Ultrasonic-assisted synthesis of 1,3-diaryl-2,2-dichloroaziridine derivatives in the presence of phase-transfer catalyst under low-concentration alkaline conditions

Article abstract of DOI:10.1246/bcsj.20110106

In this research, rapid and efficient preparation of 1,3-diaryl-2,2- dichloroaziridines through the reaction of Schiff base compounds with dichlorocarbene yielded in situ in the presence of cetyltrimethylammonium bromide (CTAB) as phase-transfer catalyst

Full text of DOI:10.1246/bcsj.20110106

1112 Bull. Chem. Soc. Jpn. Vol. 84, No. 10, 1112-1117 (2011)
© 2011 The Chemical Society of Japan
Ultrasonic-Assisted Synthesis of 1,3-Diaryl-2,2-dichloroaziridine
Derivatives in the Presence of Phase-Transfer Catalyst
under Low-Concentration Alkaline Conditions
Hossein Naeimi* and Khadijeh Rabiei
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan 87317, Iran
Received April 12, 2011; E-mail: naeimi@kashanu.ac.ir
In this research, rapid and efficient preparation of 1,3-diaryl-2,2-dichloroaziridines through the reaction of Schiff
base compounds with dichlorocarbene yielded in situ in the presence of cetyltrimethylammonium bromide (CTAB) as
phase-transfer catalyst under ultrasonic irradiation is described. The advantages of this reaction are very short reaction
times, excellent product yields, simplicity of the method, and high purity of products.
The use of ultrasonic waves in organic synthesis has been
boosted in recent years.1-12 Their specificity has been demon-
strated in homogeneous as well as in heterogeneous reac-
tions.13-16 Sonification of multiphase systems accelerates the
reaction by ensuring a better contact between the different
phases.10,11,16 Ultrasound is known to accelerate diverse types
of organic reactions and it is established as an important
technique in organic synthesis.8,17,18 Sonication also increases
the reaction rate and avoids the use of high reaction temper-
atures.10,19 A number of organic reactions have been revisited
by means of ultrasonic waves.8,17,18 Tao et al. have reported the
reaction of amines, amides, imines, alcohols, aldehyde, and
ketones with dichlorocarbene under ultrasound.20 The advan-
tages of ultrasound procedures, such as good yields, short
reaction times, and mild reaction conditions, are well docu-
mented.21
Aziridines, which are extremely important synthetic building
blocks, are nitrogen equivalents of epoxides, and can be
similarly opened in a stereocontrolled manner with various
nucleophiles, providing access to a wide range of important
nitrogen-containing products.22 These compounds are among
the most fascinating intermediates in organic synthesis, acting
as precursors of many complex molecules due to the strain
incorporated in their skeletons.23 Since the first synthesis of
an aziridine reported by Gabriel in 1888,24 the synthetic scope
of aziridine chemistry has blossomed in recent years. Thus,
obtaining aziridines, has become of great importance in organic
chemistry. In particular, the antitumor and antibiotic properties
of a great number of aziridine-containing compounds are of
high significance among other biological properties, which
make them attractive synthetic targets in their own right.25
With attention to the importance of gem-dihaloaziridines,
several methods for their synthesis have been reported. The
preparation has been accomplished by the addition of dichloro-
carbene generated from chloroform, hexachloroacetone, or
ethyl trichloroacetate with the appropriate base26-28 and chloro-
form/NaOH/TEBAC (triethylbenzylammonium chloride) as
phase-transfer catayst29-31 to imines.
Ever since Laurent and Gerhard32 synthesized the first
organic imine by condensation of benzaldehyde with aniline,
numerous investigations have dealt with this class of com-
pounds, also known as Schiff bases. These compounds have
been extensively studied in chemistry due to their facile
syntheses, easily tunable steric and electronic properties and
good solubility in common solvents.33-36
Phase-transfer catalysis (PTC) technology has been widely
applied to synthesize specialty chemicals from organic reac-
tions.37-39 Recently many chemists have investigated phase-
transfer catalysis in numerous reactions. As a result, PTC
is considered to have great potential for industrial-scale
application.40
In conjunction with ongoing work in our laboratory on the
preparation of Schiff base derivatives,41-44 here we decided to
report the synthesis of various dichloroaziridines through the
reaction of various Schiff base compounds and chloroform in
the presence of cetyltrimethylammonium bromide (CTAB) as
phase-transfer catalyst under ultrasonic irradiation.
Results and Discussion
In this research, the phase-transfer-catalyzed reaction of
dichloroaziridination of Schiff base compounds has been
studied under ultrasonic irradiation. When 0.028 mol of Schiff
base compound was reacted with dichlorocarbene intermediate
obtained in situ from the reaction of chloroform and base in the
presence of CTAB as a phase-transfer catalyst under ultrasonic
irradiation, corresponding products, 1,3-diaryl-2,2-dichloro-
aziridine compounds were obtained under low concentration
alkaline conditions (9.3% NaOH) (Scheme 1).
First, we carried out this reaction in the presence of various
amounts of NaOH under two phase-transfer catalysts, namely
CTAB and CPB (1-cetylpyridinium bromide), and ultrasonic
irradiation (55 W). The corresponding results are indicated in
Table 1.
As can be seen in this table, the desired product was obtained
with high yield in the presence of CTAB rather than CPB
as phase-transfer catalyst using NaOH (9.3%). In order to
Published on the web October 15, 2011; doi:10.1246/bcsj.20110106

H. Naeimi et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 10 (2011) 1113
Cl
N
Cl
N
Ultrasonic,
CTAB, NaOH
CHCl3
+
2
H2O
1
2
1
R
R
R
R
1a-i
2a-i
R1 = H, CH3, NO2, Cl
R2 = H, CH3, Cl, Br
Scheme 1. Preparation of 1,3-diaryl-2,2-dichloroaziridine compounds from Schiff bases.
Table 1. Enhancement of Phase-Transfer Catalyst (PTC)
and Ultrasonic Irradiation (55 W) on the Formation of
1-(4-Bromophenyl)-2,2-dichloro-3-(4-chlorophenyl)aziri-
dine in the Presence of Various Amounts of NaOH
Table 2. Survey of the Effect of Ultrasonic Irradiation on
the Formation of 1-(4-Bromophenyl)-2,2-dichloro-3-
(4-chlorophenyl)aziridine under CTAB Catalysis Condi-
tions
Amount of
NaOH/%
Time
/min
Yielda)
/%
Entry
Power/W
Time/min
Yielda)/%
Entry
PTC
1
2
3
4
5
6
7
8
9
35
40
45
50
55
60
65
70
Noneb)
100
90
75
55
25
15
8
80
85
88
90
90
94
98
98
55
1
2
3
4
5
6
7
8
CTAB
CTAB
CTAB
CTAB
CTAB
CPB
5
90
65
50
40
25
45
30
720
50
60
72
80
90
78
84
40
5.6
6.7
8.3
9.3
9.3
12
CPB
Noneb)
8
160
9.3
a) Isolated yields. b) The reaction without PTC under magnetic
stirring.
a) Isolated yields in 9.3% NaOH. b) The reaction without
ultrasonic irradiation.
determine enhancement ultrasound irradiation and phase-trans-
fer catalyst, with performance of this reaction without phase-
transfer catalyst under magnetic stirring, the products were
obtained in low yield and long reaction times (Table 1,
Entry 8).
liquid-PTC systems, cavitational coallapse near the liquid-
liquid interface disrupts the interface and impels jets of one
liquid in to the other forming fine emulsion, leading to a
dramatic increase in the interfacial contact area across which
transfer of species can take place. In the case of PTC reaction
under ultrasonic irradiation, the PTC catalyst initials’ the
reaction by transfer of species across the interface and
ultrasound merely facilitates this transfer, possibly by increas-
ing the interfacial area across which this transfer occurs. Also,
the ultrasonic irradiation increases the production of :CCl2
intermediate and causes the enhancement of addition reaction
rate and thus corresponding products are obtained in excellent
yield and very short reaction times.
To then ascertain the scope and limitation of the present
reaction, several Schiff base compounds were reacted with
CHCl3 in the presence of a mixture of CTAB and the optimum
amount of NaOH (9.3%) under ultrasonic irradiation and the
desired dichloroaziridine derivatives were prepared. The results
are summarized in Table 3. As shown in this table, the reaction
of the various Schiff bases with chloroform and NaOH (9.3%),
were sonicated and catalyzed by CTAB as two-phase transfer.
The corresponding products were obtained in excellent yields
and appropriate reaction times in the presence of PTC under
ultrasonic irradiation.
In continuation of this research, the effect of various powers
of ultrasonic irradiation has been surveyed. Initially we carried
out aziridination of 4-bromo-N-(4-chlorobenzylidene)aniline as
model reaction in order to optimize the best suited reaction
conditions. It was observed that the reaction in the presence of
NaOH 9.3% and ultrasonic irradiation of 65 W afforded the best
result as product was obtained in 98% isolated yield after 8 min
(Table 2, Entry 7), while the reaction in the presence of PTC
without ultrasonic irradiation was carried out in low yield and
long reaction time (Table 2, Entry 9). Sonification of multi-
phasic systems accelerates the reaction by ensuring a better
contact between the different phases. By executing the reaction
under sonication conditions dichlorocarbene reagent was
produced very quickly and thus corresponding products were
obtained in excellent yields and very short reaction times.
The effect of ultrasonic irradiation observed during organic
reactions is due to cavitation. In the case of volatile molecules
cavities are believed to act as a microreactor: as the volatile
molecules enter the microbubbles the high temperature and
pressure produced during cavitation break their chemical bonds
thus reacting with other species.3,45,46
The synthesis of gem-dichloroaziridines in the presence of
PTC under ultrasonic irradiation was compared with previously
reported methods. In this method, CHCl3/NaOH/Schiff base
mol ratio used was 2.5/2.5/1 and the desired product 2a was
obtained in excellent yield (94%) after short reaction time
In the PTC reactions rate enhancements are typically due to
mechanical effects, mainly through an enhancement in mass
transfer. In the presence of ultrasonic irradiation in liquid-

1114 Bull. Chem. Soc. Jpn. Vol. 84, No. 10 (2011)
Ultrasonic-Assisted Synthesis of Dichloroaziridines
Table 3. Synthesis of 1,3-Diaryl-2,2-dichloroaziridine in the Presence of CTAB Catalyst and 9.3% NaOH
under Ultrasonic Irradiation with 65 W Power
Entry
Substrate
Product
Mp/°C
Time/min
Yielda)/%
Cl
Cl
Cl
Cl
N
N
1
2a
2a
2a
2b
100-102
15
94
Cl
N
N
N
2
3
4
98-99
98-99
360
400
12
61b)
55c)
94
Cl
N
Cl
N
Cl
N
143-145
Br
Cl
Cl
Br
Cl
Cl
Cl
N
Cl
Cl
N
5
2c
72-74
12
95
Cl
N
N
N
N
N
6
7
2c
2d
2e
2f
71-72
960
8
68d)
97
98
92
92
96
Cl
Cl
Cl
Cl
N
139-141
134-136
141-143
140-142
146-148
Cl
Br
Cl
Cl
Cl
Cl
Cl
Cl
N
8
8
Br
Cl
N
9
13
14
11
Br
O2N
Br
O2N
Cl
N
Cl
Cl
N
N
10
11
2g
2h
CH3
O2N
H3C
CH3
O2N
Cl
N
Br
Br
H3C
Cl
N
Cl
N
12
2i
128-130
10
97
CH3
Cl
CH3
Cl
a) Isolated yields. b) By hexachloroacetone and sodium methoxide, Ref. 26. c) By sodium methoxide and
chloroform, Ref. 27. d) By potassium t-butoxide and chloroform, Ref. 28.
(15 min) (Table 3, Entry 1), while, in previously reported
methods, (CHCl3 or Cl3COCl3)/NaOCH3/Schiff base mol ratio
used was 4/4/1 and corresponding product was obtained in 55
and 61% yields after several hours in the absence of PTC
(Table 3, Entries 2 and 3).26,27 On the other hand, synthesis of
this compound 2a was reported in the presence of TEBAC as a
PTC without ultrasonic irradiation in which CHCl3/NaOH/
Schiff base mol ratio used was 10/25/1 and the desired product
was obtained in 74 and 88% yields.29,30 Also preparation of
product 2c by using this method was carried out in excellent
yield and very short reaction time that is comparable with the
reported method (Table 3, Entry 5 vs. 6).28 It seems this
method for preparation of gem-dichloroaziridines has some
advantages such as high efficiency, and mild conditions
compared to other protocols.
The structure of products has been confirmed by physical
1
and spectroscopic data such as IR, H NMR, 13C NMR, mass
spectroscopy, and C. H. N. elemental analyses. In the IR

H. Naeimi et al.
Bull. Chem. Soc. Jpn. Vol. 84, No. 10 (2011) 1115
(organic phase)
: CCl2
+
Schiff base
Desired Product
[Q+CCl3]
:CCl2
+
QCl
NaBr
(interface)
(aqueous)
CHCl3
+
NaOH
NaOH
+
QBr
[Q+CCl3] + NaBr + H2O
NaBr
H2O
NaCl
Q=Cetyltrimethylammonium (CTA)
Scheme 2. The proposed reaction mechanism for preparation of gem-dihaloaziridines.
spectra, the stretching frequency of aromatic C=C is formed in
recorded in DMSO/CDCl3 solvents on a Bruker DRX-400
spectrometer with tetramethylsilane as internal reference. Mass
spectra were recorded on a Finnigan MAT 44S by Electron
Ionization (EI) mode with an ionization voltage of 70 eV. The
elemental analyses (C. H. N.) were obtained from a Carlo
ERBA Model EA 1108 analyzer. A BANDELIN ultrasonic HD
3200 with probe model KE 76, 6 mm diameter, was used to
produce ultrasonic irradiation and homogenize the reaction
mixture. Piezoelectric crystals of this kind of probe normally
work in the range of 700 kHz, but using through proper clamps
the output frequency of piezoelectric crystals have been
controlled and reduced to 20 kHz. Therefore, the induced
frequency of probe to the reaction mixture is equal to 20 kHz.
By changing the power of Tip the cavitations rate is displaced
so that the Tip frequency under various amount of power is
constant. A thermal method was used for calibration of
ultrasonic power. Melting points obtained with a Yanagimoto
micro melting point apparatus are uncorrected. The purity
determination of the substrates and reaction monitoring were
accomplished by TLC on silica gel polygram SILG/UV 254
plates (from Merck Co.).
the region between ¯ = 1490-1600 cm¹1. The stretching
vibration of C-H in the alkyl groups appeared at a region
between ¯ = 2898-2930 cm¹1. In the 1H NMR spectra, one
proton of CH-N has a chemical shift at ¤ 3.65-4.40.
The signals around ¤ 6.59-8.55 are assigned to protons of
CH=CH of aromatic rings. In the 13C NMR spectra, one carbon
of C-N has a chemical shift at ¤ 52.1-55.1 and the signal
around ¤ 74.1-77.1 is assigned to one carbon of the CCl2
of aziridine ring.
The Proposed Reaction Mechanism.
The proposed
reaction mechanism for synthesis of diarylaziridines is shown
in Scheme 2. In this reaction, first, the dichlorocarbene (:CCl2)
as reactive intermediate is generated from the interfacial
reaction of chloroform, sodium hydroxide, and quaternary
ammonium salt to form an active complex (QCCl3) of the
dichlorocarbene (:CCl2) precursor.
Second, the active complex QCCl3 (or dichlorocarbene
:CCl2) transfers from the aqueous phase to the organic phase.
Then, dichlorocarbene reacts with Schiff base to produce
1,3-diaryl-2,2-dichloroaziridine in the organic phase.
Typical Procedure for the Synthesis of 1,3-Diphenyl-2,2-
dichloroaziridine. Measured quantities of NaOH (0.07 mol,
2.8 g) and CTAB (0.3 g) were dissolved in 30 mL of water.
The mixed solution was introduced to a 100 mL flask. The
ultrasonic probe was immersed directly in the reactor. The
ultrasonic generator (HD 3200) emitted the 65 W sound
vibration into the reaction mixture for two minutes. Then,
Schiff base (organic reactant; 0.028 mol, 8.2 g) dissolved in
chloroform (0.07 mol, 8.3 mL) was gradually added dropwise
to the mixed solution. The progress of the reaction was
monitored by TLC. After the completion of the reaction in
15 min, the solution was separated and the aqueous solution
was extracted twice with ether. Magnesium sulfate was also
added to adsorb the residual water. The organic solvent
(chloroform) and other residues were stripped in a vacuum
evaporator. The pale yellow solid, 1,3-diphenyl-2,2-dichloro-
aziridine, was obtained in 94% yield, mp 100-102 °C. All of
the diarylaziridine products were identified by physical and
spectroscopic data as follows.
Conclusion
In this research, we have synthesized dichloroaziridine
derivatives through the reaction of various Schiff base com-
pounds with chloroform in the presence of cetyltrimethyl-
ammonium bromide (CTAB) under ultrasonic irradiation. The
corresponding products have been obtained in excellent yields,
high purity, and short reaction times. The products have been
confirmed by physical and spectroscopic data such as; IR,
1H NMR, 13C NMR, MS spectroscopy, and C. H. N. elemental
analyses.
Experimental
Materials. All the materials were of commercial reagent
grade. All the Schiff bases were prepared according to
previously reported procedures.41,42
Apparatus. IR spectra were recorded as KBr pellets on
a Perkin-Elmer 781 spectrophotometer and an Impact 400
1
Nicolet FTIR spectrophotometer. H NMR and 13C NMR were

1116 Bull. Chem. Soc. Jpn. Vol. 84, No. 10 (2011)
1,3-Diphenyl-2,2-dichloroaziridine (2a):
Ultrasonic-Assisted Synthesis of Dichloroaziridines
1
Pale yellow
3090, 2918, 1589, 1490 (C=C, Ar); H NMR (CDCl3): ¤ 2.36
¹1
solid; mp 100-102 °C (mp 98-99 °C);26,27 IR (KBr): ¯/cm
(s, 3H, CH3), 3.89 (s, 1H, HCN), 6.59-8.31 (m, 8H, Ar);
13C NMR (CDCl3): ¤ 21.2, 53.5, 75.2, 119.6, 123.7, 128.9,
129.9, 134.6, 140.3, 141.7, 148.3; MS: m/z 326 (M + 4, 20),
324 (M + 2, 29), 322 (M+, 40), 289 (90), 287 (100), 243 (60),
241 (80), 154 (70), 152 (82), 91 (92); Anal. Calcd for
C15H12Cl2N2O2: C, 55.74; H, 3.74; N, 8.67%. Found: C, 55.75;
H, 3.74; N, 8.67%.
1
3090, 2930, 1600, 1520 (C=C, Ar); H NMR (CDCl3): ¤ 4.20
(s, 1H, HCN), 7.01-7.80 (m, 10H, Ar); 13C NMR (CDCl3):
¤ 52.1, 74.1, 119.0, 120.1, 125.1, 126.1, 127.1, 128.3, 134.2,
140.1; MS: m/z 268 (M + 4, 7), 266 (M + 2, 29), 264 (M+,
45), 233 (34), 231 (54), 229 (100), 154 (55), 152 (86), 77 (95);
Anal. Calcd for C14H11Cl2N: C, 63.65; H, 4.19; N, 5.31%.
Found: C, 63.67; H, 4.19; N, 5.30%.
1-(4-Bromophenyl)-2,2-dichloro-3-(4-methylphenyl)aziri-
¹1
1-(4-Bromophenyl)-2,2-dichloro-3-phenylaziridine (2b):
dine (2h): Yellow solid; mp 146-148 °C; IR (KBr): ¯/cm
¹1
1
White solid; mp 143-145 °C; IR (KBr): ¯/cm 3100, 2914,
3100, 2898, 1600, 1500 (C=C, Ar); H NMR (CDCl3): ¤ 2.31
1600, 1524 (C=C, Ar); 1H NMR (DMSO): ¤ 4.40 (s, 1H,
HCN), 7.10-7.80 (m, 9H, Ar); 13C NMR (DMSO): ¤ 53.4,
77.1, 120.9, 121.3, 127.8, 128.1, 130.1, 131.2, 135.2, 142.1;
MS: m/z 348 (M + 6, 10), 346 (M + 4, 25), 344 (M + 2, 45),
342 (M+, 30), 309 (85), 307 (100), 233 (65), 230 (45), 152
(80), 77 (85); Anal. Calcd for C14H10BrCl2N: C, 49.02; H,
2.94; N, 4.08%. Found: C, 49.15; H, 2.95; N, 4.12%.
1-(4-Chlorophenyl)-2,2-dichloro-3-phenylaziridine (2c):
Pale yellow solid; mp 72-74 °C (mp 71-72 °C);28 IR (KBr):
¯/cm¹1 3090, 2900, 1598, 1499 (C=C, Ar); 1H NMR (CDCl3):
¤ 4.21 (s, 1H, HCN), 7.03-7.90 (m, 9H, Ar); 13C NMR
(CDCl3): ¤ 53.1, 76.9, 119.1, 120.8, 121.1, 127.9, 128.1, 130.1,
131.2, 135.1, 142.2; MS: m/z 304.5 (M + 6, 7), 302.5 (M + 4,
15), 300.5 (M + 2, 32), 298 (M+, 35), 263 (100), 261 (85), 174
(75), 172 (80), 91 (95), 77 (45); Anal. Calcd for C14H10Cl3N:
C, 56.31; H, 3.37; N, 4.69%. Found: C, 56.31; H, 3.38; N,
4.70%.
(s, 3H, CH3), 3.75 (s, 1H, HCN), 7.04-7.48 (m, 8H, Ar);
13C NMR (CDCl3): ¤ 20.1, 55.1, 74.1, 117.9, 121.9, 128.4,
129.6, 132.1, 134.1, 138.2, 141.1; MS: m/z 362 (M + 6, <2),
360 (M + 4, 10), 358 (M + 2, 27), 356 (M+, 15), 323 (100),
321 (89), 234 (84), 232 (70), 91 (97); Anal. Calcd for
C15H12BrCl2N: C, 50.46; H, 3.39; N, 3.92%. Found: C, 50.59;
H, 3.39; N, 3.94%.
2,2-Dichloro-3-(4-chlorophenyl)-1-(4-methylphenyl)aziri-
¹1
dine (2i): White solid, mp 128-130 °C; IR (KBr): ¯/cm
1
3090, 2920, 1600, 1508 (C=C, Ar); H NMR (CDCl3): ¤ 2.35
(s, 3H, CH3), 3.65 (s, 1H, HCN), 6.94-7.47 (m, 8H, Ar);
13C NMR (CDCl3): ¤ 22.1, 54.2, 76.1, 118.1, 121.5, 128.9,
129.6, 132.1, 134.1, 138.1, 144.1; MS: m/z 318 (M + 6, <2),
316 (M + 4, 7), 314 (M + 2, 12), 312 (M+, 15), 279 (85), 277
(95), 242 (70), 154 (90), 152 (100), 91 (95); Anal. Calcd for
C15H12Cl3N: C, 57.62; H, 3.87; N, 4.48%. Found: C, 57.64; H,
3.88; N, 4.49%.
1,3-Bis(4-chlorophenyl)-2,2-dichloroaziridine (2d):
¹1
White solid; mp 139-141 °C; IR (KBr): ¯/cm 3085, 2910,
We are grateful to the University of Kashan research council
for the partial support of this work.
1600, 1504 (C=C, Ar); 1H NMR (DMSO): ¤ 4.34 (s, 1H,
HCN), 7.13-7.55 (m, 8H, Ar); 13C NMR (DMSO): ¤ 53.2,
75.9, 122.3, 128.9, 129.3, 129.7, 130.1, 132.2, 134.1, 143.6;
MS: m/z 341 (M + 8, 4), 339 (M + 6, <3), 337 (M + 4, 4),
335 (M + 2, 10), 333 (M+, 20), 298 (70), 296 (65), 174 (60),
172 (95), 161 (80), 159 (100), 89 (50), 77 (55); Anal. Calcd for
C14H9Cl4N: C, 50.49; H, 2.72; N, 4.20%. Found: C, 50.48; H,
2.74; N, 4.21%.
1-(4-Bromophenyl)-2,2-dichloro-3-(4-chlorophenyl)aziri-
dine (2e): White solid; mp 134-136 °C; IR (KBr): ¯/cm
3100, 2920, 1598, 1509 (C=C, Ar); H NMR (DMSO): ¤ 4.33
(s, 1H, HCN), 7.07-7.59 (m, 8H, Ar); 13C NMR (DMSO):
¤ 53.1, 75.9, 122.7, 128.9, 129.7, 130.1, 132.2, 132.6, 134.1,
144.1; MS: m/z 384.5 (M + 8, 6), 382.5 (M + 6, <2), 380.5
(M + 4, 10), 378.5 (M + 2, 35), 376.5 (M+, 25), 341.5 (75),
339.5 (67), 217.5 (89), 205.5 (78), 204.5 (100), 202.5 (90), 89
(60); Anal. Calcd for C14H9BrCl3N: C, 44.54; H, 2.40; N,
3.71%. Found: C, 44.64; H, 2.42; N, 3.73%.
1-(4-Bromophenyl)-2,2-dichloro-3-(4-nitrophenyl)aziri-
dine (2f): White solid; mp 141-143 °C; IR (KBr): ¯/cm
3080, 2924, 1600, 1522 (C=C, Ar); H NMR (CDCl3): ¤ 4.09
(s, 1H, HCN), 7.22-8.55 (m, 8H, Ar); 13C NMR (CDCl3):
¤ 53.9, 74.5, 121.2, 121.5, 123.7, 128.9, 132.3, 139.6, 143.3,
148.4; MS: m/z 392 (M + 6, 5), 390 (M + 4, 8), 388 (M + 2,
18), 386 (M+, 10), 353 (100), 351 (89), 307 (94), 305 (85), 153
(90), 77 (60); Anal. Calcd for C14H9BrCl2N2O2: C, 43.33; H,
2.34; N, 7.22%. Found: C, 43.43; H, 2.35; N, 7.24%.
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