Full text of DOI:10.1134/S1070363218050079

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 5, pp. 883–891. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © N.A. Anisimova, E.K. Slobodchikova, V.M. Berestovitskaya, M.E. Ivanova, A.A. Kuzhaeva, T.V. Rybalova, 2018, published in
Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 5, pp. 738–746.
Synthesis and Structure of Cyclohexenes Functionalized
by Nitro and Trifluoro(chloro)methyl Groups
a,b
a
a†
N. A. Anisimova *, E. K. Slobodchikova , V. M. Berestovitskaya ,
c
a
d,e
M. E. Ivanova , A. A. Kuzhaeva , and T. V. Rybalova
a
Herzen State Pedagogical University of Russia, nab. reki Moiki 48, St. Petersburg, 191186 Russia
e-mail: kohrgpu@yandex.ru
*
b
St. Petersburg State University of Industrial Technologies and Design, St. Petersburg, Russia
c
Altai State Agricultural University, Barnaul, Russia
d
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, Russia
e
Novosibirsk State University, Novosibirsk, Russia
Received November 16, 2017
Abstract––Cyclohexenes functionalized by nitro and trihalomethyl groups were produced by condensation of
-nitro- and 1-bromo-1-nitro-3,3,3-trifluoro(chloro)propenes with 2-methyl- and 2,3-dimethyl-1,3-butadienes;
1
1
13
19
their structure was characterized by IR, H, C, F NMR spectroscopy, and X-ray diffraction method.
Keywords: 1-nitro-3,3,3-trifluoro(chloro)propenes, cyclohexenes, Diels–Alder reaction, acyclic dienes, trihalo-
methyl group
DOI: 10.1134/S1070363218050079
The cyclohexane ring is widespread in nature; it is a
structural fragment of vitamins, terpenes, hormones,
alkaloids, shikimic acid, and other practically signi-
ficant substances [1, 2]. The growing interest in natural
compounds containing a cyclohexene or cyclohexa-
diene ring is driven by the importance of the functions
they perform (inhibitors of enzymes [3, 4]) and their
usability as key compounds for the production of
anticancer [5], narcotic [6, 7], and antiviral [8, 9]
drugs, as well as promising anti-AIDS drugs [10].
further modification of the cyclic structure and to
enhance the pharmacological activity [14].
According to available public references, 1-nitro-
3
,3,3-trichloropropene enters into diene condensation
with alkadienes like 1,3-butadiene, 2,3-dimethyl-1,3-
butadiene, isoprene, or piperylene), usually under
severe conditions (multi-hour heating in an ampule in
the medium of a high-boiling solvent) [16–18].
To obtain cyclohexenes containing CCl or CF
3
3
One convenient and affordable method for the
synthesis of functionalized cyclohexenes is the Diels–
Alder reaction involving as a dienophile the vicinal-
substituted nitroalkenes containing the second easily
modifiable group (CO R, SO Ph, CHlg ) [11, 12].
groups, we studied the diene condensation of 1-nitro-
3
1
,3,3-trifluoro(chloro)propenes 1 and 2 and 1-bromo-
-nitro-3,3,3-trifluoro(chloro)propenes 3 and 4 with
aliphatic dienes.
2
2
3
Exactly these dienophiles are used for the synthesis of
natural biologically active compounds, including the
preparation of natural analgesic epibatidine [13, 14],
morphine derivatives [15], and conduritols [10].
The reactions of nitroalkenes (1 and 2) and bromo-
nitroalkenes (3 and 4) with 2,3-dimethyl-1,3-butadiene
and isoprene have showed that these dienophiles are
reactive with acyclic dienes even without heating (at
4
–20°C, in the absence of a solvent, within 1–7 days).
Of particular interest are nitrocyclohexenes contain-
ing a trihalomethyl group, which is known to allow
Nitroalkenes 1–4, when reacted with 2,3-dimethyl-1,3-
butadiene, produced the corresponding cyclohexenes
5–8 in good yields (92–98%).
†
Deceased.
8
83

8
84
ANISIMOVA et al.
Scheme 1.
NO2
NO2
H C
H C
3
3
6
3
3
6
2
1
4
5
2
1
4
5
Br
H
CHlg3
H
H C
3
CHlg3
H C
3
5
, 6
7, 8
1_
5 days, 4 5°С
_
X = H
X = Br
H C
CH3
3
H
NO2
C C
Hlg C
X
3
1_
4
H
CH3
4_
7 days, 4 20°С
_
X = H
X = Br
NO2
NO2
H
NO2
Br
NO2
Br
H C
3
3
6
6
5
3
6
H C
3
6
2
1
4
5
1
2
2
1
4
5
1
2
5
4
+
+
H
4
3
3
H C
H C
3
3
CHlg3
CHlg3
CHlg3
CHlg3
9
a, 10a
9b, 10b
11a, 12a
11b, 12b
Hlg = F: X = H (1, 5, 9a, 9b), Br (3, 7, 11a, 11b); Hlg = Cl: X = H (2, 6, 10a, 10b), Br (4, 8, 12a, 10b).
The interaction of nitro- and gem-bromonitro-
5–12 contain the absorption bands of the non-
alkenes 1–4 with an asymmetric diene like isoprene
predictably resulted in the formation of a mixture of
regioisomeric cyclohexenes 9a–12a and 9b–12b,
which differ from one another by the mutual
arrangement (1,5- vs. 1,4-) of methyl and trihalomethyl
groups. In all cases, regioisomer b with a remote
location of the CH and CHlg groups was dominant.
conjugated NO group, which appear in the regions of
2
–
1
1
13
1322–1373 and 1558–1570 cm . In the H, C, and
1
9
F NMR spectra of nitrocyclohexenes 5–8, the stereo-
homogeneity of these compounds is observed (Table 1).
The formation of cyclohexenes 9–12 as regioisomers is
evidenced by doubling the signals of the methyl
4
5
substituent and the H and H cycle protons, as well as
3
3
the signals of carbon nuclei of compounds 9a–12a and
Judging from the experimental data, nitroalkenes 1
9
b–12b and fluorine nuclei of 9a, 9b, 11a, and 11b
and 3 with a CF group exhibited a greater activity
3
1
13
19
(
Tables 2–4) in the H, C, and F NMR spectra.
than their structural analogs 2 and 4 containing a CCl3
group. As such, gem-bromonitroalkene 3 reacted faster
4°C, 10 h) than its structural analog, nitroalkene 1
20°C, 24 h), whereas in a pair of similar compounds 2
6
'
6"
The signals of methylene protons H and H in the
3
'
3"
(
(
spectra of compounds 5–8 and 9a–12a and H and H
of 9b–12b appear as multiplets in the range of 2.22 to
and 4 containing a more bulky CCl group, on the
2.92 ppm with geminal constants of 16.6 to 18.3 Hz.
3
contrary, nitroalkene 2 showed a greater activity (20°
C, 3 days) compared to gem-bromonitroalkene 4 (20°
C, 6 days).
Under the influence of the NO group the signals of
2
3
'
3"
6'
methylene protons H , H (5–8, 9a–12a) and H ,
6
"
H
(9b–12b) are naturally located downfield (2.40–
3
.57 ppm, JH'H' 16.5–18.6 Hz).
The structure of the obtained nitrocyclohexenes 5–
2 was determined by the IR and H NMR spectro-
1
4
1
The nitromethine protons H (5, 6, 9a, and 10a) and
5
scopy methods (Tables 1–3), as well as by comparing
their spectral characteristics with those of structurally
similar compounds containing CO R and P(O)(OR)
H (9b and 10b) also have a downfield position (4.74–
5.10 ppm) as compared to the methine protons H (5,
6, 9a, and 10a) and H (9b and 10b) adjacent to the
5
4
2
2
groups [19, 20]. The IR spectra of nitrocyclohexenes
CHlg group (3.10–3.74 ppm).
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

SYNTHESIS AND STRUCTURE OF CYCLOHEXENES FUNCTIONALIZED
Table 1. H NMR spectra of nitrocyclohexenes 5–8
885
1
H'
H''
NO2
H C
3
3
6
2
1
4
5
X
H
H C
3
CHlg3
H'
H''
δ, ppm (J, Hz)
Comp.
no.
3
6
Hlg
F
Х
С Н
С Н
4
5
CH
3
CH
3
Н
Н
3
'
3''
6'
6''
Н
H
H
H
5
6
7
8
H
1.66 s 1.65 s
2.73 d.d
2.58 d.d
2.35 d.d
2.24 d.d
4.78 d.d.d
3
3.17 m
3
3
3
3
(
J
H3'H4 = 9.7, ( JH3''H4 = 5.6, ( JH6'H5 = 6.9, ( JH6''H5 = 10.1, ( JH3'H4 = 9.7,
H3'H3'' = 16.8)
2
2
2
2
3
J
J
H3'H3''
=
J
H6'H6''
=
JH6'H6'' = 18.0) 3JH4H3'' = 16.8,
1
6.8)
18.0)
J
H4H5 = 14.0)
Cl
F
H
1.71 s 1.68 s
2.78 d.d
2.64 d.d
2.66 d.d
2.38 d.d
5.00 d.t
3.70 d.t
3
3
3
3
3
3
(
J
H3'H4 = 6.8, ( JH3''H4 = 6.8, ( JH6'H5 = 7.2, ( JH6''H5 = 7.2, ( JH3'H4 = 6.8, ( JH6'H5 = 7.2,
H3'H3'' = 16.5)
2
2
2
2
3
3
J
J
H3'H3''
=
J
H6'H6''
=
JH6'H6'' = 16.8) 3JH4H3'' = 6.8,
J
H5H6'' = 10.1,
H4H5 = 5.6)
3
1
6.5)
16.8)
J
H4H5 = 5.6)
J
Br 1.69 s 1.65 s
Br 1.73 s 1.66 s
3.46 d
2.88 d
2.46 d.d
2.50 d.d
–
3.60 d.t
( JH6'H5 = 7.3,
J 5 6'' = 7.3,
H H
2
2
3
3
3
(
JH3'H3'' = 17.5) ( JH3'H3''
=
=
( JH6'H5 = 7.3, ( JH6''H5 = 7.3,
2
2
3
1
7.5)
JH6' 6''
=
JH6' 6'' = 18.3)
H
H
3
1
8.3)
J
5
= 8.5)
H F
Cl
3.53 d
H3'H3''
2.80 d
( JH3'H3''
17.4)
2.84 d.d
2.77 d.d
–
3.91 d.d
3
2
2
3
3
(
J
=
( JH6'H5 = 6.0, ( JH6''H5 = 10.3,
( JH6'H5 = 6.0,
3
2
2
1
7.4)
J
H6'H6''
=
JH6'H6'' = 16.6)
JH5H6'' = 10.3)
1
6.6)
NO2
equatorial orientation of the same groups. This fact is
H5
3
(
2)
confirmed by the coupling constants of methine
4
CH3
CH
3
(
5)
1
3
H4
6
protons J 4 5 which range between 5.6–7.7 Hz for 5,
H H ,
9
a, and 9b and 13.2–14.0 Hz for 6, 10a, and 10b [21].
CCl3
CCl
1
In the H NMR spectra of all cyclohexenes
3
5
obtained, the olefin protons appear in the range of 5.38
to 5.58 ppm. Regioisomers a and b of cyclohexenes 9–
12 were identified from the position of the methyl
H
H
H
2
6
3
1
H
4
H
H
group signal (Fig. 1). The CH group signal in isomer
3
NO2
b predictably appears downfield (1.80–1.86 ppm) as
compared to isomer a (1.72–1.75 ppm). Such assign-
To ascertain the mutual disposition of the CHlg3
and NO groups in the molecules of cyclohexenes
ment of CH group signals is additionally confirmed
3
2
obtained, the spin-spin coupling constants characte-
by the data of heteronuclear experiments, specifically
4
5
1
13
rizing the interaction of vicinal protons H and H with
one another and with the protons of adjacent
H– C HMBC (correlation of signals of CH
protons with those of the carbon atoms C of multiple
3
group
3
3
'
3"
6'
6"
1
methylene groups (H , H and H , H ) were used as
an analytical criterion. The analysis of the coupling
constants (Tables 1 and 2) of these protons discovered
that cyclohexenes 6, 9a, and 9b with equal constants of
bond and methylene groups). For example, in the H–
1
3
C HMBC spectrum of a 12a/12b mixture (12a : 12b =
1.0 : 4.0) a clear correlation between proton signals
and the corresponding signals of carbon atoms is ob-
3
3
1
methine ( J 4 5) and methylene protons ( J 5 6' =
H H
served: for isomer a, CH
3
(1.74 ppm)/C (128.83 ppm),
H H
H H
3
3
3
2
3
J 5 6'', J 4 3' = J H4H3'') have an axial orientation of
C (118.42 ppm), C (51.03 ppm); for isomer b, CH
(1.80 ppm)/C (132.34 ppm), C (115.37 ppm), C
(34.34 ppm), C (59.31 ppm); H (2.77 and 2.84 ppm)/
3
3
H H
1
2
CHlg and NO groups, while compounds 5, 10a, and
3
2
4
3',3"
1
06 with different values of these constants have an
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

8
86
ANISIMOVA et al.
1
Table 2. H NMR spectra of nitrocyclohexenes 9a, 9b, 10a, and 10b
H'
H'
H''
H'
H''
NO2
NO2
H C
3
3
6
6
3
2
1
4
5
1
2
5
4
H
H
H
H
H C
3
CHlg3
CHlg3
H''
H'
H''
a
b
δ, ppm (J, Hz)
Comp.
no.
3
6
Hlg
F
C H
C H
2
4
5
CH
3
C H
H
H
3
'
3''
6'
6''
H
H
H
H
9
9
1
1
a
1.72 s 5.38
br.s
2.80 d.d
2.70 d.d
2.60 d.d
2.45 d.d
4.75 d.t
3.10 m
3
3
3
3
3
( JH3'H4 = 3.2, ( JH3''H4 = 3.2, ( JH6'H5 = 8.1, ( JH6''H5 = 8.1, ( JH3'H4 = 3.2,
2
2
2
2
3
J
H3'H3'' =
8.6)
J
H3'H3'' = 18.6) JH6'H6'' = 17.2) JH6'H6'' = 17.2)
JH4H3'' = 3.2,
H4H5 = 7.7)
3
1
J
b
F
1.82 s 5.38
br.s
2.70 d.d
2.22 d.d
2.65 d.d
2.40 d.d
3.23 m
4.74 d.t
( JH6'H5 = 2.3,
JH5H6'' = 2.3,
H4H5 = 7.3)
3
3
3
3
3
( JH3'H4 = 9.3, ( JH3''H4 = 9.3, ( JH6'H5 = 2.8, ( JH6''H5 = 2.3,
2
2
2
2
3
J
H3'H3'' =
7.9)
JH3'H3'' = 17.9) JH6'H6'' = 18.0)
J
H6'H6'' = 18.0)
3
1
J
0a Cl 1.75 s 5.58 m
0b Cl 1.86 s 5.43 m
2.83 d.d
2.42 d.d
2.68 d.d
2.60 d.d
5.10 d.t
3.67 d.t
3
3
3
3
3
3
(
(
J
H3'H4 = 6.2, ( JH3''H4 = 6.2, ( JH6'H5 = 7.1, ( JH6''H5 = 7.1, ( JH3'H4 = 6.2, ( JH6'H5 = 7.1,
2
2
2
2
3
3
J
H3'H3'' =
8.0)
JH3'H3'' = 18.0) JH6'H6'' = 17.6)
J
H6'H6'' = 17.6)
J
H4H3'' = 6.2,
H4H5 = 13.2)
JH5H6'' = 7.1,
H4H5 = 13.2)
3
3
1
J
J
2.70 d.d
2.66 d.d
2.80 d.d
2.40 d.d
3.74 d.t
4.99 d.t
3
3
3
3
3
3
J
J
H3'H4 = 6.9, ( JH3''H4 = 6.9, ( JH6'H5 = 6.3, ( JH6''H5 = 6.3, ( JH3'H4 = 6.9, ( JH6'H5 = 6.3,
2
2
2
2
3
3
H3'H3'' = =
6.9)
JH3'H3'' = 16.9) JH6'H6'' = 18.3)
J
H6'H6'' = 18.3)
J
H4H3'' = 6.9,
H4H5 = 13.2)
JH5H6'' = 6.3,
JH4H5 = 13.2)
3
3
1
J
1
2
1
CH (22.56 ppm), C (132.34 ppm), C (115.37 ppm),
Fig. 2a . The geometries of the two independent
molecules of compound 8 are substantially the same,
the maximum difference in the length being observed
3
4
5
C (59.31 ppm), C (96.24 ppm).
1
3
In the C NMR spectra (Table 4) of cyclohexenes
–8, 9a–11a, and 9b–11b, there are signals of all
carbon atoms of the C –C cycle and CHlg groups.
The most upfield signals are from carbon atoms of
methyl groups (18.16–22.88 ppm) and methylene
groups C H and C H (25.29–52.18 ppm). The signals
of carbon atoms of methine groups C H and C H
influenced by NO and CHlg groups appear more
1
1
for the N –O bond: 1.236(3) and 1.219(3) Å. The
unsaturated six-membered cycle has typical distorted
semi-chair geometry. The almost flat (within ±0.01 Å
accuracy) fixed part of the cycle consists of carbon
5
1
6
3
2
3
4
5
2
3
4
5
3
6
atoms C , C , C , and C [the torsion angle C C C C
is 2.3(4)° and –2.0(4)° for the two independent
2
2
4
5
3
4
molecules], which implies that the C =C double bond
is not twisted, its length is 1.322(4) and is the same for
both independent molecules. The carbon atoms C and
C deviate from the coplanar part of the cycle by 0.326(3)
and 0.377(3) Å in the first independent molecule and
by 0.370(3) and 0.346(3) Å in the second.
2
3
downfield, in the ranges of 41.90–59.44 ppm
1
5
(4)
4(5)
[C
HCHlg ] and 81.08–99.17 ppm [C HNO ]. The
3
2
6
1
2
signals of carbon atoms in the C =C bond of the ring
appear in the region of 115.91–133.85 ppm. The
carbon atoms of CF and CCl groups have signals in
3
3
the regions of 123.25–126.05 and 77.12–101.47 ppm,
respectively [21].
The Br atom is in the axial position, one oxygen
atom of the nitro group is almost eclipsed by the Br
atom, the torsion angle Br C N O is 11.3° and the
1
1
1
2
The molecular structure of compound 8 was studied
by X-ray diffraction. The spatial structure of one of the
two independent molecules of compound 8 is shown in
1
The atom numbering in Fig. 2 is different from the indexes
provided above, which correspond to the nomenclature.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

SYNTHESIS AND STRUCTURE OF CYCLOHEXENES FUNCTIONALIZED
Table 3. H NMR spectra of cyclohexenes 11а, 11b, 12а, and 12b
887
1
H'
H''
H'
H''
NO2
NO2
H C
3
3
6
6
2
1
4
5
1
2
5
4
Br
H
Br
H
3
H C
3
CHlg3
CHlg3
H'
H''
H'
H''
a
b
δ, ppm (J, Hz)
Comp.
no.
3
6
Hlg
F
С Н
С Н
2
4
5
CH
3
СН
Н
Н
3
'
3''
6'
6''
Н
H
H
H
1
1а
1.75 s
1.78 s
5.46 s
5.34 d
3.43 d
H3'H3''
2.86 d.d
2.40 d.d
2.52 d.d
–
3.55 m
–
2
3
3
3
(
J
=
( JH3''H5 = 2.1, ( JH6'H5 = 7.3, ( JH6''H5 = 7.3,
H3'H3'' = 17.7) JH6'H6'' = 16.6) JH6'H6'' = 16.6)
2
2
2
1
7.7)
J
1
1b
F
2.50 d.d
2.45 d.d
3.00 d.d
3.43 d.d
3.65 m
–
4
3
3
3
5
5
(
(
J
H2H4 = 2.1) ( JH3'H4 = 5.3, ( JH3''H5 = 5.3, ( JH6F = 4.6, ( JH6''F = 4.6,
2
2
2
2
J
H3'H3'' = 17.2) JH3'H3'' = 17.2) JH6'H6'' = 17.9) JH6'H6'' = 17.9)
1
2а
Cl 1.74 s
Cl 1.80 s
5.50 d
2.88 d.d
3.57 d
2.73 d.d
2.92 d.d
3.82 d.d
( JH5H6' = 6.3,
H5Н6'' = 6.3)
3
2
3
3
3
J
H2H3 = 6.4) ( JH3'H2 = 6.4, ( JH3'H3'' = 17.9) ( JH6'H5 = 6.3, ( JH6''H5 = 6.3,
2
2
2
3
J
H3'H3'' = 17.9)
J
H6'H6'' = 17.6) JH6'H6'' = 17.6)
J
1
2b
5.33 d
2.77 d.d
2.84 d.d. d
2.98 d
3.52 d
3.92 d.d
–
3
3
3
2
2
3
( JH2H3'' = 6.1) ( JH3'H2 = 5.2, ( JH3''H2 = 6.1, ( JH6'H6'' = 17.6) ( JH6'H6'' = 17.6) ( JH4H3' = 5.2,
2
2
3
J
H3'H3'' = 17.6) 2
J
H4H3'' = 5.2,
H3'H3'' = 17.6)
JH4Н3'' = 5.2)
J
corresponding angle in the second molecule is 7.5°.
The trichloromethyl group is in the equatorial position
–76.7°. This group is in the gauche(+) position with
respect to the Br atom and in the gauche(–) position
with respect to the nitro group. The torsion angles
6
1
and its rotation is retarded with respect to the C –C
1
6
7
3
7
6
1
1
7
6
1
1
bond, the torsion angle C C C Cl is –82.3° and
C C C Br are 60.5(2)° and 62.9(2)° and C C C N are
1
0a
10b
1
0a : 10b = 1.0 : 1.5
δ, ppm
1
Fig. 1. H NMR spectrum of mixture of regioisomeric cyclohexenes 10а, 10b.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

8
88
ANISIMOVA et al.
13
1
Table 4. С{ Н} NMR spectra of cyclohexenes 5–8, 9а, 9b, 11а, 11b (δ
C
, ppm)
R2
R1
NO2
NO2
R2
NO2
3
6
3
6
6
3
2
1
4
5
2
1
4
5
1
2
5
4
X
X
Br
R1
CHlg3
CHlg3
CHlg3
5_
8
9a, 11a
9b, 11b
1
2
Comp.
no.
R , R
(СН
1
2
3
4
5
6
Hlg
Х
С
С
С
С
С
С
СHlg
3
3
)
5
6
7
F
H
18.40, 122.03
8.54
122.97
125.36
122.8
35.74
36.23
48.46
81.08 d
41.90 d
29.18 d
125.96 d
3
2
3
1
1
( JС4F = 1.1) ( JС5F = 27.5) ( JС6F = 2.5) ( JСF = 280.0)
Cl
F
Н
18.57, 122.89
8.69
84.23
56.29
33.49
31.00
77.12
1
Br
18.27, 121.57
8.48
94.66
47.81
( JС5F = 26.8)
124.80
2
1
8
Cl
Br
18.16, 120.91
8.29
123.88
52.18
99.17
59.44
35.46
98.95
1
9
9
1
1
а
Cl
Cl
F
Н
22.63
22.88
22.50
22.52
130.89
133.85
129.66
131.34
119.12
116.58
117.25
115.91
34.20
30.01
46.94
29.88
83.98
55.67
94.33
47.53
55.19
83.55
46.67
94.45
26.90
31.45
25.29
43.44
95.50
101.47
123.25
126.05
b
1а
1b
Br
F
–
61.8(2)° and –60.3(2)°. A shortened intramolecular
competes with the NO group for the regio- and
stereodirectivity of diene condensation.
2
1
2
contact O ···Cl of 3.09 and 3.06 Å (the sum of the
van der Waals radii equal to 3.34 Å [22]) leads to
deviations in the bond angles in the O N C C C Cl
chain from the ideal values. The O N C angle is 113.2(2)°
and 114.7(2)°, and C C C is 119.7(2) Å in both
1
1
1
6
7
2
EXPERIMENTAL
1
1 1
1
6
7
1
13
1
1
13
1
13
H, C{ H}, H– C HMQC, and H– C HMBC
6
7
2
molecules, while the C C Cl angle is 114.3(2)° and
13.7(2)°. The weak intramolecular hydrogen bonds
NMR spectra were recorded on a Jeol ECX400A
spectrometer at operating frequencies of 100.52 MHz
1
1
3
1
are compiled in Table 5.
( C) and 399.78 MHz ( H) in deuterochloroform-d
using the residual signal of an undeuterated solvent as
an internal reference. IR spectra were obtained on a
Shimadzu IR Prestige-21 Fourier spectrometer in
chloroform. Spectral studies were performed at the
Center for Joint Use of the Faculty of Chemistry of the
Herzen State Pedagogical University of Russia, St.
Petersburg.
In the crystalline structure molecular layers are
distinguished in the (a + c, b + c) plane (Fig. 2b). The
symmetrically independent molecules of cyclohexene
8
form pairs of associates due to intermolecular
hydrogen bonds of the C–H···O type with H···O
distances of 2.609 Å (C –H···O –N ) and 2.715 Å
6
2
1
6
A
2A
1A
(
8
C H···O –N ). The paired associates of molecules
are interconnected into layers in one direction by
Separation of the individual compounds was carried
out by column chromatography on Chemapol 100/200
silica gel using solvents according to the procedure
described in [23]. The TLC test was performed on
Silufol 254 plates, eluent a 3 : 2 hexane–acetone
mixture, developmentunder UV light. The ratios of
3
1A
shortened contacts Cl ···Br 3.407(2) Å and in the
other by Cl ···O 3.232(3) Å (the sums of the Van der
Waals radii, Cl···Br and Cl···O, amount to 3.63 Å [22]).
1
A
1
Thus, the study has demonstrated that 1-nitro- and
1
-bromo-1-nitro-3,3,3-trifluoro(chloro)propenes
are
1
active dienophiles. They successfully react with
acyclic dienes to form the corresponding cyclohexenes
with good yields. As such, the CHlg group effectively
isomers 9a–12a and 9b–12b were determined by H
NMR spectroscopy prior to chromatography of the
reaction mixture.
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

SYNTHESIS AND STRUCTURE OF CYCLOHEXENES FUNCTIONALIZED
a) (b)
889
(
Fig. 2. General view of one of the two independent molecules (a) in the crystal and (b) the molecular layer parallel to (a + c, b + c)
plane in the crystals of compound 8. (Dashed line) intermolecular hydrogen bonds and shortened contacts.
X-ray diffraction analysis of a single crystal of
compound 8 was carried out by an X-ray diffraction
analysis team of the Center for Spectral Information at
the Vorozhtsov Novosibirsk Institute of Organic
Chemistry (Siberian Branch, Russian Academy of
Sciences). An X-ray diffraction experiment on crystals
elimination of H O, AcOH) [28, 29]. gem-Bromonitro-
alkenes 3 and 4 were prepared according to the
procedures described in [30–32].
2
1
,2-Dimethyl-4-nitro-5-trifluoromethyl-1-cyclo-
hexene (5). 2.05 g (0.025 mol) of 2,3-dimethyl-1,3-
butadiene was added to 3.50 g (0.025 mol) of 1-nitro-
8
grown from hexane was performed at 296(2) K on a
3
,3,3-trifluoropropene 1. The reaction mixture was
Bruker Kappa APEX II diffractometer (MoK radiation,
a
held at 20°C for 24 h. The reaction mixture was chro-
matographed (eluent: hexane). Yield 5.43 g (98%), mp
graphite monochromator, CCD detector, 2θ 55.2°).
Single crystals 8 are triclinic, unit cell parameters are
3
5
8–40°C (hexane). Found, %: C, 47.80, 47.60; H 5.19,
.23; N 6.25, 6.14; F 25.98, 25.83. C H F NO .
as follows: a 8.720(5), b 10.832(6), c 14.546(8) Å, α
3
9
12
3
2
1
03.27(2)°, β 92.11(1)°, γ 99.18(1)°, V 1316.2(12) Å ,
Calculated: C 48.43; H 5.38; N 6.28; F 25.56.
3
space group P-1, Z 4, C H BrCl NO , d 1.774 g/cm ,
9
11
3
2
calc
–
1
μ 3.72 mm , sample size 0.48×0.26×0.09 mm. The
intensities of 7539 independent reflections were
measured. A correction for extinction was introduced
using the SADABS program (transmission 0.2685–
1,2-Dimethyl-4-nitro-5-trichloromethyl-1-cyclo-
hexene (6). 1.48 g (0.018 mol) of 2,3-dimethyl-1,3-
butadiene was added to 3.50 g (0.018 mol) of 1-nitro-
3,3,3-trichloropropene 2. The reaction mixture was
held at 20°C for 3 days. The reaction mixture was
0
.7309). The structure was solved by the direct method
by means of the SHELXS-97 program and refined in
the anisotropic-isotropic (for H) approximation using
the SHELXL-97 program. The hydrogen positions
were calculated geometrically and the parameters of
the H atoms were refined in the isotropic approxima-
tion using the rider model. The final refinement
Table 5. Weak intramolecular hydrogen bonds in the molecule
of compound 8
Hydrogen bond
H···A
2.43
2.45
2.64
2.72
2.59
2.80
2.48
2.54
D···A
D–H···A
106
2
A
1A
C –H···O
2.843(3)
2.869(4)
3.125(3)
3.154(3)
3.068(3)
3.217
parameters are as follows: wR 0.0946, S 1.034, 293
2
2
1
parameters were refined (R 0.0349 for 5633 F > 4σ).
The independent part of unit cell 8 contains two
molecules. The atomic coordinates, bond lengths, and
angles are deposited with the Cambridge Crystallo-
graphic Data Centre [24, 25] (CCDC 874993).
C –H···O
106
5A
A
2A
C –H ···Cl
111
5A
B
1A
C –H ···Cl
107
5
A
2
C –H ···Cl
110
5
B
1
Nitroalkenes 1 and 2 were synthesized according to
known literature methods through preliminary prepara-
tion of the corresponding nitro alcohols [26, 27]
followed by further transformation (acylation and
C –H ···Cl
107
6
1
C –H···O
2.848(3)
2.862
100
6A
1A
C –H···O
99
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

8
90
ANISIMOVA et al.
chromatographed (eluent: hexane). Yield 4.61 g (92%),
4(5)-Bromo-1-methyl-4(5)-nitro-5(4)-trichloro-
methyl-1-cyclohexene (12a, 12b). A mixture of 3.20 g
(0.012 mol) of 1-bromo-1-nitro-3,3,3-trichloropropene
5 and 0.81 g (0.012 mole) of 2-methyl-1,3-butadiene
was held at 20°C for 6 days and then chromatographed
on silica gel (eluent: hexane). Yield 2.27 g (56%),
colorless oil, R 0.69. Found, %: C 39.65, 39.70; H 4.35,
f
4
3
.38; N 5.16, 5.20. C H Cl NO . Calculated, %: C
9 12 3 2
9.63; H 4.41; N 5.14.
-Bromo-1,2-dimethyl-4-nitro-5-trifluoromethyl-
4
1
-cyclohexene (7). 0.90 g (0.011 mol) of 2,3-dimethyl-
isomer ratio 12a : 12b = 1 : 3, R 0.82, 0.64. Found, %:
f
1
,3-butadiene was added to a solution of about 2.50 g
C 28.42; 28.43; H 2.69, 2.65; N 4.17, 4.12.
C H BrCl NO . Calculated, %: C 28.44; H 2.67; N
(
3
0.011 mol) of 1-bromo-1-nitro-3,3,3-trifluoropropene
in diethyl ether under cooling (–10°C). The resulting
8
9
3
2
4
.15.
mixture was held at 4°C for 10 h. The reaction mixture
was chromatographed (eluent: hexane). Yield 3.12 g
ACKNOWLEDGMENTS
(
97%), mp 40–42°C (hexane). Found, %: C 35.60,
3
2
5.75; H 3.69, 3.65; N 4.71, 4.64; F 18.98, 18.75; Br
6.60, 26.63. C H F NO Br. Calculated, %: C 35.76;
The authors are grateful to the Chemical Service
9
11
3
2
Center for Joint Use of the Siberian Branch of the
Russian Academy of Sciences for performing the
X-ray diffraction analysis.
H 3.64; N 4.64; F 18.87; Br 26.49.
4-Bromo-1,2-dimethyl-4-nitro-5-trichloromethyl-
1
1
-cyclohexene (8). A mixture of 4.00 g (0.015 mol) of
-bromo-1-nitro-3,3,3-trichloropropene 4 and 1.23 g
REFERENCES
(
2
0.015 mol) of 2,3-dimethyl-1,3-butadiene was held at
0°C for 6 days and then was chromatographed on
silica gel. From a fraction washed with hexane, 4.46 g
85%) of cyclohexene 8 of mp 76–78°C was separated.
1. Ono, N., The Nitro Group in Organic Synthesis,
Organic Nitro Chem. Ser., New York: VCH, 2001,
p. 372.
(
Found, %: C 30.78; 30.83; H 3.16, 3.26; N 4.03, 4.08.
C H Cl BrNO . Calculated, %: C 30.73; H 3.13; N
2. Perekalin, V.V., Lipina, E.S., Berestovitskaya, V.M.,
and Efremov, D.A., Nitroalkenes. Conjugated Nitro
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9
11
3
2
3
.98.
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hexene (9a, 9b). A mixture of 3.00 g (0.021 mol) of
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3
4
5
. Nakai, K., Kamoshita, M., Doi, T., Yamada, H., and
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1
1
. Poigny, S., Nouri, S., Chiaroni, A., Guyot, M., and
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and then was chromatographed on silica gel (eluent:
hexane). Yield 3.82 g (87%), isomer ratio 9a : 9b = 1 : 4,
Rf 0.91, 0.78.
. Carballares, S., Craig, D., Lane, C.A.L., MacKenzie, A.R.,
Mitchell, W.P., and Wood, A., Chem. Commun., 2000,
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1
-Methyl-4(5)-nitro-5(4)-trichloromethyl-1-cyclo-
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6. Jwamatsu, S., Matsubara, K., and Nagashima, H.,
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1
1
0.1021/jo9912146
of 2-methyl-1,3-butadiene was held at 20°C for 6 days.
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7. Arce, E., Carreno, M.C., Cid, M.B., and Ruano, J.L.,
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hexane). Yield 4.42
g
(95%), isomer ratio
1
0.1021/jo00091a035
1
0a : 10b = 1.0 : 2.5, R 0.84, 0.54. Found, %: C 37.13;
f
3
7.16; H 3.87, 3.86; N 5.41, 5.45. C H Cl NO .
8. Node, M., Jmazato, H., Kurosaki, R., Kawano, Y.,
Inoue, T., Nishide, K., and Fuji, K., Heterocycles, 1996,
vol. 42, no. 2, p. 811. doi 10.3987/COM-95-S88
8
10
3
2
Calculated, %: C 37.14; H 3.87; N 5.42.
4
(5)-Bromo-1-methyl-4(5)-nitro-5(4)-trifluoro-
9
. Chandler, M., Conroy, R., Cooper, A.W.J., Lamont, R.B.,
Scicinski, J.J., Smart, J.E., Storer, R., Weir, N.G.,
Wilson, R.D., and Wyatt P.G., J. Chem. Soc., Per.
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P19950001189
methyl-1-cyclohexene (11a, 11b). 0.46 g (0.007 mol)
of 2-methyl-1,3-butadiene was added to a solution of
about 1.50 g (0.007 mol) of 1-bromo-1-nitro-3,3,3-
trifluoropropene 3 in diethyl ether under cooling (–10°C).
The mixture was held at 4°C for 10 h and then chro-
matographed on silica gel (eluent: hexane). Yield
1
0. Cere, V., Montovani, G., Peri, F., Pollicino, S., and
Ricci, A., Tetrahedron, 2000, vol. 56, no. 9, p. 1225. doi
10.1016/S0040-4020(00)00011-9
1
.31 g (65%), isomer ratio 11a : 11b = 1 : 4.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 5 2018

SYNTHESIS AND STRUCTURE OF CYCLOHEXENES FUNCTIONALIZED
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