Synthesis of bis(halovinyl)benzenes by catalytic olefination

Article abstract of DOI:10.1007/s11172-013-0091-4

Catalytic olefination of hydrazines of terephthalic and isophthalic aldehydes with polyhaloalkanes afforded the corresponding p- and m-divinylbenzene derivatives bearing halogen atoms and various functional groups at the double bonds. Stereochemical featu

Full text of DOI:10.1007/s11172-013-0091-4

Russian Chemical Bulletin, International Edition, Vol. 62, No. 3, pp. 678—682, March, 2013
678
Synthesis of bis(halovinyl)benzenes by catalytic olefination*
V. M. Muzalevskiy,a N. G. Shikhaliev,b A. M. Magerramov,b N. V. Gurbanova,b S. D. Geydarova,b
E. S. Balenkova,a A. V. Shastin,c and V. G. Nenajdenkoa
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
Build. 3, 1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: nen@acylium.chem.msu.ru
bDepartment of Chemistry, Baku State University,
23 ul. Akad. Z. Halilova, AZ1148 Baku, Azerbaidjan
cInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad.Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation
Catalytic olefination of hydrazines of terephthalic and isophthalic aldehydes with polyꢀ
haloalkanes afforded the corresponding pꢀ and mꢀdivinylbenzene derivatives bearing halogen
atoms and various functional groups at the double bonds. Stereochemical features of the reacꢀ
tion were studied.
Key words: catalytic olefination, polyhaloalkanes, alkenes, dienes, organofluorine compounds.
Divinylbenzenes and diethynylbenzenes1 are widely
Scheme 2
used monomers for the synthesis of electrically conducꢀ
tive, fluorescent, and other oligomeric and polymeric maꢀ
terials possessing valuable physicochemical properties.2
Thus, bis(2,2ꢀdihalovinyl)benzenes are used for the synꢀ
thesis of diethynylbenzenes and serve also as starting maꢀ
terials for tunable organic fluorophores.1d,2c Usually,
monoꢀ and bis(halovinyl)benzenes are prepared by the
Wittig reaction from the corresponding dialdehydes, howꢀ
ever, the significant drawback of this method is the use of
either equimolar or excess amounts of organophosphorus
and organometallic compounds.3 An alternative approach
towards these compounds is the catalytic olefination reacꢀ
tion (the Nenajdenko—Shastin reaction),4,5 which is the
reaction of Nꢀunsubstituted hydrazones of aldehydes and
ketones with polyhaloalkanes catalyzed by copper salts
providing a variety of halogenꢀcontaining olefins, includꢀ
ing functionalized ones (Scheme 1).
Scheme 1
Reagent and conditions: i. CHal2XY, CuCl (2 mol.%), base. Subꢀ
stituents X, Y, and olefination reagent (CHal2XY) are given
in Table 1.
In the present work, we describe olefination of diꢀ
hydrazones of terephthalic (1) and isophthalic (2) aldeꢀ
hydes with polyhaloalkanes (Scheme 2).
We used polyhalomethanes CBrCl3, CBr4, and CFBr3
(building blocks Cꢀ1); polyhaloethanes CF3CBr3,
CF3CCl3, and CF3CFBr2 (building blocks Cꢀ2), as well as
ethyl trichloroacetate and trichloroacetonitrile allowing
synthesis of functionalized alkenes.
* Dedicated to the Academician of the Russian Academy of
Sciences I. P. Beletskaya on the occasion of her anniversary.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0677—0681, March, 2013.
1066ꢀ5285/13/6203ꢀ678 © 2013 Springer Science+Business Media, Inc.

Divinylbenzenes
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
679
Table 1. Synthesis of divinylbenzene derivatives by catalytic
olefination reaction
molecule of E,Eꢀisomer, and two molecules of Z,Eꢀisoꢀ
mer (Z,E and E,Z) are formed. NMR spectroscopy was
used to determine the configuration and to assign the isoꢀ
mers. In the case of symmetric E,Eꢀ and Z,Zꢀisomers, the
molecule has the greater degree of symmetry leading to
simplification of the NMR spectra. Thus, in the 1H NMR
spectra of the major isomers of compounds 3, the protons
of the aromatic ring resonate as singlets. Both vinyl proꢀ
tons of compounds 3, 4 also appear as singlets, the excepꢀ
tion is the major dimers of fluorinated dienes 3e, 4e and
3h, 4h resonating as doublets with J = 32.5—35.2 Hz due
to spinꢀspin coupling with the fluorine atoms, which indiꢀ
cated E,Eꢀconfiguration for 3e, 4e and Z,Zꢀconfiguration
for 3h, 4h. The spectra of minor isomers (Z,Z and E,E,
respectively) show similar pattern with the only difference
that the coupling constant is equal to 15.2—20.5 Hz. In
the case of compounds 3c,d,f,g and 4c,d,f,g, the assignꢀ
ment of major isomer to Z,Zꢀ or E,Eꢀtype was performed
based on a comparison of the chemical shifts of the vinyl
protons with published data.5g,j,k In spectra of unsymmetꢀ
rical E,Zꢀisomers of compounds 3, 4, the vinyl proton
signals are nonꢀequivalent. Therefore, the aromatic proꢀ
tons of paraꢀ"dienes" 3 resonate as two separate doublets.
It is of note that the isomer bearing the aryl moiety and the
most bulky substituent in cisꢀpositions at both double
bonds was detected only for compounds 3e and 4e, howꢀ
ever, content of this minor isomer did not exceed 5%.
In summary, olefination of dihydrazones of tereꢀ
phthalic and isophthalic aldehydes allows development of
simple and versatile pathway towards halogenated 1,3ꢀ and
1,4ꢀdivinylbenzenes, including the corresponding fluoriꢀ
nated compounds and functionalized derivatives.
These dienes are of great interest for the synthesis of polyꢀ
mers using, for example, the Suzuki crossꢀcoupling reacꢀ
tion; the synthesis of fluorinated polymers based on comꢀ
pounds 3e,f and 4e,f is particularly promising. Functionꢀ
alized alkenes 3c,d and 4c,d may serve as unique building
blocks in the synthesis of heterocycles, which, in turn, can
be used in design of coordination polymers and supramoꢀ
lecular structures.
Dihyrꢀ Olefinaꢀ Product
azone tion reagent
X
Y
Yield
(%)
Ratio of
isomers*
1
1
1
CBrCl3
CBr4
CCl3CO2Et
3a
3b
3c
Cl
Br
Cl
Br
76
55
—
—
72 : 28
Cl CO2Et 25
(Z,Z : Z,E)
67 : 33
(E,E : Z,E)
66 : 29 : 5
(E,E : Z,E : Z,Z)
78 : 22
1
1
1
1
1
CCl3CN
CFBr3
3d
3e
3f
Cl CN
Br
39
52
17
24
69
F
CF3CBr3
CF3CCl3
CF3CFBr2
Br CF3
Cl CF3
(Z,Z : Z,E)
67 : 33
(Z,Z : Z,E)
86 : 14
3g
3h
F
CF3
(Z,Z : Z,E)
—
—
79 : 21
2
2
2
CBrCl3
CBr4
CCl3CO2Et
4a
4b
4c
Cl
Br
Cl
Br
73
81
Cl CO2Et 23
(Z,Z : Z,E)
73 : 27
(E,E : Z,E)
58 : 37 : 5
(E,E : Z,E : Z,Z)
83 : 17
2
2
2
2
2
CCl3CN
CFBr3
4d
4e
4f
Cl CN
Br
40
34
48
50
33
F
CF3CBr3
CF3CCl3
CF3CFBr2
Br CF3
Cl CF3
(Z,Z : Z,E)
65 : 35
(Z,Z : Z,E)
84 : 16
4g
4h
F
CF3
(Z,Z : Z,E)
* Configuration of isomers is given in parentheses.
The yields of target compounds 3, 4 were found subꢀ
stantially dependent on reactivity of the staring polyhaloꢀ
alkanes (Table 1). Earlier, we estimated the reactivity of
different polyhaloalkanes using the global electrophilicity
index.6 The presence of the fluorine atoms in the starting
reactant significantly decreases its activity, for example,
in the case of less reactive freons. Nevertheless, the availꢀ
ability of the starting compounds, simplicity of both proꢀ
cessing and isolation of the products are important advanꢀ
tages of catalytic olefination.
Experimental
1
H and 13C NMR spectra were run on a Bruker AMX 400
It is worthy to note that in the case of unsymmetrical
alkenes (X  Y), a mixture of E,Eꢀ,E,Zꢀ, and Z,Zꢀisomers
can be formed. We showed previously that catalytic olefiꢀ
nation is highly stereoselective and yields the least steriꢀ
cally strained alkenes. The content of minor isomer in
some cases did not exceed 5%.5o Olefination of dialdehyde
hydrazones 1 and 2 also favors formation of isomer bearꢀ
ing the aryl moiety and the most bulky substituent in trans
position to each other. Note that comparing "monoꢀ
alkenes", "dienes" 3, 4 give slightly higher amount of the
minor isomer due to statistical doubling of its content.
Indeed, upon reaction, one molecule of Z,Zꢀisomer, one
spectrometer (working frequencies of 400.1 and 100.6 MHz,
respectively) in CDCl3; chemical shifts are given in the  scale
relative to Me4Si (internal standard). 19F NMR spectra were
recorded on a Bruker AM 300 instrument (working frequencies
of 282.4 MHz). IR spectra were recorded using Carl Zeiss URꢀ20
and IR 200 spectrophotometers in neat (for liquids) and in Nujol
(for solids). TLC was performed on Merck 60 F254 plates; for
visualization of the spots, acidified KMnO4 solution and UV
irradiation were used. Column chromatography was performed
on a silica gel (63—200 mesh, Merck). In the NMR spectra of
the minor Eꢀisomers, only characteristic signals, nonꢀcoincided
with the signals of major Zꢀisomer, are given.

680
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
Muzalevsky et al.
The starting hydrazones of terephthalic and isophthalic alꢀ
66 : 29 : 5. Found (%): C, 37.19; H, 1.94. C10H6Br2F2. Calculatꢀ
dehydes were synthesized by a known procedure.5p 1H NMR
spectra of compounds 3a,5q 3b,1d and 4c3b are in agreement with
the published data.
ed (%): C, 37.07; H, 1.87. IR, /cm–1: 1647 (C=C).
1
E,Eꢀisomer. H NMR (CDCl3), : 5.98 (d, 2 H, C=CH,
J = 33.1 Hz), 7.39 (s, 4 H, C6H4). 19F NMR (CDCl3), : –67.30
(d, J = 33.1 Hz). 13C NMR (CDCl3), : 112.7 (d, C=C—F,
J = 5.9 Hz); 128.3 (d, (CH)Ar, J = 7.3 Hz); 132.0 (d, (Cquat)Ar,
J = 1.8 Hz); 134.5 (d, C=C—F, J = 332.3 Hz).
Synthesis of divinylbenzenes 3, 4 (general procedure). Tereꢀ
phthalic aldehyde dihydrazone (1) or isophthalic aldehyde dihydrꢀ
azone (2) (0.810 g, 5 mmol) was added in small portion over
a period of 2 h to a mixture of DMSO (20 mL), the correspondꢀ
ing base (25 mmol), CuCl (0.01 g, 2 mol.%), and the correꢀ
sponding polyhaloalkane(25 mmol). The reaction mixture was
stirred at room temperature for 24 h, poured into water (300 mL),
extracted with dichloromethane (3×50 mL), and dried over
MgSO4. The solvent was removed in vacuo. Column chromatoꢀ
graphy of the residue (silica gel, elution with appropriate
dichloromethane—hexane mixtures) afforded the title prodꢀ
uct. The isomeric mixtures were not separated into indivꢀ
idual isomers.
1
E,Zꢀisomer. H NMR (CDCl3), : 5.99 (d, 1 H, C=CH,
J = 32.8 Hz); 6.66 (d, 1 H, C=CH, J = 15.2 Hz), 7.41 (d, 2 H, Ar,
J = 8.3 Hz), 7.50 (d, 2 H, Ar, J = 8.3 Hz). 19F NMR (CDCl3), :
–64.71 (d, J = 15.2). 13C NMR (CDCl3), : 111.4 (d, C=C—F,
J = 24.5 Hz); 128.5 (d, (CH)Ar, J = 7.3 Hz); 128.5 (d, (CH)Ar,
J = 7.3 Hz); 128.6 (d, J = 3.3 Hz).
Z,Zꢀisomer. 1H NMR (CDCl3), : 6.67 (d, 2 H, C=CH,
J = 15.3 Hz); 7.51 (s, 4 H, Ar).
1,4ꢀBis(2ꢀbromoꢀ3,3,3ꢀtrifluoropropꢀ1ꢀenyl)benzene (3f) was
synthesized by a reaction of dihydrazone 1 with CF3CBr3 using
concentrated aqueous ammonia as a base. Yield 0.353 g (17%),
colorless oil. A mixture of Z,Zꢀ and Z,Eꢀisomers in a ratio of
78 : 22. Found (%): C, 34.12; H, 1.51. C12H6Br2F6. Calculatꢀ
ed (%): C, 33.99; H, 1.43.
Z,ZꢀIsomer. 1H NMR (CDCl3), : 7.64 (d, 2 H, C=CH,
J = 1.0 Hz); 7.64 (s, 4 H, C6H4). 13C NMR (CDCl3), : 111.0
(q, C=C—CF3, J = 37.0); 120.8 (q, CF3, J = 271.9 Hz); 129.7,
133.4 (q, C=C—CF3, J = 5.1 Hz); 134.0.
1,4ꢀBis(2,2ꢀdichlorovinyl)benzene (3a) was synthesized by
a reaction of hydrazone 1 with CBrCl3 using concentrated aqueꢀ
ous ammonia as a base. Yield 1.023 g (76%), colorless crystals,
1
m.p. 77—78 C (cf. Ref. 1d: 77—78 C). H NMR (CDCl3),
: 6.86 (s, 2 H, C=CH); 7.57 (s, 4 H, Ar).
1,4ꢀBis(2,2ꢀdibromovinyl)benzene (3b) was synthesized by
a reaction of hydrazone 1 with CBr4 using concentrated aqueous
ammonia as a base. Yield 1.219 g (55%), colorless crystals, m.p.
97—98 C (cf. Ref. 1d: 98—99 C). 1H NMR (CDCl3), : 7.48 (s,
2 H, C=CH); 7.58 (s, 4 H, Ar).
1,4ꢀBis(2ꢀchloroꢀ3ꢀethoxyꢀ3ꢀoxopropenyl)benzene (3c) was
synthesized by a reaction of 1 with CCl3CO2Et using triethylꢀ
amine as a base. Yield 0.425 g (25%), colorless heavy oil.
A mixture of Z,Zꢀ and Z,Eꢀisomers in a 72 : 28 ratio. Found (%):
C, 56.12; H, 4.80. C16H16Cl2O4. Calculated (%): C, 55.99;
H, 4.70.
Z,Zꢀisomer. 1H NMR (CDCl3), : 1.38 (t, 6 H, CH3,
J = 7.1 Hz); 4.34 (q, 4 H, CH2, J = 7.1 Hz), 7.87 (s, 6 H, =CH—,
Ar). 13C NMR (CDCl3), : 14.2 (CH3); 62.7 (CH2); 123.5
(C=C—Cl); 130.6 (CH, Ar); 134.4 ((Cquat)Ar); 135.8 (C=C—Cl);
163.1 (CO2Et).
E,Zꢀisomer. 1H NMR (CDCl3), : 1.19 (t, 6 H, CH3,
J = 7.1 Hz), 4.21 (q, 4 H, CH2, J = 7.1 Hz), 7.17 (s, 1 H, =CH—),
7.34 (d, 2 H, Ar, J = 8.3 Hz), 7.80 (d, 2 H, Ar, J = 8.3 Hz), 7.85
(s, 1 H, =CH—). 13C NMR (CDCl3), : 13.7 (CH3); 62.4 (CH2);
123.0 (C=C—Cl); 124.0 (C=C—Cl); 128.7 (CH, Ar); 130.5 (CH,
Ar); 133.3 ((Cquat)Ar); 135.5 ((Cquat)Ar); 135.9 (C=C—Cl), 136.0
(C=C—Cl); 163.1 (CO2Et). Found (%): C, 56.12; H, 4.80.
C16H16Cl2O4. Calculated (%): C, 55.99; H, 4.70.
E,ZꢀIsomer. 1H NMR (CDCl3), : 7.38 (d, 2 H, Ar, J = 8.3 Hz);
7.54 (s, 1 H, =CH—); 7.62 (s, 1 H, =CH—); 7.77 (d, 2 H, Ar,
J = 8.3 Hz). 13C NMR (CDCl3), : 111.7 (q, C=C—CF3,
J = 38.0 Hz); 117.4 (q, C=C—CF3, J = 34.0 Hz); 120.4 (q, CF3,
J = 273.7 Hz); 128.5 (q, Ar, J = 1.8 Hz); 129.6; 129.8; 136.7
(q, C=C—CF3, J = 7.0 Hz); 140.5 (q, Ar, J = 2.6 Hz). Remainꢀ
ing signals are coincide with the signals of Z,Zꢀisomer.
1,4ꢀBis(2ꢀchloroꢀ3,3,3ꢀtrifluoropropꢀ1ꢀenyl)benzene (3g) was
synthesized by a reaction of dihydrazone 1 with CF3CCl3 using
ethylenediamine as a base. Yield 24%, colorless oil. A mixture of
Z,Zꢀ and Z,Eꢀisomers in a ratio of 67 : 33. Found (%): C, 43.14;
H, 1.85. C12H6Cl2F6. Calculated (%): C, 43.01; H, 1.80. IR,
/cm–1: 1650 (C=C).
1
Z,ZꢀIsomer. H NMR (CDCl3), : 7.07 (d, 2 H, =CH—,
J = 1.0 Hz); 7.56 (br.s, 4 H, Ar). 13C NMR spectrum of the
isomeric mixture (CDCl3), : 120.9 (d, =C(Cl)CF3, J = 36.6 Hz);
120.9 (q, CF3, J = 271.6 Hz); 129.7 (d, J = 4.6 Hz), 130.1, 133.2.
1
E,ZꢀIsomer. H NMR (CDCl3), : 7.02 (s, 1 H, =CH—);
7.06 (s, 1 H, =CH—); 7.13 (d, 2 H, Ar, J = 8.2 Hz); 7.50 (d, 2 H,
Ar, J = 8.2 Hz).
1,4ꢀBis(2,3,3,3ꢀtetrafluoropropꢀ1ꢀenyl)benzene (3h) was synꢀ
thesized by a reaction of dihydrazone 1 with CF3CFBr2 using
ethylenediamine as a base. Yield 1.040 g (69%), colorless crysꢀ
tals, m.p. 42—45 C. A mixture of Z,Zꢀ and Z,Eꢀisomers in a ratio
of 84 : 16. Found (%): C, 47.81; H, 1.95. C12H6F8. Calculatꢀ
ed (%): C, 47.70; H, 2.00.
1,4ꢀBis(2ꢀchloroꢀ2ꢀcyanovinyl)benzene (3d) was synthesized
by a reaction of hydrazone 1 with CCl3CN using triethylamine
as a base. Yield 0.502 g (40%), colorless crystals. A mixture of
E,Eꢀ and Z,Eꢀisomers in a ratio of 67 : 33. Found (%): C, 57.96;
H, 2.47. C12H6Cl2N2. Calculated (%): C, 57.86; H, 2.43.
1
E,Eꢀisomer. H NMR (CDCl3), : 7.39 (s, 2 H, C=CH);
Z,ZꢀIsomer. 1H NMR (CDCl3), : 6.44 (d, 2 H, C=CH,
J = 35.2 Hz); 7.61 (s, 4 H, Ar). 13C NMR (CDCl3), : 110.7,
118.8 (qd, CF—CF3, J = 271.3 Hz, J = 41.3 Hz); 129.4, 130.1,
130.2, 130.9, 145.9 (dq, CF—CF3, J = 269.4 Hz, J = 38.7 Hz).
7.79 (s, 4 H, Ar). 13C NMR (CDCl3), : 102.4 (C=C—Cl); 114.7
(CN); 129.3 (CH, Ar); 130.9 ((Cquat)Ar); 143.7 (CH=C).
E,Zꢀisomer. 1H NMR(CDCl3), : 6.74 (s, 1 H, =CH—);
7.38 (s, 1 H, =CH—); 7.68 (d, 2 H, Ar, J = 8.6 Hz); 7.81 (d, 2 H,
Ar, J = 8.6 Hz).
1
E,ZꢀIsomer. H NMR (CDCl3), : 6.82 (d, 1 H, C=CH,
J = 20.5 Hz); 7.34 (d, 2 H, Ar, J = 8.1 Hz); 7.58 (d, 2 H, Ar,
J = 8.1 Hz). 13C NMR (CDCl3), : 129.7, 129.8.
1,3ꢀBis(2,2ꢀdichlorovinyl)benzene (4a) was synthesized by
a reaction of dihydrazone 2 with CBrCl3 using concentrated
aqueous ammonia as a base. Yield 0.974 g (73%), colorless crysꢀ
1,4ꢀBis(2ꢀbromoꢀ2ꢀfluorovinyl)benzene (3e) was synthesized
by a reaction of hydrazone 1 with CFBr3 using concentrated
aqueous ammonia as a base. Yield 0.844 g (52%), colorless crysꢀ
tals. A mixture of E,Eꢀ, Z,Eꢀ, and Z,Zꢀisomers in a ratio of

Divinylbenzenes
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 3, March, 2013
681
1
tals, m.p. 48—49 C. IR, /cm–1: 1612. 1H NMR (CDCl3),
: 6.87 (s, 2 H, C=CH); 7.39 (dd, 1 H, Ar, J = 7.0 Hz, J = 8.7 Hz);
7.47—7.51 (m, 2 H, Ar), 7.73—7.76 (m, 1 H, Ar). 13C NMR
(CDCl3), : 121.7 (CH=CCl2); 127.9 (CH=CCl2); 128.5 (Ar);
133.5 ((Cquat)Ar). Found (%): C, 44.82; H, 2.26. C10H6Cl4. Calꢀ
culated (%): C, 43.01; H, 1.80.
E,ZꢀIsomer. H NMR (CDCl3), : 5.99 (d, 1 H, C=CH,
J = 32.5 Hz); 6.65 (d, 1 H, C=CH, J = 14.9 Hz); 7.52 (s, 1 H,
Ar). 19F NMR (CDCl3), : –68.1 (d, 1 F, J = 32.5 Hz); –65.6 (d,
1 F, J = 14.9 Hz).
1
Z,ZꢀIsomer. H NMR (CDCl3), : 6.67 (d, 2 H, C=CH,
J = 14.9 Hz); 7.62 (s, 1 H, Ar).
1,3ꢀBis(2,2ꢀdibromovinyl)benzene (4b) was synthesized by
a reaction of dihydrazone 2 with CBr4 using concentrated aqueous
ammonia as a base. Yield 1.776 g (81%), colorless crystals, m.p.
60—61 C (cf. Ref. 3b: 58—59 C). H NMR (CDCl3), : 7.38
(dd, 1 H, Ar, J = 7.1 Hz, J = 8.5 Hz); 7.47—7.51 (m, 2 H, Ar),
1,3ꢀBis(2ꢀbromoꢀ3,3,3ꢀtrifluoropropꢀ1ꢀenyl)benzene (4f) was
synthesized by a reaction of dihydrazone 2 with CF3CBr3 using
concentrated aqueous ammonia as a base. Yield 1.045 g (48%),
colorless oil. A mixture of Z,Zꢀ and Z,Eꢀisomers in a ratio of
83 : 17. Found (%): C, 34.15; H, 1.49. C12H6Br2F6. Calculatꢀ
ed (%): C, 33.99; H, 1.43.
1
7.48 (s, 2 H, C=CH); 7.73—7.75 (m, 1 H, Ar).
1,3ꢀBis[2ꢀ(2ꢀchloroꢀ3ꢀethoxyꢀ3ꢀoxopropenyl)]benzene (4c)
was synthesized by a reaction of dihydrazone 2 with CCl3CO2Et
using triethylamine as a base. Yield 0.389 g (23%), colorless
viscous oil. A mixture of Z,Zꢀ and Z,Eꢀisomers in a ratio of
79 : 21. Found (%): C, 56.15; H, 4.79. C16H16Cl2O4. Calculatꢀ
ed (%): C, 55.99; H, 4.70.
Z,ZꢀIsomer. 1H NMR (CDCl3), : 1.35 (t, 6 H, CH3,
J = 7.1 Hz); 4.31 (q, 4 H, CH2, J = 7.1 Hz); 7.43 (t, 1 H, Ar,
J = 7.9 Hz); 7.80 (dd, 2 H, Ar, J = 7.9 Hz, J = 1.4 Hz); 7.86 (s, 2 H,
=CH—); 8.25 (s, 1 H, Ar). 13C NMR (CDCl3), : 14.0 (CH3),
62.5 (CH2), 123.0 (C=C—Cl), 128.6, 131.7, 132.1, 133.1, 135.8
(C=C—Cl), 162.8 (CO2Et).
E,ZꢀIsomer. 1H NMR (CDCl3), : 1.12 (t, 3 H, CH3,
J = 7.1 Hz); 4.16 (q, 2 H, CH2, J = 7.1 Hz); 7.17 (s, 1 H, =CH—);
7.28 (d, 1 H, Ar, J = 7.6 Hz); 7.35 (t, 1 H, Ar, J = 7.6 Hz); 7.72
(d, 1 H, Ar, J = 7.6 Hz); 7.73 (s, 1 H, =CH—). 13C NMR
(CDCl3), : 13.5 (CH3), 62.1 (CH2), 123.0 (C=C—Cl), 124.0
(C=C—Cl), 128.3, 129.8, 130.1, 130.7, 132.8, 134.1, 136.0
(C=C—Cl), 162.9 (CO2Et).
Z,ZꢀIsomer. 1H NMR (CDCl3), : 7.54 (d, 1 H, Ar, J = 7.9 Hz);
7.65 (s, 2 H, C=CH); 7.75 (dd, 2 H, Ar, J = 7.9 Hz, J = 1.5 Hz);
8.13 (s, 1 H, Ar). 13C NMR (CDCl3), : 111.0 (q, C=C—CF3,
J = 37.2 Hz); 120.8 (q, CF3, J = 271.6 Hz); 128.6, 130.0; 131.0;
132.9; 133.6 (q, C=C—CF3, J = 4.8 Hz).
E,ZꢀIsomer. 1H NMR (CDCl3), : 7.34 (d, 1 H, Ar, J = 7.4 Hz);
7.43—7.51 (m, 1 H, Ar); 7.70 (t, 1 H, Ar, J = 7.4 Hz); 7.91
(s, 1 H, Ar). 13C NMR (CDCl3), : 110.9 (q, C=C—CF3,
J = 37.2 Hz); 120.4 (q, CF3, J = 274.2 Hz), 128.6; 129.0; 129.6;
130.4; 131.3; 133.1; 140.4 (q, J = 2.2 Hz).
1,3ꢀBis(2ꢀchloroꢀ3,3,3ꢀtrifluoropropꢀ1ꢀenyl)benzene (4g) was
synthesized by a reaction of dihydrazone 2 with CF3CCl3 using
ethylenediamine as a base. Yield 0.832 g (50%), colorless oil.
A mixture of Z,Zꢀ and Z,Eꢀisomers in a ratio of 65 : 35.
Found (%): C, 43.12; H, 1.86. C12H6Cl2F6. Calculated (%):
C, 43.01; H, 1.80.
1
Z,ZꢀIsomer. H NMR (CDCl3), : 7.34 (s, 2 H, C=CH);
7.53 (t, 1 H, Ar, J = 7.8 Hz); 7.75 (dd, 2 H, Ar, J = 7.8 Hz,
J = 1.2 Hz); 8.13 (s, 1 H, Ar). 13C NMR (CDCl3), : 120.7
(q, CF3, J = 272.0 Hz); 120.8 (q, C=C—CF3, J = 36.9 Hz);
128.7; 129.0; 129.6; 129.8 (q, J = 4.4 Hz); 130.4; 130.9; 131.3;
131.8; 132.1; 133.1; 136.0 (q, C=C—CF3, J = 1.9 Hz).
E,ZꢀIsomer. 1H NMR (CDCl3), : 7.26—7.30 (m, 1 H, Ar);
7.30 (s, 1 H, C=CH); 7.47 (t, 1 H, Ar, J = 7.8 Hz); 7.67 (s, 1 H,
Ar); 7.70 (t, 1 H, Ar, J = 7.8 Hz).
1,3ꢀBis(2ꢀchloroꢀ2ꢀcyanovinyl)benzene (4d) was synthesized
by a reaction of dihydrazone 2 with CCl3CN using triethylamine
as a base. Yield 0.479 g (39%), colorless solid, m.p. 71—73 C.
A mixture of E,Eꢀ and Z,Eꢀisomers in a ratio of 73 : 27. IR,
/cm–1: 1698 (C=C), 2220 (CN). Found (%): C, 57.94; H, 2.49.
C12H6Cl2N2. Calculated (%): C, 57.86; H, 2.43.
1
E,EꢀIsomer. H NMR (CDCl3), : 7.39 (s, 2 H, C=CH);
1,3ꢀBis(2,3,3,3ꢀtetrafluoropropꢀ1ꢀenyl)benzene (4h) was synꢀ
thesized by a reaction of dihydrazone 2 with CF3CFBr2 using
ethylenediamine as a base. Yield 0.491 g (33%), colorless oil. IR,
/cm–1: 1702 (C=C).
7.54—7.58 (m, 1 H, Ar); 7.77 (t, 2 H, Ar, J = 7.7 Hz); 7.80—7.85
(m, 1 H, Ar); 8.07 (s, 1 H, Ar). 13C NMR spectrum of the
isomeric mixture (CDCl3), : 101.7 (C=C—Cl); 101.8 (C=C—Cl);
114.2 (CN); 115.5 (CN); 128.6, 129.3, 129.4, 129.7, 129.8, 130.1,
130.5, 131.7, 131.9, 132.0, 132.2, 132.3, 140.5, 140.6, 143.5
(CH=C); 143.6 (CH=C).
1
Z,ZꢀIsomer. H NMR (CDCl3), : 6.44 (d, 2 H, C=CH,
J = 35.2 Hz). 19F NMR (CDCl3), : –73.0 (d, J = 10.6 Hz);
–131.4 (dq, J = 35.2 Hz, J = 10.6 Hz).
1
1
E,ZꢀIsomer. H NMR (CDCl3), : 7.37 (s, 1 H, =CH—);
E,ZꢀIsomer. H NMR (CDCl3), : 6.89 (d, 1 H, C=CH,
7.65—7.69 (m, 1 H, Ar).
J = 20.3 Hz).
1,3ꢀBis(2ꢀbromoꢀ2ꢀfluorovinyl)benzene (4e) was synthesized
by a reaction of dihydrazone 2 with CFBr3 using aqueous ammoꢀ
nia as a base. Yield 0.542 g (34%), colorless oil. A mixture of
E,Eꢀ, Z,Eꢀ, and Z,Zꢀisomers in a ratio of 58 : 37 : 5. Found (%):
C, 37.21; H, 1.91. C10H6Br2F2. Calculated (%): C, 37.07;
H, 1.87. IR, /cm–1: 1652 (C=C).
This work was financially supported by the Council on
Grants of the President of the Russian Federation (Proꢀ
gram for State Support of Young PhDꢀScientists, Grant
MKꢀ7121.2012.3) and the Russian Foundation for Basic
Research (Project No. 13ꢀ03ꢀ01129ꢀa).
1
E,EꢀIsomer. H NMR (CDCl3), : 5.97 (d, 2 H, C=CH,
J = 32.5 Hz); 7.31—7.43 (m, 4 H, Ar). 19F NMR spectrum of the
isomeric mixture (CDCl3), : –68.1 (d, J = 32.5 Hz). 13C NMR
(CDCl3), : 111.2 (d, C=C—F, J = 24.3 Hz); 112.6 (d, C=C—F,
J = 6.3 Hz); 127.3 (d, J = 2.0 Hz); 127.4 (d, J = 2.0 Hz); 127.5
(d, J = 1.5 Hz); 127.5; 127.6; 127.8 (d, J = 3.0 Hz); 127.8; 127.9
(d, J = 3.0 Hz); 128.0 (d, J = 2.6 Hz); 128.5; 128.7; 129.0; 130.3
(d, C=C—F, J = 339.1 Hz); 132.0; 132.7; 132.9 (d, J = 4.8 Hz);
135.3 (d, C=C—F, J = 316.2 Hz); 136.0.
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Received January 15, 2013