Efficient halogenation of unsaturated organoaluminum compounds with sulfonyl halides

Article abstract of DOI:10.1134/S1070428013030020

Alkenylalumanes prepared by carbo-or cycloalumination of substituted acetylenes reacted with an equivalent amount of sulfonyl halide (MsCl, TsCl, PhSO₂Cl, MsBr) in methylene chloride or hexane at room temperature to produce alkenyl halides in high yields. Electron-donor solvents such as diethyl ether or tetrahydrofuran inhibited the halogenation process. β-Substituted vinylalumanes generated by hydroalumination of substituted acetylenes failed to react with sulfonyl halides.

Full text of DOI:10.1134/S1070428013030020

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 3, pp. 321–326. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © I.R. Ramazanov, R.N. Kadikova, U. M. Dzhemilev, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 3,
pp. 335–340.
Dedicated to Full Member of the Russian Academy of Sciences
I.P. Beletskaya on her jubilee
Efficient Halogenation of Unsaturated Organoaluminum
Compounds with Sulfonyl Halides
I. R. Ramazanov, R. N. Kadikova, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: iramazan@inbox.ru
Received January 11, 2013
Abstract—Alkenylalumanes prepared by carbo- or cycloalumination of substituted acetylenes reacted with
an equivalent amount of sulfonyl halide (MsCl, TsCl, PhSO2Cl, MsBr) in methylene chloride or hexane at room
temperature to produce alkenyl halides in high yields. Electron-donor solvents such as diethyl ether or tetra-
hydrofuran inhibited the halogenation process. β-Substituted vinylalumanes generated by hydroalumination of
substituted acetylenes failed to react with sulfonyl halides.
DOI: 10.1134/S1070428013030020
Halogenation with the aid of electrophilic halogen
sources is one of the most widely used methods for
functionalization of organometallic compounds. Al-
though the reaction of diethylzinc with benzenesul-
fonyl chloride, leading to ethyl chloride and zinc ben-
zenesulfinate, has been known since XIXth century [1],
only a few published data are available on the use of
sulfonyl halides as halogenating agents for functional-
ization of organometallic compounds. Triethylalumi-
num and ethylaluminum sesquichloride reacted with
sulfonyl chlorides to form sulfinic acids and ethyl
chloride [2]. Benzenesulfonyl chloride was also used
for monochlorination of alkylidenebiszinc compounds.
Zinc atom can be replaced by chlorine both at sp2- and
sp3-hybridized carbon atoms [3–5]. However, allylzinc
compounds reacted with alkane- and arenesulfonyl
chlorides to give exclusively β,γ-unsaturated sulfones
[6]. Reactions of Grignard compounds with sulfonyl
chlorides also produced the corresponding sulfones
[7]. Alkenyl sulfones were obtained by reaction of
alkenylzirconocene derivatives with alkane- and arene-
sulfonyl chlorides under mild conditions [8]. Cross-
coupling of arenesulfonyl chlorides with trialkylaryl-
stannanes at 130°C [9] and with alkenylstannanes in
the presence of a catalytic amount of palladium com-
plexes also afforded aryl sulfones [10]. Diarylcad-
miums reacted with arenesulfonyl chlorides to give
mixtures of aryl sulfones, aryl chlorides, and sulfinic
acids [11–13], whereas no sulfones were formed from
diethylcadmium. Thus, the above cross-coupling re-
actions of organometallic compounds with sulfonyl
halides are governed by both metal nature and substit-
uent attached thereto.
Alkyl sulfonates are efficient reagents for the al-
kylation of cyclic alkenylalumanes (aluminacyclopent-
2-enes) [14, 15]. The high yield of the resulting
cyclopropanes and selectivity of these reactions make
sulfonic acid derivatives promising as reagents for
transformations of organoaluminum compounds. First
of all, we planned to examine reactions with sulfonyl
halides which were assumed to be efficient sources of
electrophilic halogen. Previously, alkenylalumanes
were converted into halogen derivatives with the use of
halogens (Br2, I2) [16], N-halosuccinimides (NCS,
NBS, NIS) [17], and pseudohalogens (BrCN, ICl) [18].
Alkylaluminum compounds reacted with the above
halogen derivatives in a similar way, i.e., via cleavage
of the Al–C bond. In view of the aforesaid, in the
present work we studied reactions of sulfonyl halides
with both acyclic and cyclic alkenylalumanes with the
goal of developing an efficient procedure for the
synthesis of various vinyl halides.
Pure alkenylalumanes are difficult to isolate as
individual substances, for they readily undergo decom-
321

RAMAZANOV et al.
322
Scheme 1.
Me3Al (2 equiv)
Cp2ZrCl2 (1 equiv)
CH2Cl2, 20°C, 3 h
MsCl (1 equiv)
or MsBr (1 equiv)
20°C, 15 min
R2
R2
H
R1
R1
Me
R1
R2
+
AlMe2
Hlg
Br
Me
Me
Ia–Ic, IIa, IIb
Ph
III
I, Hlg = Cl: R1 = C6H13, R2 = H (a); R1 = Ph, R2 = H (b); R1 = R2 = Bu (c); II, Hlg = Br: R1 = C6H13, R2 = H (a); R1 = Ph, R2 = H (b).
position on attempted distillation. Therefore, alkenyl-
alumanes were generated in situ by hydro-, carbo-, and
cycloalumination of alkynes. Negishi carboalumina-
tion is one of the most useful transformations of
alkynes [19]. Alkenylalumanes obtained by Zr-cata-
lyzed methylalumination of alkynes (oct-1-yne,
phenylacetylene, dec-5-yne) [20] reacted with meth-
anesulfonyl chloride or bromide in 15 min at room
temperature in methylene chloride to give the corre-
sponding halogen derivatives Ia–Ic or IIa and IIb in
high yield (Scheme 1). The configuration of the double
bond did not change in this transformation, which was
confirmed by NOE experiments. In the NOESY spec-
trum of Ia we observed a cross peak between proton at
the double bond (singlet) and protons in the α-meth-
ylene group of the hexyl radical.
not studied due to thermal instability of the latter and
high efficiency of iodine as iodinating agent.
Taking into account simplicity of the experimental
procedure and accessibility of sulfonyl halides, halo-
genation of alkenylalumanes with various structures
was studied. β-Substituted vinylalumanes obtained by
hydroalumination of terminal alkynes (oct-1-yne and
phenylacetylene) with diisobutylaluminum hydride
(Scheme 2) [23] turned out to be inactive toward
sulfonyl halides (MsCl, TsCl, MsBr). We presumed
that the presence of Cp2ZrCl2 in the reaction mixture
could favor the reaction; however, addition of the
zirconocene catalyst (0.1 equiv with respect to alkenyl-
alumane) had no effect. This may be due to lower
nucleophilicity of β-substituted vinylalumanes com-
pared to β,β-disubstituted. Treatment with mesyl
chloride of α,β-substituted vinylalumane generated by
hydroalumination of dec-5-yne with triethylaluminum
in the presence of titanium catalyst [24] gave a mixture
of stereoisomeric alkenyl chlorides IV and V at a ratio
of ~4:3. The Z/E isomer ratio was estimated from the
1H NMR spectrum of the reaction mixture, and the
yields of IV and V were determined from the amount
of the isomer mixture isolated by distillation with
account taken of the isomer ratio. We failed to obtain
(E)- or (Z)-1-chloroalk-1-enylsilanes from the corre-
sponding alkenylalumanes [17] and mesyl chloride.
Obviously, this procedure is hardly applicable to
α,β-substituted alkenylalumanes.
The reaction of phenylacetylene with trimethyl-
aluminum, followed by treatment with MsBr, gave
a mixture of compound IIb and its Z isomer III (15%).
The latter was identified by NMR spectroscopy. The
1H NMR spectra of the Z and E isomers are fairly
similar, but signals from the methyl group and hydro-
gen at the double bond in the spectrum of Z isomer III
appeared in a stronger field (by 0.11 and 0.19 ppm,
respectively), relative to the corresponding signals of
E isomer IIb [21].
Alkenylalumane generated by zirconium-catalyzed
methylalumination of oct-1-yne was brought into reac-
tions with different sulfonyl halides, in particular
p-toluenesulfonyl chloride and fluoride, benzenesul-
fonyl chloride, and methanesulfonyl bromide. The
yield of compound Ia in the reaction with TsCl and
PhSO2Cl was 88 and 90%, respectively; analogous
result was obtained with MsCl. Methanesulfonyl
fluoride failed to react with the above alkenylalumanes
under the given conditions. Electrophilic fluorinating
agents such as N-fluoro-o-benzenedisulfonimide,
N-fluorobenzenesulfonimide, and Selectfluor [22]
contain stronger electron-withdrawing groups on the
fluorine atom as compared to sulfonyl group. Reac-
tions of alkenylalumanes with sulfonyl iodides were
Thus, the best results were obtained in the halo-
genation of α,β,β- and β,β-substituted vinylalumanes
synthesized by Negishi carboalumination of alkynes.
Zirconium-catalyzed cycloalumination of disubstituted
acetylenes with triethylaluminum, which is also known
as Dzhemilev reaction, yields aluminacyclopent-2-
enes; the latter may be regarded as α,β,β-substituted
vinylalumanes [25]. Insofar as the nucleophilicities of
α,β,β- and β,β-substituted vinyl anions in the reaction
under study are comparable, we expected successful
reaction of aluminacyclopent-2-enes with sulfonyl
halides. In fact, aluminacyclopent-2-enes obtained by
cycloalumination of dec-5-yne, oct-4-yne, 1-phenyl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

EFFICIENT HALOGENATION OF UNSATURATED ORGANOALUMINUM COMPOUNDS
323
Scheme 2.
H
Bu2AlH (1.5 equiv)
hexane, 50°C, 5 h
MsCl (1 equiv)
20°C, 15 min
R
R
H
No reaction
AlBu2
H
R = C6H13, Ph.
Et3Al (2 equiv)
Cp2TiCl2 (0.05 equiv)
hexane, 20°C, 6 h
Bu
Bu
Cl
MsCl (1 equiv)
20°C, 15 min
Bu
Bu
Bu
+
Bu
Bu
AlEt2
Cl
Bu
H
H
H
IV, 43%
V, 32%
SiMe3
AlBu2
Bu2AlH (1 equiv)
Et2O
MsCl (1 equiv)
20°C, 15 min
Bu
Bu
SiMe3
No reaction
H
SiMe3
AlBu2
Bu2AlH (1 equiv)
hexane, 20°C, 30 min
MsCl (1 equiv)
20°C, 15 min
H
Bu
SiMe3
No reaction
Bu
Scheme 3.
Et3Al (2 equiv)
Cp2ZrCl2 (0.1 equiv or 0.2 equiv for VId)
hexane, 40°C
R2
R1
(1) MsHlg (1 equiv), 20°C, 15 min
(2) D2O or H2O
R2
R1
R2
Hlg
R1
Al
Et
R3
VIa–VId, VII
VI, Hlg = Cl: R1 = R2 = Bu, R3 = D (a); R1 = R2 = Pr, R3 = H (b); R1 = Ph, R2 = Bu, R3 = H (c); R1 = Me2NCH2, R2 = Bu, R3 = H (d);
VII, Hlg = Br, R1 = R2 = Bu, R3 = H.
Atom numbering in the 1H and 13C NMR spectra.
9Me
1
Me
10
Me
9
2
1
8
1
7
5
3
7
5
3
8
Me
8
Me
Cl
2
4
2
3
7
2
7
6
Cl
Br
8
3
1
6
4
6
4
9Me
9Me
6
5
4
11
Me
Cl
5
Ia
Ib
Ic
IIa
7
Me
12
Me
10
Me
8Me
7
11
9Me
9Me
2
9
8
5
5
8
8
5
Br
6
10
6
9
3
3
2
1
7
6
7
6
2
2
1
1
1
4
4
4
4
Br
Cl
Me
Cl
3
3
5
D
IIb
III
VIa
VIb
10
12
Me
8Me
Cl
1
Me
Cl
2
7
11
3
6
8
14
9
5
4
11
9
Me
N
2
3
9
13
12
6
10
Me
7
Me
1
2
1
6
8
7
4
10
5
4
Me
Br
Me
Me
3
11
5
VIc
VId
VII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

RAMAZANOV et al.
324
hex-1-yne, and N,N-dimethylhept-2-yn-1-amine [26]
reacted with 1 equiv of MsCl in a regioselective
fashion at the double-bonded carbon atom, and the
subsequent hydrolysis or deuterolysis afforded in high
yield the corresponding alkenyl chlorides VIa–VId
(Scheme 3) with the same configuration of the double
bond as in the initial compounds (according to the
NOESY data). The second metal–carbon bond in the
metallacycle was not involved even when the amount
of mesyl chloride was increased to 5 equiv. Analogous
regioselectivity was observed previously in the alkyla-
tion of aluminacyclopent-2-enes with dialkyl sulfates
[14]. The use of mesyl bromide instead of mesyl
chloride resulted in the formation of monobromo
derivative VII, but the yield was only 63%. In the
bromination of dibutyl-substituted aluminacyclopent-
2-ene with NBS (Et2O, –20°C) alkenyl bromide VII
was formed in 55% yield, whereas the yield of alkenyl
chloride VIa in the reaction of the same substrate with
NCS (Et2O, –20°C) was similar to that obtained with
the use of MsCl, TsCl, or PhSO2Cl.
The products were analyzed by GLC on a Carlo
Erba chromatograph (HP Ultra-1 glass capillary col-
umn, 25 m×0.2 mm; flame ionization detector; oven
temperature 50–170°C; carrier gas helium). The ele-
mental compositions were determined on a Carlo Erba
1106 analyzer. The yields were determined by the
internal standard quantitation method (GLC). The
boiling points were measured according to [31]. The
concentrations of chlorine and bromine were deter-
mined by Schöniger oxidation [32].
Halogenation of alkenylalumanes (general proce-
dure). Alkenylalumanes were generated from 1 mmol
of the corresponding substituted acetylene according
to the procedures indicated in text. Methanesulfonyl
chloride, 1 mmol, was added to the reaction mixture
through a rubber septum with a syringe, and the mix-
ture was stirred for 15 min at room temperature. The
mixture was then diluted with 5 ml of hexane, 3 ml of
water was added dropwise on cooling in an ice bath,
and the precipitate was filtered off through a filter
paper. The aqueous phase was extracted with diethyl
ether, and the extract was combined with the organic
phase, dried over anhydrous CaCl2, and concentrated
under reduced pressure.
It should be noted that sulfonyl halides did not react
with alkenylalumanes in electron-donor solvents such
as diethyl ether and tetrahydrofuran. On the other
hand, the halogenation with NCS and NBS requires
ether solvents and low temperature (–20°C) [17]. The
bromination of alkenylalumanes with Br2 is carried out
at –70 to –50°C [16]. Elemental halogens (Br2, I2) and
N-halosuccinimides (NCS, NBS) ensured successful
halogenation of β-substituted vinylalumanes which
were inactive toward sulfonyl halides.
(E)-1-Chloro-2-methyloct-1-ene (Ia). Yield 81%,
1
bp 61–63°C (5 mm). H NMR spectrum (CDCl3), δ,
ppm: 0.91 t (3H, 8-H, J = 7 Hz), 1.20–1.38 m (4H,
6-H, 7-H), 1.38–1.50 m (4H, 4-H, 5-H), 1.78 s (3H,
9-H), 2.07 t (2H, 3-H, J = 8 Hz), 5.80 s (1H, 1-H).
13C NMR spectrum, δC, ppm: 14.06 (C8), 16.34 (C9),
22.58 (C7), 27.46 (C5), 28.77 (C4), 31.63 (C6), 37.09
(C3), 111.61 (C1), 138.97 (C2). Found, %: C 67.21;
H 10.55; Cl 23.2. C9H17Cl. Calculated, %: C 67.29;
H 10.59; Cl 22.12.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
a Bruker Avance 400 spectrometer at 400.13 and
100.62 MHz, respectively, using tetramethylsilane (1H)
or CDCl3 (13C) as internal reference. For atom num-
bering in the description of the NMR spectra of Ia–Ic,
IIa, IIb, III, VIa–VId, and VII, see Scheme 3.
[(E)-1-Chloroprop-1-en-2-yl]benzene (Ib). Yield
84%, bp 80–83°C (5 mm). H NMR spectrum
1
(CDCl3), δ, ppm: 2.24 s (3H, 9-H), 6.36 s (1H, 1-H),
7.28–7.45 m (5H, Ph). 13C NMR spectrum, δC, ppm:
16.89 (C9), 115.8 (C1), 125.94 and 128.54 (C4, C5, C7,
C8), 127.79 (C6), 138.56 and 140.33 (C2, C3). Found,
%: C 70.32; H 5.94; Cl 26.1. C9H9Cl. Calculated, %:
C 70.82; H 5.90; Cl 23.28.
Most reagents used were commercial products. Re-
actions with organoaluminum compounds were carried
out under dry argon. Hexane was distilled over
(i-Bu)3Al, methylene chloride was dried over P2O5,
N,N-dimethylhept-2-yn-1-amine was synthesized by
aminomethylation of hex-1-yne [27], 1-phenylhex-1-
yne was prepared according to [28], p-toluenesulfonyl
fluoride was obtained from p-toluenesulfonyl chloride
and potassium fluoride dihydrate [29], and methane-
sulfonyl bromide was prepared from methanesulfonyl
chloride [30].
(E)-6-Chloro-5-methyldec-5-ene (Ic). Yield 79%,
1
bp 78–80°C (3 mm). H NMR spectrum (CDCl3), δ,
ppm: 0.87–1.00 m (6H, 1-H, 10-H), 1.26–1.46 m (2H,
2-H), 1.46–1.60 m (6H, 2-H, 8-H, 9-H), 1.82 s (3H,
11-H), 2.11 t (4H, 4-H, 7-H, J = 7.2 Hz). 13C NMR
spectrum, δC, ppm: 13.97 (C1, C10), 19.81 (C2, C9),
22.06 and 22.57 (C3, C11), 30.25 (C8), 34.04 and 34.75
(C4, C7), 129.31 (C1), 131.25 (C2). Found, %: C 70.49;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 3 2013

EFFICIENT HALOGENATION OF UNSATURATED ORGANOALUMINUM COMPOUNDS
325
H 11.01; Cl 19.9. C11H21Cl. Calculated, %: C 70.03;
H 11.14; Cl 18.83.
12.08 (C4), 13.23 and 14.1 (C7, C10), 21.18 and 21.85
(C6, C9), 26.59 (C3), 34.04 (C5), 36.89 (C8), 129.19
(C1), 137.08 (C2). Found, %: C 68.31; H 10.84;
Cl 21.2. C10H19Cl. Calculated, %: C 68.72; H 10.92;
Cl 20.36.
(E)-1-Bromo-2-methyloct-1-ene (IIa). Yield 77%,
1
bp 64–66°C (5 mm). H NMR spectrum (CDCl3), δ,
ppm: 0.91 t (3H, 8-H, J = 8 Hz), 1.20–1.38 m (2H,
6-H, 7-H), 1.38–1.50 m (2H, 4-H, 5-H), 1.80 s (3H,
9-H), 2.12 t (2H, 3-H, J = 4 Hz), 5.90 s (1H, 1-H).
13C NMR spectrum, δC, ppm: 14.07 (C8), 19.00 (C9),
22.59 (C7), 27.47 (C5), 28.75 (C4), 31.62 (C6), 38.34
(C3), 100.84 (C1), 142.01 (C2). Found, %: C 52.81;
H 8.15; Br 39.6. C9H17Br. Calculated, %: C 52.70;
H 8.29; Br 39.01.
[(E)-1-Chloro-2-ethylhex-1-en-1-yl]benzene
1
(VIc). Yield 66%, bp 104–106°C (1 mm). H NMR
spectrum (CDCl3), δ, ppm: 0.80 t (3H, 6-H, J =
7.2 Hz), 1.16 t (3H, 8-H, J = 7.6 Hz), 1.18–1.26 m
(4H, 4-H, 5-H), 1.36–1.44 m (4H, 3-H, 7-H), 7.28–
7.38 m (5H, Ph). 13C NMR spectrum, δC, ppm: 11.94
(C8), 13.81 (C6), 22.53 (C5), 25.93 (C7), 30.59 (C3),
32.34 (C4), 127.77 (C12), 128.15 (C10, C14), 129.09
(C11, C13), 139.68 (C9), 140.31 (C2). Found, %:
C 74.53; H 8.53; Cl 16.9. C14H19Cl. Calculated, %:
C 74.82; H 8.15; Cl 17.03.
[(E)-1-Bromoprop-1-en-2-yl]benzene (IIb). Yield
1
68%, bp 81–83°C (5 mm). H NMR spectrum
(CDCl3), δ, ppm: 2.26 s (3H, 9-H), 6.48 s (1H, 1-H),
7.20–7.46 m (5H, Ph). 13C NMR spectrum, δC, ppm:
19.66 (C9), 105.39 (C1), 126.00 and 128.54 (C4, C5, C7,
C8), 127.84 (C6), 140.96 and 141.53 (C2, C3). Found,
%: C 57.70; H 4.16; Br 35.5. C9H9Br. Calculated, %:
C 57.75; H 4.81; Br 37.44.
(E)-2-Chloro-3-ethyl-N,N-dimethylhept-2-en-
1-amine (VId). Yield 84%, bp 84–85°C (1 mm).
1H NMR spectrum (CDCl3), δ, ppm: 0.93 t (3H, 7-H,
J = 6.8 Hz), 1.05 t (3H, 9-H), 1.25–1.48 m (4H, 5-H,
6-H), 2.18 t (2H, 4-H, J = 7.2 Hz), 2.20–2.34 m (2H,
8-H), 2.27 s (6H, 10-H, 11-H), 3.13 s (2H, 1-H).
13C NMR spectrum, δC, ppm: 11.91 (C9), 13.93 (C7),
22.76 (C6), 26.86 (C8), 30.76, 31.92 (C4, C5), 44.84
(C10, C11), 61.74 (C1), 125.72 (C2), 141.8 (C3). Found,
%: C 64.53; H 10.51; Cl 16.4; N 6.35. C11H22ClN.
Calculated, %: C 64.71; H 10.78; Cl 17.65; N 6.86.
[(Z)-1-Bromoprop-1-en-2-yl]benzene (III). Yield
1
15%, bp 87–90°C (5 mm). H NMR spectrum
(CDCl3), δ, ppm: 2.15 s (3H, 9-H), 6.29 s (1H, 1-H),
7.20–7.45 m (5H, Ph). 13C NMR spectrum, δC, ppm:
17.34 (C9), 125.30 (C1), 125.08, 128.32 (C4, C5, C7,
C8), 126.62 (C6), 133.03 and 141.94 (C2, C3).
(E)-5-Chlorodec-5-ene (IV) and (Z)-5-chlorodec-
5-ene (V) (isomer mixture). Overall yield 75%;
IV/V ~4:3 (GLC); bp 71–73°C (5 mm). H NMR
spectrum (CDCl3), δ, ppm: 0.70–1.05 m (6H, CH3),
1.10–1.75 m (8H, CH2CH2CH3), 1.90–2.20 m (2H,
CH2CH=), 2.20–2.35 m (2H, CH2CCl=), 5.40–5.55 m
(1H, =CH–).
(E)-5-Bromo-6-ethyldec-5-ene (VII). Yield 63%,
bp 80–82°C (5 mm). H NMR spectrum (CDCl3), δ,
1
1
ppm: 0.90–0.98 m (6H, 8-H, 12-H), 1.02 t (3H, 4-H,
J = 7.6 Hz), 1.28–1.63 m (8H, 6-H, 7-H, 10-H, 11-H),
2.08–2.18 m (2H, 3-H), 2.20–2.28 m (2H, 5-H), 2.44–
13
2.50 m (2H, 9-H). C NMR spectrum, δC, ppm: 12.05
(C4), 13.95 and 14.02 (C8, C12), 21.88, 22.75 (C7, C11),
29.87 (C3), 30.87 and 31.01 (C6, C10), 31.83 (C5),
37.09 (C9), 123.17 (C1), 143.96 (C2). Found, %:
C 58.11; H 9.23; Br 31.2. C12H23Br. Calculated, %:
C 58.30; H 9.31; Br 32.39.
(E)-5-Chloro-6-[(2-2H1)ethyl]dec-5-ene (VIa).
1
Yield 83%, bp 80–83°C (5 mm). H NMR spectrum
(CDCl3), δ, ppm: 0.88–1.10 m (6H, 8-H, 12-H), 1.28–
1.41 m (2H, 4-H), 1.50–1.60 m (2H, 10-H), 2.05–
2.15 m (4H, 7-H, 11-H), 2.15–2.28 m (2H, 6-H), 2.15–
2.45 m (6H, 3-H, 5-H, 9-H). 13C NMR spectrum, δC,
ppm: 11.79 t (2H, C4, J = 19 Hz), 13.95 and 13.98 (C8,
C12), 22.01 and 22.76 (C7, C11), 26.52 (C10), 30.26
(C3), 30.89 (C5), 31.72 (C6), 34.83 (C9), 129.17 (C1),
136.94 (C2). Found, %: C 70.53; Cl 11.8. C12H22ClD.
Calculated, %: C 70.67; Cl 10.80.
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