Synthesis and transformations of metallacycles 26. Cp2ZrCl2-catalyzed cycloalumination of substituted allenes with Et3Al

Article abstract of DOI:10.1023/A:1015069822374

Catalytic cycloalumination of 1-alkyl(phenyl)alleres with triethylaluminum (5 mol.% of Cp₂ZrCl₂ as the catalyst, -20 °C, 4 h, hexane) afforded methylene- and alkyl(benzyl)idene-substituted alumacyclopentanes.

Full text of DOI:10.1023/A:1015069822374

2188
Russian Chemical Bulletin, International Edition, Vol. 50, No. 11, pp. 2188—2192, November, 2001
Organometallic Chemistry
Synthesis and transformations of metallacycles
26.* Cp2ZrCl2-Catalyzed cycloalumination of substituted allenes with Et3Al
L. O. Khafizova, A. G. Ibragimov, G. N. Gil´fanova, L. M. Khalilov, and U. M. Dzhemilev«
Institute of Petrochemistry and Catalysis,
Bashkortostan Republic Academy of Sciences and Ufa Scientific Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. E-mail: ink@anrb.ru
Catalytic cycloalumination of 1-alkyl(phenyl)allenes with triethylaluminum (5 mol.% of
Cp2ZrCl2 as the catalyst, ∼20 °C, 4 h, hexane) afforded methylene- and alkyl(benzyl)idene-
substituted alumacyclopentanes.
Key words: organoaluminum compounds, catalysis, cyclometallation, alumacyclopentanes,
allenes.
Previously, we have demonstrated2—7 that cyclo-
deuterolysis 5a—c and 6a—c were established by spec-
tral methods.8 The numbering of C atoms used for the
description of the 13C NMR spectrum of compound 1a
is given below:
alumination of aliphatic α-olefins, arylethylenes,
norbornenes, and functionally substituted N-, O-, and
S-containing α-olefins with Et3Al or EtAlCl2 in the
presence of catalytic amounts of Cp2ZrCl2 afforded
alumacyclopentanes (ACP).
3
2
10
8
6
As part of continuing studies of these reactions and
with the aim of extending this procedure, which has
been developed for the synthesis of cyclic organo-
aluminum compounds (OAC), to 1,2-dienes, we exam-
ined the reactions of 1-alkyl(aryl)-substituted allenes
with Et3Al catalyzed by zirconium complexes.
We found that the reactions of 1,2-alkadienes with
an excess of Et3Al under the conditions used previ-
ously2,3 (5 mol.% of Cp2ZrCl2, 4 h, hexane) afforded
regioisomeric alumacyclopentanes 1a—c and 2a—c in a
ratio of (6—7) : 1 in a total yield of 85—95% de-
pending on the structures of the starting allenes
(Scheme 1).
1
11
9
7
5
4
Al
CH2 CH3
12
13
Since compounds 2a—c were obtained as minor
products and mixtures of organoaluminum compounds
were difficult to separate, we failed to make the reliable
assignment of the signals in the 13C NMR spectra. At
the same time, the yields of compounds 1a—c and 2a—c
can be determined by GLC based on the products of
their hydrolysis (3a—c and 4a—c, respectively). The
subsequent isolation and identification of the deuterolysis
products (5a—c and 6a—c, respectively) and the deter-
mination of the position of the deuterium atom made it
possible to unambiguously judge the structures of the
resulting OAC 1a—c and 2a—c.
The structures of regioisomeric ACP 1a—c and 2a—c
and the products of their hydrolysis 3a—c and 4a—c and
* For Part 25, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2089—2093, November, 2001.
1066-5285/01/5011-2188 $25.00 © 2001 Plenum Publishing Corporation

Cycloalumination of substituted allenes with Et3Al Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2189
Scheme 1
R
R
H3O+
+
H H
H H
R
R
[Zr]
3a—c
4a—c
R CH C CH2 + Et3Al
+
–C2H6
R
Al
Al
R
D3O+
Et
Et
+
1a—c
2a—c
D D
D D
5a—c
6a—c
R = n-C6H13 (a); n-C8H17 (b); n-C9H19 (c)
Thus, the 13C NMR spectrum of olefin 3a is charac-
terized by the presence of high-field signals for the allylic
C(3) and C(6) atoms (δ 29.11 and 27.35, respectively)
corresponding to the Z configuration of the double bond
in the alkane chain of the molecule. In the spectrum of
the dideuterated analog of this compound (5a), the upfield
α-isotopic shifts are observed for the C(1) and C(4) atoms
(∆δ = 0.26 and 0.33, respectively). The formation of
1,4-dideuterated hydrocarbons 5a and 6a upon deuterolysis
of OAC 1a and 2a indicates that the Al atoms in the latter
compounds are bound simultaneously to two C atoms.
The above-considered results provide evidence that
cycloalumination of allenes with Et3Al gave rise to five-
membered OAC 1a and 2a. Analogously, we proved the
structures of other cyclic OAC, viz., 1b,c and 2b,c.
Cyclometallation of 1,2-alkadienes proceeded in ali-
phatic (hexane or cyclohexane) or aromatic (benzene or
toluene) solvents as well as in dichloromethane during
4—5 h (Tables 1 and 2). In ethereal solvents (THF) or in
the absence of the solvent, the reactions proceeded in
low yields due to polymerization of the starting allene.
At ∼0 °C, the reaction in hexane proceeded more
slowly and the conversion of the initial 1,2-alkadienes
was at most 40% after 8 h. The highest yields of ACP 1b
and 2b were obtained at 20 °C and at the concentration
of the catalyst Cp2ZrCl2 equal to 5 mol.%. Under these
conditions, the total yield of regioisomeric products 1b
Table 2. Dependence of the yields of ACP
1b and 2b on the reaction time*
Reaction
time/h
Yield of ACP (%)
1b
2b
0.5
1
2
3
4
36
47
62
75
80
82
6
8
10
12
13
13
5
* The reaction conditions: hexane, ∼20 °C,
n-C8H17—CH=C=CH2 : Et3Al : Cp2ZrCl2 =
10 : 13 : 0.5.
and 2b was 93%. The total yield of a mixture of ACP 1b
and 2b falled to 55% as the concentration of the catalyst
was decreased to 1 mol.%, the ratio of the regioisomers
remaining unchanged.
Under the optimum conditions (∼20 °C, 4 h, hexane,
5 mol.% of Cp2ZrCl2), cyclometallation of phenylallene
with triethylaluminum afforded mixtures of unsaturated
cyclic OAC 7, 8, and 9 in a ratio of ∼4 : 2 : 1 in a total
yield of ∼90% (Scheme 2).
Treatment of unsaturated OAC 7 with an aqueous
solution of HCl gave rise to olefin 10 with the
Z configuration of the double bond, which is charac-
terized by the vicinal spin-spin coupling constant
3JH,H = 11.6 Hz for the cis-protons of the double bond
Table 1. Effect of the nature of the solvent on
the yields of ACP 1b and 2b*
3
(cf. lit. data9: Jtrans = 18 Hz). Analogously, hydrocar-
bons 11 and 12 were prepared from compounds 8 and 9,
respectively. Deuterolysis of OAC 7—9 afforded prod-
ucts 13—15, respectively. Compounds 10—15 were char-
acterized by the physicochemical parameters consis-
tent with their structures (see the Experimental section),
which confirmed the structures of the starting OAC 7—9.
According to the data published in the literature,10—14
the generation of five-membered OAC in our experi-
ments is attributable to the formation of five- and seven-
membered bimetallic Zr—Al complexes 16 and 17a,b as
intermediates whose successive transformations afforded
the target regioisomeric unsaturated alumacyclopentanes
1 and 2 according to Scheme 3.
Solvent
Yield of ACP (%)
1b
2b
Hexane
Cyclohexane
Benzene
Toluene
CH2Cl2
THF
80
70
77
75
92
18
12
13
15
12
10
3
3
3
—
* The reaction conditions: ∼20 °C, 4 h,
n-C8H17—CH=C=CH2 : Et3Al : Cp2ZrCl2 =
10 : 13 : 0.5.

2190
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Khafizova et al.
Scheme 2
[Zr]
CH C CH2 + Et3Al
+
+
–C2H6
Al
Al
Et
8
Al
Et
Et
7
9
4
5
4
5
3
6
11
3
H3O+
6
2
1
9
10
7
5
3
6
2
8
9
8
2
1
1
9
4
10
+
+
7
11
7
8
11 10
H H
H H
H H
10
11
12
4
5
4
2
5
3
6
11
3
D3O+
6
2
1
9
10
7
5
3
6
2
8
9
8
1
1
9
4
10
+
+
7
11
7
8
11 10
D D
D D
D D
13
14
15
the sp2-hybridized carbon atoms of 1,2-alkadienes or
with the π—d interaction between the double bond of
the allene and the unoccupied d orbital of the Zr atom.
Both alternatives can favor a particular spatial orienta-
tion of allenes at the central atom of the catalyst and
their insertion at the Zr—C bond to form intermediate
bimetallic complexes 17a,b, which contain the alkylidene
or methylene substituents at the C atom bound to the Zr
atom. For the same reason, cyclometallation of phenyl-
allene with Et3Al additionally afforded3 regioisomeric
ACP 9 containing the phenyl substituent at the carbon
atom bound to the Al atom.
Scheme 3
Cp2ZrCl2 + 2 Et3Al
Et2AlCl
C2H6
Cp2Zr
AlEt2
Cl
16
R
CH
C
CH2
To summarize, cyclometallation of monosubstituted
allenes with triethylaluminum under the action of the
catalyst Cp2ZrCl2 proceeds both at the terminal and
disubstituted double bonds to form regioisomeric unsat-
urated alumacyclopentanes in high yields.
R
R
+
Cp2Zr
Cp2Zr
AlEt2
AlEt2
Cl
Cl
17a
17b
Experimental
Cp2ZrEtCl
The starting allenes and Cp2ZrCl2 were prepared according
to known procedures.15,16 The solvents were distilled over
LiAlH4 immediately before use; commercial 95% Et3Al (the
Redkinskii pilot-production plant, Russia) was used. The
hydrolysis and deuterolysis products were analyzed by GLC on
a Chrom-5 chromatograph (a 1200½3-mm column; 5% SE-30
or 15% PEG-6000 on Chromaton N-AW) under a stream of
He. The IR spectra were measured on an IR-75 spectrometer
(film). The mass spectra were obtained on an MÕ-1306 spec-
trometer (70 eV, 200 °C). The 1H and 13C NMR spectra were
recorded in CDCl3 on Jeol FX-90 Q (90 and 22.5 MHz) and
R
R
Al
Al
Et
Et
1
2
The observed regioselectivity of the reaction is, prob-
ably, associated with the electron density distribution on

Cycloalumination of substituted allenes with Et3Al Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001 2191
Bruker AM-300 (300 and 75 MHz) spectrometers, respec-
tively, with Me4Si as the internal standard. The 13C NMR
spectra of OAC were measured with the use of C6D6 as the
solvent and the internal standard.
Cp2ZrCl2-Catalyzed cyclometallation of allenes with Et3Al
(general procedure). Allene (10 mmol), Cp2ZrCl2 (0.5 mol),
hexane (10 mL), and Et3Al (13 mmol) were placed with
stirring in a glass reactor under an atmosphere of dry argon at
0 °C. The reaction mixture was heated to 20 °C and stirred for
4 h. Then the mixture was treated with a 7—10% solution of
HCl or DCl in D2O, extracted with hexane, and dried with
MgSO4. The reaction products were isolated by vacuum distil-
lation on a Widmer column.
E-1-Ethyl-2-hexylidenealumacyclopentane (1a). 13C NMR,
δ: 18.10 (t, C(1)); 32.41 (t, C(2)); 34.88 (t, C(3)); 143.0
(s, C(4)); 170.40 (d, C(5)); 25.45 (t, C(6)); 28.77 (t, C(7));
29.61 (t, C(8)); 32.15 (t, C(9)); 23.11 (t, C(10)); 14.33
(q, C(11)); 0.81 (t, C(12)); 8.26 (q, C(13)).
Z-Undec-4-ene (3a). B.p. 81 °C (20 Torr). Found (%):
C, 85.50; H, 14.10. C11H22. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2920, 2850, 2300, 1640, 1460, 910, 720.
1H NMR, δ: 0.77—0.92 (m, 6 H, Me); 1.06—1.55 (m, 10 H,
CH2); 1.76—1.99 (m, 4 H, CH2—C=C); 5.26—5.36 (m, 2 H,
CH=CH). 13C NMR, δ: 13.89 (q, C(1)); 23.00 (t, C(2)); 29.11
(t, C(3)); 129.71 (d, C(4)); 130.17 (d, C(5)); 27.35 (t, C(6));
29.89 (t, C(7)); 29.43 (t, C(8)); 31.90 (t, C(9)); 22.74 (t, C(10));
14.15 (q, C(11)). MS, m/z: 154 [M]+.
3-Ethyldodec-1-ene (4c). B.p. 95 °C (2 Torr). Found (%):
C, 85.52; H, 14.24. C14H28. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2940, 2900, 2800, 1450, 910, 895, 720.
1H NMR, δ: 0.83—0.96 (m, 6 H, Me); 1.20—1.57 (m, 18 H,
CH2); 1.95—2.17 (m, 1 H, CH—C=C); 4.46—5.20 (m, 3 H,
CH2=CH). 13C NMR, δ: 114.20 (t, C(1)); 143.80 (d, C(2));
45.20 (d, C(3)); 34.80 (t, C(4)); 27.65 (t, C(5)); 29.56 (t, C(6));
29.76 (t, C(7)); 29.50 (t, C(8)); 29.32 (t, C(9)); 32.10 (t, C(10));
22.82 (t, C(11)); 14.15 (q, C(12)); 27.74 (t, C(13)); 12.70
(q, C(14)). MS, m/z: 196 [M]+.
Z-1,4-Dideuteroundec-1-ene (5a). B.p. 75 °C (14 Torr).
Found (%): C, 84.42; H, D, 15.25. C11H20D2. Calculated (%):
C, 84.62; H, 12.82; D, 2.56. IR, ν/cm–1: 3080, 2920, 2850,
1
2160 (CD), 1450, 910, 790, 720. H NMR, δ: 0.77—0.91 (m,
5 H, Me); 1.22—1.53 (m, 10 H, CH2); 1.90—2.07 (m, 4 H,
CH2—C=C); 5.37 (t, 1 H, CD=CH, 3J = 7 Hz). 13C NMR, δ:
1
13.63 (t, C(1), JC,D = 19.5 Hz); 22.80 (t, C(2)); 29.11
(t, C(3)); 129.38 (s, C(4), 1JC,D = 23.4 Hz); 130.04 (d, C(5));
27.29 (t, C(6)); 29.89 (t, C(7)); 29.30 (t, C(8)); 31.90 (t, C(9));
22.80 (t, C(10)); 14.22 (q, C(11)). MS, m/z: 156 [M]+.
Z-1,4-Dideuterotridec-4-ene (5b). B.p. 90 °C (4 Torr).
Found (%): C, 84.62; H, D, 15.10. C13H24D2. Calculated (%):
C, 84.78; H, 13.04; D, 2.18. IR, ν/cm–1: 3080, 2950, 2900,
2850, 2170 (CD), 1640, 1450, 1370, 910, 895, 720. 1H NMR,
δ: 0.83—0.96 (m, 5 H, Me); 1.10—1.48 (m, 14 H, CH2);
1.92—2.10 (m, 4 H, CH2—C=C); 5.34 (t, 1 H, CD=CH,
1
3J = 7 Hz). 13C NMR, δ: 12.75 (t, C(1), JC,D = 19.1 Hz);
1
Z-Tridec-4-ene (3b). B.p. 85 °C (2 Torr). Found (%):
C, 85.20; H, 14.20. C13H26. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2950, 2900, 2850, 1640, 1450, 1370, 910,
23.06 (t, C(2)); 29.56 (t, C(3)); 129.58 (s, C(4), JC,D
=
23.0 Hz); 132.40 (d, C(5)); 27.42 (t, C(6)); 29.76 (t, C(7));
29.76 (t, C(8)); 29.80 (t, C(9)); 29.89 (t, C(10)); 32.10 (t, C(11));
22.87 (t, C(12)); 14.15 (q, C(13)). MS, m/z: 184 [M]+.
Z-1,4-Dideuterotetradec-4-ene (5c). B.p. 95 °C (4 Torr).
Found (%): C, 84.46; H, D, 15.05. C14H26D2. Calculated (%):
C, 84.55; H, 13.13; D, 2.02. IR, ν/cm–1: 3080, 2950, 2850,
1
895, 720. H NMR, δ: 0.80—0.96 (m, 6 H, Me); 1.10—1.57
(m, 14 H, CH2); 1.90—2.11 (m, 4 H, CH2—C=C); 5.24—5.70
(m, 2 H, CH=CH). 13C NMR, δ: 13.83 (q, C(1)); 23.06
(t, C(2)); 29.30 (t, C(3)); 129.58 (d, C(4)); 130.10 (d, C(5));
27.42 (t, C(6)); 29.56 (t, C(7)); 29.76 (t, C(8)); 29.76 (t, C(9));
29.89 (t, C(10)); 32.10 (t, C(11)); 22.87 (t, C(12)); 14.15
(q, C(13)). MS, m/z: 182 [M]+.
1
2170 (CD), 1450, 910, 895, 720. H NMR, δ: 082—0.95 (m,
5 H, Me); 1.21—1.45 (m, 16 H, CH2); 1.95—2.10 (m, 4 H,
CH2—C=C); 5.32 (t, 1 H, CD=CH, 3J = 7 Hz). 13C NMR, δ:
1
Z-Tetradec-4-ene (3c). B.p. 97 °C (4 Torr). Found (%):
C, 85.60; H, 14.12. C14H28. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2950, 2910, 2850, 1450, 910, 895, 720.
1H NMR, δ: 0.75—0.93 (m, 6 H, Me); 1.17—1.45 (m, 16 H,
CH2); 1.95—2.10 (m, 4 H, CH2—C=C); 5.10—5.83 (m, 2 H,
CH=CH). 13C NMR, δ: 13.50 (q, C(1)); 23.00 (t, C(2)); 29.30
(t, C(3)); 129.97 (d, C(4)); 132.10 (d, C(5)); 27.20 (t, C(6));
29.50 (t, C(7)); 29.56 (t, C(8)); 29.89 (t, C(9)); 29.76 (t, C(10));
29.76 (t, C(11)); 32.04 (t, C(12)); 22.87 (t, C(13)); 14.50
(q, C(14)). MS, m/z: 196 [M]+.
3-Ethylnon-1-ene (4a). B.p. 77 °C (20 Torr). Found (%):
C, 85.52; H, 14.26. C11H22. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2900, 2850, 2300, 1640, 1450, 910, 720.
1H NMR, δ: 0.73—0.98 (m, 6 H, Me); 1.09—1.51 (m, 12 H,
CH2); 1.76—2.07 (m, 1 H, CH—C=C); 4.76—5.69 (m, 3 H,
CH2=CH). 13C NMR, δ: 114.04 (t, C(1)); 143.50 (d, C(2));
45.95 (d, C(3)); 34.77 (t, C(4)); 27.29 (t, C(5)); 29.56 (t, C(6));
32.04 (t, C(7)); 22.80 (t, C(8)); 14.22 (q, C(9)); 27.81 (t, C(10));
11.68 (q, C(11)). MS, m/z: 154 [M]+.
13.50 (t, C(1), JC,D = 19.1 Hz); 22.80 (t, C(2)); 29.30
(t, C(3)); 129.25 (s, C(4), 1JC,D = 22.0 Hz); 129.97 (d, C(5));
27.35 (t, C(6)); 29.50 (t, C(7)); 29.76 (t, C(8)); 29.76 (t, C(9));
29.76 (t, C(10)); 29.50 (t, C(11)); 32.04 (t, C(12)); 22.80
(t, C(13)); 14.15 (q, C(14)). MS, m/z: 198 [M]+.
2-Deutero-3-(2-deuteroethyl)non-1-ene (6a). B.p. 74 °C
(20 Torr). Found (%): C, 84.30; H, D, 15.13. C11H20D2.
Calculated (%): C, 84.62 H, 12.82; D, 2.56. IR, ν/cm–1: 3080,
2920, 2850, 2160 (CD), 1450, 910, 790, 720. 1H NMR, δ:
0.83—0.94 (m, 5 H, Me); 1.28—1.53 (m, 12 H, CH2);
1.93—2.07 (m, 1 H, CH—C=C); 4.69—5.55 (m, 2 H,
CD=CH2). 13C NMR, δ: 113.91 (t, C(1)); 45.82 (d, C(3));
34.77 (t, C(4)); 27.29 (t, C(5)); 29.56 (t, C(6)); 31.90 (t, C(7));
22.80 (t, C(8)); 14.22 (q, C(9)); 27.74 (t, C(10)); 13.89
(t, C(11), 1JC,D = 20.5 Hz). MS, m/z: 156 [M]+.
2-Deutero-3-(2-deuteroethyl)undec-1-ene (6b). B.p. 75 °C
(2 Torr). Found (%): C, 84.50; H, D, 15.07. C13H24D2.
–1
Calculated (%): C, 84.78; H, 13.04; D, 2.18. IR, ν/cm
:
3080, 2950, 2840, 2170 (CD), 1640, 1450, 1370, 910, 895,
720. H NMR, δ: 0.83—0.95 (m, 5 H, Me); 1.12—1.57 (m,
1
3-Ethylundec-1-ene (4b). B.p. 78 °C (2 Torr). Found (%):
C, 84.99; H, 14.15. C13H26. Calculated (%): C, 85.71; H, 14.29.
IR, ν/cm–1: 3080, 2950, 2910, 2840, 1640, 1450, 1370, 910,
16 H, CH2); 1.90—2.27 (m, 1 H, CH—C=C); 4.60—5.69 (m,
2 H, CD=CH2). 13C NMR, δ: 115.04 (t, C(1)); 45.96 (d,
C(3)); 34.90 (t, C(4)); 27.94 (t, C(5)); 29.52 (t, C(6)); 29.80
1
895, 720. H NMR, δ: 0.80—0.99 (m, 6 H, Me); 1.10—1.57
(m, 16 H, CH2); 1.85—2.11 (m, 1 H, CH—C=C); 4.67—5.61
(m, 3 H, CH2=CH). 13C NMR, δ: 114.10 (t, C(1)); 143.23
(d, C(2)); 46.15 (d, C(3)); 34.96 (t, C(4)); 27.42 (t, C(5));
29.56 (t, C(6)); 29.76 (t, C(7)); 29.89 (t, C(8)); 32.10 (t, C(9));
22.87 (t, C(10)); 14.15 (q, C(11)); 27.94 (t, C(12)); 11.68
(q, C(13)). MS, m/z: 182 [M]+.
(t, C(7)); 29.89 (t, C(8)); 32.10 (t, C(9)); 22.80 (t, C(10));
1
14.15 (q, C(11)); 27.74 (t, C(12)); 12.74 (t, C(13), JC,D
20.4 Hz). MS, m/z: 184 [M]+.
=
2-Deutero-3-(2-deuteroethyl)dodec-1-ene (6c). B.p. 93 °C
(2 Torr). Found (%): C, 84.55; H, D, 15.12. C14H26D2.
–1
Calculated (%): C, 84.85; H, 13.13; D, 2.02. IR, ν/cm
:

2192
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 11, November, 2001
Khafizova et al.
3080, 2940, 2900, 2800, 2170 (CD), 1450, 910, 895, 720.
1H NMR, δ: 0.82—0.95 (m, 5 H, Me); 1.21—1.45 (m, 18 H,
CH2); 1.95—2.18 (m, 1 H, CH—C=C); 4.68—5.23 (m, 2 H,
CD=CH2). 13C NMR, δ: 113.91 (t, C(1)); 45.82 (d, C(3));
34.83 (t, C(4)); 27.68 (t, C(5)); 29.76 (t, C(6)); 29.76 (t, C(7));
29.50 (t, C(8)); 29.30 (t, C(9)); 32.10 (t, C(10)); 22.80
(t, C(11)); 14.15 (q, C(12)); 27.35 (t, C(13)); 11.36 (t, C(14),
1JC,D = 19.1 Hz). MS, m/z: 198 [M]+.
CH2=C); 7.16—7.27 (m, 5 H, Ph). 13C NMR, δ: 145.19
(s, C(1)); 128.54 (d, C(2), C(6)); 128.86 (d, C(3), C(5)); 128.15
(d, C(4)); 43.29 (d, C(7)); 23.19 (t, C(9)); 13.70 (t, C(10),
1JC,D = 19.1 Hz); 109.23 (t, C(11)). MS, m/z: 148 [M]+.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 00-03-
32736 and 01-03-32705).
Z-1-Pentenylbenzene (10). B.p. 78 °C (6 Torr). Found (%):
C, 90.10; H, 9.28. C11H14. Calculated (%): C, 90.41; H, 9.59.
IR, ν/cm–1: 3080, 2900, 1450, 910, 750, 700. 1H NMR, δ:
0.93 (t, 3 H, Me, 3J = 7 Hz); 1.27—1.68 (m, 2 H, CH2);
2.18—2.44 (m, 2 H, CH2—C=C); 5.51—5.80 (m, 1 H, CH=C);
6.33—6.50 (m, 1 H, CH=C); 7.16—7.35 (m, 5 H, Ph).
13C NMR, δ: 133.09 (s, C(1)); 128.86 (d, C(2), C(6)); 128.15
(d, C(3), C(5)); 126.52 (d, C(4)); 128.94 (d, C(7)); 128.54
(d, C(8)); 30.80 (t, C(9)); 23.26 (t, C(10)); 13.96 (q, C(11)).
MS, m/z: 146 [M]+.
1-[(1-Ethyl)-2-propenyl]benzene (11). B.p. 71 °C (10 Torr).
Found (%): C, 90.25; H, 9.40. C11H14. Calculated (%): C, 90.41;
H, 9.59. IR, ν/cm–1: 3080, 2950, 2920, 2860, 1640, 1600, 1490,
1450, 1375, 910, 730, 700. 1H NMR, δ: 0.86 (t, 3 H, Me,
3J = 7 Hz); 1.57—1.81 (m, 2 H, CH2); 3.18 (q, 1 H, CH—Ph,
3J = 7 Hz); 4.90—5.13 (m, 2 H, CH2=C); 5.77—6.15 (m, 1 H,
CH=C); 7.07—7.38 (m, 5 H, Ph). 13C NMR, δ: 144.54 (s, C(1));
127.69 (d, C(2), C(6)); 128.41 (d, C(3), C(5)); 126.13 (d, C(4));
51.80 (d, C(7)); 28.39 (t, C(8)); 12.20 (q, C(9)); 142.33
(d, C(10)); 114.10 (t, C(11)). MS, m/z: 146 [M]+.
1-[(2-Ethyl)-2-propenyl]benzene (12). B.p. 73 °C (6 Torr).
Found (%): C, 90.34; H, 9.28. C11H14. Calculated (%):
C, 90.41; H, 9.59. IR, ν/cm–1: 3080, 2950, 1500, 1450, 910,
720, 700. 1H NMR, δ: 1.02 (t, 3 H, Me, 3J = 7 Hz); 1.95 (q,
2 H, CH2, 3J = 7 Hz); 3.35 (s, 2 H, CH2—Ph); 4.74—4.82 (m,
2 H, CH2=); 5.77—6.15 (m, 1 H, CH=); 7.02—7.23 (m, 5 H,
Ph). 13C NMR, δ: 139.56 (s, C(1)); 126.06 (d, C(2), C(6));
130.88 (d, C(3), C(5)); 126.13 (d, C(4)); 43.35 (d, C(7));
145.90 (C(8)); 28.33 (t, C(9)); 12.27 (q, C(10)); 109.94
(t, C(11)). MS, m/z: 146 [M]+.
References
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1-[(2,5-Dideutero)-1-pentenyl]benzene (13). B.p. 75 °C
(6 Torr). Found (%): C, 89.07; H, D, 10.50. C11H12D2.
Calculated (%): C, 89.19; H, 8.11; D 2.70. IR, ν/cm–1: 3080,
2950, 2160 (CD), 1500, 1450, 910, 750, 700. 1H NMR, δ: 0.85
(tt, 2 H, CH2D, 2JH,D = 2 Hz, 3JH,H = 2 Hz); 1.24—1.59 (m,
2 H, CH2); 2.24 (t, 2 H, CH2—C=C, 3J = 7 Hz); 6.32 (t, 1 H,
4
CH=C, J = 2 Hz); 7.16—7.30 (m, 5 H, Ph). 13C NMR, δ:
137.90 (s, C(1)); 128.80 (d, C(2), C(6), C(7)); 128.15 (d,
C(3), C(5)); 126.46 (d, C(4)); 30.70 (t, C(9)); 23.13 (t, C(10));
13.63 (t, C(11), 1JC,D = 19.1 Hz). MS, m/z: 148 [M]+.
1-[2-Deutero-1-(2-deuteroethyl)-2-propenyl]benzene (14).
B.p. 70 °C (10 Torr). Found (%): C, 89.02; H, D, 10.20.
C11H12D2. Calculated (%): C, 89.19; H, 8.11; D 2.70. IR,
ν/cm–1: 3080, 2950, 2170 (CD), 1500, 1450, 910, 750, 700.
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CH2); 3.13 (t, 1 H, CH—Ph, 3J = 7 Hz); 4.73—5.05 (m, 2 H,
CH2=C); 7.08—7.38 (m, 5 H, Ph). 13C NMR, δ: 144.77
(s, C(1)); 127.69 (d, C(2), C(6)); 128.41 (d, C(3), C(5));
126.13 (d, C(4)); 51.67 (d, C(7)); 28.26 (t, C(8)); 11.94
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1
(t, C(9), JC,D = 19.0 Hz); 142.54 (d, C(10)); 113.91 (t,
C(11)). MS, m/z: 148 [M]+.
1-[1-Deutero-2-(2-deuteroethyl)-2-propenyl]benzene (15).
B.p. 70 °C (6 Torr). Found (%): C, 89.10; H, D, 10.50.
C11H12D2. Calculated (%): C, 89.19; H, 8.11; D 2.70. IR,
ν/cm–1: 3080, 2950, 2170 (CD), 1500, 1450, 910, 720, 700.
1H NMR, δ: 0.77—0.93 (m, 2 H, CH2D); 1.19—1.81 (m, 2 H,
CH2); 3.62—3.65 (m, 1 H, CH—Ph); 4.46—5.12 (m, 2 H,
Received April 24, 2001