NMR structural elucidation and photochromic behavior of new 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives

Article abstract of DOI:10.1134/S1070428010060175

Several 6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives having various substituents on C² were synthesized, and their ¹H NMR spectra and photochromic behavior were examined.

Full text of DOI:10.1134/S1070428010060175

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 884–889. © Pleiades Publishing, Ltd., 2010.
Published in Russian in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 6, pp. 888–893.
NMR Structural Elucidation and Photochromic Behavior
of New 1,3-Diazabicyclo[3.1.0]hex-3-ene Derivatives*
N. O. Mahmoodi, H. Kiyani, K. Tabatabaeian, M. A. Zanjanchi,
M. Arvand, and B. Sharifzadeh
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box 41335-1914, Rasht, Iran
e-mail: mahmoodi@guilan.ac.ir
Received October 2, 2007; revised April 9, 2009
Abstract—Several 6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives having various
substituents on C2 were synthesized, and their 1H NMR spectra and photochromic behavior were examined.
DOI: 10.1134/S1070428010060175
Study on photochromic materials has drawn great
attention due to their applications in optical data stor-
age devices, holographic storage, solar cells, and sensi-
tizers [1, 2]. Photochromism is a vast field encompas-
sing well-known phenomena associated with reversible
transformations upon irradiation with UV and visible
light. In this chemical process, a compound absorbs
electromagnetic radiation and undergoes a reversible
change between two states that display different ab-
sorption spectra, i.e. different colors. In the recent
time, various photochromic dyes have been developed
to improve major photochromic properties such as
reversibility and stability [3, 4].
the possibility for recycling without loss of perform-
ance, (3) repeatable cycle number > 104, (4) high sen-
sitivity (quantum yield > 0.5), (5) rapid response,
(6) non-destructive readout capability, and (7) reactiv-
ity in the solid state. Among these, thermal stability
and fatigue resistance are the most important.
We recently used novel potentiometric membrane
sensors based on 6-(4-nitrophenyl)-2,4-diphenyl-3,5-
diazabicyclo[3.1.0]hex-2-ene and 6-(4-nitrophenyl)-2-
phenyl-4,4-dipropyl-3,5-diazabicyclo[3.1.0]hex-2-ene
for detection of tin(II) [8] and strontium(II) ions [9],
respectively, at trace levels in real samples. In the
present article we report on several new photochromic
compounds that are derivatives of well known photo-
chromic 1,3-diazabicyclo[3.1.0]hex-3-ene system.
Compounds I–XII with different substituents in the
2-position were synthesized following a slightly mod-
ified known procedure [10–14] (Scheme 1). Benzoyl-
aziridines XV were prepared starting from chalcones
XIII which were subjected to bromination at the
double bond with bromine in chloroform solution to
obtain dibromo derivatives XIV, followed by azir-
idination with a solution of ammonia in anhydrous
ethanol at room temperature [10]. In a typical proce-
dure for the preparation of I–XII, instead of commonly
used 1 mmol of gaseous ammonia and 1 mmol of
NH4Br in anhydrous ethanol, 5 mmol of NH4OAc and
1 mmol of NH4Br in the same solvent also worked
very well; in this case, the reaction was complete in
2–4 days instead of 1–2 weeks. The merits of this
system include the following: (1) new photochromic
azirinoimidazoles can be synthesized using a variety of
We have recently become interested in photo-
chromism and photoreproduction of 3,5-diazabicyclo-
[3.1.0]hex-3-ene derivatives with various substituents
[5]. In addition, synthesis of several fluorescence emis-
sion producers based on symmetrical and unsymmet-
rical trisannelated benzene constructions was attempt-
ed [6, 7]. Applications of photochromic compounds
directly depend upon color change produced by
variation of the molecular and electronic structures in
going from the initial to photoinduced form and their
corresponding absorption or emission spectra. They
can be used as variable-transmission optical materials
for photochromic ophthalmic lenses or camera filters,
fluid flow visualization, optical information storage,
novelty items (e.g., toys, T-shirts, etc.), authentication
systems (security printing inks), and cosmetics.
Requirements for photonics devices are as follows: (1)
thermal stability of both isomers, (2) low fatigue, i.e.,
* The text was submitted by the authors in English.
884

NMR STRUCTURAL ELUCIDATION AND PHOTOCHROMIC BEHAVIOR
885
Scheme 1.
H
O
Br
O
N
Ar
Br2/CHCl3
NH4OH/EtOH
Ph
Ar
Ph
Ar
Ph
O
Br
XIII
XIV
XV
H
N
Ph
O2N
R1R2C=O, NH4OAc
NH4Br, EtOH
N
R1
R2
I–XII
I, R1 = R2 = Me; II, R1 = Me, R2 = Et; III, R1 = R2 = Pr; IV, R1 = Me, R2 = i-Bu; V, R1 = H, R2 = PhCH2CH2; VI, R1 = H, R2 =
MeCH(Ph); VII, R1 = Me, R2 = 4-O2NC6H4; VIII, R1 = H, R2 = 4-MeOC6H4; IX, R1 = H, R2 = 2,4-(MeO)2C6H3; X, R1 = H, R2 =
4-Me2NC6H4; XI, R1 = H, R2 = 2,4,6-Me3C6H2; XII, R1 = H, R2 = 4-FC6H4; XIII–XV, Ar = 4-O2NC6H4.
ketones and aldehydes, (2) starting materials are acces-
sible compounds with perspective of industrial scale,
and (3) simple experimental procedure and high yield
of products (see table).
The presence of a dimethylamino group in the para
position of the phenyl ring in X considerably increased
photochromic sensitivity.
Photochromic properties of zeolite disks (molecular
sieves, mesoporous and microporous mordenite) con-
taining several 1,3-diazabicyclo[3.1.0]hex-3-ene deriv-
atives were recently studied by solid-state diffuse
reflectance spectroscopy. The diffuse reflectance spec-
tra of MCM-41-supported (Mobile Crystalline Materi-
al) compound XII in solid-state indicated absorption
maxima at λmax 265 and 612 nm after irradiation with
UV light for five minutes, i.e., absorption of electro-
magnetic radiation initiated a reversible transformation
between two forms (see figure).
According to the electronic absorption spectra, all
compounds I–XII exhibit positive photochromism
(see table). Compounds I–XII can undergo reversible
photocyclization between bicyclic structure (A) and
open isomer (B) under ordinary room light or irradia-
tion using a light source of appropriate wavelength.
Irradiation of Ia–XIIa (cyclic structure A) in ethanol
over a period of 20 min gives rise to zwitterionic
double-charged imine ylides Ib–XIIb (structure B,
Scheme 2) whose absorption maxima are given in
table. The absorption spectra of colorless compounds
Ia–XIIa (c = 1.4 ×10–4 M, EtOH, cell path length
1 cm) changed immediately after irradiation at
λ 254 nm for 0.5, 1, 5, 10, 15, and 20 min, respec-
tively. All spectra indicated formation of photosta-
tionary states. However, the absorption intensity of
VIIIb–XIIb was higher. The stability of colored inter-
mediates is strongly influenced by electronic effect.
Thus removal of the nitro group or shifting it to meta
position markedly reduced photochromic sensitivity.
Detailed NMR interpretation for these compounds
was considered. Examination of the stereochemistry of
compounds I–IV left no uncertainty that the methyl
group on C2 in molecules I, II, and IV lies below the
1
plane of the imidazole ring. The H NMR spectrum
of II showed two well resolved triplets at δ 1.03 (J =
7.5 Hz) and 1.12 ppm (J = 7.5 Hz) corresponding to
the terminal methyl protons in the ethyl group attached
to C2 for mixture of two diastereoisomers at a ratio of
~2:1 (the ethyl group is located above the imidazole
Scheme 2.
Ph
Ph
Ph
Ph
N
N
N
N
hν1
R1
R2
R1
R2
R1
R2
R1
R2
hν2 or Δ
N
N
N
N
·
·
Ar
Ar
Ar
Ar
A
B
Ar = 4-O2NC6H4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

MAHMOODI et al.
886
Scheme 3.
Ph
Ph
Ph
hν1
hν1
N
N
N
conrotatory
disrotatory
Me
Me
Me
Me
Me
H
H
H
hν2 or Δ
hν2 or Δ
N
N
·
N
Me
·
Ar
H
Ar
Ar
H
syn-Ib (colored)
Ia (colorless)
hν2 < hν1
anti-Ib' (colorless)
Ar = 4-O2NC6H4.
1
ring plane compared to methyl). The H NMR spec-
trum of I contained two signals from methyl groups at
δ 1.616 and 1.631 ppm. The methyl group located
below the imidazole ring plane is slightly more shield-
ed than the upper one due to overlap and the tendency
of nitrogen to feed electrons to the π system in con-
rotatory fashion (σ2s + n2s).
mism) or photochemically (type P photochromism) in
the solid phase. In contrast to the solid phase, the life-
time of colored photoinduced forms Ib–XIIb in solu-
tion was much shorter (several hours at room tempera-
ture), and their formation was not entirely reversible
due to competing enimine formation. It should be
avoided to allow solutions of Ia–XIIa to stand on ex-
posure to light for a long period. Under these condi-
tions, yellow impurities were formed, which can be
removed by double recrystallization.
The 1H NMR spectra of 6-(4-nitrophenyl)-2-phen-
yl-4-(2-phenylethyl)-1,3-diazabicyclo[3.1.0]hex-3-ene
(Va) and 6-(4-nitrophenyl)-4-(1-phenylethyl)-1,3-di-
azabicyclo[3.1.0]hex-2-ene (VIa) displayed splitting of
the 2-H signal at δ 5.5 (t, J = 7 Hz) and 5.66 ppm (d,
J = 7 Hz), respectively. The corresponding proton in
compounds VIIIa–XIIa resonated as a singlet at
δ 6.78, 6.76, 6.78, 6.80 and 6.78 ppm, respectively. No
proton–proton coupling was observed for 5-H and 6-H
(aziridine ring), in keeping with the vicinal Karplus
correlation (φ ≈ 90°), and the corresponding signals
were singlets located in the upfield region of the
1H NMR spectra of all compounds.
Ultimately, UV light causes heterolytic cleavage of
the three-membered ring to form colored imine ylide
(Scheme 3). The latter may have syn or anti structure
(Ib or Ib′, respectively). The syn structure is likely to
be formed via suprafacial symmetry-allowed conrota-
tory process which predominates [15].
Irradiation of colorless compounds Ia–XIIa in
ethanol with UV light at λ 254 nm over a period of
20 min causes ring opening with formation of colored
highly conjugated species Ib–XIIb which were iden-
tified by electronic absorption spectra in the UV and
visible regions. Photochromic transformations of Ia–
XIIa in toluene, ether, and other solvents were also
examined. In all cases, ethanol worked well. The back
reaction usually occurred thermally (type T photochro-
Irradiation of a powdered sample of Xa in an elec-
tric field produced an insignificant increase (about
1.13%) of the total capacitance which we ascribe to
the formation of dipolar intermediate [16]. The internal
reflectance IR spectrum of the irradiated solid showed
new bands at 1450, 1320, and 1270 cm–1; the latter two
bands were assigned to the conjugated nitro group in
the colored intermediate.
3
EXPERIMENTAL
2
1
The electronic absorption spectra were recorded on
a Shimadzu UV-2100 spectrophotometer in the range
from 200 to 800 nm from solutions in ethanol with
a concentration c of 2×10–4 M; the positions of ab-
sorption maxima for the initial (A) and photoinduced
forms (B) were measured. The melting points were
220
400
600
λ, nm
Diffuse reflectance spectra of XII–MCM-41 disks after ir-
radiation with UV light over a period of (1) 5, (2) 20, and
(3) 60 min.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

NMR STRUCTURAL ELUCIDATION AND PHOTOCHROMIC BEHAVIOR
887
Yields, excitation wavelengths, and absorption maxima of the colorless (A) and colored (B) forms of compounds I–XII
in ethanol
Compound no.
Yield, %
λ
excit, nm
λAmax, nm (colorless)a
λBmax, nm (color)a
285, 400 (blue)
I
79
85
85
65
70
71
78
78
78
78
61
80
345
340
370
350
–
286
280
282
281
280
280
280
280
280
277
280
280
II
280, 405 (blue)
III
IV
V
282, 415 (blue)
281, 401 (blue)
290, 400 (blue)
VI
VII
VIII
IX
X
–
281, 371 (pale blue)
280, 408 (deep blue)
283, 408 (violet)
282, 409 (pink)
320
–
–
250
–
282, 304, 345, 425 (blue)
281, 405 (blue)
XI
XII
344
285, 410 (deep blue)
a
In the solid state.
determined on a Mettler Fp5 melting point apparatus
and are uncorrected. The H NMR spectra were ob-
trum, λmax, nm: 285, 400. Found, %: C 70.33; H 5.56;
N 13.65. C18H17N3O2. Calculated, %: C 70.34; H 5.58;
N 13.67.
1
tained from solutions in CDCl3 on a Bruker Avance
spectrometer (500 MHz); the chemical shifts were
measured relative to the residual solvent signal. The IR
spectra were recorded in KBr on a Shimadzu IR-470
spectrometer. All chemicals used were purchased from
Fluka, Merck, and Aldrich. 3-(4-Nitrophenyl)-1-phen-
ylprop-2-en-1-one (XIII) [17], 2,3-dibromo-3-(4-nitro-
phenyl)-1-phenylpropan-1-one (XIV) [11, 13], and
[3-(4-nitrophenyl)aziridin-2-yl](phenyl)methanone
(XV) [10] were prepared according to known methods.
Compounds II–XII were synthesized in a similar
way.
2-Ethyl-2-methyl-6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-3-ene (II). Yield 85%,
colorless solid with mp 136–137°C. IR spectrum, ν,
cm–1: 3100, 3080, 2980, 2920, 1600, 1570, 1510, 1450,
1340, 1160, 1100, 930, 860, 820, 770, 740, 690.
1H NMR spectrum, δ, ppm: 1.03 t (3H, J = 7.4 Hz),
1.12 t (3H, J = 7.5 Hz), 1.56 s (6H), 1.69–1.74 m (1H),
1.87–2.02 m (3H), 2.62 s (2H), 3.52 d (1H, J =
1.4 Hz), 3.6 d (1H, J = 1.3 Hz), 7.44–7.53 m (10H),
7.88 d (4H, J = 7.2 Hz), 8.2 d (4H, J = 8.6 Hz). Elec-
tronic absorption spectrum, λmax, nm: 280, 405. Found,
%: C 71.00; H 5.94; N 13.07. C19H19N3O2. Calculated,
%: C 71.01; H 5.96; N 13.08.
2,2-Dimethyl-6-(4-nitrophenyl)-4-phenyl-1,3-di-
azabicyclo[3.1.0]hex-3-ene (I). A mixture of 0.268 g
(1 mmol) of [3-(4-nitrophenyl)aziridin-2-yl](phenyl)-
methanone (XV), 0.38 g (5 mmol) of ammonium
acetate, and 1 mmol of acetone in 6 ml of anhydrous
ethanol was stirred at room temperature. The reaction
was complete in 2–4 days. The originally colorless
mixture turned blue or greenish blue. The precipitate
was filtered off, washed with ethanol, dried in air,
purified by column chromatography on silica gel, and
recrystallized from ethanol, methanol, or another ap-
propriate solvent. Yield 79%, colorless solid with
mp 181–182°C. IR spectrum, ν, cm–1: 3050, 2980,
2920, 1600, 1570, 1510, 1440, 1340, 1220, 1100, 910,
6-(4-Nitrophenyl)-4-phenyl-2,2-dipropyl-1,3-di-
azabicyclo[3.1.0]hex-3-ene (III). Yield 85%, colorless
solid with mp 139–140°C. IR spectrum, ν, cm–1: 3100,
3080, 2950, 2920, 2880, 1600, 1570, 1510, 1440, 1340,
1
1240, 1140, 960, 860, 830, 760,740, 690. H NMR
spectrum, δ, ppm: 0.93–0.99 t.t (6H, J = 7.0, 7.3 Hz),
1.28–1.36 m (1H), 1.51–1.58 m (2H), 1.65–1.7 m
(2H), 1.88–1.94 m (3H), 2.65 s (1H), 3.54 s (1H),
7.45–7.54 m (5H), 7.89 d (2H, J = 7.5 Hz), 8.23 d (2H,
J = 8.5 Hz). Electronic absorption spectrum, λmax, nm:
282, 415 nm. Found, %: C 72.68; H 6.93; N 11.55.
C22H25N3O2. Calculated, %: C 72.70; H 6.93; N 11.56.
1
860, 820, 760, 740, 690. H NMR spectrum, δ, ppm:
1.61 s (3H), 1.63 s (3H), 2.63 s (1H), 3.63 s (1H),
7.46–7.55 m (5H), 7.88 t (2H, J = 1.1, 7.06 Hz,),
8.23 d (2H, J = 8.6 Hz). Electronic absorption spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

MAHMOODI et al.
888
2-Isobutyl-2-methyl-6-(4-nitrophenyl)-4-phenyl-
2-(4-Methoxyphenyl)-6-(4-nitrophenyl)-4-phen-
yl-1,3-diazabicyclo[3.1.0]hex-3-ene (VIII). Yield
78%, colorless solid with mp 162–163°C. IR spectrum,
ν, cm–1: 3050, 3000, 2950, 2850, 1600, 1570, 1520,
1510, 1440, 1340, 1250, 1170, 1030, 860, 790, 765,
1,3-diazabicyclo[3.1.0]hex-3-ene (IV). Yield 65%,
colorless solid with mp 147–148°C. IR spectrum, ν,
cm–1: 3050, 2950, 2900, 2850, 1600, 1570, 1510, 1440,
1
1340, 1100, 940, 860, 760, 740, 695. H NMR spec-
1
trum, δ, ppm: 1.03 d (3H, J = 6.6 Hz, 3H), 1.07 d (3H,
J = 6.6 Hz), 1.57 s (3H), 1.77–1.87 m (2H), 1.94–
1.98 m (1H), 2.64 s (1H), 3.52 s (1H), 7.44–7.53 m
(5H), 7.87 d (2H, J = 7.4 Hz), 8.2 d (2H, J = 8.6 Hz).
Electronic absorption spectrum, λmax, nm: 281, 401.
Found, %: C 72.15; H 6.62; N 12.01. C21H23N3O2.
Calculated, %: C 72.18; H 6.63; N 12.03.
740, 690. H NMR spectrum, δ, ppm: 2.54 s (1H),
3.79 s (1H), 3.81 s (3H), 6.78 s (1H), 6.9 d (2H, J =
8.4 Hz), 7.42 d (2H, J = 8.5 Hz), 7.45 d (2H, J =
8.4 Hz), 7.53 t (2H, J = 7.5 Hz), 7.59 t (1H, J =
7.3 Hz), 8.02 d (2H, J = 7.6 Hz), 8.19 d (2H, J =
8.4 Hz). Electronic absorption spectrum, λmax, nm: 283,
408. Found, %: C 71.66; H 4.97; N 10.91. C23H19N3O3.
Calculated, %: C 71.67; H 4.97; N 10.90.
6-(4-Nitrophenyl)-4-phenyl-2-(2-phenylethyl)-
1,3-diazabicyclo[3.1.0]hex-3-ene (V). Yield 70%,
colorless solid with mp 169–170°C. IR spectrum, ν,
cm–1: 3100, 3080, 3040, 2900, 2850, 1590, 1570, 1510,
1440, 1340, 1100, 1040, 860, 830, 770, 740, 690.
1H NMR spectrum, δ, ppm: 2.03–2.1 m (1H), 2.28–
2.35 m (1H), 2.67 s (1H), 2.93–3.04 m (2H), 3.61 s
(1H), 5.55 t (1H, J = 6.8, 7.2 Hz), 7.17–7.20 m (1H),
7.25–7.30 m (4H), 7.45–7.55 m (5H), 7.90 d (2H, J =
7.4 Hz), 8.22 d (2H, J = 8.7 Hz). Electronic absorption
spectrum: λmax 290 nm. Found, %: C 75.17; H 5.50;
N 10.95. C24H21N3O2. Calculated, %: C 75.18; H 5.52;
N 10.96.
2-(3,4-Dimethoxyphenyl)-6-(4-nitrophenyl)-4-
phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene (IX). Yield
78%, colorless solid with mp 153–154°C. IR spectrum,
ν, cm–1: 3050, 2950, 2900, 2850, 1600, 1570, 1510,
1440, 1410, 1340, 1280, 1250, 1240, 1130, 1020, 980,
1
860, 790, 760, 740, 690. H NMR spectrum, δ, ppm:
2.52 s (1H), 3.79 s (1H), 3.82 s (3H), 3.86 s (3H),
6.76 s (1H), 6.83 d (1H, J = 8.3 Hz), 7.05 d (1H, J =
8.3 Hz), 7.09 d (1H, J = 1.4 Hz), 7.42 d (2H, J =
8.7 Hz), 7.51 t (2H, J = 7.1, 7.7 Hz), 7.56 t (1H, J =
7.2, 7.3 Hz), 8.00 d (2H, J = 7.2 Hz), 8.17 d (2H, J =
8.7 Hz). Electronic absorption spectrum, λmax, nm: 282,
409. Found, %: C 69.37; H 5.07; N 10.07. C24H21N3O4.
Calculated, %: C 69.39; H 5.10; N 10.11.
6-(4-Nitrophenyl)-4-phenyl-2-(1-phenylethyl)-
1,3-diazabicyclo[3.1.0]hex-3-ene (VI). Yield 71%,
colorless solid with mp 174–175°C. IR spectrum, ν,
cm–1: 3100, 3050, 3020, 2950, 2900, 2860, 1600, 1570,
1510, 1490, 1440, 1340, 1180, 1100, 1040, 1020, 980,
N,N-Dimethyl-2-[6-(4-nitrophenyl)-2-phenyl-1,3-
diazabicyclo[3.1.0]hex-3-en-2-yl]benzenamine (X).
Yield 78%, colorless solid with mp 154–155°C. IR
spectrum, ν, cm–1: 3050, 2850, 2800, 1610, 1590,
1570, 1520, 1505, 1440, 1340, 1040, 860, 805, 765,
1
860, 840, 760, 740, 690. H NMR spectrum, δ, ppm:
1.69 d (3H, J = 6.9 Hz), 2.69 s (1H), 2.87–2.93 m
(1H), 3.5 s (1H), 5.66 d (1H, J = 9.7 Hz), 7.15–7.25 m
(7H), 7.48 t (2H, J = 7.1, 7.7 Hz), 7.54 t (1H, J = 7.2,
7.4 Hz), 7.93 d (2H, J = 7.2 Hz), 8.07 d (2H, J =
8.7 Hz). Electronic absorption spectrum, λmax, nm: 281,
371. Found, %: C 75.14; H 5.49; N 10.95. C24H21N3O2.
Calculated, %: C 75.18; H 5.52; N 10.96.
1
740, 690. H NMR spectrum, δ, ppm: 2.57 s (1H),
2.96 s (6H), 3.76 s (1H), 6.74 d (2H, J = 7.8 Hz),
6.76 s (1H), 7.39 d (2H, J = 7.0 Hz), 7.43 d (2H, J =
8.5 Hz), 7.51 t (2H, J = 7.5 Hz), 7.56 t (1H, J =
7.3 Hz), 8.0 d (2H, J = 7.5 Hz), 8.18 d (2H, J =
8.5 Hz). Electronic absorption spectrum, λmax, nm: 282,
304, 345, 425. Found, %: C 72.31; H 5.52; N 14.04.
C24H22N4O2. Calculated, %: C 72.34; H 5.57; N 14.06.
2-Methyl-2,6-bis(4-nitrophenyl)-4-phenyl-1,3-di-
azabicyclo[3.1.0]hex-3-ene (VII). Yield 78%, color-
less solid with mp 191–192°C. IR spectrum, ν, cm–1:
3100, 3000, 2950, 2850, 1600, 1570, 1510, 1440, 1340,
6-(4-Nitrophenyl)-4-phenyl-2-(2,4,6-trimethyl-
phenyl)-1,3-diazabicyclo[3.1.0]hex-3-ene (XI). Yield
61%, colorless solid with mp 162–163°C. IR spectrum,
ν, cm–1: 3050, 2950, 2900, 2850, 1600, 1570, 1510,
1440, 1340, 1040, 1020, 960, 850, 760, 740, 690.
1H NMR spectrum, δ, ppm: 2.26 s (3H), 2.5 s (6H),
2.59 s (1H), 3.65 s (1H), 6.8 s (1H), 6.85 s (2H), 7.4 d
(2H, J = 8.7 Hz), 7.52–7.59 m (3H), 8.02 d (2H, J =
7.1 Hz), 8.14 d (2H, J = 8.6 Hz). Electronic absorption
spectrum, λmax, nm: 281, 405. Found, %: C 75.53;
1
1240, 1140, 1100, 940, 860, 770, 740, 690. H NMR
spectrum, δ, ppm: 1.86 s (3H), 2.93 s (1H), 3.63 s
(1H), 7.48 t (2H, J = 7.4, 7.6 Hz), 7.5 t (1H, J =
7.3 Hz), 7.63 d (2H, J = 8.6 Hz), 7.94 d (2H, J =
7.4 Hz), 8.10 d (2H, J = 8.7 Hz), 8.25 d (2H, J =
8.7 Hz), 8.26 d (2H, J = 8.5 Hz). Electronic absorption
spectrum, λmax, nm: 280, 408 nm; Found, %: C 66.62;
H 4.35; N 13.50. C23H18N4O4. Calculated, %: C 66.66;
H 4.38; N 13.52.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 4 2010

NMR STRUCTURAL ELUCIDATION AND PHOTOCHROMIC BEHAVIOR
889
3. Sasaki, K. and Nagamura, T., J. Appl. Phys., 1998,
vol. 83, p. 2894.
4. Chen, Q., Hiraga, T., Men, L., Tominaga, J., and
H 5.81; N 10.55. C25H23N3O2. Calculated, %: C 75.54;
H 5.83; N 10.57.
2-(4-Fluorophenyl)-6-(4-nitrophenyl)-4-phenyl-
1,3-diazabicyclo[3.1.0]hex-2-ene (XII). Yield 80%,
colorless solid with mp 165–166°C. IR spectrum, ν,
cm–1: 3050, 1600, 1510, 1440, 1340, 1220, 1180, 1100,
1040, 1020, 990, 880, 860, 800, 770, 760, 690.
1H NMR spectrum, δ, ppm: 2.48 s (1H), 3.80 s (1H,),
6.78 s (1H), 7.06 t (2H, J = 8.6 Hz), 7.42 d (2H, J =
8.6 Hz), 7.53 t (4H, J = 7.7 Hz), 7.58 t (1H, J =
7.3 Hz), 8.00 d (2H, J = 7.4 Hz), 8.19 d (2H, J =
8.6 Hz). Electronic absorption spectrum: λmax 285 nm.
Found, %: C 70.75; H 4.30; F 5.07. N 11.22.
C22H16FN3O2. Calculated, %: C 70.77; H 4.32; F 5.09;
N 11.25.
Atoda, N., J. Luminescence, 2000, vol. 87, p. 776.
5. Sharifzadeh, B., M.S. Thesis, University of Guilan,
2006; Kiyani, H., M.S. Thesis, University of Guilan,
2004.
6. Mahmoodi, N.O. and Hajati, N., J. Chin. Chem. Soc.,
2002, vol. 49, p. 91.
7. Mahmoodi, N.O. and Mostaghni, F., J. Korean Chem.
Soc., 2002, vol. 46, p. 52.
8. Arvand, M., Moghimi, A.M., Afshari, A., and
Mahmoodi, N.O.. Anal. Chim. Acta, 2006, vol. 579,
p. 102.
9. Zanjanchi, M.A., Arvand, M., Islamnezhad, A., and
Mahmoodi, N.O., Talanta, 2007, vol. 74, p. 125.
Molecular sieve MCM-41 was prepared by a room
temperature synthesis using tetraethyl orthosilicate
(Merck No. 800658) as source of silicon and hexa-
decyltrimethylammonium bromide as surfactant. Addi-
tion of ethylamine to the reaction mixture favored
preparation of more structurally ordered and stable ma-
terial having a high surface area. To remove occluded
template molecules from MCM-41 channels, the prod-
uct was heated in a muffle furnace for 5 h at 550°C.
10. Heine, H.W., Weese, R.H., and Cooper, R.A., J. Org.
Chem., 1967, vol. 32, p. 2708.
11. Mahmoodi, N.O., Zanjanchi, M.A. and Kiyani, H.,
J. Chem. Res., 2004, p. 438.
12. Mahmoodi, N.O. and Kiyani, H., Bull. Korean Chem.
Soc., 2004, vol. 25, p. 1417.
13. Mahmoodi, N.O., Yazdanbakhsh, M.R., Kiyani, H., and
Sharifzadeh, B., J. Chin. Chem. Soc., 2007, vol. 54,
p. 635.
14. Mahmoodi, N.O., Tabatabaeian, K., and Kiyani, H.,
Abstracts of Papers, Int. Symp. Advances in Synthetic
and Medicinal Chemistry, St. Petersburg, 2007, p. 225.
The authors thank the Research Council of
University of Guilan for financial support.
15. Do Minh, T. and Trozzolo, A.M., J. Am. Chem. Soc.,
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