Studies on the reaction of nitric oxide with α,β-unsaturated hydrazones

Article abstract of DOI:10.1139/v2012-022

α,β-Unsaturated arylhydrazones (1) reacted with nitric oxide (NO) in the presence of a trace of oxygen to give α-(2a-2c, 2e, and 2f) or β-nitro (2d and 2g) unsaturated hydrazones in good yield and with high stereoselectivity. The reaction occurs most likely by an electrophilic addition of NO₂ to the carbon-carbon double bond of 1 at its α-or β-position.

Full text of DOI:10.1139/v2012-022

510
Studies on the reaction of nitric oxide with α,β-
unsaturated hydrazones
Desuo Yang, Xiaolin Luo, Haiyun Zhu, Yaning Guo, and Longmin Wu
Abstract: a,b-Unsaturated arylhydrazones (1) reacted with nitric oxide (NO) in the presence of a trace of oxygen to give a-
(2a–2c, 2e, and 2f) or b-nitro (2d and 2g) unsaturated hydrazones in good yield and with high stereoselectivity. The reaction
occurs most likely by an electrophilic addition of NO2 to the carbon–carbon double bond of 1 at its a- or b-position.
Key words: a,b-unsaturated hydrazone, nitric oxide, nitration reaction, electrophilic addition.
Résumé : Les arylhydrazones a,b-insaturées (1) réagissent avec l’oxyde nitrique (NO), en présence d’une trace d’oxygène
pour conduire à la formation d’a- (2a–2c, 2e et 2f) ou de b-nitrohydrazones (2d et 2g) insaturées, avec des bons rendements
et une grande stéréosélectivité. La réaction se produit très probablement par une addition électrophile de NO2 sur les posi-
tions a ou b de la double liaison carbone–carbone du composé 1.
Mots‐clés : hydrazone a,b-insaturée, oxyde nitrique, réaction de nitration, addition électrophile.
[Traduit par la Rédaction]
unsaturated hydrazones with NO is suggested to occur by a
different mechanism from saturated hydrazones because of
the existence of both C=C and C=N bonds in a,b-unsaturated
hydrazones. In the present work we will report research on
the reaction of NO with a,b-unsaturated aldehyde and ke-
tone arylhydrazones.
Introduction
Studies on nitric oxide (NO) associated with life processes
have attracted more attention from scientists. The proper reg-
ulation of NO levels has been proposed as a desirable target
for developing new medicines.1 Therefore, intensive investi-
gations have been directed toward reactions of NO with bio-
logical molecules2 and various organic molecules, such as
alkenes,3 Schiff bases or oximes,4 epoxides,5 polycyclic aro-
matic hydrocarbons,6 chalcone derivatives,7 coumarins,8 fla-
vanones,9 and hydrazones.10
Hydrazone compounds with an active imine double bond
are widely used to construct chiral configurations and certain
specific skeletons in organic synthesis.11 In recent years,
some hydrazones and their complexes have been found to
have good bioactivity in the anticancer,12 antimalarial,13 and
antiviral aspects.14 As part of continuing efforts to explore
biological applications of NO chemistry and ongoing studies
on the reaction of NO with organic molecules, we studied
the reaction of NO with saturated arylhydrazones in the pres-
ence of trace oxygen. It was found that the reaction of NO
with aldehyde arylhydrazones provided exclusively C(1’)-
nitrohydrazones with E-configurations,15 and that ketone
arylhydrazones afforded mononitrated azo-compounds.16
Gillis and LaMontagne17 studied the oxidation of cinna-
maldehyde monomethylhydrazone with lead tetraacetate and
obtained the corresponding N-acetylcinnamic acid methylhy-
drazide. Kamitori et al.18 reported that the trifluoroacetylation
of dialkylhydrazones of a,b-unsaturated aldehydes occurred
at the terminal carbon of the conjugate system. In conjunc-
tion with alkenes and simple hydrazones, the reaction of a,b-
a,b-Unsaturated arylhydrazones (1) were prepared by the
reaction of an a,b-unsaturated ketone with 2,4-dinitrophenyl-
hydrazine in ethanol. The crude products were obtained after
removal of the solvent. Further purifications were done ac-
cording to literature procedure.19 The products were charac-
terized by NMR, MS, and IR. The reaction of NO with 1
was examined in the presence of trace oxygen in CH2Cl2 at
room temperature (Scheme 1). The unique products, a-nitro-
hydrazones (2a–2c, 2e, and 2f) or b-nitrohydrazones (2d and
2g), were obtained in high yield. In the case of 1e a small
quantity of a-nitro alkenyl azo-compound (2e’) was also ob-
tained. These results indicate that the reaction of NO with 1
occurs in a different way, compared with those of saturated
hydrazones. It is proposed that the p bond of the C=C of 1
breaks during the reaction and a fresh C=C double bond is
regenerated by an elimination reaction.
Results and discussion
Nitration reaction of NO with a,b-unsaturated
arylhydrazones
Under similar conditions, compound 1 reacted with NO in
the presence of minute amounts of oxygen affording a more
complex pattern of products than the saturated hydra-
zones.15,16 One hydrogen atom at the C=C bond of 1 was
Received 29 June 2011. Accepted 27 March 2012. Published at www.nrcresearchpress.com/cjc on 10 May 2012.
D. Yang, X. Luo, H. Zhu, and Y. Guo. Department of Chemistry & Engineering, Baoji University of Arts & Science, Baoji, 721013, P.
R. China.
L. Wu. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, P.R. China.
Corresponding author: D. Yang (e-mail: yangds09@163.com).
Can. J. Chem. 90: 510–516 (2012)
doi:10.1139/V2012-022
Published by NRC Research Press

Yang et al.
511
Scheme 1.
R2
R1
R3
R2
O2N
R3
R2
R1
NO2
NO2
R2
R1
NO (trace O2)
CH2Cl2, rt
R4
N
N
N
R4
N
N
HN Ar
R4
R4
HN Ar
Ar
HN Ar
1
R2, R4 = alkyl or aryl ; R1, R3=H
R1, R4= alkyl ; R2 , R3=H
2a-2c
2e, 2f
2d
2g
R1, R2, R4= alkyl ; R3=H
R2, R3, R4= alkyl ; R1=H
2e'
Table 1. Reaction of NO with a,b-unsatured hydrazones in CH2Cl2.
Time
(h)*
Yield of 2
Entry
Substrate
Product
(%)†
a
11
84
H
NO
2
H
H
N
N
H
C
H C
3
HN A r
3
HN A r
Ph
H
H
Ph
H
NO2
b
c
8
9
82
71
N
N
H3C
HN Ar
H3C
HN Ar
NO2
Ph
H
H
Ph
H
N
N
Ph
Ph
HN Ar
HN Ar
H
H
H
O2N
d
13
12
76
73
N
N
HN Ar
HN Ar
NO2
H3C
N
H
H3C
HN Ar
N
NO2
H3C
e
f
12
8
14
89
86
HN Ar
N
Ar
N
2e’
H3C
H3C
H
H C
3
NO
2
H C
3
N
N
H3C
H C
3
HN Ar
HN Ar
g
14
N
H
N
O2N
H3C
H3C
HN Ar
HN Ar
*The reaction time.
†Yield of the isolated product.
exclusively substituted by a nitro group in all cases. It was
also found that the nitro group replaces an a-hydrogen atom
at the C=C bond with two hydrogen atoms in trans-positions
(2a–2c), whereas the nitro group replaces a b-hydrogen atom
(2d) when these two hydrogen atoms lay in cis-positions. It
was found that 1e reacted with NO to give 2e and, in addition,
a small amount of an a-nitro alkenyl azo-compound (2e’),
where the substitution of a hydrogen atom at the C=C
bond by a nitro group did not occur.
oxidized with oxygen to give nitrogen dioxide (NO2). NO2
then undergoes an electrophilic addition to either the a-carbon
(1a–1c, 1e, and 1f) or b-carbon (1d and 1g) at the C=C
bond of 1, leading to the formation of a carbon radical.
Afterwards, the resulting carbon radical couples with three
molecules of NO to give a N-nitroso-N-nitrite compound,15
followed by a rearrangement, an elimination of HNO3, and
an expulsion of N2, giving compound 2 (Table 1).
As such, the amount of O2 in the whole system would play
a key role and is closely related to the composition of prod-
ucts and the reaction rate. No product was obtained when
oxygen was rigorously excluded from the system.15
The nitration reaction of 1 with NO is assumed to occur
by an electrophilic addition of NO2 to the C=C double bond
of 1, most likely similar to that of alkenes.3,20 At first, NO is
Published by NRC Research Press

512
Can. J. Chem. Vol. 90, 2012
Fig. 1. gHSQC of 2b.
Fig. 2. HMBC of 2b.
Identification of products
An NOE enhancement was observed at the CH3 (d 2.30 ppm)
protons in 2a upon irradiation of the NH proton (d
11.32 ppm). This indicates that NH is related to the –CH3 at
the C=N bond, i.e., –CH3 and the NH–Ar groups are on the
same side of the C=N bond with an E-configuration. When
the =CH (d 7.19 ppm) proton was irradiated, the signal of
–CH3 (d 2.30 ppm) at the C=N bond was enhanced, indi-
cating the nitro and the isopropyl groups are on the same
sides of the C=C bond with a Z-configuration.
To determine the position of the nitro group at the C=C
bond in 2b, gHSQC and HMBC experiments were performed
(Figs. 1 and 2). Three types of hydrogen, 2,4-dinitrophenyl
(H3, H5, and H6), CH3 (H16), and –NH (H7) in the 1H
NMR spectrum of 2b are easily assigned. A singlet peak at
d ∼ 8.20 ppm for one hydrogen is assigned to =CH (H11),
and a group of multiple peaks at 7.39–7.49 ppm are assigned
MS and HR-MS detections show that all the products were
formed by loss of a hydrogen atom from 1 and by introduc-
tion of a nitro group. Except for 2e’, the nN–H of –NH stretch-
ing bands is observed at ~3300 cm–1 in the IR spectra of 2.
The observations of a singlet peak at d ∼ 11.0 ppm for one
hydrogen and another singlet peak and two doublet peaks at
1
d 7.2–9.2 ppm in the H NMR spectra of 2 are assigned to
–NH and 2,4-dinitrophenyl protons, respectively. 1H NMR
spectra of 2a–2d also exhibit the loss of one hydrogen at
the C=C bond in 1a–1d. These detections indicate that the
2,4-dinitrophenylamino group remains unchanged, and the
reaction occurs at the C=C bond rather than at the C=N
bond.
A doublet peak at d ∼ 7.20 ppm and a multiplet peak at
d ∼ 2.71 ppm are assigned to an isopropyl group (Scheme 1).
Published by NRC Research Press

Yang et al.
513
Table 2. Crystal data and structure refinement of 2e.
to the hydrogens on the substituted phenyl (H13 and H13’,
H14 and H14’, and H15). DEPT and gHSQC experiments in-
dicate that H11 connects to C11 (~136.8 ppm). It can also be
seen from the HMBC that H11 at the C=C bond is obviously
related to a substituted phenyl (7.39–7.49 ppm) (Fig. 2). Sim-
ilarly, C9 and C10 are relevant to H16 and H11, respectively.
Thus, the nitro group can be deduced to lie at the a-position
of 2b. An NOE enhancement establishes the Z-configuration
at the C=C bond.
Parameter
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
C13H13N5O6
335.28
293 (2)
0.71073
Monoclinic
P2(1) /c
Unit cell dimensions
a (Å)
b (Å)
c (Å)
a (°)
The 1H NMR spectrum of 2c shows a singlet at d
8.15 ppm assigned to the proton at the C=C double bond
(=CH) and manifests, from its HMBC spectrum, that the =CH
proton is related to the substituted phenyl protons (7.06–
7.33 ppm). Therefore, the nitro group in 2c is thought to
be also connected to the a-position. NOE enhancements
were observed at the phenyl protons of C=N bond upon ir-
radiation of the NH proton (~11.38 ppm) and the proton at
the C=C bond. These observations indicate that the phenyl
and –NHAr groups are on the same side of the C=N bond
and the –NO2 and =CH groups are on opposite sides of the
C=C bond. Therefore, a Z-configuration at the C=C bond
of 2c is assigned.
14.501(2)
6.362(1)
17.166(2)
90
b (°)
g (°)
110.913(9)
90
1479.3(3)
4
1.505
0.122
Volume (Å3)
Z
Density (calcd; g cm–3)
Absorption coefficient (mm–1)
F (000)
696
Crystal description
Crystal colour
Crystal size (mm)
q range for data collection (°)
Limiting indices
Needles
Red
0.58×0.32×0.32
1.50–25.25
0≤h≤17, 0≤k≤7,–
20≤l≤19
3177
The 1H NMR spectrum of 2d shows a singlet at d
7.66 ppm assigned to the =CH proton. Thus, the nitro group
is thought to be connected to the b-position. An NOE en-
hancement was observed at the a-CH2 protons (~2.64 ppm)
of the C=N bond upon irradiation of the NH proton
(~11.50 ppm). An E-configuration is assigned to the C=N
bond of 2d.
Reflections collected
Independent reflections
Absorption correction
Refinement method
2681 (Rint = 0.0145)
None
There is one hydrogen atom at the C=C bonds of 1e–1g.
Full-matrix least-squares
on F2
1H NMR spectra of their products (2e–2g) display no proton
linking at the C=C bond. The 13C NMR spectra of 2e–2g
show that the proton of the double bond was replaced by a
nitro group. An NOE experiment for 2e shows its a-CH2 pro-
ton (~2.68 ppm) at the C=N bond was related to the proton
of NH (~11.20 ppm). Thus, the C=N group of 2e with an E-
configuration is established.
Data/restraints/parameters
Goodness-of-fit on F2
2681/0/219
1.015
Final R indices (I > 2s(I))
R1 = 0.0530, wR2 =
0.0928
R indices (all data)
R1 = 0.0342, wR2 =
0.0868
Extinction coefficient
0.0136(15)
0.162 and –0.149
Compound 1e reacted with NO to give a small amount of
Largest diff. peak and hole (e Å–3)
2e’ in addition to 2e. MS and HR-MS detections show 2e’
1
and 2e have the same molecular formula. The H NMR spec-
trum of 2e’ displays a singlet at d 7.28 ppm assigned to the
=CH, and its 13C NMR spectrum shows a singlet at dc
87.1 ppm assigned to a quaternary carbon associated with an
NO2. IR and H NMR spectra indicate that there is no NH
group in 2e’. Therefore, product 2e’ may be inferred to be an
azo-compound.
to the plane constructed by the remaining five carbon atoms
is 0.5 Å. The dihedral angle between the nitro group at C5
(a-carbon) and the six-membered ring plane is 78°. A hydro-
gen bond exists between the hydrogen atom of NH and the
oxygen atom of the ortho-nitro group on the benzene ring
(Table 4; Fig. 3b).
1
Crystal structure of 2e
Conclusion
X-ray crystallography data for 2e are shown in Table 2
(see the Supplementary data). Crystal structure and a packing
diagram of 2e are illustrated in Fig. 3, and the selected bond
lengths and bond angles are summarized in Table 3. The an-
alytical results indicate that the nitro group is linked at C-5, i.e.,
the a-carbon (Fig. 3a) and the N(3)–C(5) is a single bond
(1.476(2) Å). Both the C(4)–C(5) bond length of 1.334(2) Å
and the N(1)–C(6) bond length of 1.288(2) Å are assigned
to an ethylenic bond and an imine double bond, respec-
tively, in 2e.
The present study reports that the reaction of NO with a,b-
unsaturated arylhydrazones (1) in the presence of a trace of
oxygen at room temperature gives a-nitro (2a–2c, 2e, and
2f) or b-nitro (2d and 2g) unsaturated hydrazones in good
yield and with high stereoselectivity. The nitration reaction is
most likely initiated by an electrophilic addition reaction of
NO2 to the C=C double bond of substrate 1. A small quan-
tity of a-nitro alkenyl azo-compound (2e’) was also formed in
the case of 1e. The nitration reaction discussed herein offers
an efficient method for preparing a,b-nitro unsaturated hydra-
zones and a,b-nitro unsaturated ketones.
The C(1)–C(2)–C(3)–C(4)–C(5)–C(6) six-membered ring
is an envelope-type structure. The vertical distance from C2
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514
Can. J. Chem. Vol. 90, 2012
m/z calcd for C13H15N5O6 (M+): 337.1022; found: 337.1011.
EIMS m/z: 337(M+), 320, 291, 278, 249, 181, 169, 122, 108,
93, 77, 67, 55.
Experimental
All solvents were distilled prior to use according to standard
procedures. Methylene dichloride was dehydrated with CaH2
by refluxing.
1H and 13C NMR spectra were recorded on a Bruker
Avance 400 (1H, 400 MHz; or 13C, 100 MHz; d downfield
from TMS). IR analysis was performed on a Nicolet NEXUS
670 FT-IR. Mass data were obtained on a HP-5988A GC–
MS, and HR-ESI-MS data were obtained on a Bruker Dalton-
ics APEx II FT-ICR. Melting points were determined with an
XT4-100X micromelting point apparatus and not corrected.
X-ray analysis on single crystals was carried out at 293(2) K
on a Nonius CAD4 automatic diffractometer using graphite-
monochromated Mo Ka radiation (l = 0.710 73 Å). Struc-
tural solutions and full-matrix least-squares refinements
based on F2 were performed with the SHELXS-97 and
SHELXL-97 program packages,21 respectively. All the non-
hydrogen atoms were anisotropically positioned. Hydrogen
atoms were placed in geometrical positions and constrained to
ride on their parent atoms. Analytical expressions of neutral-
atom scattering factors were employed, and anomalous dis-
persion corrections were incorporated (see the Supplemen-
tary data for crystallographic data (excluding structure
factors)).22
(E)-1-(2,4-Dinitrophenyl)-2-((Z)-3-nitro-4-phenylbut-3-en-2-
ylidene)hydrazine (2b)
Orange needles, mp 147–149 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 2.36 (s, 3H), 7.39–7.49 (m, 5H), 7.23 (d,
J = 9.6 Hz, 1H), 8.20 (s, 1H), 8.26 (dd, J = 9.6, 2.4 Hz,
1H), 9.15 (d, J = 2.4 Hz, 1H), 11.36 (s, 1H). 13C NMR
(100 MHz, CDCl3, ppm) d: 16.7, 116.8, 123.0, 129.4, 130.2,
130.4, 130.6, 131.8, 136.8, 139.4, 144.4, 144.5, 147.1. IR
(KBr, cm–1) nmax: 3308, 3107, 1652, 1615, 1514, 1333,
1139, 1095, 968, 935, 836, 743, 688, 581, 504. HR-ESI-MS
+
m/z calcd for C16H17N6O6 (M + NH4 ): 389.1209; found:
389.1218. EIMS m/z: 371 (M+), 354, 336, 278, 232, 128,
102, 77, 63, 51, 43.
(E)-1-(2,4-Dinitrophenyl)-2-((E)-2-nitro-1,3-
diphenylallylidene)hydrazine (2c)
Orange needles, mp 184–186 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 7.06–7.33 (m, 10H), 7.68 (d, J = 12.8 Hz,
1H), 8.15 (1H, s), 8.30 (d, J = 12.8 Hz, 1H), 9.03 (s, 1H),
11.38 (1H, s). 13C NMR (100 MHz, CDCl3, ppm) d: 117.1,
119.7, 123.4, 126.1, 127.8, 128.1, 128.6, 129.6, 130.1,
130.6, 131.8, 136.5, 139.4, 144.2, 144.6, 147.7, 155.1. IR
(KBr, cm–1) nmax: 3268, 3080, 2923, 2851, 1613, 1497,
1423, 1333, 1135, 1099, 919, 830, 767, 692, 632, 510. HR-
ESI-MS m/z calcd for C21H15N5O6 (M+): 433.1023; found:
433.1016. EIMS m/z: 433 (M+), 403, 386, 294, 207, 189,
165, 135, 105, 77, 63, 51, 44, 39.
General procedure for the synthesis of 2a–2g
A solution of 1 was prepared by dissolving 1 (0.5 mmol)
in 100 mL of anhydrous dichloromethane. NO was produced
by dropwise addition of 1 mol L–1 H2SO4 solution to a
stirred saturated aqueous solution of NaNO2 under an argon
atmosphere. NO gas was purified by passing through a series
of scrubbing bottles containing 4 mol L–1 NaOH, distilled
water, and anhydrous CaCl2 pellets in this order. The purified
NO was bubbled through the stirred solution of 1, which was
previously degassed by argon for approx. 5–10 min and kept
at a pressure of up to +10 mm H2O column over local at-
mospheric pressure, at ambient temperature for 8–14 h. In
the course of the reaction, the argon flow rate was controlled
by regulating the flow meter at 0.8 L min–1. A rough esti-
mate of the total amount of NO passing through the solution
was about 1000 mmol at the local atmosphere pressure using
the ideal gas law. The progress of the reaction was monitored
by TLC. After the reaction was complete, the mixture was
dried over anhydrous MgSO4, concentrated under vacuum,
and purified by column chromatography on silica gel (200–
300 mesh; ethyl acetate – petroleum ether, 1:6 v/v), giving
pure product 2 (Table 1).
(E)-1-(2,4-Dinitrophenyl)-2-(3-nitrocyclohex-2-enylidene)
hydrazine (2d)
Orange needles, mp 216–217 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 2.15 (tt, J = 6.4, 6.8 Hz, 2H), 2.64 (t, J =
6.8 Hz, 2H), 2.90 (t, J = 6.4 Hz, 2H), 7.66 (s, 1H), 8.10 (d,
J = 9.6 Hz, 1H), 8.42 (dd, J = 9.6, 2.8 Hz, 1H), 9.16 (d, J =
2.8 Hz, 1H), 11.50 (s, 1H). 13C NMR (100 MHz, CDCl3,
ppm) d: 20.3, 21.2, 22.9, 23.7, 29.7, 116.9, 123.1, 129.6,
130.4, 130.6, 139.6, 143.9, 149.7, 153.5. IR (KBr, cm–1)
nmax: 3302, 3097, 2937, 1614, 1498, 1419, 1313, 1100, 925,
850, 792, 592, 518. HR-ESI-MS m/z calcd for C12H11N5O6
(M+): 321.0709; found: 321.0721. EIMS m/z: 321 (M+),
181, 152, 109, 77, 65, 55, 51, 44, 39.
(E)-1-(2,4-Dinitrophenyl)-2-(3-methyl-2-nitrocyclohex-2-
enylidene)hydrazine (2e)
(E)-1-(2,4-Dinitrophenyl)-2-((Z)-5-methyl-3-nitrohex-3-en-
2-ylidene)hydrazine (2a)
Red needles, mp 214–215 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 1.98 (s, 3H), 2.04–2.11 (m, 2H), 2.46 (t,
J = 7.2 Hz, 2H), 2.68 (t, J = 8.8 Hz, 2H), 7.83 (d, J =
12.8 Hz, 1H), 8.32 (dd, J = 12.8, 2.4 Hz, 1H), 9.11 (d, J =
2.4 Hz, 1H), 11.20 (s, 1H). 13C NMR (100 MHz, CDCl3,
ppm) d: 19.7, 20.0, 23.7, 30.0, 117.0, 123.3, 130.3, 130.6,
Yellow needles, mp 129–130 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 1.15(d, 6H, J = 4.6 Hz), 2.30 (s, 3H), 2.67–
2.73 (m, 1H), 7.21 (d, J = 12.8 Hz, 1H), 7.89 (d, J = 9.6 Hz,
1H), 8.39 (dd, J = 9.6, 2.8 Hz, 1H), 9.18 (d, J = 2.8 Hz,
1H), 11.32 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm) d:
16.6, 22.1, 28.4, 63.4, 116.5, 123.2, 130.3, 130.4, 139.2,
144.4, 144.5, 146.9, 147.6. IR (KBr, cm–1) nmax: 3308, 3105,
2973, 2919, 2873, 2848, 1616, 1593, 1501, 1423, 1337,
1136, 1095, 953, 920, 831, 797, 740, 577, 505. HR-ESI-MS
139.1, 139.9, 144.4, 144.6, 146.7. IR (KBr, cm–1) nmax
:
3305, 3105, 2963, 2938, 1611, 1501, 1427, 1333, 1306,
1137, 1113, 1062, 914, 848, 769, 739, 708, 680, 576, 556,
499. HR-ESI-MS m/z calcd for C13H13N5O6Na (M + Na+):
Published by NRC Research Press

Yang et al.
515
Fig. 3. (a) Crystal structure and (b) a packing diagram for 2e.
Table 3. Selected bond lengths (Å) and
bond angles (°) of 2e.
358.0758; found: 358.0769. EIMS m/z: 335 (M+), 318, 288,
271, 241, 181, 167, 152, 121, 106, 91, 77, 65, 53, 41, 38.
Bond lengths (Å)
1-(2,4-Dinitrophenyl)-2-(3-methyl-3-nitrocyclohex-1-enyl)
diazene (2e’)
N(1)–C(6)
1.2884(19)
1.3686(17)
1.353(2)
1.4757(19)
1.2111(16)
1.2169(17)
1.490(2)
1.454(2)
1.334(2)
1.503(2)
1.504(2)
N(1)–N(2)
Orange needles, mp 173–175 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 1.77–2.02 (m, 6H), 2.35–2.39 (m, 1H),
2.49–2.53 (m, 1H), 2.63–2.66 (m, 1H), 7.28 (s, 1H), 7.68 (d,
J = 11.8 Hz, 1H), 8.51 (dd, J = 11.8, 2.8 Hz, 1H), 8.79 (d,
J = 2.8 Hz, 1H). 13C NMR (100 MHz, CDCl3, ppm) d: 18.5,
21.9, 27.2, 34.1, 76.7, 87.1, 119.7, 120.1, 127.9, 141.6,
147.8, 148.6, 157.6. IR (KBr, cm–1) nmax: 3100, 2961, 2867,
1603, 1537, 1447, 1344, 1273, 1175, 1061, 906, 848, 741.
HR-ESI-MS m/z calcd for C13H13N5O6Na (M + Na+):
358.0758; found: 358.0777. EIMS m/z: 335 (M+), 289, 236,
208, 125, 115, 77, 65, 55, 51, 43, 39.
N(2)–C(7)
N(3)–C(5)
N(3)–O(2)
N(3)–O(1)
C(4)–C(13)
C(5)–C(6)
C(4)–C(5)
C(1)–C(6)
C(3)–C(4)
N(4)–C(12)
1.447(2)
1.460(2)
N(5)–C(10)
Bond angles (°)
C(6)–N(1)–N(2)
C(7)–N(2)–N(1)
O(2)–N(3)–O(1)
O(2)–N(3)–C(5)
O(1)–N(3)–C(5)
N(2)–C(7)–C(8)
C(13)–C(4)–C(3)
C(5)–C(4)–C(13)
C(4)–C(5)–N(3)
C(6)–C(5)–N(3)
N(1)–C(6)–C(1)
N(2)–C(7)–C(12)
N(1)–C(6)–C(5)
C(5)–C(6)–C(1)
C(4)–C(5)–C(6)
O(6)–N(5)–O(5)
O(4)–N(4)–O(3)
116.30(13)
120.02(12)
124.08(14)
118.58(14)
117.33(13)
120.75(14)
118.00(15)
123.87(16)
118.23(14)
114.97(13)
127.51(15)
122.59(14)
116.51(14)
115.95(14)
126.71(15)
123.74(16)
121.83(14)
(E)-1-(2,4-Dinitrophenyl)-2-(4-methyl-3-nitropent-3-en-2-
ylidene)hydrazine (2f)
Orange needles, mp 123–124 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 2.08 (s, 3H), 2.22 (s, 3H), 2.23 (s, 3H),
7.93 (d, J = 9.2 Hz, 1H), 8.36 (dd, J = 9.2, 3.2 Hz, 1H),
9.16 (d, J = 9.2 Hz, 1H), 11.25 (s, 1H); 13C NMR
(100 MHz, CDCl3, ppm) d: 15.9, 22.3, 23.2, 117.2, 123.2,
130.2, 139.0, 144.2, 144.6, 145.9, 146.6. IR (KBr, cm–1)
nmax: 3298, 3116, 1645, 1617, 1589, 1515, 1492, 1417,
1366, 1331, 1296, 1266, 1132, 1103. HR-ESI-MS m/z calcd
for C12H13N5O6 (M+): 323.0866; found: 323.0877. EIMS
m/z: 323 (M+), 308, 277, 269, 230, 181, 79.
(E)-1-(2,4-Dinitrophenyl)-2-(1-(2-nitrocyclohex-1-enyl)
ethylidene)hydrazine (2g)
Red needles, mp 202–204 °C. 1H NMR (400 MHz,
CDCl3, ppm) d: 1.79–1.81 (m, 2H), 1.86–1.89 (m, 2H), 2.22
(s, 3H), 2.52–2.54 (m, 2H), 2.71–2.74 (m, 2H), 7.86 (d, J =
9.2 Hz, 1H), 8.32 (dd, J = 9.2, 2.4 Hz, 1H), 9.14 (d, J =
2.4 Hz, 1H), 11.14 (s, 1H). 13C NMR (100 MHz, CDCl3,
ppm) d: 15.6, 21.1, 25.9, 29.6, 116.5, 123.3, 129.8, 130.0,
Table 4. Hydrogen bond geometry of 2e.
D–H
(Å)
H···A
(Å)
1.97
D–H···A
D–H···A
D···A (Å)
2.5993(17)
(°)
138.4, 140.1, 144.7, 147.5, 152.8. IR (KBr, cm–1) nmax
3312, 3105, 2929, 2866, 2824, 1613, 1586, 1508, 1414,
1326, 1105, 1076, 978, 918, 835, 734, 674, 639, 590,
557, 527, 503. HR-ESI-MS m/z calcd for C14H15N5O6Na
:
N2–H2N···O3
0.86
129.1
Published by NRC Research Press

516
Can. J. Chem. Vol. 90, 2012
(M + Na+): 372.0914; found: 372.0927. EIMS m/z: 349
(8) Lei, L. D.; Yang, D. S.; Liu, Z. Q.; Wu, L. M. Synth. Commun.
2004, 34 (6), 985. doi:10.1081/SCC-120028628.
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1248.
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Lett. 1997, 38 (23), 4117. doi:10.1016/S0040-4039(97)00840-
X.
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S. Z. Z. Tetrahedron 2009, 65 (33), 6730. doi:10.1016/j.tet.
2009.04.027; (b) Dang, T. T.; Dang, T. T.; Fischer, C.; Görls,
H.; Langer, P. Tetrahedron 2008, 64 (9), 2207. doi:10.1016/j.
tet.2007.12.024; (c) Wang, J. P.; Fu, Y. J.; Yin, W. P.; Wang, J.
G.; Qin, J. H. Chin. J. Org. Chem. 2007, 27 (4), 524; (d)
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(12) (a) Zhong, X.; Wei, H. L.; Liu, W. S.; Wang, D. Q.; Wang, X.
Bioorg. Med. Chem. Lett. 2007, 17 (13), 3774. doi:10.1016/j.
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(M+), 319, 303, 269, 238, 195, 154, 108, 100, 84, 55, 43.
Supplementary data
Supplementary data are available with the article through
the journal Web site at http://nrcresearchpress.com/doi/suppl/
10.1139/v2012-022. CCDC 220502 contains the X-ray data in
CIF format for this manuscript. These data can be obtained, free
of charge, via http://www.ccdc.cam.ac.uk/products/csd/request
(Or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
33603; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgements
This work was financially supported by the Shaanxi Pro-
vincial Natural Science Foundation of China (Grant No.
2009K01-51) and the Phytochemistry Key Laboratory of
Shaanxi Province (Grant No. 05JS43).
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