Synthesis and photochromic properties of new heterocyclic derivatives of 1,3-diazabicyclo[3.1.0]hex-3-ene

Article abstract of DOI:10.1002/jccs.200700091

The facile synthesis of several 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with varying substitutions such as 2-methyl-6-(4-nitrophenyl)-2,4- diphenyl-(1), 2-methyl-6-(4-nitrophenyl)-4-phenyl-2-(pyridin-3-yl)-(2), 2-(furan-2-yl)-6-(4-nitrophenyl)-4-phenyl-(3), 2-(furan-2-yl)-6-(3-nitrophenyl)- 4-phenyl-(4), 6-(3-nitrophenyl)-2,4-diphenyl-(5) and 6-(4-chlorophenyl)-4-(3- nitrophenyl)-2-phenyl-(6) that all behave as "intelligent materials" are reported.

Full text of DOI:10.1002/jccs.200700091

Journal of the Chinese Chemical Society, 2007, 54, 635-641
635
Synthesis and Photochromic Properties of New Heterocyclic Derivatives
of 1,3-diazabicyclo[3.1.0]hex-3-ene
Nosrat O. Mahmoodi,* Mohammad R. Yazdanbakhsh, Hamzeh Kiyani and Bahman Sharifzadeh
Chemistry Department, Faculty of Science, Guilan University, P.O. Box 41335-1914, Rasht, Iran
The facile synthesis of several 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with varying substitu-
tions such as 2-methyl-6-(4-nitrophenyl)-2,4-diphenyl-(1), 2-methyl-6-(4-nitrophenyl)-4-phenyl-2-
(pyridin-3-yl)-(2), 2-(furan-2-yl)-6-(4-nitrophenyl)-4-phenyl-(3), 2-(furan-2-yl)-6-(3-nitrophenyl)-4-
phenyl-(4), 6-(3-nitrophenyl)-2,4-diphenyl-(5) and 6-(4-chlorophenyl)-4-(3-nitrophenyl)-2-phenyl-(6)
that all behave as “intelligent materials” are reported.
Keywords: Aziridine ring; Imine ylide; 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives; Intelligent
material; Photochromism.
INTRODUCTION
Photochromism is a vast field encompassing well-
of aziridine derivatives has therefore attracted considerable
attention, and the search for a means of rapid access to
these heterocycles and their diverse biological properties is
well documented in the literature.4
known phenomena associated with reversible transforma-
tions a and b, having different absorptions upon irradiation
with UV and visible light (Fig. 1).
Functionalized aziridines are an extremely important
class of compounds; as they are precursors of new biologi-
cally active compounds, they are very useful synthetic in-
termediates.1
RESULTS AND DISCUSSION
Our research in this area has been concerned with the
synthesis of 1,3-diazabicyclo[3.1.0]hex-3-ene derivatives
with varying substitutions and their application as photo-
chromics and in photoreproduction.5 The synthesis of sev-
eral fluorescence emission producers based on symmetri-
cal and unsymmetrical trisannelated benzene constructions
and several related photochromic compounds was at-
tempted.6,7 Here we describe an effiecient approach to the
synthesis of stereodefined bridgehead aziridines 1-6 (Fig.
2) with varying heterocyclic substitutions at the 2-position.
According to the recorded UV-Vis spectra all are consid-
ered as positive photochromism compounds and behave as
intelligent materials.8
Study of photochromic materials has drawn great at-
tention to their significant application in optical data stor-
age, holographic storage, solar cells, and as sensitizers. In
this chemical process, a compound undergoes a reversible
change between two states having separate absorption
spectra, i.e. different colors. Typical photochromic optical
switching devices include ophthalmic and sunglass lenses.2,3
Various photochromic dyes have been developed to im-
prove major photochromic properties such as reversibility
and stability. Examination of new methods of the synthesis
H
Currently, there are no published data available on the
synthesis of 1-4 with the heterocyclic moieties at the 2 po-
sition of imidazol (d ring, Fig. 3). Synthesis of compound 6
with substitution on the b ring for the first time is reported.
A synthesis sequence for the preparation of the precursor
aziridine 12c has not been previously reported (Scheme II).
In our approach to aziridine 12c, the dibromination of 8
Ar1
Ar3
H
Ar3
hv
1
N
N
N
N
Ar1
Ar2
hv
R
2
Ar2
R
b
a
Fig. 1
* Corresponding author. E-mail: Mahmoodi@guilan.ac.ir

636 J. Chin. Chem. Soc., Vol. 54, No. 3, 2007
Mahmoodi et al.
was made practical by the addition of Br2/CHCl3 to a solu-
tion of chalcone 8. Employment of the same brominating
procedure to the other 4,4¢-disubstitutedchalcone with sub-
stitutions such as (R1 = OCH3, R2 = NO2; R1 = NO2, R2 =
OCH3 and R1 = OCH3, R2 = OCH3) failed. The molecular
creation of the color produced upon contact of the light is
quite notable. Irradiation after 20 min with 254 nm light in
ethanol of colorless 1a-6a with UV light causes heterolytic
cleavage of the aziridine ring in a conrotatory fashion (s2s
+ n2s) and opens to form a double charged imine ylide
mainly colored highly conjugated species 1b-6b (Scheme
I). Upon UV irradiation, a solution of colorless or weakly
colored solid 1a-6a becomes colored.
to involve a conrotation which is a symmetry-allowed con-
certed process.
Treatment of the dibromides 10a-10c with a saturated
solution of ammonia in ethanol initiates a series of three
consequence reactions which ultimately lead to the in situ
formation of aziridines 13 via intermediates of 11 and 12
((1,2-E2 reaction of HBr) and (Michael addition of NH3)),
followed by an intramolecular nucleophilic substitution.12
A subsequent addition of ammonia to either the carbonyl
groups of 14 (path a) or alternatively, to the carbonyl of al-
dehydes or ketones and formation of aldimine (path b)
yielded the desired 1a-8a. In the typical procedure for prep-
aration of 1a-8a, instead of the more traditional 1 mmol
gaseous ammonia and 1 mmol NH4Br in absolute ethanol, 5
mmol NH4OOCCH3 and1 mmol NH4Br in absolute ethanol
also work very well; in this case, the reaction was com-
pleted after 4 days instead of 1 week.
The photochromic properties of solutions of 1b-6b
were assigned based upon their UV-visible absorption spec-
tra in ethanol, toluene, ether, ketone and ester solutions. In
our procedure the ethanol mostly works well. Irradiation of
the powder of 5a in an electric field produced a significant
increase (~1.13%) of the total capacitance which we as-
cribe to the formation of the dipolar intermediate. The back
reaction usually occurred thermally (photochromism of
type T) or photochemically (photochromism of type P) in
the solid phase. The key for success of this typical photo-
chemical reaction arose from an intramolecular rearrange-
ment of chemical bonds. The internal reflection ir spectrum
of the irradiated solid of 5a discovered new bands at 1450,
1320, and 1270 cm-1; the latter two bands may be ascribed
to an extensively conjugated nitro group in the colored in-
termediate. The IR (KBr) spectrum of other solids 1-4 and
6 remained almost identical for a-b isomers.
The UV-visible spectrum of 1-6 in ethanol solution
exhibits absorption maximums at 282 nm for 1a, 270 nm
Fig. 3. Compounds 6 with three stereocenters are cre-
ated and only one of the possible diastereoisomers
is produced as a racemic mixture of (2R,5R,6S)
and (2S,5S,6R)-6-(4-chlorophenyl)-4-(3-nitro-
phenyl)-2-phenyl-1,3-diazabicyclo[3.1.0]hex-
3-ene.
Diffuse reflectance spectra of solid-state 5a-Al-MCM-
41 after five min irradiation with UV indicate a maximum
at 594 and 668 nm.9 The two possible ylides derived from
1a are syn- and anti- (Scheme I). The syn structure appears
NO
2
O N
2
R
1
H
Cl
H
H
H
R
2
NO
2
N
N
X
N
N
N
N
N
N
CH
3
X
H
H
5
3) R = NO , R = H, X = O
1
6
1 = X = CH
2 = X = N
2
2
4) R = H, R = NO , X = O
1
2
2
Fig. 2

Preparation of Intelligent Diazabicyclic Compounds
J. Chin. Chem. Soc., Vol. 54, No. 3, 2007 637
Scheme I
Scheme II
O
O
Br
10
O
R
R
R
3
2
R
R
3
2
R
R
R
3
2
1
i
ii
Br
Br
1
9
R
1
a) R = NO , R = H, R = H
1
11
2
2
3
b) R = H, R = NO
2
, R = H
3
1
2
c) R = Cl, R = H, R3 = NO
1
2
2
R
R
3
3
R
3
R
1
R
O
1
R
R
O
1
2
H
HN
iii
H
H
H
R
Br
2
R
2
H
Path a
H
N
H
N
H
14
H
H N
2
13
12
O
NH
iii path b
H
H
R
R
R
1
3
R
R
1
R
3
H
-H O
2
2
2
H
NH
OH
R'
N
H
N
N
R'
R
R
15
1a-8a

638 J. Chin. Chem. Soc., Vol. 54, No. 3, 2007
Mahmoodi et al.
Table 1. Physical properties of all synthesized compounds
m.p
No
IR (KBr) cm-1 Ms spectra
1H NMR (500 MHz) & 13C NMR (125 MHz) (CDCl3) d ppm
Yield %
°C
1a
3100, 3060, 3990, 2940, 2850, 1595,
1515, 1440, 1340, 1240, 1140, 760,
590; MS: (M+): (EI); exact mass:
calcd for C23H19N3O2, 369.1477;
Found 369.1476.
1.9 (s, 3H), 2.9 (s, 1H), 3.6 (s, 1H), 7.3 (t, 1H, J = 6.9, 7.1
Hz), 7.4-7.5 (m, 4H), 7.5 (t, 1H, J = 6.9 Hz), 7.6 (d, 2H, J =
8.4 Hz), 7.9 (d, 1H, J = 8.0 Hz), 7.9 (d, 2H, J = 8.0 Hz), 8.3
(d, 2H, J = 8.0 Hz,); 13C NMR, 42.3, 58.3, 93.4, 122.1,
123.1, 126.3, 127.7, 129.4, 129.5, 130.0, 131.4, 132.7,
133.3, 140.6, 141.1, 148.9, 171.8.
186-187
65.5
(EtOH)
2a
3a
4a
3100, 3050, 3000, 2980, 1600, 1510,
1445, 1340, 925; MS: (M+): (EI);
exact mass: calcd for: C22H18N4O2,
370.1430; Found 370.1430.
1.9 (s, 3H), 2.9 (s, 1H), 3.6 (s, 1H), 7.3 (t, 1H, J = 4.8, 7.9
Hz), 7.5 (t, 2H, J = 7.6 Hz), 7.6 (d, 2H, J = 8.5 Hz), 7.9 (d,
2H, J = 7.6 Hz), 8.2 (d, 1H, J = 7.9 Hz), 8.2 (d, 2H, J = 8.5
Hz), 8.6 (d, 1H, J = 4.3 Hz), 9.1 (s, 1H); 26.8, 44.3, 57.3,
97.8, 123.7, 124.3, 128.0, 129.1, 129.4, 131.8, 132.5, 134.2,
143.0, 145.9, 148.2, 148.8, 149.0, 169.9.
194-195
169-170
56
(EtOH)
3100, 3050, 2890, 1600 (C=N), 1575, 2.9 (s, 1H), 3.8 (s, 1H), 6.3 (dd, J = 3.0, 1.55, 2.9 Hz, 1H),
75
1510 (N=O), 1345 (N=O), 1280,
1100, 740, 690; MS: (M+): (EI);
exact mass: calcd for C20H16N2O.
Exact Mass: 345.1113; Found 345:
345.3514.
6.7 (s, 1H), 7.5 (d, 2H, J = 8.8 Hz), 7.5 (d, 1H, J = 4.8 Hz),
7.5 (d, 2H, J = 7.6 Hz), 7.5 (d, 2H, J = 7.6 Hz), 8.0 (d, 2H, J
= 7.3 Hz), 8.2 (d, 2H, J = 8.6 Hz); 42.9, 58.3, 93.4, 122.1,
123.6, 126.5, 127.0, 127.8, 129.0, 129.4, 129.9, 131.8,
132.5, 133.3, 140.6, 141.0, 149.0, 171.6.
(EtOH)
blue
3100, 3050, 2890, 1600 (C=N), 1575, 2.7 (s, 1H), 3.8 (d, 1H, J = 0.6 Hz), 6.9 (s, 1H), 7.00 (dd, 1H, 176-177
33
1510 (N=O), 1345 (N=O), 1280,
1100, 740, 690; (EI); exact mass:
calcd for C20H15N3O3. Exact Mass:
345.1113; Found 345.1113.
J = 3.6, 3.7 Hz), 7.2 (dd, 1H, J = 0.8, 1.3 Hz), 7.3 (d, 1H, J =
5.4 Hz), 7.5 (d, 1H, J = 3.5), 7.5 (d, 1H, J = 2.8 Hz), 7.5 (d,
1H, J = 2.4 Hz), 7.6 (t, 1H, J = 7.5 Hz), 7.62 (d, 1H, J = 7.6
Hz), 8 (d, 2H, J = 7.6 Hz), 8.1 (dd, 1H, J = 1.3, 0.9 Hz), 8.2
(s, 1H), 42.7, 58.4, 93.5, 122.2, 123.1, 126.1, 126.4, 127.5,
129.1, 129.4, 129.9, 133.3, 140.6, 141.0, 149.0, 171.6.
2.5 (s, 1H), 3.8 (s, 1H), 6.8 (s, 1H), 7.3 (t, 1H, J = 7.4 Hz),
7.4 (t, 2H, J = 7.5 Hz), 7.4-7.6 (m, 7H), 8.00 (d, 1H, J = 8
Hz), 8.12 (s, 1H), 42.1, 58.3, 96.7, 124.2, 127.8, 128.09,
128.4, 129.0, 129.1, 129.4, 132.2, 132.4, 139.2, 141.9, 142.6
146.1, 147.8, 171.0.
(MeOH)
5a
6a
3050, 3020, 2900, 1610, 1570, 1525,
1480, 1440, 1340, 1040, 790, 690;
MS: (M+): (EI); exact mass:
C22H17N3O2, 355.1321; Found,
355.1323.
139-140
202-206
68
(EtOH)
3010, 3020, 2900, 1605, 1575, 1510,
1490, 1440, 1340, 1040, 780, 695;
MS: (M+): (EI); exact mass: calcd for
C22H16ClN3O2: 389.0931, Found;
389.0930.
2.5 (s, 1H), 3.7 (s, 1H), 6.8 (s, 1H), 7.18 (d, 2H, J = 8.4 Hz),
7.3 (s, 1H), 7.31 (t, 2H, J = 7.0 Hz), 7.4 (t, 2H, J = 7.6 Hz),
7.5 (d, 2H, J = 7.4 Hz), 7.7 (t, 1H, J = 8.0 Hz), 8.3 (d, 1H, J
= 7.7 Hz), 8.4 (dd, 1H, J = 1.2 Hz), 8.8 (s, 1H), 42.1, 52.9,
96.4, 123.2, 126.0, 127.4, 127.1, 127.1, 128.6, 128.7, 129.9,
133.5, 133.7, 134.0, 135.1, 138.3, 148.6, 168.9.
65
(EtOH)
blue
for 2a, 284 nm for 3a, 284 nm for 4a, 277 nm for 5a and 275
nm for 6a, respectively. By comparison, for the zwiterionic
double charged imine ylide, 20 min UV irradiation causes
absorption in the visible range maximum at 300, 420 for
1b, maximum at 400, 260, 230 nm for 2b, maximum at 284,
405 nm for 3b, 283, 420 nm for 4b, 278, 370 nm for 5b, and
362, 280 nm for 6b, respectively, due to the breaking of the
aziridine ring and formation of a conjugation system. Ab-
sorption spectra changes of colorless 1a-6a (1.4 ´ 10-4
mol-1 dm-3 in EtOH; cell length 1 cm), irradiation time/min,
0, 0.5, 1, 5, 10, 15, and 20 were obtained immediately after
254-nm light irradiation, respectively. All spectra afforded
the photostationary states, respectively. The quantum yields
for the formation of 1b-6b after 20 min irradiation with 254
nm light in EtOH on parallel irradiation of samples of iden-
tical volumes and concentrations have been determined
(Table 2).
The 13C NMR of recrystallized 2a and 6a both showed
18 peaks, correspondingly. Considering the 1H NMR spec-
tra of 1a-6a the proton-proton coupling between hydrogens
on C5 and C6 in the aziridine ring in such a rigid system is
about 0 Hz (in accord with the vicinal Karplus correlation,
presumably the f ~ 90°).
In the upfield region of 1H NMR for all compounds

Preparation of Intelligent Diazabicyclic Compounds
J. Chin. Chem. Soc., Vol. 54, No. 3, 2007 639
EXPERIMENTAL SECTION
Table 2. Quantum yields for photochromic conversion of 1a-8a
to 1b-8b
Chemicals were purchased from Fluka, Merck, and
Aldrich. Melting points are uncorrected and determined by
a Mettler Fp5 melting point apparatus. IR spectra were ob-
tained on a Shimadzu IR-470. Products were characterized
by IR, NMR, GC-MS, TLC, and m.p.). All NMR data were
recorded in CDCl3 using a Bruker Avance 500-MHz spec-
trometer. Chemical shifts are reported in ppm (d) using
TMS as internal reference. Mass spectra were obtained
from a GC-MS Agilent Technologies QP-5973N MSD in-
strument. The UV/Vis spectra were recorded on a Shimadzu
UV-2100. The 4-nitrochalcone and 2,3-dibromo-4-nitro-
chalcone were prepared according to a standard proce-
dure.12
Entry
Fa
Fb
Fc
Fd
Fss
1a
2a
3a
4a
5a
6a
7a
8a
0.11
0.27
0.38
0.35
0.23
0.16
0.40
0.33
0.23
0.22
0.27
0.26
0.40
0.28
0.07
0.04
0.06
0.25
0.09
0.04
0.01
0.05
0.04
0.03
0.01
0.01
0.10
0.10
0.01
0.01
0.02
0.02
0.42
0.75
0.85
0.75
0.65
0.50
0.54
0.42
0.10 M EtOH solutions irradiated at 254 nm Uv-Vis. ss Total
quantum yield for conversion of isomer a to isomer b in EtOH at
stationary states (~ after 20 min); a Maximum quantum yields
obtained upon 0-5 min; b Maximum quantum yields obtained
upon 5-10 min; c Maximum quantum yields obtained upon 10-15
min; d Maximum quantum yields obtained upon 15-20; the
convergent after 20 min is insignificant and was ignored.
Synthesis of 2,3-dibromo-4-nitrochalcone (10a;
C15H11NO3Br2)
1a-6a just two singlets for C5 and C6 protons were ob-
served. Spectroscopic data for all compounds are shown in
(Table 1).
The 4-nitrochalcone 9a was prepared according to a
standard procedure.11 4-Nitrochalcone (0.413 g, 1 mmol)
was dissolved in 12 mL CHCl3 inside a hood. Then, 5 mL
bromine-CHCl3 was added dropwise to the cooled homog-
enous 4-nitochalcone solution with stirring at room tem-
perature. After 5-10 minutes, the bromine color was dis-
charged and a lemon yellow solution remained. At this
point, an additional 0.5-1 mL of the bromine-CHCl3 solu-
tion was added. When the bromine color persists for longer
than 30 min., the reaction is completed. The solution was
evaporated under vacuum. The solid residue was purified
by silicagel column chromatography and recrystallized
from CH2Cl2/hexane to afford a white solid 0.493 g (98%
yield) m.p. = 137-139 °C. IR (KBr): 3050, 1680, 1590,
1522, 1342, 1265, 1220, 1100, 980, 844, 775, 720, 484,
620, 570 cm-1; 1H NMR (CDCl3) d: 5.7 (d, J = 11.2 Hz, 1H),
5.8 (d, J = 11.5 Hz, 1H), 7.6 (t, J = 7.7 Hz, 1H), 7.8 (m, 3H),
1H NMR of 7 and 8 with 4-NO2-Ph-, and 4-CH3-Ph-,
substitutions at the carbon-2 of imidazole rings, both indi-
cate the equilibrium ratio between 7a:7b and 8a:8b isomers
at steady states upon exposure to room light. The 1H NMR
of compound 7 consists of a virtually pure mixture of 7a
and 7b. This is best ascertained by monitoring the total in-
tegral for the two characteristic singlets for each isomer,
e.g. 4-Me and 2-H. Thus, the ratio of the combined integral
for the peaks at d = s, 2.4 (4-Me) and s, 6.3 (C2-H) for 7a to
corresponding peaks 7b at d = s, 2.3 and s, 6.8 was 1.95 to
1.33 ca for 7a:7b, ~60:40% in equilibrium (Scheme III).
For 8a:8b this ratio at steady state was found to be ~67:33.
Therefore, the a-b percentage is the upper limit of the quan-
tum yield at room temperature compared to 1a-6a.
Scheme III

640 J. Chin. Chem. Soc., Vol. 54, No. 3, 2007
8.1 (d, J = 7.7 Hz, 2H), 8.3 (d, 8.5 Hz, 2H) ppm.
Mahmoodi et al.
mass: calcd for C15H12N2O3 268.2674; Found 268.2671.
Synthesis of 2,3-dibromo-3-nitrochalcone (10b;
C15H11NO3Br2)
Synthesis of (3-(3-chlorophenyl)aziridin-2-yl)(3-nitro-
phenyl)methanone (13c; C15H11ClN2O3)
A similar procedure as used for 13a was applied. The
solid residue was purified by silicagel column chromatog-
raphy and recrystallized from CH2Cl2/hexane to afford a
white solid 0.201 g (73% yield) m.p. = 150-153 °C. IR
(KBr): 3250, 3050, 1675, 1590, 1520, 1350, 1255, 1220,
1100, 1010, 930, 845, 770, 730, 705, 680 cm-1; 1H NMR
(CDCl3) d: 2.7 (br, 1H), 3.2 (s, 1H), 3.5 (s, 1H), 7.3 (t, J =
8.44, 2H), 7.4 (d, J = 2.2, 2H), 7.7 (t, J = 8.0 Hz, 1H), 8.3
(dd, J = 1.0 Hz, 1H), 8.5 (dddd, J = 1.0 Hz, 1H), 8.8 (t, J =
1.43 Hz, 1H) ppm; 13C NMR (CDCl3): d; 43.8, 44.2, 123.2,
127.6, 128.1, 128,9, 130.2, 133.7, 134.1, 136.3, 137.1,
148.6. MS: (M+): (EI); exact mass: calcd for C15H11ClN2O3,
302.0458; Found 302.0456.
A similar procedure as used for 10a was applied. The
solid residue was purified by silicagel column chromatog-
raphy and recrystallized from CH2Cl2/hexane to afford a
white solid 0.388 g (94% yield) m.p. = 126-129 °C. IR
(KBr): 3050, 3000, 1680, 1570, 1520, 1440, 1344, 1270,
1220, 980, 840, 810, 720, 680, 580 cm-1; 1H NMR (CDCl3)
d: 5.7 (d, J = 11.3 Hz, 1H), 5.8 (d, J = 11.2 Hz, 1H), 7.6 (t, J
= 7.7 Hz, 2H), 7.7 (t, J = 7.9 Hz, 1H), 7.8 (t, J = 7.3 Hz, 1H),
7.9 (d, J = 7.7 Hz, 1H), 8.1 (d, J = 7.6 Hz, 2H), 8.3 (dd, J =
0.7, 8.1 Hz, 1H), 8.5 (s, 1H) ppm.
Synthesis of (3-(4-nitrophenyl)aziridin-2-yl)(phenyl)-
methanone (13a; C15H12N2O3)
A total of 3 mL solution of concentrated ammonia
was added to a solution of 2,3-dibromo-4-nitrochalcone
(0.413 g, 1 mmol) in 6 mL of 96% EtOH with stirring at
room temperature. After 4 days, the reaction mixture was
filtered, the solid was washed with methanol and dried in
the air, and the resulting residue was purified with a silica
gel column and recrystallized from ethanol to give an or-
ange solid 0.196 g (73% yield) m.p = 139-140 °C lit13
136.8-137 °C. IR (KBr): 3260, 3050, 1662, 1600, 1512,
Preparation of 4-methyl-6-(4-nitrophenyl)-2,4-diphen-
yl-3,5-diazabicyclo[3.1.0]hex-3-ene: A Typical Proce-
dure (1a; C23H19N3O2)
(3-(4-Nitrophenyl)aziridin-2-yl)(phenyl)methanone
13a (0.268 g, 1 mmol), NH4Br (0.1 g, 1 mmol) and the ap-
propriate ketone (1 mmol) were dissolved in 6 mL of abso-
lute ethanol and stirred at room temperature. Anhydrous
gaseous ammonia is gently blown into the reaction mixture
for several hours. Alternatively, instead of gaseous ammo-
nia, 5 mmol NH4OOCCH3 was used. In this case, the reac-
tion was completed after 4 days instead of 1 week. A color
change in the reaction mixture from orange into blue or
greenish blue is characteristic for product formation. The
reaction mixture was filtered, washed with ethanol, dried in
the air and the resulting solid recovered 0.36 g (97.45), pu-
rified by silica gel column chromatography and recrystal-
lized by ethanol (65.5% yield), methanol or some other
suitable solvent. The color of 1a changes from colorless to
1b gray m.p. = 186-187 °C. Spectroscopic data and yield
for all of compounds 1a-6a are shown in (Table 1).
1
1445, 1343, 1265, 1230, 1020, 825, 747, 710 cm-1; H
NMR (CDCl3) d: 2.8 (br, t, J = 8.5 Hz, 1H), 3.3 (dd, J = 2.0,
9.2 Hz, 1H), 3.5 (dd, J = 2.1, 8.1 Hz, 1H), 7.5-7.6 (m, 4H),
7.66 (t, J = 7.4 Hz, 1H), 8.0 (d, J = 7.5 Hz, 2H), 8.2 (d, J =
8.6 Hz, 2H) ppm. MS: (M+): (EI); exact mass: calcd for
C15H12N2O3 268.2674, Found 268.2673.
Synthesis of (3-(3-nitrophenyl)aziridin-2-yl)(phenyl)-
methanone (13b; C15H12N2O3)
A similar procedure as used for 13a was applied. The
solid residue was purified by silicagel column chromatog-
raphy and recrystallized from CH2Cl2/hexane to afford a
white solid 0.185 g (69% yield) m.p. = 97-98 °C. IR (KBr):
3260, 3050, 1660, 1590, 1520, 1350, 1260, 1220, 1080,
1010, 920, 840, 770, 730, 705, 680 cm-1; 1H NMR(CDCl3)
d: 2.8-2.8 (br, t, J = 8.6 Hz, 1H), 3.3 (dd, J = 2, 9.3 Hz, 1H),
3.6 (dd, J = 2.1, 8.1 Hz, 1H), 7.5-7.6 (m, 3H), 7.7 (t, J = 7.4
Hz, 1H), 7.7 (d, J = 7.7 Hz, 1H), 8.0 (d, J = 7.6 Hz, 1H), 8.2
(d, J = 8.6 Hz, 1H), 8.3 (s, 1H) ppm. MS: (M+): (EI); exact
ACKNOWLEDGMENTS
We thank the Research Committee of Guilan Univer-
sity for their financial support. We also acknowledge the
useful suggestions made by Professor John L Belletire of
Adelphia Pharma, U.S.A., and Professor D. Fry of Norac

Preparation of Intelligent Diazabicyclic Compounds
Pharma, U.S.A.
J. Chin. Chem. Soc., Vol. 54, No. 3, 2007 641
Kiyani, H. J. Chem. Res. 2004, 438. (c) Mahmoodi, N. O.;
Kiyani, H. Bull. Korean Chem. Soc. 2004, 25, 1417. (d)
Sharifzadeh, B. M. S. Thesis, University of Guilan, January
2006. (e) Kiyani, H. M. S. Thesis, University of Guilan, Oc-
tober 2004.
Received May 22, 2006.
6. Mahmoodi, N. O.; Hajati, N. J. Chin. Chem. Soc. 2002, 49,
91.
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