Olefination of aromatic ketones: Synthesis of mono- and dihaloalkenes

Article abstract of DOI:10.1039/b201131j

A new simple and efficient transformation of various aromatic ketones to the corresponding halo (dihalo) alkenes is described. The reaction proceeds under mild conditions to give the target products in good yields.

Full text of DOI:10.1039/b201131j

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Olefination of aromatic ketones: synthesis of mono- and
dihaloalkenes
Vasily N. Korotchenko,a Alexey V. Shastin,b Valentine G. Nenajdenko*a and
Elisabeth S. Balenkovaa
1
a Moscow State University, Department of Chemistry, Leninskie Gory, Moscow 119899, Russia.
E-mail: nen@acylium.chem.msu.ru; Fax: ϩ7-(095)-9328846; Tel: ϩ7-(095)-9392276
b Institute of Problems of Chemical Physics, Chernogolovka, Moscow region, 142432, Russia
Received (in Cambridge, UK) 30th January 2002, Accepted 13th February 2002
First published as an Advance Article on the web 28th February 2002
A new simple and efficient transformation of various aromatic ketones to the corresponding halo (dihalo) alkenes is
described. The reaction proceeds under mild conditions to give the target products in good yields.
Introduction
Olefination of carbonyl compounds, that is the R1R2C᎐O–
᎐
R1R2C᎐CXY transformation is one of the most successful syn-
᎐
thetic routes to a wide variety of substituted alkenes.1 Vinylic
mono- (R1R2C᎐CHHal) and dihalides (R1R2C᎐CHal ) have
᎐
᎐
2
attracted increasing interest in modern organic chemistry as
precursors of the corresponding carbenoids R1R2C᎐CHalMet
᎐
(Met = Li, ZnR2Li, NiL2Cl, SmIII).2 Such α-haloorganometallic
compounds, possessing both electrophilic and nucleophilic
reactivities, are versatile intermediates in C–C bond formation
procedures.3 It is well-known that the Wittig reaction and
its modifications are the most common approaches for the
synthesis of vinylic halides and dihalides from carbonyl pre-
cursors.2a,b,4 Treatment of carbonyl compounds with trihalo-
methyllithiums is a key stage in an alternative three-step route
to these types of alkenes.5 However, the need to use equimolar
amounts of PPh3 and/or organometallic reagents is a significant
disadvantage of these methods. This problem can be avoided
by elaboration of new catalytic routes for the olefination of
carbonyl compounds.
Scheme 1
of CCl4 or CBr4 in the presence of a copper catalyst (10 mol%).
The transformation of 1 into 1,1-dichloroalk-1-enes 2 and 1,1-
dibromoalk-1-enes 3, respectively, takes place (Scheme 2).
Recently we elaborated
a novel catalytic, non-Wittig
approach to the preparation of substituted alkenes from
aldehydes.6 The proposed approach is based on the new redox
reaction between the hydrazones of aromatic and hetero-
aromatic aldehydes, Ar(Het)(H)C᎐NNH , and CCl under
᎐
2
4
copper catalysis. This reaction and its synthetic scope are now
under intensive investigation in our group. We found that
CCl4,6a–c CHBr3,6d CBr4,6e and the freons CF3CCl3 and CF2Cl–
CFCl2 can be utilized as C1 and C2 units respectively for the
preparation of the corresponding haloalkenes in high yields
(Scheme 1).
Scheme 2
6f
We found that a wide range of aromatic ketones can be
converted into alkenes 2 and 3 in good yields (Table 1). The
yields of dibromoalkenes were generally higher than the yields
of dichloroalkenes, probably because of the higher activity of
CBr4 in comparison with CCl4.7 We also investigated the kinetic
features of reactions between hydrazones and polyhalogeno-
alkanes. It was found that their activity diminishes in order
CBr4 ӷ CCl4 > CHBr3.8
The proposed method represents a new general type of
reaction for C᎐C bond formation. The aim of presented work is
᎐
to extend the scope of the novel reaction to the olefination of
ketones.
It should be noted that the proposed olefination procedure
is compatible with the presence of both electron-donating
(MeO) and electron-withdrawing (NO2, MeSO2) groups in the
aromatic ring. Hydrazones of cyclic compounds 1i and 1j and
heterocyclic ketone 1g can also be transformed into the target
alkenes.
We also investigated the transformation of ketones into vinyl
bromides using CHBr3 as the olefinating agent (Scheme 3).
It was demonstrated that the reaction proceeds similarly.
Results and discussion
Previously we found the optimal conditions for the reaction
between hydrazones of aromatic aldehydes and CCl4 (solvent,
base, quantity and nature of the catalyst).6b The reaction pro-
ceeds smoothly in DMSO solution at room temperature in the
presence of aqueous ammonia as a base and CuCl as a catalyst.
Using the same conditions, hydrazones 1, prepared from corre-
sponding aromatic ketones, were treated with 3 mol equivalents
DOI: 10.1039/b201131j
J. Chem. Soc., Perkin Trans. 1, 2002, 883–887
This journal is © The Royal Society of Chemistry 2002
883

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Scheme 3
A wide range of hydrazones of aryl(hetaryl) methyl ketones
(electron-rich and electron-poor) was converted into the mono-
bromoalkenes 4 in good yields (Table 2).
Scheme 4
The bromoalkenes 4 were obtained as a mixture of E- and Z-
isomers (the E-isomer is formed predominantly). To determine
the structure of isomers we performed NOE experiments on
compound 4f (Scheme 4). It was found that the major isomer
has the E-configuration.
the E-isomers). The olefin proton (marked in Scheme 4) in the
E-isomers is shifted downfield (0.2–0.4 ppm) compared with
the chemical shift of this same proton in the Z-isomers.
Reaction mechanism
The structures of the other bromoalkenes can be unambigu-
ously established from their 1H NMR data. For all of the vinyl
In order to elucidate the mechanistic aspects of the ketone
olefination we studied the reaction between hydrazone 1b and
CCl4 in more detail (Scheme 5). The target dichloroalkene 2b
4
bromides the allylic J value is larger in the Z-isomers of 4
4
(4JH–H 1.5–1.7 Hz for the Z-isomers and JH–H 1.1–1.3 Hz for
Table 1 Synthesis of dichloroalkenes 2 and dibromoalkenes 3
Product
yield (%)
Starting material
R1
Entry
R2
2
3
1a
1b
1c
1d
1e
1f
4-MeC6H4
4-ClC6H4
4-MeOC6H4
4-O2NC6H4
4-MeSO2C6H4
2-Naphthyl
2-Thienyl
Me
Me
Me
Me
Me
Me
Me
Et
65
82
70
58
33
31
42
57
45
32
52
75
92
74
45
41
62
75
51
23
Scheme 5
(82%) and corresponding sym-azine of 4-chloroacetophenone
(14%) were obtained in 96% total yield, accompanied by the
evolution of dinitrogen.
Mass spectrometric study of the reaction mixture confirmed
these results. Dichloroalkene 2b (m/z = 220) and azine
(m/z = 304) were detected by GCMS of the reaction mixture
1g
1h
1i
Ph
–o-C6H4–(CH2)2–
–o-C6H4–(CH2)3–
1j
Table 2 Synthesis of bromoalkenes 4
Starting material
Product, 4
Yield (%)
55
E : Z ratioa
1a
5 : 4
1b
1c
73
54
4 : 3
2 : 1
1d
1e
1f
47
21
39
5 : 4
1 : 1
3 : 1
1g
60
2 : 1
a Ratio E : Z of isomers was determined by 1H NMR spectroscopy.
884
J. Chem. Soc., Perkin Trans. 1, 2002, 883–887

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as the main reaction product (more than 90%). Traces of side
products 4-chloroacetophenone (m/z = 154) and stilbene
Hydrazones of ketones 1a,11 1b,11 1c,12 1d,13 1f,14 1g,15 1h,16
1i16 and 1j17 were prepared according to literature procedures.
ClC H (CH )C᎐C(CH )C H Cl (m/z
=
276) were also
᎐
6
4
3
3
6
4
observed.
1-[4-(Methylsulfonyl)phenyl]ethanone hydrazone 1e
Similar results were previously obtained in the reaction
between hydrazones of aldehydes and polyhalogenoalkanes.6
Therefore we believe that the proposed mechanism of olefin-
ation (ref. 6f ) can be extended to the reaction of aromatic
ketones. The catalytic cycle illustrating the reaction mechan-
ism and formation of all of the reaction products is given in
Scheme 6.
1-[4-(Methylsulfonyl)phenyl]ethanone (9.90 g, 50 mmol) was
dissolved in EtOH (100 cm3) and added dropwise to a solution
of 100% hydrazine hydrate (7.5 cm3, 150 mmol) in EtOH
(100 cm3). The reaction mixture was refluxed (3 hours) and
evaporated in vacuo. The residue of crude hydrazone was
recrystallized from EtOH to give colourless crystals (8.30 g,
78%); mp 132–133 ЊC (from EtOH). Found: C, 51.14; H, 5.87.
Calc. for C9H12N2O2S: C, 50.92; H, 5.70%; νmax(Nujol)/cmϪ1
1630 (C᎐N); δ (400 MHz; DMSO-d ; Me Si) 2.14 (3 H, s, Me-
᎐
H
6
4
C᎐N), 3.05 (3 H, s, MeSO ), 5.62 (2 H, br s, NH ), 7.82 (2 H, d,
᎐
2
2
J 8.5, Ar), 7.89 (d, 2 H, J 8.5, Ar); δC (100 MHz; DMSO-d6;
Me4Si) 11.11 (Me), 43.66 (MeSO2), 125.06, 126.89, 138.41,
139.38, 144.58.
Preparation of halo (dihalo) alkenes
1,1-Dichloroalk-1-enes 2. A 25% aqueous solution of ammo-
nia (3.33 cm3) and freshly purified CuCl18 (100 mg, 1 mmol)
were added to a solution of freshly prepared hydrazone 1a–j
(10 mmol) in DMSO (10 cm3). Then CCl4 (2.89 cm3, 30 mmol)
was added dropwise over 10 min, maintaining the temperature
at 20 ЊC (water bath). The reaction mixture was stirred for 24 h
and quenched with water (300 cm3). The reaction products were
extracted with CH2Cl2 (50 cm3 × 3). The extracts were dried
over sodium sulfate, CH2Cl2 was evaporated and the residue
was purified by column chromatography (eluents: hexane,
CH2Cl2 or a mixture).
1,1-Dibromoalk-1-enes 3 and 1-bromoalk-1-enes 4 were pre-
pared similarly by reaction of 1 with 3 mol equivalents of CBr4
(9.95 g, 30 mmol) and CHBr3 (2.62 cm3, 30 mmol), respectively.
CBr4 was added to hydrazone 1 in DMSO (20 cm3) solution.
The known compounds 2a,4b 2b,4b 2c,4b 2d,19 2f,20,21 2g,4a 2h,2b
2i,21 2j,21 3g,21 3h,5 3j,2c 4a2a and 4b22 were identified by their
1H NMR spectra and/or by comparison of the spectral data
and physical constants with literature data.
Scheme 6
In the initial step copper() is oxidized to copper() by
CCl4 in DMSO solution.6 The Cu2ϩ species formed oxidizes
hydrazones to the corresponding diazoalkanes. Earlier we
postulated the copper–carbene complex I as a key intermediate
of the olefination reaction.6d,f This complex is formed in the
copper-catalysed decomposition of diazoalkane. Similar
copper–carbene complexes are universally accepted as labile
intermediates in the copper-catalysed decomposition of diazo-
alkanes and consequent carbene-transfer processes.9
Two possible routes for the further transformation of I are
usually observed. Labile intermediate I reacts with a molecule
of polyhaloalkane giving the target alkene with regeneration of
copper() (the target route). A competitive reaction between I
and another molecule of diazoalkane gives the corresponding
sym-azine. Stilbene is likely formed by the coupling of two
copper–carbene species in line with a similar reaction of Pt()–
and Au()–carbene complexes.10
1-(2,2-Dichloro-1-methylvinyl)-4-(methylsulfonyl)benzene 2e.
Colourless crystals (0.88 g, 33%); mp 54–55 ЊC (from EtOH);
Rf (CH2Cl2) 0.70. Found: C, 45.52; H, 3.66. Calc. for C10H10-
Cl2O2S: C, 45.30; H, 3.80%; νmax(Nujol)/cmϪ1 1610 (C᎐C);
᎐
δH (400 MHz; CDCl3; Me4Si) 2.22 (3 H, s, Me), 3.09 (3 H,
s, MeSO2), 7.48 (2 H, d, J 8.5, Ar), 7.96 (2 H, d, J 8.5, Ar);
δC (100 MHz; CDCl3; Me4Si) 22.64 (Me), 44.29 (MeSO2),
118.67 (CCl2), 127.41, 128.82, 134.01, 139.60, 145.46.
1-(2,2-Dibromo-1-methylvinyl)-4-methylbenzene 3a. Colour-
less oil (1.51 g, 52%); Rf (hexane) 0.65. Found: C, 41.25; H,
3.67. Calc. for C10H10Br2: C, 41.42; H, 3.48%; νmax(Nujol)/cmϪ1
1605 (C᎐C); δ (400 MHz; CDCl ; Me Si) 2.17 (3 H, s, Me-C᎐
In conclusion, we have studied the catalytic transformation
of ketones into mono- and dihalo-alkenes. The presented reac-
tion proceeds under mild conditions using readily available
reagents. The simplicity of the experimental technique and
good yields of the target alkenes are the remarkable features of
the method.
᎐
᎐
H
3
4
C), 2.33 (3 H, s, Me-Ar), 7.10 (2 H, d, J 8.2, Ar), 7.15 (2 H, d,
J 8.2, Ar); δC (100 MHz; CDCl3; Me4Si) 21.24 (Me-Ar), 26.14
(Me-C᎐C), 87.24 (CBr ), 127.28, 129.03, 137.49, 139.02, 143.00.
᎐
2
1-Chloro-4-(2,2-dibromo-1-methylvinyl)benzene 3b. Colour-
less oil (2.33 g, 75%); Rf (hexane) 0.65. Found: C, 35.12; H,
2.44. Calc. for C9H7Br2Cl: C, 34.82; H, 2.27%; νmax(Nujol)/cmϪ1
Experimental
General procedures
1615 (C᎐C); δ (400 MHz; CDCl3; Me4Si) 2.17 (3 H, s, Me),
᎐
H
Melting points were determined in sealed capillaries and are
uncorrected. NMR spectra were recorded on Varian VXR-400
and Bruker AM 400C spectrometers in CDCl3 or DMSO-d6
with TMS as an internal standard. J values are given in Hz. The
IR spectra were obtained with a UR-20 spectrometer. Silica
gel Merck 60 and Merck 60F254 plates were used for con-
ventional and analytical (TLC) chromatography, respectively.
Mass spectra were recorded on an HP5890 mass spectrometer
(70 eV) with a 5989x-G detector.
7.16 (2 H, d, J 8.8, Ar), 7.32 (2 H, d, J 8.8, Ar); δC (100 MHz;
CDCl3; Me4Si) 25.98 (Me), 88.29 (CBr2), 128.59, 128.83,
133.53, 140.21, 141.82.
1-(2,2-Dibromo-1-methylvinyl)-4-methoxybenzene 3c. Colour-
less crystals (2.82 g, 92%); mp 56–57 ЊC; Rf (hexane–CH2Cl2,
2 : 1) 0.70. Found: C, 39.28; H, 3.19. Calc. for C10H10Br2O:
C, 39.25; H, 3.29%; νmax(Nujol)/cmϪ1 1620 (C᎐C); δ (400 MHz;
᎐
H
CDCl ; Me Si) 2.15 (3 H, s, Me-C᎐C), 3.75 (3 H, s, MeO), 6.84
᎐
3
4
J. Chem. Soc., Perkin Trans. 1, 2002, 883–887
885

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(2 H, d, J 8.2, Ar), 7.13 (2 H, d, J 8.2, Ar); δC (100 MHz; CDCl3;
1-(2-Bromo-1-methylvinyl)-4-nitrobenzene 4d. Obtained as a
Me Si) 26.07 (Me-C᎐C), 55.11 (MeO), 87.13 (CBr ), 113.58,
128.66, 133.97, 142.53, 158.85.
mixture of E–Z isomers 5 : 4 (after purification); colourless oil
(1.14 g, 47%); Rf (hexane–CH2Cl2, 2 : 1) 0.60. Found: C, 44.42;
H, 3.09. Calc. for C9H8BrNO2: C, 44.66; H, 3.33%; νmax(Nujol)/
᎐
4
2
1-(2,2-Dibromo-1-methylvinyl)-4-nitrobenzene 3d. Colourless
crystals (2.38 g, 74%); mp 84–85 ЊC; Rf (hexane–CH2Cl2, 2 : 1)
0.70. Found: C, 33.43; H, 2.01. Calc. for C9H7Br2NO2: C, 33.68;
cmϪ1 1620 (C᎐C). E-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.26
᎐
(3 H, d, J 1.3, Me-C᎐C), 6.66 (1 H, q, J 1.3, -CH᎐), 7.49 (2 H, d,
᎐
᎐
J 9.0, Ar), 8.17 (2 H, d, J 9.0, Ar). Z-Isomer: δH (400 MHz;
H, 2.20%; νmax(Nujol)/cmϪ1 1600 (C᎐C); δH (400 MHz; CDCl3;
CDCl ; Me Si) 2.15 (3 H, d, J 1.6, Me-C᎐C), 6.36 (1 H, q, J 1.6,
᎐
᎐
3
4
Me4Si) 2.21 (3 H, s, Me), 7.40 (2 H, d, J 8.8, Ar), 8.21 (2 H, d,
J 8.8, Ar); δC (100 MHz; CDCl3; Me4Si) 25.80 (Me), 89.47
(CBr2), 123.67, 128.61, 141.17, 146.92, 148.30.
-CH᎐), 6.93 (2 H, d, J 8.7, Ar), 7.48 (2 H, d, J 8.7, Ar). For the
mixture of isomers: δC (100 MHz; CDCl3; Me4Si) 19.32 (Me),
᎐
24.49 (Me), 103.76 (᎐CHBr), 109.18 (᎐CHBr), 123.46, 123.75,
᎐
᎐
126.55, 128.71, 139.75, 146.88; m/z (EI) 243 (Mϩ, 57%), 213
(Mϩ Ϫ NO, 10), 115 (Mϩ Ϫ NO2 Ϫ Br Ϫ H, 100).
1-(2,2-Dibromo-1-methylvinyl)-4-(methylsulfonyl)benzene 3e.
Colourless crystals (1.59 g, 45%); mp 100–101 ЊC (from EtOH);
Rf (CH2Cl2) 0.70. Found: C, 34.17; H, 2.96. Calc. for C10H10-
1-(2-Bromo-1-methylvinyl)-4-(methylsulfonyl)benzene
4e.
Br2O2S: C, 33.92; H, 2.85%; νmax(Nujol)/cmϪ1 1600 (C᎐C);
Obtained as a mixture of E–Z isomers 1 : 1 (after purification);
colourless oil (0.58 g, 21%); Rf (CH2Cl2) 0.70. Found: C,
43.65; H, 4.03. Calc. for C10H11BrO2S: C, 43.65; H, 4.03%;
᎐
δH (400 MHz; CDCl3; Me4Si) 2.19 (3 H, s, Me), 3.07 (3 H, s,
MeSO2), 7.43 (2 H, d, J 8.8, Ar), 7.93 (2 H, d, J 8.8, Ar); δC (100
MHz; CDCl3; Me4Si) 25.79 (Me), 44.27 (MeSO2), 89.18 (CBr2),
127.48, 128.45, 139.54, 141.25, 147.35.
νmax(Nujol)/cmϪ1 1620 (C᎐C). E-Isomer: δH (400 MHz; CDCl3;
᎐
Me Si) 2.17 (3 H, d, J 1.3, Me-C᎐C), 3.79 (3 H, s, MeSO ), 6.33
᎐
4
2
(1 H, q, J 1.3, -CH᎐), 6.88 (2 H, d, J 8.8, Ar), 7.28 (2 H, d, J 8.8,
Ar). Z-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.07 (3 H, d, J 1.7,
᎐
2-(2,2-Dibromo-1-methylvinyl)naphthalene 3f. Colourless oil
(1.34 g, 41%); Rf (hexane) 0.60. Found: C, 48.14; H, 3.27. Calc.
Me-C᎐C), 3.77 (3 H, s, MeSO ), 6.15 (1 H, q, J 1.7, -CH᎐), 6.82
᎐
᎐
2
for C13H10Br2: C, 47.89; H, 3.09%; νmax(Nujol)/cmϪ1 1600 (C᎐C);
(2 H, d, J 8.8, Ar), 7.25 (2 H, d, J 8.8, Ar). For the mixture of
isomers: δC (100 MHz; CDCl3; Me4Si) 19.84 (Me), 25.18 (Me),
᎐
δH (400 MHz; CDCl3; Me4Si) 2.23 (Me), 7.28 (1 H, dd, J 8.5,
J 1.8, Naphth), 7.42–7.45 (2 H, m, Naphth), 7.64 (1 H, d,
J 1.8, Naphth), 7.74–7.79 (3 H, m, Naphth); δC (100 MHz;
CDCl3; Me4Si) 26.25 (CH3), 87.90 (CBr2), 125.70, 126.62,
126.76, 126.79, 127.90, 128.24, 128.34, 132.52, 133.02, 139.22,
143.64.
37.61 (MeO), 38.01 (MeO), 99.87 (᎐CHBr), 101.54 (᎐CHBr),
᎐
᎐
113.16, 113.69, 123.72, 124.43, 138.13, 138.30, 143.69, 143.83,
152.58, 153.22.
2-(2-Bromo-1-methylvinyl)naphthalene 4f. Obtained as
a
mixture of E–Z isomers 3 : 1 (after purification); colourless oil
(0.96 g, 39%); Rf (hexane) 0.70. Found: C, 63.46; H, 4.73. Calc.
1-(Dibromomethylene)indane 3i. Colourless oil (1.47 g, 51%);
Rf (hexane) 0.60. Found: C, 41.46; H, 2.55. Calc. for C10H8Br2:
C, 41.71; H, 2.80%; νmax(Nujol)/cmϪ1 1610 (C᎐C); δ (400 MHz;
CDCl3; Me4Si) 2.85–2.92 (2 H, m, CH2), 2.95–3.02 (2 H,
m, CH2), 7.20–7.35 (3 H, m, Ar), 8.28–8.33 (1 H, m, Ar);
δC (100 MHz; CDCl3; Me4Si) 31.14 (CH2), 33.26 (CH2), 85.94
(CBr2), 124.88, 125.93, 126.77, 131.15, 133.62, 137.28, 145.77.
for C13H11Br: C, 63.18; H, 4.49%; νmax(Nujol)/cmϪ1 1605 (C᎐C).
᎐
᎐
H
E-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.39 (3 H, d, J 1.1, Me-
C᎐C), 6.67 (1 H, q, J 1.1, -CH᎐), 7.50–7.56 (3 H, m), 7.83–7.93
᎐
᎐
(4 H, m). Z-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.27 (3 H,
d, J 1.5, Me-C᎐C), 6.37 (1 H, q, J 1.5, -CH᎐), other signals
᎐
᎐
are overlapped by those of the E-isomer. For the mixture of
isomers: δC (100 MHz; CDCl3; Me4Si) 20.73 (Me), 22.26 (Me),
1-(2-Bromo-1-methylvinyl)-4-methylbenzene 4a. Obtained as
a mixture of E–Z isomers 5 : 4 (after purification); colourless
oil (1.16 g, 55%); Rf (hexane) 0.65. E-Isomer: δH (400 MHz;
100.37 (᎐CHBr), 103.18 (᎐CHBr), 123.62, 123.94, 127.32,
᎐
᎐
127.76, 129.58, 129.90, 130.54, 130.79, 131.81, 132.52, 133.02,
137.42, 144.17, 144.27.
CDCl ; Me Si) 2.16 (3 H, d, J 1.3, Me-C᎐C), 2.29 (3 H, s,
᎐
3
4
Me-Ar), 6.37 (1 H, q, J 1.3, -CH᎐), 7.07–7.22 (4 H, m, Ar).
Z-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.05 (3 H, d, J 1.6, Me-
᎐
2-(2-Bromo-1-methylvinyl)thiophene 4g. Obtained as
a
mixture of E–Z isomers 2 : 1 (after purification); colourless oil
(1.22 g, 60%); Rf (hexane) 0.65. Found: C, 41.54; H, 3.68. Calc.
C᎐C), 2.32 (3 H, s, Me-Ar), 6.15 (1 H, q, J 1.6, -CH᎐), 7.07–7.22
᎐
᎐
(4 H, m, Ar).
for C7H7BrS: C, 41.40; H, 3.47%; νmax(Nujol)/cmϪ1 1610 (C᎐C).
᎐
E-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.23 (3 H, d, J 1.1,
1-(2-Bromo-1-methylvinyl)-4-chlorobenzene 4b. Obtained as
a mixture of E–Z isomers 4 : 3 (after purification); colourless
oil (1.69 g, 73%); Rf (hexane) 0.70. E-Isomer: δH (400 MHz;
Me-C᎐C), 6.62 (1 H, q, J 1.1, -CH᎐), 6.98 (1 H, dd, J 5.1, J 3.6,
᎐
᎐
Th), 7.04 (1 H, dd, J 3.6, J 1.3, Th), 7.18 (1 H, dd, J 5.1, J 1.3,
Th). Z-Isomer: 2.24 (3 H, d, J 1.5, Me-C᎐C), 6.22 (1 H, q,
᎐
CDCl ; Me Si) 2.17 (3 H, d, J 1.3, Me-C᎐C), 6.42 (1 H, q, J 1.3,
᎐
3
4
J 1.5, -CH᎐), 7.02 (1 H, dd, J 5.1, J 3.8, Th), 7.24 (1 H, dd, J 3.8,
᎐
-CH᎐), 7.19–7.33 (4 H, m, Ar). Z-Isomer: δ (400 MHz; CDCl ;
᎐
H
3
J 1.2, Th), 7.33 (1 H, dd, J 5.1, J 1.2, Th). For the mixture
of isomers: δC (100 MHz; CDCl3; Me4Si) 19.38 (Me), 24.57
Me Si) 2.06 (3 H, d, J 1.6, Me-C᎐C), 6.21 (1 H, q, J 1.6, -CH᎐),
᎐
᎐
4
7.19–7.33 (4 H, m, Ar).
(Me), 100.43 (᎐CHBr), 104.16 (᎐CHBr), 123.62, 124.50, 126.02,
᎐
᎐
126.23, 127.31, 127.46, 134.83.
1-(2-Bromo-1-methylvinyl)-4-methoxybenzene
4c.
was
obtained as a mixture of E–Z isomers 2 : 1 (after purification);
colourless oil (1.23 g, 54%); Rf (hexane–CH2Cl2, 2 : 1) 0.55.
Found: C, 53.17; H, 5.16. Calc. for C10H11BrO: C, 52.89; H,
4.88%; νmax(Nujol)/cmϪ1 1600 (C᎐C). E-Isomer: δ (400 MHz;
GCMS analysis of the reaction mixture
A 25% aqueous solution of ammonia (0.33 cm3) and freshly
purified CuCl18 (10 mg, 0.1 mmol) were added to a solution
of freshly prepared hydrazone 1b (169 mg, 1 mmol) in DMSO
(1 cm3). Then CCl4 (0.29 cm3, 3 mmol) was added dropwise
over 10 min, with the temperature maintained at 20 ЊC (water
bath). The reaction mixture was stirred for 24 h and quenched
with water (50 cm3). The reaction products were extracted with
CH2Cl2 (10 cm3 × 3). The extracts were dried over sodium
sulfate, CH2Cl2 was evaporated and the residue was analysed by
GCMS. The following products were detected in the reaction
mixture.
᎐
H
CDCl ; Me Si) 2.21 (3 H, d, J 1.3, Me-C᎐C), 3.82 (3 H, s,
᎐
3
4
MeO), 6.38 (1 H, q, J 1.3, -CH᎐), 6.88 (2 H, d, J 8.9, Ar), 7.27
᎐
(2 H, d, J 8.9, Ar). Z-Isomer: δH (400 MHz; CDCl3; Me4Si) 2.11
(3 H, d, J 1.6, Me-C᎐C), 3.83 (3 H, s, MeO), 6.19 (1 H, q, J 1.6,
᎐
-CH᎐), 6.93 (2 H, d, J 8.9, Ar), 7.19 (2 H, d, J 8.9, Ar). For
᎐
the mixture of isomers: δC (CDCl3) 19.53 (Me), 24.84 (Me),
55.09 (MeO), 55.17 (MeO), 100.72 (᎐CHBr), 103.68 (᎐CHBr),
᎐
᎐
113.38, 113.75, 126.97, 128.87, 132.13, 133.30, 140.69, 158.85,
159.22.
886
J. Chem. Soc., Perkin Trans. 1, 2002, 883–887

View Article Online
V. N. Korotchenko, V. G. Nenajdenko and E. S. Balenkova,
1-Chloro-4-(2,2-dichloro-1-methylvinyl)benzene 2b. m/z (EI)
220 (Mϩ, 100%), 185 (Mϩ Ϫ Cl, 17), 149 (Mϩ Ϫ 2 Cl, 92), 112
(Mϩ Ϫ 2 Cl Ϫ C3H3, 50).
Tetrahedron, 2000, 56, 6557; (c) V. G. Nenajdenko, V. N.
Korotchenko, A. V. Shastin and E. S. Balenkova, Russ. Chem. Bull.,
2001, 50, 1047; (d ) A. V. Shastin, V. N. Korotchenko,
V. G. Nenajdenko and E. S. Balenkova, Russ. Chem. Bull., 2001,
50, 1401; (e) A. V. Shastin, V. N. Korotchenko, V. G. Nenajdenko
and E. S. Balenkova, Synthesis, 2001, 2081; ( f ) V. N. Korotchenko,
A. V. Shastin, V. G. Nenajdenko and E. S. Balenkova, Tetrahedron,
2001, 57, 7519.
sym-Azine of 4-chloroacetophenone. m/z (EI) 304 (Mϩ, 49%),
289 (Mϩ Ϫ CH , 100), 152 [ClC H C(CH )᎐N].
᎐
3
6
4
3
4-Chloroacetophenone. m/z (EI) 154 (Mϩ, 33%), 139 (Mϩ
CH3, 100), 111 (Mϩ Ϫ CH3CO, 47).
Ϫ
7 K.-W. Lee and T. L. Brown, J Am. Chem. Soc., 1987, 109, 3269;
E. Abele, M. Fleisher, K. Rubina, R. Abele and E. Lukevics, J. Mol.
Catal. A: Chem., 2001, 165, 121.
1-Chloro-4-[2-(4-chlorophenyl)-1-methylprop-1-enyl]benzene,
8 V. N. Korotchenko, A. V. Shastin, V. G. Nenajdenko and E. S.
Balenkova, presented in part at the 12th European Symposium on
Organic Synthesis (ESOC-12), Groningen, Netherlands, 2001.
9 D. S. Wulfman and B. Poling, in Reactive Intermediates,
ed. R. A. Abramovitch, Plenum Press, New York, 1980, vol. 1,
p. 321; M. P. Doyle, Chem. Rev., 1986, 86, 919; V. K. Aggarwal,
J. G. Ford, R. V. H. Jones and R. Fieldhouse, Tetrahedron:
Asymmetry, 1998, 1801.
ClC H (CH )C᎐C(CH )C H Cl. m/z (EI) 276 (Mϩ, 100%), 261
᎐
6
4
3
3
6
4
(Mϩ Ϫ CH3, 10), 226 (Mϩ Ϫ CH3 Ϫ Cl, 28).
Acknowledgements
Financial support from the Russian Fundamental Investigation
Foundation (Grants No. 00-03-32760 and No. 00-03-32763) is
gratefully acknowledged.
10 R. Bertani, R. A. Michelin, M. Mozzon, P. Traldi, R. Seraglia,
l. Busetto, M. C. Cassani, P. Tagliatesta and G. D’Arcangelo,
Organometallics, 1997, 16, 3229.
11 G. Lock and K. Stach, Chem. Ber., 1944/46, 77/79, 293.
12 H. F. Harnsberger, E. L. Cochran and H. H. Szmant, J Am. Chem.
Soc., 1955, 77, 5048.
13 D. E. Pearson, K. N. Carter and C. M. Greer, J Am. Chem. Soc.,
1953, 75, 5905.
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J. Chem. Soc., Perkin Trans. 1, 2002, 883–887
887