Synthesis and transformations of metallacycles 28. Reactions of allenes with EtAlCl2 and Et2AlCl catalyzed by Ti and Zr complexes

Article abstract of DOI:10.1023/A:1022191520197

Catalytic cycloalumination of allenes with EtAlCl₂ in the presence of Ti or Zr complexes afforded methylidene- and alkyl(benzyl)idenealuminacyclopropanes and the corresponding aluminacyclopentanes, which were identified by analyzing the hydroly

Full text of DOI:10.1023/A:1022191520197

Russian Chemical Bulletin, International Edition, Vol. 51, No. 12, pp. 2255—2260, December, 2002
2255
Synthesis and transformations of metallacycles
28.* Reactions of allenes with EtAlCl2 and Et2AlCl catalyzed by Ti and Zr complexes
ꢀ
A. G. Ibragimov, L. O. Khafizova, G. N. Gil´fanova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis,
Bashkortostan Republic Academy of Sciences and Ufa Research Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. Eꢀmail: ink@anrb.ru
Catalytic cycloalumination of allenes with EtAlCl2 in the presence of Ti or Zr complexes
afforded methylideneꢀ and alkyl(benzyl)idenealuminacyclopropanes and the corresponding
aluminacyclopentanes, which were identified by analyzing the hydrolysis products. The reacꢀ
tions with the use of Et2AlCl instead of EtAlCl2 produced 1,2ꢀ and 1,4ꢀdialuminum comꢀ
pounds.
Key words: organoaluminum compounds, catalysis, cycloalumination, aluminacycloꢀ
propanes, aluminacyclopentanes, allenes.
Cycloalumination of allenes with Et3Al catalyzed by
Cp2ZrCl2 afforded 2ꢀalkylideneꢀ1ꢀethylaluminacycloꢀ
pentanes (Scheme 1).2
zyl,phenyl)ꢀ1ꢀethylꢀ2ꢀmethylidenealuminacyclopropanes
(2), 2ꢀalkyl(benzyl)ideneꢀ1ꢀethylaluminacyclopropanes
(3), and 2,5ꢀdi(alkyl(benzyl)idene)ꢀ1ꢀethylaluminacycloꢀ
pentanes (4), which were identified by analyzing the
hydrolysis products.
Scheme 1
The effect of the nature of the solvent on the yields
and compositions of the reaction products was studied. In
THF, cycloalumination of nonaꢀ1,2ꢀdiene (1c) with
EtAlCl2 in the presence of 5 mol.% of Cp2TiCl2 afforded
organoaluminum compounds 2c, 3c, and 4c in the ratio
6 : 1 : 2 in a total yield of ∼80% (Scheme 2). In aliphatic
(hexane, heptane, cyclohexane) or aromatic (benzene,
toluene, xylene) solvents, cycloalumination of allenes did
not virtually take place. In diethyl ether, cyclic organoꢀ
aluminum compounds 2c, 3c, and 4c were generated in
the ratio 9 : 1 : 10 in a total yield of ∼60%.
With the aim of extending the scope of this reaction,
applying it to other organoaluminum compounds (OAC),
and synthesizing new classes of threeꢀ and fiveꢀmemꢀ
bered unsaturated OAC, we studied cycloalumination of
alkylꢀ and phenylallenes with EtAlCl2 in the presence of
metallic Mg as the acceptor of chloride ions and Cp2TiCl2
as the catalyst, which exhibits3—6 high activity and selecꢀ
tivity in the formation of threeꢀmembered OAC from
EtAlCl2 and αꢀolefins or acetylenes.
The structures of unsaturated cyclic organoalumiꢀ
num compounds 2—4 were established by analyzing the
hydrolysis (5—7) or deuterolysis products (8—10). Acꢀ
cording to the 13C NMR spectroscopic data, alkenes 6a,b
(9a,b) and 7a—e (10a—e) contain Zꢀdisubstituted double
bonds, whereas the double bonds in molecules 6c—e
(9c—e) have the Z/E configurations in a ratio of ∼2 : 1.
Results and Discussion
1
According to the H NMR spectra, hydrolysis products
We studied the reactions of allenes which differ in the
nature of the substituent (Ph (1a), CH2Ph (1b), Alk) and
the length of the alkyl chain (C6H13, C8H17, C9H19
(1c—e, respectively)) with EtAlCl2. Preliminary experiꢀ
ments demonstrated that the reactions in the presꢀ
ence of Mg and the catalyst Cp2TiCl2 (molar ratio
RCH=C=CH2 : [Al] : Mg : [Ti] = 20 : 26 : 24 : 1) afforded
in 8—12 h unsaturated cyclic OAC, viz., 3ꢀalkyl(benꢀ
7a—e contain the cisꢀdouble bonds (spinꢀspin coupling
constant of the alkene protons 3J is 11.7 Hz for 7a; cf. lit.
data7: 3Jtrans = 18 Hz). The cis configuration of the double
bond in compounds 7c—e is confirmed by the fact that
their 13C NMR spectra have characteristic8 highꢀfield sigꢀ
nals for the allylic C atoms at δ 26—28. Mass spectrometꢀ
ric analysis of deuterolysis products showed that the mixꢀ
tures contained dideuterioalkenes 8—10 along with monoꢀ
deuterated alkenes as the minor products (10—12%),
* For Part 27, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2095—2100, December, 2002.
1066ꢀ5285/02/5112ꢀ2255 $27.00 © 2002 Plenum Publishing Corporation

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Ibragimov et al.
Scheme 2
R = Ph (a), CH2Ph (b), nꢀC6H13 (c), nꢀC8H17 (d), nꢀC9H19 (e);
[Ti] = Cp2TiCl2
which indicates that cyclometallation was accompanied
by competitive hydrometallation of the starting allenes.
The formation of unsaturated cyclic organoaluminum
compounds 2—4 is attributable to transmetallation of the
in situ generated unsaturated titanacyclopropane and
titanacyclopentane intermediates with the starting EtAlCl2
according to a scheme analogous to that proposed in our
previous study9 for cyclometallation of arylethenes. In
these processes, the configurations of the in situ generꢀ
ated alkylidenetitanacyclopropane and ꢀtitanacycloꢀ
pentane intermediates dictate the stereoconfigurations of
the alkylideneꢀsubstituted organoaluminum compounds
3 and 4. Apparently, hydride titanium complexes are reꢀ
sponsible for the formation of minor hydrometallation
products of allenes. Under the reaction conditions, these
complexes are generated through dehydrogenolysis of
THF with lowꢀvalent titanium complexes,10 as we have
demonstrated previously11 in the investigation of hydroꢀ
metallation of αꢀolefins.
and a complex mixture of unsaturated aluminacycloꢀ
pentanes in ∼50% yield.
The reactions with Et2AlCl instead of EtAlCl2 follow
another pathway. Under the optimum conditions, these
reactions afford predominantly unsaturated 1,2ꢀ and
1,4ꢀdialuminum compounds (Scheme 3). Actually, the
reactions of allenes 1a,c—e with Et2AlCl in THF in
the presence of Cp2TiCl2 as the catalyst taken in the
[Al] : RCH=C=CH2 : Mg : [Ti] ratio of ∼44 : 20 : 24 : 1
gave rise to 2ꢀalkyl(phenyl)ꢀ1,2ꢀbis(diethylaluminio)ꢀ1ꢀ
methylidenoethanes (11a,c—e) and 1,4ꢀdialkyl(benꢀ
zyl)ideneꢀ1,4ꢀbis(diethylaluminio)butanes (12a,c—e) in
a ratio of ∼5 : 4 in a total yield of 75—80%. Massꢀspectroꢀ
metric analysis demonstrated that deuterolysis afforded
not only 1,2ꢀ and 1,4ꢀdideuterated compounds 8 and 10
but also monodeuterated alkenes in 10—15% yields, which
indicates that dialumination was accompanied by comꢀ
petitive hydroalumination of allenes according to a scheme
proposed previously.10
When studying cycloalumination of nonaꢀ1,2ꢀdiene
(1c) with EtAlCl2, we found that the reactions with the
use of titanium alkoxides or halides (Ti(OPri)4 or TiCl4)
instead of Cp2TiCl2 proceeded less selectively to give
1ꢀethylꢀ3ꢀ(nꢀhexyl)ꢀ2ꢀmethylidenealuminacyclopropane
2c (15—20%), 1ꢀethylꢀ2ꢀheptylidenealuminacycloproꢀ
pane 3c (8—10%), and a mixture of unidentified unsaturꢀ
ated aluminacyclopentanes and aluminacycloheptanes
(55—60%). This is attributable to the insertion of an addiꢀ
tional molecule of the starting allene at the Ti—C bond of
intermediate titanacyclopentanes followed by transꢀ
metallation of in situ generated unsaturated titanacycloꢀ
heptanes with the starting EtAlCl2. Cycloalumination of
nonaꢀ1,2ꢀdiene (1c) with EtAlCl2 in the presence of
5 mol.% of Cp2ZrCl2 or ZrCl4 afforded organoaluminum
compounds 2c and 3c in a ratio of ∼5 : 1 in ∼30% yield
It should be noted that dialumination of allenes in the
presence of Cp2ZrCl2 or ZrCl4 (5 mol.%) as the catalyst
facilitates the formation of unsaturated acyclic organoꢀ
aluminum compounds 11 and a complex mixture of unꢀ
saturated regioisomeric 1,4ꢀdialuminum compounds (acꢀ
cording to the results of GLC and mass spectrometry of
deuterolysis products) in a ratio of 1 : 2 in a total yield
of ∼80%.
The experimental results obtained in the present study
and the published data1—6 on cycloalumination of unsatꢀ
urated compounds allowed us to suggest the most probꢀ
able scheme of 1,2ꢀ and 1,4ꢀdialumination of allenes in
the presence of Cp2TiCl2 as the catalyst (Scheme 4). Acꢀ
cording to this scheme, Mg used in this reaction reduces
Cp2TiCl2 to "Cp2Ti". The formally divalent "titanocene"
coordinates the allene molecule to form titanacycloꢀ

Cycloalumination of allenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 12, December, 2002 2257
Scheme 3
R = Ph (a), nꢀC6H13 (c), nꢀC8H17 (d), nꢀC9H19 (e);
[Ti] = Cp2TiCl2
propane intermediate 13 whose transmetallation with
Et2AlCl affords 2ꢀalkyl(phenyl)ꢀ1,2ꢀbis(diethylaluminio)ꢀ
1ꢀmethylidenoethane 11. The insertion of the second
allene molecule at the Ti—C bond of titanacyclopropane
intermediate 13 facilitates the highly regioselective forꢀ
mation of 2,5ꢀdialkyl(benzyl)idenetitanocyclopentane 14
whose transmetallation with the starting Et2AlCl affords
1,4ꢀdialkyl(benzyl)ideneꢀ1,4ꢀbis(diethylaluminio)buꢀ
tane 12.
Thus, the reactions of allenes with EtAlCl2 or Et2AlCl
in the presence of Tiꢀ or Zrꢀcontaining complex catalysts
afford unsaturated aluminacyclopropanes and aluminaꢀ
cyclopentanes or 1,2ꢀ and 1,4ꢀdialuminum compounds
depending on the structures of the starting OAC.
Experimental
The reactions with organometallic compounds were carried
out under dry argon. The starting allenes, Cp2TiCl2, and
Cp2ZrCl2 were prepared according to known procedures.12—15
Commercially available 86% EtAlCl2 and 86% Et2AlCl were
purchased from the Redkinskii pilotꢀproduction plant (Russia).
Tetrahydrofuran was distilled from LiAlH4 immediately beꢀ
fore use. The GLC analysis of the hydrolysis and deuteroꢀ
lysis products was carried out on a Chromꢀ5 chromatograph
(Ar as the carrier gas, 1200×3ꢀmm column with 5% SEꢀ30 or
15% PEGꢀ6000 on Chromaton NꢀAW). The IR spectra were
measured on a URꢀ20 spectrometer (films). The mass spectra
were recorded on an MKhꢀ1306 mass spectrometer (70 eV,
200 °C). The 1H NMR spectra were measured on a Tesla BSꢀ567
Scheme 4

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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 12, December, 2002
Ibragimov et al.
spectrometer (100 MHz, Me4Si as the internal standard) in
CDCl3. The 13C NMR spectra were recorded on JEOL FXꢀ90Q
(22.5 MHz) and Bruker AMꢀ300 spectrometers (75.46 MHz)
with the JMOD mode broadꢀband and offꢀresonance proton
decoupling. Elemental analysis was performed on a Carlo Erba
instrument (model 1106). The yields and ratios of unsaturated
OAC were determined by GLC of hydrolysis or deuteroꢀ
lysis products. The spectroscopic parameters of unsaturated
OAC 2—4, 11, and 12 are not reported because of the complexꢀ
ity of their interpretation (13C NMR spectra of these compounds
have highꢀfield signals for the Cα atoms characteristic of OAC,
which are broadened due to relaxation on the 27Al nuclei).
Reactions of allenes with EtAlCl2 catalyzed by Cp2TiCl2
(ZrCl4). A mixture of Cp2TiCl2 (ZrCl4) (0.5 mmol), Mg (powꢀ
der, 12 mgꢀat.), THF (10 mL), 1,2ꢀdiene (10 mmol), and EtAlCl2
(13 mmol) was placed with stirring in a glass vessel under dry
argon at 0 °C. The mixture was warmed to ∼20 °C and stirred for
8—12 h. The reaction mixture was treated with 7—10% HCl or
DCl in D2O. The products were extracted with hexane, dried
with MgSO4, and isolated by distillation.
(m, 5 H, Ph). 13C NMR, δ: 14.00 (q, C(3´)); 125.31 (d, C(2´));
126.03 (d, C(4)); 128.57 (d, C(2), C(6)); 129.37 (d, C(3), C(5));
131.04 (t, C(1´)); 139.95 (s, C(1)). MS, m/z: 118 [M]+.
((Z )ꢀButꢀ2ꢀenyl)benzene (6b). B.p. 64—65 °C (10 Torr).
1H NMR, δ: 1.58 (d, 3 H, =CMe, J = 7 Hz); 3.36 (d, 2 H,
CH2Ph, J = 7 Hz); 5.27—5.98 (m, 2 H, CH=CH); 7.02—7.30
(m, 5 H, Ph). 13C NMR, δ: 13.99 (q, C(4´)); 39.20 (t, C(1´));
122.39 (d, C(3´)); 125.90 (d, C(4)); 128.38 (d, C(3), C(5));
128.51 (d, C(2), C(6)); 129.74 (t, C(2´)); 141.81 (s, C(1)). MS,
m/z: 132 [M]+.
Nonꢀ2ꢀene (Z(E )) (6c). B.p. 66—67 °C (40 Torr). 1H NMR,
δ: 0.82—0.94 (m, 3 H, Me); 1.20—1.52 (m, 8 H, CH2);
1.56—1.68 (m, 3 H, =CMe); 1.77—2.13 (m, 2 H, —CH2—C=);
5.21—5.58 (m, 2 H, —HC=CH—). 13C NMR, δ: 12.66 (17.86)
(q, C(1)); 14.15 (q, C(9)); 22.80 (t, C(8)); 27.03 (32.82) (t, C(4));
29.17, 29.37 (t, C(5), C(6)); 31.90 (t, C(7)); 123.60 (124.57)
(d, C(2)); 130.95 (131.70) (d, C(3)). MS, m/z: 126 [M]+.
Undecꢀ2ꢀene (Z(E )) (6d). B.p. 83—84 °C (20 Torr).
1H NMR, δ: 0.82—0.96 (m, 3 H, Me); 1.04—1.28 (m, 12 H,
CH2); 1.56—1.68 (m, 3 H, =CMe); 1.77—2.13 (m, 2 H,
—CH2—CH=); 5.27—5.55 (m, 2 H, —HC=CH—). 13C NMR,
δ: 12.86 (17.96) (q, C(1)); 22.87 (t, C(10)); 27.03 (33.82)
(t, C(4)); 28.46, 29.17, 29.56, 29.82 (t, C(5), C(6), C(7), C(8));
32.17 (t, C(9)); 123.53 (124.51) (d, C(2)); 130.88 (131.73)
(d, C(3)). MS, m/z: 154 [M]+.
The reactions of allenes with Et2AlCl catalyzed by Cp2TiCl2
(ZrCl4) were carried out under the same conditions with the use
of 2.2 mol. equiv. of Et2AlCl (with respect to 1,2ꢀdiene).
Allylbenzene (5a). B.p. 74—75 °C (20 Torr). IR, ν/cm–1
:
3020, 2950, 2850, 1600, 1490, 1450, 940, 850. 1H NMR, δ: 3.36
(d, 2 H, PhCH2, J = 7 Hz); 4.98—5.64 (m, 3 H, —CH=CH2);
6.94 (m, 5 H, Ph). 13C NMR, δ: 40.16 (t, C(1´)); 115.63
(t, C(3´)); 126.03 (d, C(4)); 128.24 (d, C(3), C(5)); 128.57
(d, C(2), C(6)); 137.45 (d, C(2´)); 143.90 (s, C(1)). MS,
m/z: 118 [M]+.
Dodecꢀ2ꢀene (Z(E )) (6e). B.p. 94—95 °C (5 Torr). 1H NMR,
δ: 0.82—0.96 (m, 3 H, Me); 1.09—1.28 (m, 14 H, CH2);
1.56—1.68 (m,
3 H, =CMe); 1.74—2.13 (m, 2 H,
—CH2—CH=); 5.27—5.58 (m, 2 H, —HC=CH—). 13C NMR,
δ: 12.82 (18.02) (q, C(1)); 14.22 (t, C(12)); 22.87 (t, C(11));
29.17, 29.37, 29.56, 29.89 (2 s, C(5), C(6), C(7), C(8), C(9));
32.82 (t, C(10)); 123.96 (124.87) (d, C(2)); 130.95 (131.79)
(d, C(3)). MS, m/z: 168 [M]+.
Butꢀ3ꢀenylbenzene (5b). B.p. 62—63 °C (10 Torr). 1H NMR,
δ: 2.25—2.42 (m, 2 H, CH2—C=); 3.37 (t, 2 H, PhCH2, J =
7 Hz); 4.85—6.08 (m, 3 H, —CH=CH2); 7.00—7.29 (m, 5 H,
Ph). 13C NMR, δ: 35.35 (t, C(2´)); 39.00 (t, C(1´)); 114.60
(t, C(4´)); 125.72 (d, C(4)); 128.11 (d, C(3), C(5)); 129.15
(d, C(2), C(6)); 137.61 (d, C(3´)); 138.03 (s, C(1)). MS,
m/z: 132 [M]+.
(1Z,5Z )ꢀ1,6ꢀDiphenylhexaꢀ1,5ꢀdiene (7a). B.p. 180—182 °C
(5 Torr). Found (%): C, 92.03; H, 7.20. C18H18. Calculated (%):
C, 92.30; H, 7.70. IR, ν/cm–1: 3050, 3020, 2920, 2250, 1600,
1
1500, 1490, 1450, 1080, 1030, 1000, 910, 720, 700. H NMR,
Nonꢀ1ꢀene (5c). B.p. 58—59 °C (30 Torr). IR, ν/cm–1: 2990,
2950, 2850, 1630, 1470, 910. 1H NMR, δ: 0.81—0.93 (m,
3 H, Me); 1.07—1.46 (m, 10 H, CH2); 1.81—2.17 (m, 2 H,
CH2—CH=CH2); 4.86—5.11 (m, 2 H, CH2=); 5.57—6.04 (m,
1 H, CH=CH2). 13C NMR, δ: 14.22 (q, C(9)); 22.87 (t, C(8));
29.17, 29.37, 29.63 (t, C(4), C(5), C(6)); 32.10 (t, C(7)); 34.05
(t, C(3)); 114.17 (t, C(1)); 139.82 (d, C(2)). MS, m/z: 126 [M]+.
δ: 2.20—2.45 (m, 4 H, CH2—C=C); 5.45—5.73 (m, 2 H,
CH2—CH=); 6.39 (d, 2 H, =CH—Ph, JH,H = 11.7 Hz);
7.04—7.43 (m, 10 H, Ph). 13C NMR, δ: 28.72 (t, C(3), C(4));
126.59 (d, Co Ph); 128.15 (d, Co Ph); 128.73 (d, Cm Ph); 129.45
(d, C(1), C(6)); 131.47 (d, C(2), C(5)); 137.51 (s, Cipso Ph).
MS, m/z: 234 [M]+.
3
(2Z,6Z )ꢀ1,8ꢀDiphenyloctaꢀ2,6ꢀdiene (7b). B.p. 182—183 °C
(2 Torr). Found (%): C, 91.06; H, 8.25. C20H22. Calculated (%):
C, 91.60; H, 8.40. IR, ν/cm–1: 3050, 3020, 2900, 2800,
1
Undecꢀ1ꢀene (5d). B.p. 77—78 °C (15 Torr). H NMR, δ:
0.77—0.89 (m, 3 H, Me); 1.07—1.46 (m, 14 H, CH2); 1.80—2.17
(m, 2 H, CH2—CH=CH2); 4.83—5.11 (m, 2 H, CH2=);
5.35—5.58 (m, 1 H, —CH=C—). 13C NMR, δ: 14.09 (q, C(11));
22.74 (t, C(10)); 28.98; 29.17; 29.37 (2 C); 29.56 (t, C(4), C(5),
C(6), C(7), C(8)); 31.97 (t, C(9)); 33.26 (t, C(3)); 114.04
(t, C(1)); 139.27 (d, C(2)). MS, m/z: 154 [M]+.
1
1600, 1450, 900, 720, 700. H NMR, δ: 2.20—2.55 (m, 4 H,
CH2—C=C); 3.36 (d, 4 H, Ph—CH2—C=, J = 7 Hz); 5.45—5.80
(m, 2 H, CH2—CH=); 7.00—7.40 (m, 10 H, Ph). 13C NMR,
δ: 28.93 (t, C(4), C(5)); 34.49 (t, C(1), C(8)); 126.62
(d, Cp Ph); 128.51 (d, Co Ph); 129.10 (d, Cm Ph); 129.42 (d,
C(2), C(7)); 130.75 (d, C(3), C(6)); 140.33 (s, Cipso Ph). MS,
m/z: 262 [M]+.
(7Z,11Z )ꢀOctadecaꢀ7,11ꢀdiene (7c). B.p. 137—139 °C
(2 Torr). Found (%): C, 85.90; H, 13.42. C18H34. Calculated (%):
C, 86.40; H, 13.60. IR, ν/cm–1: 3000, 2950, 2900, 2820, 1640,
1450, 900, 730. 1H NMR, δ: 0.76—0.90 (m, 6 H, Me); 1.06—1.43
(m, 16 H, CH2); 1.90—2.33 (m, 8 H, CH2—C=C); 5.28—5.38
(m, 4 H, CH=CH). 13C NMR, δ: 14.22 (q, C(1), C(18)); 22.80
(t, C(2), C(17)); 27.35 (t, C(6), C(13)); 27.55 (t, C(9), C(10));
29.43, 29.63 (t, C(4), C(5), C(14), C(15)); 32.04 (t, C(3),
1
Dodecꢀ1ꢀene (5e). B.p. 90—91 °C (10 Torr). H NMR, δ:
0.83—0.96 (m, 3 H, Me); 1.09—1.46 (m, 16 H, CH2); 1.81—2.17
(m, 2 H, CH2—CH=CH2); 4.86—5.07 (m, 2 H, CH2=);
5.33—5.58 (m, 1 H, —CH=CH2). 13C NMR, δ: 14.22 (q, C(12));
22.87 (t, C(11)); 29.17; 29.37; 29.56; 29.89 (t, 3 C, C(4), C(5),
C(6), C(7), C(8), C(9)); 32.17 (t, C(10)); 34.05 (t, C(3)); 114.17
(t, C(1)); 139.22 (t, C(2)). MS, m/z: 168 [M]+.
((Z )ꢀPropꢀ1ꢀenyl)benzene (6a). B.p. 67—68 °C (15 Torr).
1H NMR, δ: 1.58 (d, 3 H, Me, J = 7 Hz); 5.33—5.73 (m, 1 H,
3
MeCH=); 6.40 (d, 1 H, =CHPh, JH,H = 12.0 Hz); 6.98—7.30

Cycloalumination of allenes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 12, December, 2002 2259
C(16)); 129.25 (d, C(8), C(11)); 130.49 (d, C(7), C(12)). MS,
m/z: 250 [M]+.
(d, C(3), JC,D = 20.5 Hz); 114.00 (t, C(1)); 138.84 (s, C(2),
JC,D = 23.4 Hz). MS, m/z: 156 [M]+.
(9Z,13Z )ꢀDocosaꢀ9,13ꢀdiene (7d). B.p. 189—191 °C
(2 Torr). Found (%): C, 86.12; H, 13.50. C22H42. Calculated (%):
C, 86.27; H, 13.73. IR, ν/cm–1: 3000, 2950, 2850, 1640, 1450,
1380, 970, 810, 790, 720. 1H NMR, δ: 0.76—0.89 (m, 6 H, Me);
1.10—1.45 (m, 24 H, CH2); 1.95—2.12 (m, 8 H, CH2—C=C);
5.22—5.35 (m, 4 H, CH=CH). 13C NMR, δ: 14.22 (q, C(1),
C(22)); 22.80 (t, C(2), C(21)); 27.35 (t, C(8), C(15)); 27.55 (t,
C(11), C(12)); 29.43 (2 C); 29.63, 29.89 (t, C(4), C(5), C(6),
C(7), C(16), C(17), C(18), C(19)); 32.04 (t, C(3), C(20)); 129.25
(d, C(10), C(13)); 130.49 (d, C(9), C(14)). MS, m/z: 306 [M]+.
(10Z,14Z )ꢀTetracosaꢀ10,14ꢀdiene (7e). B.p. 217—218 °C
(2 Torr). Found (%): C, 85.96; H, 13.60. C24H46. Calculated (%):
C, 86.23; H, 13.77. IR, ν/cm–1: 3000, 2950, 2920, 2850, 1640,
1480, 1380, 970, 810, 790, 720. 1H NMR, δ: 0.81—0.94 (m,
6 H, Me); 1.19—1.28 (m, 28 H, CH2); 1.99—2.11 (m, 8 H,
CH2—C=C); 5.32—5.44 (m, 4 H, CH=CH). 13C NMR, δ: 14.22
(q, C(1), C(24)); 22.80 (t, C(2), C(23)); 27.35 (t, C(9), C(16));
27.55 (t, C(12), C(13)); 29.50 (2 C); 29.70 (3 C) (t, C(4), C(5),
C(6), C(7), C(8), C(17), C(18), C(19), C(20), C(21)); 32.04 (t,
C(3), C(22)); 129.25 (d, C(11), C(14)); 130.49 (d, C(10), C(15)).
MS, m/z: 334 [M]+.
2,3ꢀDideuteriododecꢀ1ꢀene (8e). B.p. 72—73 °C (2 Torr).
Found (%): C, 84.22; H, D, 15.06. C12H22D2. Calculated (%):
C, 84.70; H, 12.94; D, 2.36. IR, ν/cm–1: 3065, 2950, 2900,
2800, 2170 (C—D), 1480, 900, 820, 750. 1H NMR, δ: 0.76—0.96
(m, 3 H, Me); 1.20—1.44 (m, 16 H, CH2); 1.94—2.14 (m, 1 H,
CHD—C=C); 4.89 (s, 2 H, CH2=CD—). 13C NMR, δ: 14.22
(q, C(12)); 22.80 (t, C(11)); 28.98; 29.30; 29.50; 29.69; 29.76
(2 C) (t, C(4), C(5), C(6), C(7), C(8), C(9)); 32.04 (t, C(10));
33.47 (t, C(3), JC,D = 20.0 Hz); 114.04 (t, C(1)); 138.96 (s,
C(2), JC,D = 23.0 Hz). MS, m/z: 170 [M]+.
(2,3ꢀDideuterioꢀ(Z )ꢀpropꢀ1ꢀenyl)benzene (9a). B.p.
73—74 °C (20 Torr). Found (%): C, 89.32; H, D, 9.66. C9H8D2.
Calculated (%): C, 90.00; H, 6.67; D, 3.33. IR, ν/cm–1: 3020,
1
2950, 2850, 2160 (C—D), 1650, 1450, 940, 850. H NMR, δ:
1.58 (br.s, 2 H, CH2D); 6.39 (br.s, 1 H, —CH=CD); 7.00—7.27
(m, 5 H, Ph). 13C NMR, δ: 13.89 (t, C(3´), JC,D = 19.0 Hz);
C(2´)*; 126.00 (d, C(4)); 128.40 (d, C(2), C(6)); 129.76 (d, C(3),
C(5)); 130.20 (d, C(1´)); 139.95 (s, C(1)). MS, m/z: 120 [M]+.
(3,4ꢀDideuterioꢀ(Z )ꢀbutꢀ2ꢀenyl)benzene (9b). B.p. 72—73 °C
(15 Torr). Found (%): C, 89.14; H, D, 10.27. C10H10D2. Calcuꢀ
lated (%): C, 89.55; H, 7.46; D, 2.99. IR, ν/cm–1: 3080, 2920,
2160 (C—D), 1650, 1460, 900, 740, 700. 1H NMR, δ: 1.60 (br.s,
2 H, CH2D); 3.36 (d, 2 H, —CH2—Ph, J = 7 Hz); 5.42 (t, 1 H,
CH=CD, J = 7 Hz); 7.00—7.25 (m, 5 H, Ph). 13C NMR, δ:
13.89 (t, C(4´), JC,D = 20.4 Hz); C(3´)*; 39.25 (t, C(1´)); 125.90
(d, C(4)); 128.35 (d, C(3), C(5)); 128.52 (d, C(2), C(6)); 130.00
(d, C(2´)); 141.81 (s, C(1)). MS, m/z: 134 [M]+.
1,2ꢀDideuteriononꢀ2ꢀene (Z(E)ꢀ9c)). B.p. 67—68 °C
(40 Torr). Found (%): C, 83.88; H, D, 15.36. C9H16D2. Calcuꢀ
lated (%): C, 84.37; H, 12.50; D, 3.13. IR, ν/cm–1: 3030, 2950,
2850, 2170 (C—D), 1640, 1450, 900, 850, 720. 1H NMR, δ:
0.82—0.94 (m, 3 H, Me); 1.04—1.38 (m, 8 H, CH2); 1.56
and 1.68 (both s, 2 H, CH2D—C=C); 1.86—2.34 (m, 2 H,
CH2—C=C); 5.21—5.52 (m, 1 H, CH=CD—). 13C NMR, δ:
12.48 (17.99) (t, C(1), JC,D = 19.5 Hz); 14.15 (q, C(9)); 23.06
(t, C(8)); 26.96 (33.99) (t, C(4)); 29.63, 29.80 (t, C(5), C(6));
32.40 (t, C(7)); 123.53 (124.51) (s, C(2), JC,D = 22.4 Hz);
130.88 (131.73) (t, C(3)). MS, m/z: 128 [M]+.
(1,2ꢀDideuterioallyl)benzene (8a). B.p. 81—82 °C (30 Torr).
Found (%): C, 89.62; H, D, 9.87. C9H8D2. Calculated (%):
C, 90.00; H, 6.67, D, 3.33. IR, ν/cm–1: 3070, 3050, 3010, 2910,
1
2170 (C—D), 1600, 1490, 1450, 1020, 920, 700. H NMR, δ:
3.35 (s, H, Ph—CHD); 5.04 (s, 2 H, CH2=CD); 6.38—7.27 (m,
5 H, Ph). 13C NMR, δ: 39.80 (d, C(1´), JC,D = 19.8 Hz); 115.63
(t, C(3´)); 126.03 (d, C(4)); 128.24 (d, C(2), C(6)); 128.37 (d,
C(3), C(5)); 137.12 (s, C(2´), JC,D = 23.4 Hz); 143.91 (s, C(1)).
MS, m/z: 120 [M]+.
(2,3ꢀDideuteriobutꢀ3ꢀenyl)benzene (8b). B.p. 70—71 °C
(15 Torr). Found (%): C, 89.16; H, D, 9.90. C10H10D2. Calcuꢀ
lated (%): C, 89.55; H, 7.46; D, 2.99. IR, ν/cm–1: 3075, 3020,
2920, 2840, 2170 (C—D), 1600, 1490, 1450, 1020, 910, 740,
700. 1H NMR, δ: 2.25—2.46 (m, 1 H, CHD—C=C); 3.23—3.44
(m, 2 H, CH2—Ph); 5.03 (s, 2 H, CH2=CD); 6.94—7.25 (m,
5 H, Ph). 13C NMR, δ: 35.03 (d, C(2´), JC,D = 19.8 Hz); 38.99
(t, C(1´)); 114.62 (t, C(4´)); C(3´)*; 125.68 (d, C(4)); 128.06
(d, C(3), C(5)); 128.21 (d, C(2), C(6)); 138.03 (s, C(1)). MS,
m/z: 134 [M]+.
1,2ꢀDideuterioundecꢀ2ꢀene (Z(E )ꢀ9d)). B.p. 83—84 °C
(20 Torr). Found (%): C, 84.17; H, D, 15.14. C11H20D2. Calcuꢀ
lated (%): C, 84.62; H, 12.82; D, 2.56. IR, ν/cm–1: 3020, 2900,
2850, 2170 (C—D), 1620, 1450, 900, 720. 1H NMR, δ: 0.82 (m,
3 H, Me); 1.04—1.36 (m, 12 H, CH2); 1.56 and 1.61 (both s, 2 H,
CH2D—C=C); 1.92—2.12 (m, 2 H, CH2—C=C); 5.25—5.56
2,3ꢀDideuteriononꢀ1ꢀene (8c). B.p. 52—54 °C (20 Torr).
Found (%): C, 83.92; H, D, 15.20. C9H16D2. Calculated (%):
C, 84.37; H, 12.50; D, 3.13. IR, ν/cm–1: 3070, 2920, 2830, 2160
(C—D), 1460, 910, 800, 740. 1H NMR, δ: 0.76—0.96 (m,
3 H, Me); 1.29—1.76 (m, 10 H, CH2); 1.96—2.05 (m, 1 H,
CHD—C=C); 4.95 (s, 2 H, CH2=CD—). 13C NMR, δ: 14.15
(q, C(9)); 22.87 (t, C(8)); 29.34; 29.59; 29.76 (t, C(4), C(5),
C(6)); 32.10 (t, C(7)); 34.05 (d, C(3), JC,D = 20.0 Hz); 115.00
(t, C(1)), 139.20 (s, C(2), JC,D = 23.0 Hz). MS, m/z: 128 [M]+.
2,3ꢀDideuterioundecꢀ1ꢀene (8d). B.p. 72—73 °C (10 Torr).
Found (%): C, 84.15; H, D, 15.12. C11H20D2. Calculated (%):
C, 84.62; H, 12.82; D, 2.56. IR, ν/cm–1: 3070, 2950, 2910,
(m, 1 H, CH=CD). 13C NMR, δ: 12.76 (17.87) (t, C(1), JC,D
=
19.0 Hz); 14.22 (q, C(11)); 22.80 (t, C(10)); 26.96 (33.83) (t,
C(4)); 29.17, 29.55, 29.75, 29.86 (t, C(5), C(6), C(7), C(8));
32.04 (t, C(9)); 123.66 (124.57) (s, C(2), JC,D = 22.4 Hz);
131.01 (131.79) (d, C(3)). MS, m/z: 156 [M]+.
1,2ꢀDideuteriododecꢀ2ꢀene (Z(E )ꢀ9e). B.p. 94—95 °C
(5 Torr). Found (%): C, 84.37; H, D, 15.06. C12H22D2. Calcuꢀ
lated (%): C, 84.70; H, 12.94; D, 2.36. IR, ν/cm–1: 3025, 2950,
1
1
2850, 2170 (C—D), 1620, 1450, 900, 810, 750. H NMR, δ:
2900, 2850, 2170 (C—D), 1620, 1450, 920, 710. H NMR, δ:
0.76—0.96 (m, 3 H, Me); 1.24—1.59 (m, 14 H, CH2); 1.94—2.16
(m, 1 H, CHD—C=C); 4.93 (s, 2 H, CH2=CD—). 13C NMR,
δ: 14.11 (q, C(11)); 22.76 (t, C(10)); 28.94; 29.26; 29.46; 29.65
(2 C) (t, C(4), C(5), C(6), C(7), C(8)); 32.06 (t, C(9)); 32.91
0.82—0.94 (m, 3 H, Me); 1.05—1.41 (m, 14 H, CH2); 1.56
and 1.61 (both s, 2 H, CH2D—C=C); 1.92—2.16 (m, 2 H,
CH2—C=C); 5.32—5.65 (m, 1 H, CD=CH). 13C NMR, δ: 12.75
(17.99) (t, C(1), JC,D = 20.5 Hz); 14.15 (q, C(12)); 22.80
* The signal is not observed.
* The signal is not observed.

2260
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 12, December, 2002
Ibragimov et al.
(t, C(11)); 27.45 (t, C(9)); 27.03 (34.05) (t, C(4)); 29.40, 29.68,
29.76, 29.80 (2 C) (t, C(5), C(6), C(7), C(8)); 32.04 (t, C(10));
123.66 (124.57) (s, C(2), JC,D = 22.4 Hz); 130.95 (131.79)
(d, C(3)). MS, m/z: 170 [M]+.
(t, C(2), C(23)); 27.42 (t, C(9), C(12), C(13), C(16)); 29.56
(2 C), 29.76 (3 C) (t, C(4), C(5), C(6), C(7), C(8), C(17),
C(18), C(19), C(20), C(21)); 32.04 (t, C(3), C(22)); 130.40 (d,
C(10), C(15)); C(11)*; C(14)*. MS, m/z: 236 [M]+.
2,5ꢀDideuterioꢀ(1Z,5Z )ꢀ1,6ꢀdiphenylhexaꢀ1,5ꢀdiene (10a).
B.p. 180—182 °C (5 Torr). Found (%): C, 91.16; H, D, 8.26.
C18H16D2. Calculated (%): C, 91.53; H, 6.77; D, 1.70. IR,
ν/cm–1: 3030, 2900, 2800, 2165 (C—D), 1600, 1500, 1450, 1080,
References
1
1. S. V. Rusakov, L. M. Khalilov, L. V. Parfenova, A. G.
Ibragimov, O. A. Ponomarev, and U. M. Dzhemilev, Izv.
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Ed., 2001, 50, 2336].
2. L. O. Khafizova, A. G. Ibragimov, G. N. Gil´fanova, L. M.
Khalilov, and U. M. Dzhemilev, Izv. Akad. Nauk, Ser. Khim.,
2001, 2089 [Russ. Chem. Bull., Int. Ed., 2001, 50, 2188].
3. U. M. Dzhemilev, A. G. Ibragimov, L. O. Khafizova,
S. V. Rusakov, and L. M. Khalilov, Mendeleev Commun.,
1997, 198.
4. U. M. Dzhemilev and A. G. Ibragimov, J. Organometal.
Chem., 1994, 466, 1.
5. U. M. Dzhemilev and A. G. Ibragimov, Izv. Akad. Nauk,
Ser. Khim., 1998, 816 [Russ. Chem. Bull., 1998, 47, 786 (Engl.
Transl.)].
6. U. M. Dzhemilev and A. G. Ibragimov, Usp. Khim., 2000,
69, 134 [Russ. Chem. Rev., 2000, 69, 121 (Engl. Transl.)].
7. A. J. Gordon and R. A. Ford, The Chemist´s Companion,
J. Wiley and Sons, New York—London—Sydney—Toronꢀ
to, 1972.
8. E. BreitꢀMaier and W. Voelter, 13C NMR Spectroscopy, Verlag
Chemie GmbH, Weinheim, 1974, 276.
9. A. G. Ibragimov, L. O. Khafizova, K. G. Satenov, L. M.
Khalilov, L. G. Yakovleva, S. V. Rusakov, and U. M.
Dzhemilev, Izv. Akad. Nauk, Ser. Khim., 1999, 1594 [Russ.
Chem. Bull., 1999, 48, 1574 (Engl. Transl.)].
10. P. Sobota, T. Pluzinski, B. JezowskaꢀTrzebiatowska, and
S. Rummel, J. Organometal. Chem., 1980, 185, 69.
11. A. G. Ibragimov, L. O. Khafizova, I. V. Zagrebel´naya, L. V.
Parfenova, R. M. Sultanov, L. M. Khalilov, and U. M.
Dzhemilev, Izv. Akad. Nauk, Ser. Khim., 2001, 280 [Russ.
Chem. Bull., Int. Ed., 2001, 50, 292].
900, 720, 700. H NMR, δ: 2.42 (br.s, 4 H, CH2—C=C); 6.40
(br.s, 2 H, C=CH—Ph); 7.04—7.55 (m, 10 H, Ph). 13C NMR,
δ: 28.72 (t, C(3), C(4)); 126.59 (d, Cp Ph); 128.15 (d, Co Ph);
128.73 (d, Cm Ph); 129.45 (d, C(1), C(6)); 131.47 (s, C(2),
C(5), J = 23.4 Hz); 137.51 (s, Cipso Ph). MS, m/z: 236 [M]+.
3,6ꢀDideuterioꢀ(2Z,6Z )ꢀ1,8ꢀdiphenyloctaꢀ2,6ꢀdiene (10b).
B.p. 182—183 °C (2 Torr). Found (%): C, 90.56; H, D, 8.94.
C20H20D2. Calculated (%): C, 90.90; H, 7.58; D, 1.52. IR,
ν/cm–1: 3050, 3020, 2900, 2800, 2160 (C—D), 1600, 1500, 1450,
1
900, 720, 700. H NMR, δ: 2.45 (br.s, 4 H, CH2—C=C); 3.36
(d, 4 H, Ph—CH2—, J = 7 Hz); 5.43 (t, 2 H, CD=CH, J =
7 Hz); 7.00—7.35 (m, 10 H, Ph). 13C NMR, δ: 28.90 (t, C(4),
C(5)); 34.42 (t, C(1), C(8)); 126.60 (d, Cp Ph); 128.52 (d, Co Ph);
129.06 (d, Cm Ph); 129.40 (d, C(2), C(8)); 130.40 (s, C(3),
C(6), JC,D = 22.5 Hz); 140.38 (s, Cipso Ph). MS, m/z: 264 [M]+.
8,11ꢀDideuterioꢀ(7Z,11Z )ꢀoctadecaꢀ7,11ꢀdiene (10c). B.p.
137—138 °C (2 Torr). Found (%): C, 85.33; H, D, 14.08.
C18H32D2. Calculated (%): C, 85.71; H, 12.70; D, 1.59. IR,
ν/cm–1: 3040, 3020, 2900, 2850, 2170 (C—D), 1640, 1450, 900,
720, 700. 1H NMR, δ: 0.82—0.95 (m, 6 H, Me); 1.07—1.46 (m,
16 H, CH2); 1.81—2.07 (m, 8 H, CH2—C=C); 5.38 (t, 2 H,
CD=CH, J = 7 Hz). 13C NMR, δ: 14.22 (q, C(1), C(18)); 22.80
(t, C(2), C(17)); 27.42 (t, C(6), C(9), C(10), C(13)); 29.43,
29.63 (t, C(4), C(5), C(14), C(15)); 31.90 (t, C(3), C(16));
C(8)*; C(11)*; 130.30 (d, C(7), C(12)). MS, m/z: 252 [M]+.
10,13ꢀDideuterioꢀ(9Z,13Z)ꢀdocosaꢀ9,13ꢀdiene (10d). B.p.
190—192 °C (2 Torr). Found (%): C, 85.41; H, D, 13.96.
C22H40D2. Calculated (%): C, 85.71; H, 12.99; D, 1.30. IR,
ν/cm–1: 3040, 3025, 2900, 2850, 2170 (C—D), 1640, 1450, 900,
720, 700. 1H NMR, δ: 0.82—0.95 (m, 6 H, Me); 1.08—1.51 (m,
24 H, CH2); 1.89—2.07 (m, 8 H, CH2—C=C); 5.36 (t, 2 H,
CD=CH, J = 7 Hz). 13C NMR, δ: 14.15 (q, C(1), C(22)); 22.87
(t, C(2), C(21)); 27.41 (t, C(8), C(11), C(12), C(15)); 29.56
(4 C); 29.76 (4 C) (t, C(4), C(5), C(6), C(7), C(16), C(17),
C(18), C(19)); 32.17 (t, C(3), C(20)); C(10)*; C(13)*; 130.17
(d, C(9), C(14)). MS, m/z: 308 [M]+.
12. F. Sato, K. Oguro, and M. Sato, Chem. Lett., 1978, 805.
13. A. N. Nesmeyanov, T. V. Nikitina, and O. V. Nogina, Metody
elementoorganicheskoi khimii. Podgruppa aktinoidy [Methods
of Organometallic Chemistry. Actinide Subgroup], Nauka,
Moscow, 1974, 335 pp. (in Russian).
14. G. Wilkinson and J. M. Birmingham, J. Am. Chem. Soc.,
1954, 76, 4281.
15. R. Kh. Freidlina, E. M. Brainina, and A. N. Nesmeyanov,
Dokl. Akad. Nauk SSSR, 1961, 138, 1369 [Dokl. Chem., 1969
(Engl. Transl.)].
11,14ꢀDideuterioꢀ(10Z,14Z )ꢀtetracosaꢀ10,14ꢀdiene (10e).
B.p. 218—219 °C (2 Torr). Found (%): C, 85.29; H, D, 14.06.
C24H44D2. Calculated (%): C, 85.71; H, 13.09; D, 1.20. IR,
ν/cm–1: 3035, 2900, 2850, 2170 (C—D), 1620, 1450, 970, 720,
700. 1H NMR, δ: 0.82—0.94 (m, 6 H, Me); 1.08—1.52 (m,
28 H, CH2); 1.90—2.07 (m, 8 H, CH2—C=C); 5.36 (t, 2 H,
CD=CH, J = 7 Hz). 13C NMR, δ: 14.15 (q, C(1), C(24)); 22.80
Received July 2, 2001;
* The signal is not observed.
in revised form July 19, 2002