'One-pot' synthesis of 1,1-disubstituted cyclopropanes in the presence of metal complex catalysts

Article abstract of DOI:10.1016/S0022-328X(01)01168-8

A 'one-pot' catalytic method for the synthesis of 1,1-disubstituted cyclopropanes starting from olefins, acetylenes and AlEt₃ in the presence of Cp₂ZrCl₂, via a step involving in situ formation of aluminacyclopentanes and aluminacyclopentenes, respectively, was developed. Five-membered organoaluminium compounds obtained without preliminary isolation are transformed to cyclopropanes under the effect of Ni(acac)₂ in combination with allylhalogenides in the case of aluminacyclopentanes and alkylsulphates in experiments with aluminacyclopentenes.

Full text of DOI:10.1016/S0022-328X(01)01168-8

Journal of Organometallic Chemistry 636 (2001) 76–81
www.elsevier.com/locate/jorganchem
‘
One-pot’ synthesis of 1,1-disubstituted cyclopropanes in the
presence of metal complex catalysts
Usein M. Dzhemilev*, Askhat G. Ibragimov, Leyla O. Khafizova,
Ilfir R. Ramazanov, Dina F. Yalalova, Genrikh A. Tolstikov
Institute of Petrochemistry and Catalysis, Bashkortostan Republic Academy of Sciences, Ufa Scientific Centre of Russian Academy of Sciences,
50075, Ufa, Russia
4
Received 26 February 2001; accepted 28 July 2001
Dedicated to Academician Oleg M. Nefedov on his 70th birthday
Abstract
A ‘one-pot’ catalytic method for the synthesis of 1,1-disubstituted cyclopropanes starting from olefins, acetylenes and AlEt in
3
the presence of Cp ZrCl , via a step involving in situ formation of aluminacyclopentanes and aluminacyclopentenes, respectively,
2
2
was developed. Five-membered organoaluminium compounds obtained without preliminary isolation are transformed to cyclo-
propanes under the effect of Ni(acac) in combination with allylhalogenides in the case of aluminacyclopentanes and alkylsul-
2
phates in experiments with aluminacyclopentenes. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Substituted cyclopropanes; Olefins; Acetylenes; Aluminacyclopentanes; Aluminacyclopentenes; Catalysis
1
. Introduction
According to [8] a limited number of the simplest
aluminacyclopentanes generated in situ from a-olefins
and AlEt in the presence of catalyst Cp ZrCl was
Carbene reactions, such as cyclopropanation accord-
3
2
2
ing to Simmons–Smith [1] halogencyclopropanation us-
ing halogensubstituted carbenes [2] and synthesis of
cyclopropanecarbenic acid derivatives by thermocata-
lytic reactions of diazo esters [3] are reported to be
well-known methods for a synthesis of cyclopropanes
and their derivatives. The recent papers on cyclic carboa-
lumination of unsaturated compounds using organopal-
ladium, -zinc and -aluminium reagents have determined
the new technique for a synthesis of substituted cyclo-
propanes [4–8]. The synthesis of cyclopropanes [6,8]
based on skeleton transformations of forming in situ
aluminacyclopentanes and aluminacyclopentenes by cy-
cloalumination of a-olefins and acetylenes effected by
complex metal catalysts [9–12] is of special interest.
involved in this reaction. Five-membered organoalu-
minium compounds OAC 1, synthesized by the present
method, could be transformed into the corresponding
1,1-disubstituted cyclopropanes
2
using catalytic
amounts of Ni(acac) and allylchloride, without prelim-
2
inary isolation from the reaction mixture.
2. Results and discussion
To extend the area of reaction developed [8] as well as
to investigate the structural effect of initial five-mem-
bered OAC, the nature of the central atom of a catalyst
and the effect of reaction conditions on yield and
selectivity of cyclopropanes, we studied skeleton trans-
formations of aluminacyclopentanes [13] and aluminacy-
clopentenes [14], using Ni- and Ti-containing complex
catalysts.
In the course of preliminary experiments it was estab-
lished that the highest yields of 1,1-disubstituted cyclo-
propanes were allowed from the reaction of aluminacy-
*
Corresponding author. Fax: +7-3472-312750.
E-mail address: ink@anrb.ru (U.M. Dzhemilev).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01168-8

U.M. Dzhemile6 et al. / Journal of Organometallic Chemistry 636 (2001) 76–81
77
clopentanes in the presence of 5 mol% freshly subli-
mated Ni(acac) and three-fold excess of allylchloride
2
as reoxidant (reaction conditions: 20 °C, 8 h, solvent—
(
C H ) O).
2 5 2
Apparently, the formation of substituted cyclo-
propanes has not ever been observed with the use of
metallylchloride.
Under selected conditions functionally substituted
five-membered OAC react with allylhalides to afford
1
,1-disubstituted cyclopropanes. For example, during
Thus, 1-ethyl-3-(n-hexyl)aluminacyclopentane (1b)
the interaction of 1-hydroxy- or 1-methoxyocta-2E,7-di-
obtained in situ by the reaction of oct-1-ene with AlEt3,
under conditions [13] using freshly sublimated Ni(acac)2
enes with AlEt over the catalyst Cp ZrCl aluminacy-
3
2
2
clopentanes (9a,b) [15] are formed, which further react
in situ with allylchloride in the presence of Ni(acac)2
leading to corresponding 1,1-disubstituted oxygen-con-
taining cyclopropanes 10a,b in ca. 50% yield.
and
hexyl)cyclopropane (2b), 3-methylenenonane (3b) and
-methylnonene (4b) in total yield ca. 80% (quoted
allylchoride,
affords
1-(but-3-enyl)-1-(n-
3
To determine the structure of intermediate com-
pounds obtained during transformation of aluminacy-
clopentanes to 1,1-disubstituted cyclopropanes we have
studied the reaction 1 with allylchloride in the presence
yields were obtained after distillation) and in a ratio of
ca. 12:1:3, respectively. The analogous results were
obtained during the study of the reaction of 1-ethyl-3-
(
n-butyl)- and 1-ethyl-3-(n-nonyl)aluminacyclopentanes
of Ni(acac) by dynamic NMR-spectroscopy along with
2
(
1a,c) with allylchloride over the catalyst Ni(acac)2
identification of compounds formed. Experiments were
carried out in an inert gas flow, by mixing of alumina-
cyclopentane (1) with allylchloride and a catalytic
amount of Ni(acac) in Et O solution at −5 °C in the
leading to cyclopropanes 2a,c and olefins 3a,c and 4a,c,
respectively in 75–85% yields.
The replacement of allylchloride by crotylbromide
leads to the formation of regioisomeric by alkenyl
substituent 1,1-disubstituted cyclopropanes 5, 6 in ratio
ca. 1:1 and in total yield of ca. 60%.
2
2
glass reactor, with subsequent injection of the reaction
mixture into the NMR spectrometer cell. Spectra were
recorded at ca. 20 °C.
The model interaction reaction of 1-ethyl-3-(n-
hexyl)aluminacyclopentane (1) with an excess of al-
lylchloride ([Al]–CH CHCH Cl=1:3) in the presence
2
2
of 5 mol% Ni(acac) reveals that initially AlꢀC bond in
2
ACP (1) is opened as a result of b-hydrogen abstraction
effected by low-valence Ni complexes to afford hydride
complexes 11, 12. At the same time stoichiometric
amount of propylene is isolated, thus indicating the
evidence of alkenylhalogenalanes 13, 14 formation.
Above-mentioned is confirmed by following results.
NMR-spectrum of reaction mixture shows a significant
decrease in signal intensity at 155.1 and 107.1 ppm
assigned to carbon atoms of methylene double bond in
The direction of the aforesaid catalytic reaction com-
pletely changes when metallylchloride is used as allyl-
haloid (reoxidant). For example, under selected optimal
conditions ACP (1) turns into regioisomeric hydrocar-
bons—2-methyl-6-methylenedodec-1-ene (7) and 2-
methyl-5-vinylundec-1-ene (8) over the catalyst
Ni(acac) in the presence of metallylchloride.
2

78
U.M. Dzhemile6 et al. / Journal of Organometallic Chemistry 636 (2001) 76–81
OAC 13b in 60 min after the beginning of reaction
between 1b and allylchloride over the catalyst Ni(a-
reaction step the use of aliphatic or aromatic solvents
(hexane, cyclohexane, toluene) is required [14].
The mechanistic study of transformation 16 into 18
cac) . Signals disappear completely in 24 h. Probably,
2
under selected conditions intramolecular carboalumina-
tion in 13b takes place leading to cyclopropylhaloge-
nalane (15b) with subsequent cross-coupling with
allylchloride to afford 1,1-disubstituted cyclopropane
by the model interaction between 16a and (CH ) SO
3 2 4
using the dynamic NMR-spectroscopy method revealed
that typical for aluminacyclopentene ring resonance
peaks have disappeared in 60 min after beginning of the
13
2b. In contrast to OAC 13b compound 14b seems not
reaction. At the same time C-NMR-spectrum of reac-
tion mixture shows the peaks assigned to homoallylic
OAC 17a and cyclopropane 18a. Reaction is completed
to undergo aforesaid transformations and retains its
structure.
Apparently homoallylic OAC 13b is the key interme-
diate in the above reaction; subsequent transformations
in ca. 5 h. Thus, on basis of experimental data the
formation of 18 from 16 could be represented by the
following Scheme.
of this compound over Ni(acac) afford 1,1-disubsti-
2
tuted cyclopropane.
Developed by us the catalytic method of skeleton
transformations of aluminacyclopentanes to disubsti-
tuted cyclopropanes was applied to 2,3-disubstituted
aluminacyclopentenes (16) synthesized by cycloalumi-
nation of 1,2-disubstituted acetylenes using AlEt over
3
the catalyst Cp ZrCl [14].
2
2
At the same time under above conditions (catalyst
Ni(acac) , ca. 20 °C, 8 h; solvent—Et O) aluminacy-
2
2
clopentenes (16) were found to react with allylchloride
non-selectively leading upon hydrolysis to the mixture
of hydrocarbons, the content of substituted cyclo-
propanes in which does not exceed ca. 30%.
Dialkylsulphates (MeSO , Et SO ) were used as alky-
4
2
4
lating agents.
The interaction of 1-ethyl-2,3-di(n-propyl)- or 1-
ethyl-2,3-di(n-butyl)-aluminacyclopent-2-enes (16a,b)
with four-fold excess of (CH ) SO under optimal con-
ditions (ca. 20 °C, 12 h, hexane) was established to
afford 1-propyl-1-(2-methylpentane-2-yl)cyclopropanes
We have shown the possibility of aluminacyclopente-
nes (16) transformation into corresponding tetrasubsti-
tuted olefins 19 and conjugated dienes 20 with high
yields under the influence of alkyltosilates or alkylac-
etates effected by complex palladium catalyst
[Pd(acac) –PPh ].
3
2
4
2
3
(
18a,b) in \80% yields.
The nature of solvents used (hexane, cyclohexane,
The examples of ‘one-pot’ synthesis of 1,1-disubsti-
tuted cyclopropanes from a-olefines and acetylene via
formation in situ five-membered OAC are a great evi-
dence of synthetic capability of this method.
benzene, toluene, diethyl ester, tetrahydrofuran) almost
have no influence on the yield of 16a,b, however at first

U.M. Dzhemile6 et al. / Journal of Organometallic Chemistry 636 (2001) 76–81
79
3
.1.1. 1-(n-Butyl)-1-(but-3-enyl)cyclopropane (2a)
22
−1
b.p. 63–64 °C (10 Torr), nD 1.4390. IR w˜ (cm ):
3
085, 2970, 2940, 2870, 1650, 1470, 1385, 1025, 1015, 925.
1
H-NMR (l ppm): 0.22 (s, 4H, CH cycl); 0.89 (m, 3H,
2
CH ); 1.20–1.39 (m, 4H, CH CH ); 1.39–1.68 (m, 4H,
3
2
2
CH CCH ); 1.81–2.11 (m, 2H, CH CH); 4.68–5.70 (m,
2
2
2
13
3
(
(
H, CH.CH ). C-NMR (l ppm): 12.1 (C ), 19.2
2
1
C ), 35.6 (C ), 31.1 (C ), 139.3 (C ), 113.8 (C ), 35.7
2 3 4 5 6
+
C ), 28.9 (C ), 23.1 (C ), 14.2 (C ). M 152.
7
8
9
10
3
.1.2. 1-(n-Hexyl)-1-(but-3-enyl)cyclopropane (2b)
22 1
b.p. 73–74 °C (5 Torr), nD 1.4445. H-NMR (l
ppm): 0.18 (s, 4H, CH2 cycl); 0.88 (m, 3H, CH3);
.18–1.29 (m, 8H, CH2); 1.40–1.65 (m, 4H,
CH CCH ); 1.70–2.03 (m, 2H, CH ); 4.52–5.55 (m,
1
2
2
2
13
3
H, CH.CH ). C-NMR (l ppm): 12.1 (C ), 19.2
2
1
(
(
(
C ), 35.6 (C ), 31.1 (C ), 139.4 (C ), 113.8 (C ), 36.0
C ), 26.6 (C ), 29.7 (C ), 32.0 (C ), 22.5 (C ), 14.1
C ). M 180.
2 3 4 5 6
7
8
9
10
11
+
12
3. Experimental
3
.1.3. 1-(n-Nonyl)-1-(but-3-enyl)cyclopropane (2c)
b.p. 89–90 °C (2 Torr), nD 1.4499. H-NMR (l
22 1
All reactions were carried out under argon. For all
synthesises dry solvents were used. The compounds
obtained were analyzed by a Chrom-5 chromatograph
ppm): 0.21 (s, 4H, CH2 cycl); 0.88 (m, 3H, CH3);
1.15–1.30 (m, 14H, CH2); 1.38–1.66 (m, 4H,
CH CCH ); 2.08–2.20 (m, 2H, CH ); 4.70–5.80 (m,
(
1
1200×3 mm column packed with 5% of SE-30 and
5% of PEG-6000 on Chromosorb N-AW, flame-ion-
2
2
2
13
3H, CH.CH ). C-NMR (l ppm): 12.1 (C ), 19.2
2
1
ization detector, carrier-gas—helium, working temper-
ature 50–170 °C). Mass spectral measurements were
performed on Finnigan 4021 gas chromatograph–mass
(C ), 35.5 (C ), 31.1 (C ), 139.4 (C ), 113.9 (C ), 36.1
2 3 4 5 6
(C ), 26.6 (C ), 29.6 (C ), 29.7 (C , C ), 29.4 (C ), 32.0
7
8
9
10
11
12
+
(C ), 22.8 (C ), 14.1 (C ). M 222.
13
14
15
1
13
spectrometer at 70 eV. H- and C-NMR spectra were
recorded as CDCl3 solutions on spectrometers ‘Jeol
3.1.4. 1-(n-Hexyl)-1-(trans-pent-3-enyl)cyclopropane
(5)
13
1
FX-90Q’ (22.5 MHz for C and 90 MHz for H) and
1
3
22
1
‘
Bruker AM-300’ (75.46 MHz for C and 300 MHz for
b.p. 79–80 °C (2 Torr), n
ppm): 0.84 (t, 3H, CH , J=6.4 Hz); 1.11–1.35 (m,
12H, CH ); 0.04 (s, 4H, CH cycl); 1.74–2.02 (m, 2H,
CH ); 1.45–1.69 (m, 3H, CH ); 4.66–5.59 (m, 2H,
D
1.4621. H-NMR (l
1
H). Internal standard: Me Si; for cyclopropane deriva-
tives—C D . C-NMR spectra were recorded using
3
4
1
3
6
6
2
2
complete and partially proton-decoupled mode, and
with the use of INEPT (Insensitive Nuclei Enhanced by
Polarization Transfer) technique.
2
3
13
CH.CH). C-NMR (l ppm): 10.3 (C ), 18.6 (C ), 38.2
1
2
(
(
(
C ), 25.8 (C ), 131.5 (C ), 124.6 (C ), 17.9 (C ), 37.24
3 4 5 6 7
C ), 28.1 (C ), 29.6 (C ), 32.1 (C ), 22.8 (C ), 14.1
8
9
10
11
12
+
C ). M 194.
1
3
3.1. Synthesis of 1-alkyl-1-(but-3-enyl)cyclopropanes
from h-olefines
3.1.5. 1-(n-Hexyl)-1-(2-methyl-trans-but-3-enyl)-
cyclopropane (6)
b.p. 74–75 °C (2 Torr), nD 1.4541. H-NMR (l
ppm): 0.83 (t, J=6.4 Hz, 3H, CH ); 1.04–1.30 (m,
A glass reactor was charged with Cp ZrCl2 (0.5
22
1
2
mmol), a-olefin (10 mmol) and AlEt (12 mmol) under
3
3
dried nitrogen at 0 °C; the reaction mixture was stirred
for 8 h at 21–23 °C. To resulted 1-ethyl-3-(al-
1
2H, CH ); 0.15 (s, 4H, CH cycl); 0.88–1.04 (m, 3H,
2 2
CH ); 1.80–2.10 (m, 1H, CH); 4.66–5.59 (m, 3H,
3
13
kyl)aluminacyclopentane Et O (8 ml), freshly subli-
2
CH .CH).
C-NMR (l ppm): 11.4 (C ), 19.7
2
1
mated Ni(acac)2 (0.5 mmol) and allylchloride
metallylchloride, crotylbromide) (36 mmol) were added
(C ), 45.2 (C ), 35.0 (C ), 143.3 (C ), 114.2 (C ), 19.3
2
3
4
5
6
(
(C ), 43.7 (C ), 28.5 (C ), 29.2 (C ), 32.1 (C ), 22.8
7 8 9 10 11
+
at −5 °C; the reaction mixture was stirred for 8–10 h
at room temperature (r.t.). The mixture was treated
then by 10% HCl, washed by water to neutral reaction.
An organic layer was separated from aqueous. Resulted
solution was dried over calcined Na SO . After evapo-
(C ), 14.2 (C ). M 194.
12 13
3.1.6. 2-Methyl-6-methylenedodec-1-ene (7)
1
22
b.p. 99–100 °C (5 Torr), nD 1.4421. H-NMR (l
ppm): 0.81 (t, J=6.1 Hz, 3H, CH ); 1.04–1.34 (m,
2
4
3
ration of solvents the crude product was purified by
vacuum distillation.
10H, CH ); 1.01 (s, 3H, CH ); 1.86–2.01 (m, 6H, CH );
2
3
2
13
4.40–5.67 (m, 4H, CH .C). C-NMR (l ppm):
2

80
U.M. Dzhemile6 et al. / Journal of Organometallic Chemistry 636 (2001) 76–81
1
1
4.2, 21.1, 25.9, 27.2, 29.2, 29.5, 32.0, 35.7, 36.2, 37.6,
08.7, 109.9, 146.0, 150.1. M 194.
(C ), 20.1 (C ), 15.3 (C ), 25.2 (C , C ), 43.5 (C ), 17.8
4 5 6 7 7% 8
(C ), 15.1 (C ). M 168.
9 10
+
+
3
.1.7. 2-Methyl-5-6inylundec-1-ene (8)
3
.2.2. 1-(n-Butyl)-1-(2-methylhexane-2-yl)cyclopropane
(18b)
b.p. 102–103 °C (9 Torr). H-NMR (300 MHz, l
2
2
1
b.p. 80–81 °C (2 Torr), n 1.4422. H-NMR (l
D
ppm): 0.81 (t, J=6.1 Hz, 3H, CH ); 1.02–1.42 (m,
1
1
NMR (l ppm): 14.2, 22.5, 25.4, 29.6, 29.8, 32.0, 33.0,
3
1
3
2H, CH ); 1.82–1.93 (m, 2H, CH C); 1.93–2.10 (m,
1
3
2
2
2
ppm): 0.12 (BB , JBB%, cis=9.5,
J
AB,
3
gem= −5.4,
13
H, CH); 4.40–5.67 (m, 5H, CH .C, CH .CH). C-
3
2
1
2
2
JAB%, trans=5.5, 2H); 0.33 (AA , JAA%, cis=9.5,
JAB, gem=−5.4, JAB%, trans=5.5, 2H,); 0.70 (c, 6H,
3
+
5.2, 35.5, 43.9, 109.6, 114.4, 143.4, 146.4. M 194.
C(8)H , C(8%)H ); 0.83–0.93 (m, 6H, C(7)H , C(12)H );
3
3
3 3
1
.05–1.57 (m, 12H, C(4)H ꢀC(6)H , C(9)H ꢀC(11)H ).
2
2
2
2
3
.1.8. 1-(But-3-enyl)-1-(6-hydroxyhex-4-enyl)cyclo-
13
C-NMR (l ppm): 6.97 (C , C ), 25.0 (C ), 35.0
1
1%
2
propane (10a)
(
C ), 32.0 (C ), 29.2 (C ), 23.9 (C ), 14.3 (C ), 25.2 (C ,
3 4 5 6 7 8
+
8% 9 10 11 12
2
2
−1
b.p. 120–121 °C (1 Torr), n 1.4902. IR w˜ (cm ):
D
C ), 40.7 (C ), 26.7 (C ), 23.7 (C ), 14.3 (C ). M 196.
3
,
360, 3080, 3010, 2935, 2865, 1645, 1470, 1105, 1030, 985
1
925. H-NMR (l ppm): 0.24 (s, 4H, CH cycl); 1.10–
2
3.2.3. 1-(n-Butyl)-1-(3-ethylheptane-3-yl)cyclopropane
1.62 (m, 8H, CH ); 1.84–2.20 (m, 4H, CH CH); 4.06 (d,
2
2
(
18c)
J=4.0 Hz, 2H, CH OH,); 4.82–5.90 (m, 5H, olefinic).
1
1
2
H-NMR (l ppm): 0.10 (m, 2H, BB ); 0.40 (m, 2H,
1
3
C-NMR (l ppm): 12.0 (C ), 19.0 (C ), 35.4 (C ), 31.0
1
1
2
3
AA ); 0.76 (t, 6H, C(9)H , C(9%)H , J=7.81 Hz); 1.17–
3
3
(
(
C ), 139.3 (C ), 113.9 (C ), 35.5 (C ), 26.1 (C ), 32.4
C ), 129.0 (C ), 133.6 (C ), 63.8 (C ). M 194.
4 5 6 7 8
+
1
1
.34 (m, 10H, C(7)H , C(8)H , C(8%)H , C(13)H ); 1.40–
3 3 3 3
9
10
11
12
.62 (m, 12H, C(4)H ꢀC(6)H , C(10)H ꢀC(12)H ).
2
2
2
2
1
3
C-NMR (l ppm): 5.3 (C , C ), 20.7 (C ), 39.0
1
1%
2
3.1.9. 2-(n-Hexyl)-4-(ethylchloroaluminia)-but-1-ene
(
C ), 32.4 (C ), 26 1 (C ), 24.0 (C ), 14.3 (C ), 26.0 (C ,
3 4 5 6 7 8
(
13b)
C ), 8.50 (C , C ), 33.3 (C ), 28.8 (C ), 23.8 (C ), 14.3
1
3
8%
9
9%
10
11
12
C-NMR (l ppm): 107.1 (C ), 155.1 (C ), 40.5
+
1
2
(
C ). M 224.
13
(
(
C ), 16.2 (C ), 1.2 (C ), 9.0 (C ), 36.5 (C ), 28.7
C ), 30.0 (C ), 32.6 (C ), 23.4 (C ), 14.5 (C ).
3 4 5 6 7
8
9
10
11
12
3.3. Synthesis of (Z)-1,2-dialkyl-1,2-diethylethylenes
from acetylenes
3.1.10. 3-(n-Hexyl)-4-(ethylchloroaluminia)-but-1-ene
(
14b)
1
3
To the mixture of disubstituted acetylene (10 mmol)
and Cp ZrCl (0.3 mmol) in dried hexane (8 ml), Et Al
C-NMR (l ppm): 111.5 (C ), 148.2 (C ), 41.8
1
2
2
2
3
(
(
C ), 16.2 (C ), 1.2 (C ), 9.0 (C ), 32.7 (C ), 28.4
3 4 5 6 7
(
15 mmol) was added under dried argon at 0 °C; the
C ), 30.3 (C ), 32.1 (C ), 23.4 (C ), 14.5 (C ).
8
9
10
11
12
solution was stirred for 8 h at r.t. Ethyltosylate (50
mmol) was then added to the mixture of forming in situ
cyclic OAC at 0 °C; the reaction solution was stirred for
3
.2. Synthesis of 1,1-dialkylcyclopropanes from
acetylenes
1
5
8 h at r.t. The reaction mixture was hydrolyzed with
% HCl, the organic layer was extracted with diethyl
To the mixture of disubstituted acetylene (2 mmol)
and Cp ZrCl (0.01 mmol) in dried hexane (5 ml), Et Al
(
was stirred for 10 h at ca. 20 °C. To the resulting
mixture, dialkylsulphate (8 mmol) was added dropwise
at 0 °C, and the reaction solution was stirred for 12 h
at 20 °C. Hexane (5 ml) was then added, and the
reaction mixture was hydrolized by 5% HCl. The or-
ganic layer was extracted with diethyl ether, washed
with Na CO to neutral reaction and dried over CaCl .
ether, washed with Na CO3 to neutral reaction and
2
2
2
3
dried over CaCl . After removing the solvent the residue
2
5 mmol) was added under argon at 0 °C; the solution
was distilled in vacuo.
3
.3.1. 5,6-Diethyldec-5Z-ene (19b)
b.p. 113 °C (14 Torr). H-NMR (l ppm): 0.66–0.96
1
(
m, 12H, CH ); 1.00–1.23 (m, 8H, CH ); 1.30 (q, 4H,
3
2
1
3
CH , J=7.1 Hz); 1.90 (t, 4H, CH , J=7.3 Hz). C-
2
2
NMR (l ppm): 14.1 (C ), 24.4 (C ), 31.1 (C ), 31.6
1
2
3
2
3
2
+
(
C ), 134.5 (C ), 23.2 (C ), 13.9 (C ). M 196.
4 5 6 7
After removing the solvent the residue was distilled.
3
(
.2.1. 1-(2-Methylpentane-2-yl)-1-propylcyclopropane
18a)
b.p. 86–87 °C (15 Torr). H-NMR (l ppm): 0.14 (m,
3.4. Synthesis of 1,2-dialkyl-1Z,3-butadienes from
acetylenes
1
1
1
2
H, BB ); 0.35 (m, 2H, AA ); 0.73 (s, 6H, C(7)H ,
To the mixture of disubstituted acetylene (10 mmol)
and Cp ZrCl (0.3 mmol) in dried hexane (8 ml), Et Al
3
C(7%)H ); 0.83–0.88 (m, 6H, C(6)H , C(10)H ); 1.01–
1
3
3
3
2
2
3
13
.52 (m, 8H, C(4)H , C(5)H , C(8)H , C(9)H ). C-
(15 mmol) was added under dried argon at 0 °C; the
2
2
2
2
NMR (l ppm): 7.1 (C , C ), 24.9 (C ), 35.2 (C ), 35.4
solution was stirred for 8 h at r.t. THF (20 mmol),
1
1%
2
3

U.M. Dzhemile6 et al. / Journal of Organometallic Chemistry 636 (2001) 76–81
81
allylacetate (40 mmol) and Pd(acac) (0.3 mmol) were
References
2
added to the mixture at −5 °C; the reaction solution
was stirred for 10 h at r.t. The reaction mixture was
hydrolyzed with 5% HCl, the organic layer was sepa-
[
[
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2
[
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2
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[
[
3
.4.1. (3E)-3-propylhepta-1,3-diene (20a)
9
1
b.p. 63–64 °C (25 Torr). H-NMR (l ppm): 0.92
3
(
t, 6H, CH3, JCH=6.8); 1.22–1.63 (m, 4H, CH2);
1
5
M
.98–2.29 (m, 4H, CH ); 4.84–5.19 (m, 2H, CH );
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2
2
3
.47 (t, 1H, CH, JCH=7.3); 6.12–6.43 (m, 1H, CH).
+
138.
[
Bull. Acad. Sci. USSR, Div. Chem. Sci. 39 (1990) 1071 (Engl.
Transl.)].
3
.4.2. (3E)-3-butylocta-1,3-diene (20b)
b.p. 80–81 °C (10 Torr). H-NMR (l ppm): 0.71–
[
9] U.M. Dzhemilev, A.G. Ibragimov, J. Organometal. Chem. 466
(1994) 1.
1
1
2
1
1
.10 (m, 6H, CH ); 1.14–1.60 (m, 8H, CH ); 1.99–
[10] U.M. Dzhemilev, Tetrahedron 51 (1995) 4333.
3
2
[
[
[
11] U.M. Dzhemilev, A.G. Ibragimov, Russian Chem. Bull. 47 (1998)
786.
12] U.M. Dzhemilev, A.G. Ibragimov, Russian Chem. Rev. 69 (2000)
.29 (m, 4H, CH ); 4.82–5.16 (m, 2H, CH ); 5.42 (t,
2
2
3
+
H, CH, JCH=7.3); 6.09–6.40 (m, 1H, CH). M
66.
1
21.
13] U.M. Dzhemilev, A.G. Ibragimov, A.P. Zolotarev, Izv. Acad.
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Acknowledgements
[
[
14] U.M. Dzhemilev, A.G. Ibragimov, A.P. Zolotarev, Mendeleev
Commun. 4 (1992) 135.
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stikov, Izv. Acad. Nauk SSSR, Ser. Khim. (1990) 2831 [Bull. Acad.
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The research work was sponsored by Russian Fed-
eration for Basic Research (grant Nos. 00-15-97312,
00-03-32736).