-membered heterocycles [9, 10]. The published
data on preparative procedures for substituted
alumacyclopenta-2,4-dienes [11, 12] are virtually lacking.
(20–22°C, THF, 8 h) resulted in 1-ethyl-2,3,4,5-tetra-
alkylalumacyclopentadienes Ia–Ic in 80–90% yields.
The reaction products were identified by their 13C NMR
spectra and by deuterolysis products II (Scheme 1). For
instance, in the 13C NMR spectrum of compound Ia the
characteristic signals of the ethyl group cabon at
2.15 ppm and of sp2-hybridized C2 and C5 atoms at
140.19 ppm are broadened due to the quadrupole
interaction with the Al atom (I 5/2). The triplet signal at
123.18 ppm with a characteristic value of the direct
coupling constant JCD 24.0 Hz in the spectrum of
deuterolysis product IIa corresponds to C3 and C6 atoms
linked to deuterium. In the 13C NMR spectra of com-
pounds Ib and Ic analogous signals were observed. To
obtain a more reliable proof of the structure of aluma-
cyclopentadienes we carried out the reaction of compound
Ia (Scheme 1) with maleic anhydride along the [4+2]-
cyclization pattern to furnish adduct IV. The hydrolysis
of compound IV gave tetrahydro-3,4,5,6-tetraethyl-o-
phthalic anhydride (V) that contained in the 13C NMR
spectrum signals at 172.44 ppm characteristic of carbonyl
group.
In the reaction mixtures hexaalkylsubstituted benzenes,
products of cyclotrimerization of the initial acetylenes,
were found in minor amounts (5–10%) [12], and also
substituted alumacyclopropenes were present (5–8%).
The latter are target products (65–90%) of analogous
reaction catalyzed by Cp2TiCl2 [12].At application of ZrCl4
(5 mol%) in this reaction the yield of alumacyclo-
pentadienes Ia–Ic was ~70%, however, the content of
homotrimerization product of the initial acetylene in the
reaction mixture increased.
Aiming at extension of applications for cyclo-
aluminizing of unsaturated compounds catalyzed by
transition metal complexes and with a goal of developing
synthetic procedures for substituted alumacyclopenta-2,4-
dienes we studied reactions of mono- and disubstituted
acetylenes and 1,4-enynes [4-octyne, 5-decyne, phenyl-
methylacetylene, phenylallylacetylene, 1-heptyne, butyl-
(amyl, phenyl)allylacetylenes] with RAlCl2 (R = Et, BuO,
Et2N) and Et3Al in the presence of Zr-containing catalysts
which were the most active in cycloaluminizing of
unsaturated compounds [1, 2]. In experiments with
RAlCl2 we used magnesium metal as chlorine ions
acceptor [13].
We presumed that the reduction of zirconcocene
dichloride (Cp2ZrCl2) with Mg in the presence of
disubstituted acetylenes afforded zirconacyclopentadienes
[14] that would be capable of transmetallation [15] by
EtAlCl2 into the corresponding alumacyclopentadienes.
We established by our investigations that the reaction of
3-hexyne, 4-octyne, and 5-decycne with EtAlCl2 in the
presence of metallic Mg and Cp2ZrCl2 catalyst taken in
molar ratio 100:75:75:10 under given reaction conditions
The reaction of EtAlCl2 with phenylmethylacetylene
and phenylallylacetylene furnished regioisomeric organo-
1070-4280/05/4105-0667Ó2005 Pleiades Publishing, Inc.

DZHEMILEV et al.
668
Scheme 1.
5
5
5
5
5
5
0Jꢀꢁ>=U@
0J&O
' 2
5
(W$O&O
5
5
5
5
5
5
5
$O
' '
' '
(W
,D ,H
,,D ,,H
,,,Gꢀꢁ,,,H
2
(W
$O (W
(W
+
ꢂDꢃ
2
2
(W
(W
2
2
+ 2
2
2
(W
(W
ꢄꢅ &ꢀꢁꢆꢁ
(W
(W
+
2
2
,9
9
I–III, R1 = R2 = Et (a), Pr (b), Bu (c); R1 = Ph, R2 =All (d), Me (e).
Scheme 2.
5ꢈ
5ꢈ
5ꢈ
0Jꢀꢁ>=U@
ꢇ
5$O&O
5ꢈ
5ꢈ
5ꢈ
5ꢈ
0J&O
$O
$O
$O
5
9,,,
5
9,,
5
9,
' 2
5ꢈ
5ꢈ
5ꢈ
5ꢈ
5ꢈ
5ꢈ
' '
' '
' '
,;
;
;,
R = Et, BuO, Et2N; R' =Amyl.
aluminum compounds Id and Ie that on deuterolysis were
converted into 1,4-dideutero-1,3-butadienes IId and IIe,
IIId and IIIe in a ratio ~ 3:1. The cycloaluminizing of 1-
heptyne with RAlCl2 (R = Et, BuO, Et2N) in the presence
of Mg and 10 mol% of Cp2ZrCl2 with respect to the
acetylene (THF, 21–22°C, 12 h) furnished a mixture of
regioisomeric trisubstituted alumacyclopentadienes in
a ratio VI:VII:VIII ~ 2:2:1 and an overall yield 55–60%,
that were identified by analysis of the deuterolysis
products IX–XI. Like in the reactions with disubstituted
acetylenes here also formed in minor amounts (5–25%)
the regioisomeric trialkylbenzenes, the cyclotrimerization
products of the initial acetylenes (Scheme 2).
XII, and from 1,4-enynes and Et3Al under catalysis with
Cp2ZrCl2 (1,4-enyne:[Al]:[Zr] = 10:25:0.5) under the
reaction conditions (~20°C, 8 h, hexane) a mixture of
regioisomeric 2,3-disubstituted alumacyclopent-2-enes
XIIIa and XIIIb could be obtained with the retention of
the allyl double bond [17].
We found that the reaction of 1,4-enynes with fourfold
excess of Et3Al in the presence of 10–15 mol% of
Cp2ZrCl2 catalyst with respect to the initial 1,4-enyne at
20–21°C in 8–10 h gave rise to regioisomeric (aluma-
cyclopent-3-ylmethyl)alumacyclopent-2-enes XIVa and
XIVb, and XVa and XVb that were identified by con-
version into partly deuterated compounds XVIa, XVIb/
XVIIa, XVIIb ~ 1:1, and also by transformation into 1,1-
dialkyl-substituted cyclopropanes XVIIIb/XIXb ~ 1:1
effected by Me2SO4 [18]. The phenylallylacetylene, in
It was shown formerly [16], that the cycloaluminizing
of 1,6- and 1,7-enynes with Et3Al in the presence of
Cp2ZrCl2 catalyst gave bicycloalumacyclopent-2-enes
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

CYCLOALUMINIZINGOFACETYLENESAND1,4-ENYNES
669
Scheme 3.
6L0H
5
6L0H
ꢀ&+ ꢁ
5
5
$O(W
$O (W
ꢀ&+ ꢁ
$O
(W
$O
(W
>=U@
>=U@
;,,,D
;,,,E
;,,
R = Bu (a),Amyl (b), Ph (c).
Scheme 4.
5
$O (W
>=U@
$O (W
$O(W
5
5
$O
(W
$O
(W
;,9Dꢀꢁ;,9E
;9D ;9F
0H 62
' 2
ꢀ
ꢀ
5
ꢀ
ꢀ
'
'
'
'
5
5
ꢀ
ꢀ
' '
ꢀ
ꢀ
' '
;9,Dꢀꢁ;9,E
;,;Eꢀꢁ;,;F
;9,,D ;9,,F
;9,,,E
contrast to alkylallylacetylenes, in this reaction gave rise
predominantly to regioisomer XVc (~75%) identified by
analysis of the corresponding deuterolysis product XVIIc
and 1,1-disubstituted cyclopropane XIXc (Scheme 4).
solutions in CDCl3 on a spectrometer JEOL FX-90 Q
[89.55 (1H) and 22.5 MHz (13C)]. Yields of compounds
were estimated by GLC of the hydrolysis products. The
separation of regioisomer mixtures was carried out on a
preparative gas chromatograph Carlo Erba Fractovap
Mod.GW, carrier gas He, column 4000´6 mm, stationary
phase SE-30.
Hence the reaction of acetylenes with RAlCl2–Mg or
1,4-enynes with Et3Al catalyzed by Zr compounds permits
preparation under mild conditions in sufficient yields of
the substituted alumacyclopentadienes and (alumacyclo-
pent-3-ylmethyl)alumacyclopent-2-enes. These findings
open the way to the synthesis of new types of five-
membered unsaturated cyclic organoaluminum
compounds promising for the designed synthesis of
heterocycles and the other valuable synthons for the
organic synthesis.
In the study commercial 86% EtAlCl2 and 98% Et3Al
(Public Joint Stock Co “Redkinskii Opytnyi Zavod”) were
used as received. The initial aluminum amides and
alkoxides were prepared by known procedures [19, 20].
The reactions with organometallic compounds were
carried out in an atmosphere of dry argon. THF was
distilled from LiAlH4 just before use.
Reactions of acetylenes with EtAlCl2 catalyzed
by Cp2ZrCl2. General procedure. Into a glass reactor
in an atmosphere of dry argon at ~0°C while stirring was
charged 1.0 mmol of Cp2ZrCl2, 7.5 gram-atom of
powdered Mg, 10 mmol of acetylene, 10 ml of THF, and
7.5 mmol of EtAlCl2. The reaction mixture was warmed
to the room temperature (20–22°C), and the stirring was
continued for 8 h. To identify the substituted aluma-
cyclopentadienes (for instance, Ia) by its 13C NMR
EXPERIMENTAL
Products of hydrolysis and deuterolysis were analyzed
on a chromatograph Chrom-5, carrier gas He, column
1200´3 mm, stationary phase 5% SE-30 or 15% PEG-
6000 on Chromaton N-AW. IR spectra were recorded
on spectrometer 75IR (from films), mass spectra were
measured on an MKh-1306 instrument at 70 eV and
1
13
200°C. H and C NMR spectra were registered from
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

DZHEMILEV et al.
670
spectrum the solvent and unreacted acetylene from the
reaction mixture was distilled off in a vacuum, Mg was
precipitated from the residue by centrifugation, and under
argon the substance thus obtained was transferred into
the NMR tube. The identification of the substituted
alumacyclopentadienes by the deuterolysis products was
performed as follows: The reaction mixture was treated
with an 8% DCl solution in D2O, the products were
extracted with ether or hexane, and dried with MgSO4.
Compounds IIa–IIc and regiisomers mixture IId, IIe,
IIId, and IIIe, IX-XI were isolated by vacuum
distillation, regiisomers IId, IIe, IIId, and IIIe were
separated by column chromatography on silica gel L,100/
250m, eluent benzene–ethyl acetate, 5:1, partitioning of
IX–XI was performed by preparative GLC. Compound
IIb was identified by comparison with an authentic sample
[12].
=C–CH2). 13C NMR spectrum, d, ppm: 13.66, 14.10
(C1,12), 22.54, 22.87 (C2,11), 27.81 (C3,10), 28.00 (C4,9),
31.10, 31.25, 125.81 t (C5,8, JCD 24 Hz), 141.22 (C6,7).
Found, % : C 85.45; (H+D) 14.17. [M]+ 142. C20H36D2.
Calculated, % : C 85.63; H 12.94; D 1.43. M 142.
4,5-Bis[deutero(phenyl)methylidene]octa-1,7-
–1
diene (IIg). Yield 56%, Rf 0.52. IR spectrum, cm : 3050,
3010, 2950, 2920, 2860, 2175 (CD), 1950, 1600, 1490,
1440, 1380, 1230, 1030, 910, 750, 700. 1H NMR spectrum,
d, ppm : 2.54–2.77 m (4H, =–CH2–=), 4.91–5.20 m (4H,
CH2=), 5.85–6.30 m (2H, =CH–), 7.04–7.83 m (10H,
C6H5). 13C NMR spectrum, d, ppm: 32.82 (C3,6), 118.21
(C1,8), 115.92 t (JCD 23.5 Hz), 126.86, 128.23 (2C), 128.54
(2C), 131.60 (C2,7), 136.75 (C6H5), 144.02 (C4,5). Found,
%: C 91.43; (H+D) 8.17. [M]+ 288. C22H20D2. Calculat-
ed, % : C 91.62; H 6.99; D 1.39. M 288.
1-(1,4-Dideutero-2,3-dimethyl-4-phenylbuta-1,3-
dienyl)benzene (IIe). Yield 54%, Rf 0.48. IR spectrum,
cm : 3050, 3010, 2960, 2910, 2850, 2180 (CD), 1950,
To obtain adduct IV alumacyclopentadiene Ia formed
in situ under the reaction conditions was treated at –5°C
with 12 mmol of maleic anhydride, and the reaction
mixture was stirred at room temperature for 7 h. Then
the reaction mixture at –10°C was treated with 10% HCl.
Product V was extracted with ether or hexane, dried over
MgSO4, and the solvent was removed in a vacuum.
–1
1710, 1680, 1590, 1530, 1490, 1440, 1250, 1170, 1020,
795, 750, 695. 1H NMR spectrum, d, ppm: 2.14 s (6H,
CH3), 7.06–7.40 m (10H, C6H5). 13C NMR spectrum, d,
ppm: 15.81, 118.26 t (JCD 22.5 Hz), 127.48, 128.23 (2C),
129.52 (2C), 138.75 (C6H5), 139.03. Found, %: C
91.31; (H+D) 8.32. [M]+ 236. C18H16D2. Calculated, %:
C 91.48; H 6.83; D 1.69. M 236.
1-Ethyl-2,3,4,5-tetraethylalumacyclopenta-2,4-
diene (Ia). 13C NMR spectrum, d, ppm: 2.15 br.s (Al–
CH2–CH3), 9.91 (Al–CH2–CH3), 14.02, 14.28, 22.43,
22.67, 140.19 br.s (C2,5), 153.15 (C3,4).
4-Deutero-6-[deutero(phenyl)methylidene]-5-
phenylnona-1,4,8-triene (IIId). Yield 19%, Rf 0.45.
–1
1
IR spectrum, cm : 2175 (CD). H NMR spectrum, d,
ppm: 2.55–2.77 m (4H, =–CH2–=), 4.85–5.22 m (4H,
CH2=), 5.85–6.30 m (2H, =CH–), 7.00–7.83 m (10H,
C6H5). 13C NMR spectrum, d, ppm: 26.57 (C7), 33.99
(C3), 113.13 (C9), 121.58 (C1), 126.85, 128.21 (2C),
128.54 (2C), 128.73 t (C6, JCD 22.0 Hz), 131.62 (C2),
132.44 (C8), 137.06 (C6H5), 139.46 (C4), 141.42 (C6H5),
144.02 (C5). The signal of carbon atom linked to deuterium
and phenyl at a double bond was not observed. Found,
%: C 91.44; (H+D) 8.18. [M]+ 288. C22H20D2. Calculat-
ed, % : C 91.62; H 6.99; D 1.39. M 288.
1-Ethyl-2,3,4,5-tetrapropylalumacyclopenta-2,4-
13
diene (Ib). C NMR spectrum, d, ppm: 2.71 br.s (Al–
CH2–CH3), 10.32 (Al–CH2–CH3), 13.63, 14.02, 22.28,
23.38, 29.43, 31.06, 140.63 br.s (C2,5), 153.30 (C3,4).
1-Ethyl-2,3,4,5-tetrabutylalumacyclopenta-2,4-
13
diene (Ic). C NMR spectrum, d, ppm: 2.77 br.s (Al–
CH2–CH3), 10.51 (Al–CH2–CH3), 13.00, 13.24, 22.02,
23.64, 26.05, 27.29, 28.85, 31.25, 140.70 br.s (C2,5), 151.17
(C3,4).
3,6-Dideutero-4,5-diethylocta-3,5-diene (IIa).
–1
Yield 90%, bp 80–82°C (1 mm Hg). IR spectrum, cm :
1-[2-Deutero-1-(2-deutero-1-methyl-2-phenyl-
2175 (CD). 1H NMR spectrum, d, ppm: 0.88–1.00 m (12H,
CH3), 1.97–2.16 m (8H, =C–CH2). 13C NMR spectrum,
d, ppm: 14.15 (C1,8), 14.21, 22.19 (C2,7), 22.35, 123.18 t
(C3,6, JCD 24 Hz), 139.61 (C4,5). Found, %: C 85.47;
(H+D) 14.16. [M]+ 168. C12H20D2. Calculated, %:
C 85.64; H 11.98; D 2.38. M 168.
ethenyl)-1-propenyl]benzene (IIIe). Yield 18%,
–1
1
Rf 0.42. IR spectrum, cm : 2180 (CD). H NMR
spectrum, d, ppm: 1.55 d (3H, CH3, J 7.0 Hz), 1.72 s
13
(3H, CH3), 6.78–7.29 m (10H, C6H5). C NMR spec-
trum, d, ppm: 18.57, 22.28, 123.27 t (C–Ph, JCD 23.5 Hz),
126.13, 126.59, 128.08 (4C), 129.25 (4C), 133.03 t
(=CHD–CH3, JCD 23.5 Hz), 137.77 (C6H5), 138.55 (=C–
CH3), 139.79 (C6H5), 145.51 (=C–Ph). Found, %:
C 91.29; (H+D) 8.30. [M]+ 236. C18H16D2. Calculat-
ed, %: C 91.48; H 6.83; D 1.69. M 236.
5,7-Dideutero-6,7-dibutyldodeca-5,7-diene (IIc).
–1
Yield 80%, bp 143–145°C (2 mm Hg). IR spectrum, cm :
1
2170 (CD). H NMR spectrum, d, ppm: 0.88–1.00 m
(12H, CH3), 1.13–1.72 m (16H, CH2), 1.97–2.16 m (8H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005

CYCLOALUMINIZINGOFACETYLENESAND1,4-ENYNES
671
1,7,8,9,10-Pentaethyl-4-oxo-10-alumatricyclo-
[5.2.1.02,6]dec-8-ene-3,5-dione (IV). 13C NMR spec-
trum, d, ppm (C6D6): 7.15 (Al–CH2–CH3), 9.60 (Al–
CH2–CH3), 12.50, 14.13, 20.18, 25.70, 40.86, 42.79,
135.91, 172.77.
argon at ~0°C while stirring was charged 1.5 mmol of
Cp2ZrCl2, 10 mmol of an appropriate 1,4-enyne, 10 ml of
hexane, and 40 mmol of Et3Al. The reaction mixture was
warmed to the room temperature (20–22°C), and the
stirring was continued for 8-10 h. The reaction mixture
was treated with 8% DCl in D2O. The reaction products
were extracted with ether or hexane, the extracts were
dried with MgSO4, passed through a small bed of aluminum
oxide, the solvent was distilled off, and the residue was
subjected to a fractional distillation in a vacuum.
4,5,6,7-Tetraethyl-3a,4,7,7a-tetrahydro-1,3-iso-
–1
benzofurandione (V). Yield 85%. IR spectrum, cm :
1
1670 (C=O). H NMR spectrum, d, ppm: 0.80 t (6H,
CH3, J 7.0 Hz), 1.22 t (6H, CH3, J 7.0 Hz), 1.78–1.89 m
(2H, CH), 1.98–2.18 m (8H, CH2), 3.30–3.88 m (2H,
CH). 13C NMR spectrum, d, ppm: 12.23, 14.65, 19.82,
20.40, 40.32 (C4,7), 42.56 (C3,8), 138.08 (C5,6), 172.24
(C2,9). Found, %: C 72.48; H 8.96. [M]+ 264. C16H24O3.
Calculated, % : C 72.69; H 9.15. M 264.
The 1,1-disubstituted cyclopropanes were obtained by
adding dropwise at 0°C 42 mmol of dimethyl sulfate to
the stirred solutions of bicyclic organoaluminum compounds
XIVb and XVb obtained in situ under reaction conditions.
The reaction mixture was stirred for 12 h at 20°C. Then
the reaction mixture was subjected to hydrolysis with 10%
HCl. The organic substances were extracted into ether
or hexane, the extract was washed with Na2CO3 till
neutral reaction, and dried with CaCl2. The reaction
products were isolated by vacuum distillation.
1,4-Dideutero-2(pentyl)nona-1,3-diene (IX).
–1
Yield 24%, nD20 1.4568. IR spectrum, cm : 3080, 2970,
2920, 2180 (CD), 1640, 1380, 1480, 970, 890, 790, 720.
1H NMR spectrum, d, ppm: 0.89 t (6H, CH3, J 6.8 Hz),
1.13–1.72 m (12H, CH2), 1.97–2.16 m (4H, =C–CH2),
4.85 s (1H, CHD=C), 6.04 s (1H, CH=). 13C NMR
spectrum, d, ppm: 14.22, 22.67, 22.80, 27.09, 29.50, 31.58,
31.90, 32.17, 33.73, 136.45 (C3), 149.68 (C2). The signals
of carbon atoms linked to deuterium at a double bond
were not observed. Found, %: C 84.59; (H+D) 15.02.
[M]+ 198. C14H26D2. Calculated, % : C 84.77; H 13.21;
D 2.02. M 198.
(Z)-1,5-Dideutero-6-(2-deuteroethyl)-3-
(deuteromethyl)dec-5-ene (XVIa)/(Z)-1,6-di-
deutero-5-(2-deuteroethyl)-3-(deutero-methyl)dec-
5-ene (XVIIa) ~(1:1). Yield 78%, bp 65–69°C (2 mm
Hg). 1H NMR spectrum, d, ppm: 0.78–0.98 m (9H, CH3,
CH2D), 1.04–1.48 m (7H, CH, CH2), 1.88–2.14 m (6H,
CH2–=). 13C NMR spectrum (XVIa), d, ppm: 11.47 t
(J 19.1 Hz), 12.86 (C1, J 19.1 Hz), 14.20 (C10), 18.90 t
(J 19.1 Hz), 22.96 (C9), 28.09, 29.80 (C8), 30.17 (C2),
31.26 (C7), 34.71 (C4), 37.43 (C3), 121.87 (C5,
J 22.0 Hz), 139.50 (C6). 13C NMR spectrum (XVIIa), d,
ppm: 11.47 t (J 19.1 Hz), 12.88 t (C1, J 19.1 Hz),
14.20 (C10), 18.97 t (J 19.1 Hz), 22.96 (C9), 28.46,
29.80 (C8), 30.40 (C2), 32.31 (C7), 33.45 (C4), 35.72 (C3),
123.85 t (C6, J 22 Hz), 141.67 (C5). Found, %: C 84.42;
(H+D) 12.58. [M]+186. C13H22D4. Calculated, %:
C 83.80; H 11.90; D 4.30. M 186.
6,9-Dideuterotetradeca-6,8-diene (X). Yield 24%,
nD20 1.4436. IR spectrum, cm : 3030, 2950, 2920, 2850,
–1
2180 (CD), 1640, 1480, 1380, 990, 950, 790, 720. 1H NMR
spectrum, d, ppm: 0.88 t (6H, CH3, J 7.0 Hz), 1.10–
1.72 m (12H, CH2), 1.97–2.30 m (4H, –CH2–C=),
5.99 s (2H, –HC=CD–). 13C NMR spectrum, d, ppm:
14.09, 22.61, 25.01, 31.90, 32.75, 133.35 (C7,8). The
signals of carbon atoms linked to deuterium at a double
bond were not observed. Found, %: C 84.43; (H+D)15.00.
[M]+ 196. C14H26D2. Calculated, %: C 84.59; H 13.21;
D 2.02.
(Z)-6-Deuteroethyl-3-deuteromethyl-1,5-di-
deuteroundec-5-eneen (XVIb)/(Z)-1,6-dideutero-5-
(2-deuteroethyl)-3-(deuteromethyl)undec-5-ene
(XVIIb) ~(1:1). Yield 80%, bp 65–68°C (1 mm Hg). 1H
NMR spectrum, d, ppm: 0.78–0.98 m (9H, CH3, CH2D),
1.05–1.50 m (9H, CH, CH2), 1.82–2.18 m (6H, CH2 –=).
13C NMR spectrum (XVIb), d, ppm: 11.49 t (C1,
J 19.1 Hz), 12.85 t (J 19.1 Hz), 14.22 (C11), 18.96 t
(J 19.1 Hz), 22.93 (C10), 28.07, 29.50 (C8), 29.76 (C9),
30.15 (C2), 32.04 (C7), 34.77 (C4), 37.43 (C3), 121.97 t
(C5, J 22.00 Hz), 139.59 (C6). 13C NMR spectrum
(XVIIb), d, ppm: 11.49 t (J 19.1 Hz), 12.85 t (C1,
1,4-Dideutero-2,3-di(pentyl)buta-1,3-diene (XI).
–1
1
Yield 12%. IR spectrum, cm : 2175 (CD). H NMR
spectrum, d, ppm: 0.89 t (6H, CH3, J 7.0 Hz), 1.13–
1.72 m (12H, CH2), 1.97–2.16 m (4H, =C–CH2), 4.69 s
(2H, –C=CHD). 13C NMR spectrum, d, ppm: 14.15,
22.67, 28.19, 29.23, 31.96, 146.68 (C2,3). The signals of
carbon atoms linked to deuterium at a double bond were
not observed. Found, %: C 84.40; (H+D) 14.98. [M]+
196. C14H26D2. Calculated, %: C 84.59; H 13.21; D 2.02.
Reactions of 1,4-enynes with Et3Al catalyzed by
Cp2ZrCl2. Into a glass reactor in an atmosphere of dry
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DZHEMILEV et al.
672
J 19.1 Hz), 14.22 (C11), 18.96 t (J 19.1 Hz), 22.93 (C10),
28.46, 29.50 (C8), 29.76 (C9), 30.41 (C2), 32.36 (C7), 33.47
(C4), 35.74 (C3), 124.64 t (C6, J 22.0 Hz), 141.61 (C5).
Found, % : C 85.43; (H+D) 12.58. [M]+ 200. C14H24D4.
Calculated, % : C 85.64; H 12.32; D 2.04. M 200.
REFERENCES
1. Dzhemilev, U.M., Tetrahedron, 1995, vol. 51, p. 4333.
2. Dzhemilev, U.M. and Ibragimov,A.G., Izv. Akad. Nauk, Ser.
Khim., 1998, p. 816.
3. Dzhemilev, U.M. and Ibragimov, A.G., Usp. Khim., 2000,
vol. 69, p. 134.
4. Ibragimov,A.G., Zolotarev,A.P., Muslukhov, R.R., Lomaki-
na, S.I., and Dzhemilev, U.M., Izv. Akad. Nauk, Ser. Khim.,
1995, p. 118.
1-[(Z)-1,6-Dideutero-2-(2-deuteroethyl)-4-
(deuteromethyl)-1-hex-1-enyl]benzene (XVIIc).
Yield 75%, bp 102–103°C (2 mm Hg). IR spectrum,
–1
cm : 3400, 2950, 2910, 2855, 2170 (CD), 1700, 1600,
1450, 750, 700. 1H NMR spectrum, d, ppm: 0.72–0.99 m
(6H, CH2D), 1.06–1.73 m (3H, CH, CH2), 2.08–2.23 m
(4H, CH2–=), 7.02–7.56 m (5H, C6H5). 13C NMR
spectrum, d, ppm: 11.56 t (J 19.1 Hz), 12.79 t (C6,
J 19.1 Hz), 19.02 t (J 19.1 Hz), 29.66, 29.99 (C5), 32.84
(C3), 37.45 (C4), 125.63, 127.90 (2C), 128.94 (2C), 139.01
(C6H5), 143.99 (C2). The signal of carbon atom linked to
deuterium at a double bond was not observed. Found, %:
C 87.12; (H+D) 12.49. [M]+ 206. C15H18D4. Calculated,
%: C 87.33; H 8.79; D 3.88. M 206.
5. Khafizova, L.O., Ibragimov,A.G., Yalalova, D.F., Boriso-
va, A.L., Khalilov, L.M., and Dzhemilev, U.M., Izv. Akad.
Nauk, Ser. Khim., 2003, p. 1905.
6. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P., Mus-
lukhov, R.R., and Tolstikov, G.A., Izv. Akad. Nauk, Ser.
Khim., 1990, p. 1190.
7. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P., Mus-
lukhov, R.R., and Tolstikov, G.A., Izv. Akad. Nauk, Ser.
Khim., 1989, p. 2152.
8. Dzhemilev, U.M., Ibragimov,A.G., Khafizova, L.O., Gilya-
zev, R.R., and D’yakonov, V.A., Izv. Akad. Nauk, Ser. Khim.,
2004, p. 130.
9. Dzhemilev, U.M., Ibragimov, A.G., Zolotarev, A.P., and
Tolstikov, G.A., Izv. Akad. Nauk, Ser. Khim., 1989, p. 1444.
10. Dzhemilev, U.M., Ibragimov, A.G., Gilyazev, R.R., and
Khafizova, L.O., Tetrahedron, 2004, vol. 60, p. 1281.
11. Negishi, E., Kondakov, D.Y., Choueiry, D., Kasai, K., and
Takahashi, T., J. Am. Chem. Soc., 1996, vol. 116, p. 9577.
12. Dzhemilev, U.M., Ibragimov, A.G., Ramazanov, I.R., and
Khalilov, L.M., Izv. Akad. Nauk, Ser. Khim., 1997, p. 2269.
13. Negishi, E., Holmes, S.J., Tour, J.M., and Miller, J.A., J. Am.
Chem. Soc., 1985, vol. 107, p. 2568.
2,4-Dimethyl-2-(1-pentylcyclopropyl)hexane
(XVIIIb)/2-methyl-2-[1-(2-methylbutyl)cyclo-
propyl]heptane (XIXb) ~(1:1). Yield 76%, bp 121–
–1
124°C (2 mm Hg). IR spectrum, cm : 3080, 2950, 2900,
2850, 2170 (CD), 1450, 1380, 1140, 800, 760. 1H NMR
spectrum, d, ppm: 0.10–0.22 m (2H, CH2, c-Pr), 0.36–
0.48 m (2H, CH2, c-Pr), 0.74–0.98 m (5H, CH3), 1.17–
13
1.58 m (3H, CH2, CH). C NMR spectrum (XVIIIb),
d, ppm: 7.27, 7.36 (c-Pr), 11.68 (C6), 14.22, 20.98, 22.87,
24.10 (c-Pr), 25.08 (2C), 26.51, 30.93 (C5), 32.75 (C4),
32.88, 33.08, 35.22 (C2), 40.42 (C3). 13C NMR spectrum
(XIXb), d, ppm: 6.92, 6.78 (c-Pr), 11.68, 14.22 (C7),
20.98, 22.87 (C6), 24.82 (c-Pr), 25.08 (2C), 26.51(C4),
30.93, 31.45, 32.75(C5), 33.08(C3), 35.03 (C2), 39.77.
Found, % : C 85.44; H 14.22. [M – C2H4]+ 196. C16H32.
Calculated, % : C 85.63; H 14.37.
14. Thanedar, S. and Farona, M.F., J. Organometal. Chem.,
1982, vol. 235, p. 65.
15. Fagan, P.J. and Nugent, W.A., J. Am. Chem. Soc., 1988,
vol. 110, p. 2310.
1-{1-Methyl-1-[1-(2-methylbutyl)cyclo-propyl]-
ethyl}benzene (XIXc). Yield 67%. 1H NMR spectrum,
d, ppm: 0.10–0.36 m (2H, CH2,c-Pr), 0.58–0.95 m (14H,
CH2, c-Pr, CH3), 1.17–1.58 m (5H, CH2, CH), 6.98–7.40
m (5H, C6H5). 13C NMR spectrum, d, ppm: 8.24 (2C, c-
Pr), 11.62, 20.72, 26.57 (2C), 29.56 (c-Pr), 30.47, 31.12,
39.45, 40.49, 125.48, 126.85 (2C), 127.76 (2C), 141.85
(C6H5). Found, % : C 88.46; H 11.20. [M – C2H4]+ 202.
C17H26. Calculated, %: C 88.62; H 11.38.
16. Negishi, E., Montchamp, I.-L., Anastasia, L., Elizarov,A.,
and Choueiry, D., Tetrahedron Lett., 1998, vol. 39, p. 2503.
17. Dzhemilev, U.M., Ibragimov, A.G., Ramazanov, I.R.,
Luk’yanova, M.P., and Sharipova, A.Z., Izv. Akad. Nauk,
Ser. Khim., 2001, p. 465.
18. Dzhemilev, U.M., Ibragimov, A.G., Ramazanov, I.R.,
Luk’yanova, M.P., Sharipova,A.Z., and Khalilov, L.M., Izv.
Akad. Nauk, Ser. Khim., 2000, p. 1092.
19. Zakharkin, L.I. and Savina, L.A., Izv. Akad Nauk SSSR.,
Ser. Khim., 1962, p. 824.
20. Haage, M., Starowieysky, K.B., and Chwojnowski, A.,
J. Organometal. Chem., 1979, vol. 174, p. 149.
The study was carried out under financial support of
the Russian Foundation for Basic research (grants
nos. 03-03-33050, 02-03-97904, 04-03-97510).
RUSSIAN JOURNALOF ORGANIC CHEMISTRYVol. 41 No. 5 2005