Ultrasonic assisted synthesis of gem-dichloroaziridine derivatives using Mg/CCl4 under neutral conditions

Article abstract of DOI:10.1016/j.ultsonch.2014.12.011

A novel and convenient method for synthesis of gem-dichloroaziridine derivatives was reported in that was utilized Mg powder with CCl₄ for dichlorocarbene generation under ultrasonic irradiation. In this clean and efficient reaction procedure,

Full text of DOI:10.1016/j.ultsonch.2014.12.011

Ultrasonics Sonochemistry xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson
Ultrasonic assisted synthesis of gem-dichloroaziridine derivatives using
Mg/CCl4 under neutral conditions
b
Khadijeh Rabiei a, , Hossein Naeimi
⇑
a Department of Chemistry, Faculty of Basic Science, Qom University of Technology, Qom 37195, Iran
b Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan 87317, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel and convenient method for synthesis of gem-dichloroaziridine derivatives was reported in that
was utilized Mg powder with CCl4 for dichlorocarbene generation under ultrasonic irradiation. In this
clean and efficient reaction procedure, the desired products were purely obtained in excellent yields.
The other advantages of this method are availability of reagents, very short reaction times, simplicity
of the method, easily work up, neutral reaction medium and high purity of products.
Ó 2014 Elsevier B.V. All rights reserved.
Received 1 November 2014
Received in revised form 17 December 2014
Accepted 18 December 2014
Available online xxxx
Keywords:
Ultrasonic
Schiff base
Dichlorocarbene
Dichloroaziridine
Magnesium
1. Introduction
interest contain the aziridine framework in their structure. The
antitumor and antibiotic properties of a great number of aziri-
The use of ultrasonic waves is a convenient technique in organic
synthesis [1–13]. Sonochemistry is also becoming more and more
important for a variety of synthetic organic reactions as an energy
source to generate radicals and initiate the electron transfer pro-
cess. Many metal-involved organic reactions have been accelerated
under ultrasound [14,15]. Sonochemical generation of dichlorocar-
bene has also been reported [16,17]. Recently, syntheses of fluoro
aziridines in the presence of phase transfer catalyst under ultra-
sonic irradiation have been reported [18]. The advantages of ultra-
sound procedures, such as; good yields, short reaction times and
mild reaction conditions are well documented [19]. Aziridines
are an important class of three-membered heterocycles containing
one nitrogen atom with a rapidly expanding scope of applications
in organic synthesis [20]. 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 and can be opened in a stereo controlled manner with
various nucleophiles, providing access to a wide range of important
nitrogen-containing products [21–25].
dine-containing compounds are of high significance among other
biological properties, which make them attractive synthetic targets
in their own right [31–33]. As a result, several methods for synthe-
sis of gem-dichloroaziridines have been reported. The preparation
has been accomplished by the addition of dichlorocarbene gener-
ated from chloroform, hexachloroacetone or ethyltrichloroacetate
with the appropriate base under phase transfer catalyst to imines
[34–38].
In continuation of our research onto preparation of dichloroaz-
iridines [39–41], we hope to report a novel procedure for prepara-
tion of these compounds using the addition reaction of
dichlorocarbene generated through the reaction of Mg powder
and CCl4 under ultrasonic irradiation to Schiff base compounds.
2. Experimental section
2.1. Materials and apparatus
Since the first synthesis of an aziridine reported by Gabriel in
1888, the synthetic scope of aziridine chemistry has blossomed
in recent years [26–30]. Many synthetic compounds of biological
All the materials were of commercial reagent grade. All the
Schiff bases have been prepared in laboratory in accordance to
the previously reported method in literature [42].
IR spectra were recorded as KBr pellets on a Perkin-Elmer 781
spectrophotometer and an Impact 400 Nicolet FTIR spectropho-
tometer. 1H NMR and 13C NMR were recorded in DMSO/CDCl3
⇑
Corresponding author. Fax: +98 25 36641604.
E-mail address: kh_rabiei@yahoo.com (K. Rabiei).
http://dx.doi.org/10.1016/j.ultsonch.2014.12.011
1350-4177/Ó 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: K. Rabiei, H. Naeimi, Ultrasonic assisted synthesis of gem-dichloroaziridine derivatives using Mg/CCl4 under neutral con-
ditions, Ultrason. Sonochem. (2015), http://dx.doi.org/10.1016/j.ultsonch.2014.12.011

2
K. Rabiei, H. Naeimi / Ultrasonics Sonochemistry xxx (2015) xxx–xxx
solvents on a Bruker DRX-400 spectrometer with tetramethylsil-
ane as internal reference. Mass spectra were recorded on a Finni-
gan 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. The BANDELIN ultra-
sonic HD 3200 with probe model US 70/T, 6 mm diameter, was
used to produce ultrasonic irradiation and homogenizing the reac-
tion mixture. Piezoelectric crystal of this kind of probe normally
works in the range of 700 kHz, but using through some proper
clamps the output frequency of piezoelectric crystal have con-
trolled and reduced to 20 kHz. Therefore, the induced frequency
of probe to the reaction mixture is equal to 20 kHz. Melting points
obtained with a Yanagimoto micro melting point apparatus are
uncorrected. The purity determination of the substrates and reac-
tion monitoring were accomplished by TLC on silica-gel polygram
SILG/UV 254 plates (from Merck Company).
337 (M+4 + 4, 4), 335 (M+2 + 2, 10), 333 (M+, 20), 298 (70), 296
(65), 174 (60), 172 (95), 161 (80), 159 (100), 89 (50), 77 (55); Anal.
Calcd. For C14H9NCl4: C, 50.45; H, 2.70; N, 4.20. Found: C, 50.48; H,
2.74; N. 4.21.
2,2-dichloro-1-(4-bromophenyl),3-(4-chlorophenyl) aziridine (2e);
white solid; m.p. = 136-138 °C; IR (KBr)/t
(cmÀ1): 3100, 2920, 1598,
1509 (C@C, Ar); 1H NMR (DMSO)/d ppm: 4.34 (s, 1 H, HCN), 7.08 (d,
2 H, Ar), 7.50–7.56 (m, 4 H, Ar), 7.58 (d, 2 H, Ar); 13C NMR/(DMSO)/
d ppm: 53.0, 76.9, 122.3, 129.1, 129.3, 130.1, 131.8, 134.5, 137.6,
150.1; MS: m/z: 384.5 (M+8 + 8, 6), 382.5 (M+6 + 6, <2), 380.5
(M+4 + 4, 10), 378.5 (M+2 + 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 C14H9NBrCl3: C, 44.62; H, 2.39; N, 3.72.
Found: C, 44.64; H, 2.42: N, 3.73.
2,2-dichloro-1-(4-bromophenyl),3-(4-nitrophenyl) aziridine (2f);
white solid; m.p. = 143–145 °C; IR (KBr)/t
(cmÀ1): 3080, 2924,
1600, 1522 (C@C, Ar); 1H NMR (CDCl3)/d ppm: 3.79 (s, 1 H, HCN),
6.95 (d, 2 H, Ar), 7.50 (d, 2 H, Ar), 7.71 (d, 2 H, Ar), 8.31 (d, 2 H,
Ar); 13C NMR/(DMSO)/d ppm: 53.2, 75.9, 122.3, 128.9, 129.2,
129.7, 130.2, 132.2, 134.1, 143.6; MS: m/z: 392 (M+6 + 6, 5), 390
(M+4 + 4, 8), 388 (M+2 + 2, 18), 386 (M+, 10), 353 (100), 351 (89),
307 (94), 305 (85), 153 (90), 77 (60); Anal. Calcd. For C14H9N2O2-
BrCl2: C, 43.41; H, 2.33; N, 7.24. Found: C, 43.43; H, 2.35; N, 7.24.
2,2-dichloro-1-(4-methylphenyl),3-(4-nitrophenyl) aziridine (2g);
2.2. The power measurement by calorimetric method
We assessed the cavitational energy applied by ultrasonication
calorimetrically with water. The piezoelectric transducer was con-
nected to the frequency generator, HD-3200 (with frequency;
20 kHz). The probe (US 70 T) was dipped in a jacketed cylindrical
vessel. For calorimetric measurement, the jacket was empty and
connected to vacuum to minimize heat losses. In this method, by
measuring the rate of temperature increase due to the conversion
of ultrasound energy into heat and calculating Pacoustic according
yellow solid; m.p. = 142–144 °C; IR (KBr)/t
(cmÀ1): 3090, 2918,
1589, 1490 (C@C, Ar); 1H NMR (DMSO)/d ppm: 2.29 (s, 3 H, CH3)
4.45 (s, 1 H, HCN), 7.02 (d, 2 H, Ar), 7.21 (d, 2 H, Ar), 7.80 (d, 2 H,
Ar)8.31 (d, 2 H, Ar); 13C NMR/(DMSO)/d ppm: 20.9, 53.5, 75.1,
119.6, 123.7, 128.9, 134.6, 140.3, 141.7, 148.3; MS: m/z: 326
(M+4 + 4, 20), 324 (M+2 + 2, 29), 322 (M+, 40), 289 (90), 287 (100),
243 (60), 241 (80), 154 (70), 152 (82), 91 (92); Anal. Calcd. For
to: P = mc
D
T/t, where m is the mass of water (g), c is the specific
T is the difference in tem-
heat capacity of water (4.18 JgÀ1 kÀ1),
D
perature (k) and t is the sonication time (s).
2.3. General procedure for the synthesis of 2,2-dichloro-1,3-
diphenylaziridines
C15H12N2O2Cl2: C, 55.73; H, 3.72; N, 8.67, Found: C, 55.75; H,
3.74; N, 8.67.
2,2-dichloro-1-(4-bromophenyl),3-(4-methylphenyl) aziridine (2h);
A mixture of magnesium powder (80 mmol), Schiff base com-
pounds 1a (40 mmol) and CCl4 (80 mmol) in anhydrous tetrahy-
drofuran (8 mL) was placed in flask equipped with ultrasonic
prob. The mixture was then treated with ultrasonic irradiation
until all magnesium was consumed. To the reaction mixture was
then added 10% NH4Cl solution (30 mL) and the aqueous layer
was extracted with diethyl ether (3 Â 10 mL). The combined
organic layer was dried over anhydrous sodium sulfate. The sol-
vent was evaporated and desired product, gem-dichloroaziridine,
was obtained in excellent yield. All of the diarylaziridine products
were identified by physical and spectroscopic data as following
and were consistent in comparison with authentic samples
[34,36–38].
yellow solid; m.p. = 148–150 °C; IR (KBr)/t
(cmÀ1): 3100, 2898,
1600, 1500 (C@C, Ar); 1H NMR (CDCl3)/d ppm: 2.38 (s, 3 H, CH3)
3.41 (s, 1 H, HCN), 7.15 (d, 2 H, Ar), 7.21 (d, 2 H, Ar), 7.45 (d, 2 H,
Ar), 7.84 (d, 2 H, Ar); 13C NMR/(CDCl3)/d ppm: 20.9, 51.0, 72.9,
120.1, 129.8, 130.1, 135.0, 136.7, 137.8, 149.3; MS: m/z: 362
(M+6 + 6, <2), 360 (M+4 + 4, 10), 358 (M+2 + 2, 27), 356 (M+, 15),
323 (100), 321 (89), 234 (84), 232 (70), 91 (97); Anal. Calcd. For
C
15H12NBrCl2: C, 50.56; H, 3.37; N, 3.93, Found: C, 50.59; H, 3.39;
N, 3.94.
2,2-dichloro-1-(4-methylphenyl),3-(4-chlorophenyl) aziridine (2i);
white solid, m.p. = 130–132 °C; IR (KBr)/
(cmÀ1); 3090, 2920,
t
1600, 1508 (C@C, Ar); 1H NMR (CDCl3)/d ppm: 2.36 (s, 3 H, CH3)
3.65 (s, 1 H, HCN), 6.95 (d, 2 H, Ar), 7.18 (d, 2 H, Ar), 7.36–7.47
(m, 5 H, Ar); 13C NMR/(CDCl3)/d ppm: 21.5, 53.1, 73.1, 121.0,
128.5, 129.9, 130.1, 138.1, 138.5, 138.1, 139.0, 149.3; MS: m/z:
318 (M+6 + 6, <2), 316 (M+4 + 4, 7), 314 (M+2 + 2, 12), 312 (M+,
15), 279 (85), 277 (95), 242 (70), 154 (90), 152 (100), 91 (95); Anal.
Calcd. For C15H12NCl3: C, 57.60; H, 3.84; N, 4.48, Found: C, 57.64; H,
3.88; N, 4.49.
2,2-dichloro-1,3-diphenylaziridine (2a); pale yellow solid;
m.p. = 101–103 °C (m.p. = 98–99 °C) [34,37,38].
2,2-dichloro-1-(4-bromophenyl)-3-phenylaziridine (2b); white
solid; m.p. = 145–147 °C; IR (KBr)/t
(cmÀ1): 3100, 2914, 1600,
1524 (C@C, Ar); 1H NMR (DMSO)/d ppm: 4.34 (s, 1 H, HCN), 7.14
(d, 2 H, Ar), 7.45 (d, 2 H, Ar), 7.50–7.55 (m, 4 H, Ar); 13C NMR/
(DMSO)/d ppm: 50.0, 71.0, 119.4, 122.7, 128.9, 129.0, 131.9,
132.3, 136.2, 151; MS: m/z: 348 (M+6 + 6, 10), 346 (M+4 + 4, 25),
344 (M+2 + 2, 45), 342 (M+, 30), 309 (85), 307 (100), 233 (65),
230 (45), 152 (80), 77 (85); Anal. Calcd. For C14H10NBrCl2: C,
49.12: H, 2.92; N. 4.11. Found: C, 49.15; H, 2.95; N. 4.12.
3. Results and discussion
Here, the ultrasonic irradiation catalyzed reaction of dichloro
aziridination of Schiff base compounds under neutral conditions
has been studied. In order to enhance the yields of gem-dichloro-
aziridin derivatives, it is necessary to control the molar ratios of
reactants. Firstly, we have carried out this reaction in the presence
of various molar ratios of Mg, CCl4 and Schiff base under ultrasonic
irradiation (60 W). The corresponding results are indicated in
Table 1.
2,2-dichloro-1-(4-chlorophenyl)-3-phenylaziridine (2c); pale yel-
low solid; m.p. = 73–75 °C (m.p. = 71–72 °C) [36].
2,2-dichloro-1,3-bis(4-chlorophenyl)aziridine (2d); white solid;
m.p. = 141–143 °C; IR (KBr)/t
(cmÀ1): 3085, 2910, 1600, 1504
(C@C, Ar); 1H NMR (DMSO)/d ppm: 4.34 (s, 1 H, HCN), 7.14 (d, 2
H, Ar), 7.45 (d, 2 H, Ar), 7.50–7.58 (m, 4 H, Ar); 13C NMR/
(DMSO)/d ppm: 53.15, 75.9, 122.3, 128.9, 129.3, 129.7, 130.1,
132.2, 134.1, 143.6; MS: m/z: 341 (M+8 + 8, 4), 339 (M+6 + 6, <3),
As can be seen in this Table, the desired product was obtained
with good yield using Mg: CCl4: Schiff base with 2:2:1 molar ratio.
Please cite this article in press as: K. Rabiei, H. Naeimi, Ultrasonic assisted synthesis of gem-dichloroaziridine derivatives using Mg/CCl4 under neutral con-
ditions, Ultrason. Sonochem. (2015), http://dx.doi.org/10.1016/j.ultsonch.2014.12.011

K. Rabiei, H. Naeimi / Ultrasonics Sonochemistry xxx (2015) xxx–xxx
3
Table 1
the initiation and enhancement of synthetic reaction involving
metals as a reagent. Also, ultrasound irradiation accelerates the
reaction by ensuring a better contact between the reactants. By
occurring the reaction under sonication conditions dichloro car-
bene intermediate was produced very fast and thus corresponding
products were obtained in excellent yields and very short reaction
times.
The effects of ultrasonic irradiation observed during organic
reactions are due to cavitations. In the case of volatile molecules
cavities are believed to act as a microreactor: as the volatile mole-
cules enter the microbubbles and the high temperature and pres-
sure produced during cavitations break their chemical bonds
thus reacting with other specie.
Enhancement of ultrasonic irradiation (60 W) on the formation of 2,2-dichloro-1-(4-
methylphenyl)-3-(4-nitrophenyl) aziridine in the presence of various molar ratio of
Mg/CCl4.
Entry
Mg:CCl4:Schiff base (molar ratio)
Time (min)
Yielda (%)
1
2
3
4
5
6
7
8
1:1:1
30
30
30
30
30
30
30
30
45
55
60
70
75
80
1.2:1.2:1
1.4:1.4:1
1.6:1.6:1
1.8:1.8:1
2:2:1
2.2:2.2:1
2:2:1
80
<10b
a
Isolated yields.
Isolated yield under silent conditions.
b
Then to ascertain the scope and limitation of the present
reaction, several Schiff base compounds were reacted with CCl4
in the presence of Mg powder under ultrasonic irradiation and
the desired dichloroaziridine derivatives were prepared
(Scheme 1).
In order to determine enhancement of ultrasound irradiation with
performance of this reaction under silent condition and magnetic
stirring, the products were obtained in very low yield (Table 1,
entry 8).
In continuation of this research, the effect of various powers of
ultrasonic irradiation has been surveyed. Initially we carried out
aziridination of (4-nitrophenyl)methylene(4-methylphenyl)amine
as model reaction in order to optimize the best suited reaction con-
ditions. It was observed that the reaction in the presence of ultra-
sonic irradiation with power 75 W was afforded the best result as
obtained product with 93% isolated yield during 11 min (Table 2,
entry 5).
Cl
Cl
H
N
N
))))
Mg
+
CCl4
R
R
R
THF
2
R
1
2
1
1a-i
2a-i
R1 = H, CH3, NO2, Cl
R2 = H, CH3, Cl, Br
Table 2
Scheme 1. Preparation of 2,2-dichloro-1,3-diarylaziridine compounds from Schiff
bases.
Survey the effect of ultrasonic irradiation on the formation of 2,2-dichloro-1-(4-
methylphenyl)-3-(4-nitrophenyl) aziridine.
Entry
Power (W)
Time (min)
Yielda (%)
The results are summarized in Table 3. As shown in this
Table, the reaction of the various Schiff bases with CCl4 and
Mg powder, were catalyzed by ultrasonic irradiation. The
corresponding products were obtained in excellent yields and
appropriate reaction times under ultrasonic irradiation. It seems
this method for preparation of dichloroaziridines has some
advantages. The main advantages of this method is that the
reaction carried out in a neutral medium, some side reactions
caused by the strong base in phase transfer catalyst system
can be avoided and highly efficiently, appropriately, mildly and
useful in compare to previously reported methods [34,36–38]
(Table 3, entries 2, 3, 4, 5 and 7).
1
2
3
4
5
6
60
64
68
72
75
80
30
30
20
15
11
11
80
85
85
90
93
93
a
Isolated yields.
3.1. Survey the effect of ultrasonic irradiation
Sonication is able to effect reactions proceeding through radi-
cals, and ultrasound has also provided a distinct alternative to
Table 3
Synthesis of gem-dichloro-1,3-diarylaziridines by using Mg powder/CCl4 under ultrasonic irradiation with 75 (W) power and neutral conditions.
Entry
Substrate
Product
M.P. (°C)
Time (min)
Silent
Yielda (%)
Silent
Ultrasonic
12
Ultrasonic
96
N
N
N
N
1
2
3
4
2a
2a
2a
2a
100–102
98–99
98–99
99
960
360
40
30
–
–
–
61b
74c
88d
–
–
–
–
(continued on next page)
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4
K. Rabiei, H. Naeimi / Ultrasonics Sonochemistry xxx (2015) xxx–xxx
Table 3 (continued)
Entry
Substrate
Product
M.P. (°C)
Time (min)
Silent
Yielda (%)
Silent
Ultrasonic
–
Ultrasonic
–
N
5
6
2a
2b
98–99
400
55e
26
N
143–145
1000
9
9
–
7
7
7
95
96
–
Br
Cl
Cl
N
N
7
2c
2c
2d
2e
2f
72–74
1050
960
900
900
940
29
68f
39
40
30
8
71–72
N
N
9
139–141
134–136
141–143
98
97
94
Cl
Br
Cl
10
11
Cl
N
Br
O2N
N
12
13
2g
2h
2i
140–142
146–148
128–130
955
900
900
11
8
26
36
39
93
97
98
CH3
O2N
H3C
Cl
N
Br
N
14
7
CH3
a
Isolated yields based on Schiff base.
b
c
d
e
f
By hexachloroacetone and sodium methoxide, Ref. [34].
By sodium hydroxide(50%), chloroform in the presence of PTC [37].
By sodium hydroxide(50%), chloroform in the presence of PTC [38].
By sodium methoxide and chloroform, Ref. [35].
By potassium t-butoxide and chloroform, Ref. [36].
CCl4
-Cl-
Among these, dichlorocarbene which is generated from CHCl3
CCl3
:CCl2
Mg
under PTC conditions is most frequently used because the yields
are acceptable. In our report on synthesis of dichloroaziridine
derivatives under ultrasonic irradiation, the mol ratio of magne-
sium and CCl4 into the Schiff base was 2, while in other reports,
high alkaline medium conditions was applied for dichloroaziridin-
ation of Schiff bases. Also, the yields of products were higher and
the reaction time was shorter than the other previously reported
methods [34,36–38].
))))
e
))))
Mg
e
CCl4
Mg2+
.
Cl-
CCl3
Cl
Cl
H
3.2. The proposed reaction mechanism
N
N
))))
+
:CCl2
The proposed reaction mechanism for the preparation of dichlo-
roaziridines via formation of carbene intermediate was shown in
Scheme 2. The reaction between Mg and CCl4 may be involving a
single electron transfer from magnesium to carbon tetrachloride.
Sonication of the reaction through cavitations is able to affect the
reaction proceeding through generated radicals from metal as
reagent. In the case of volatile molecules, cavities are believed to
act as microreactor. By using ultrasonic irradiation, treatment of
Mg with CCl4, the activated surface of Mg can be achieved due to
the clean and oxide free of Mg surface. Dichlorocarbene in situ gen-
erated was trapped by Schiff base compound and corresponding
product was obtained.
R
R
R
1
2
R
2
1
Addition
Cyclization
CCl2
+
H
N
R
R
2
1
Scheme 2. Proposed mechanism for the preparation of 2,2-dichloro-1,3-
diarylaziridines.
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K. Rabiei, H. Naeimi / Ultrasonics Sonochemistry xxx (2015) xxx–xxx
5
Fig. 1. The mass spectrum of compound (2g).
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copy and C. H. N. analyses. In the IR spectra, the stretching fre-
quency of aromatic C@C is formed in the region between
m
= 1490–1600 cmÀ1. The stretching vibration of C–H in the alkyl
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m
= 2898–2930 cmÀ1. In
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4. Conclusion
In this study, we have synthesized gem-dichloroaziridine deriv-
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Mg/CCl4 under ultrasonic irradiations. The corresponding products
have been obtained in excellent yields, high purity and short reac-
tion times under neutral conditions. The products have been con-
firmed by physical and spectroscopic data such as; IR, 1H NMR,
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Acknowledgments
The authors are grateful to Qom University of Technology
research council for the partial support of this work and University
of Kashan for supporting this work by Grant No. 159148/50.
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Please cite this article in press as: K. Rabiei, H. Naeimi, Ultrasonic assisted synthesis of gem-dichloroaziridine derivatives using Mg/CCl4 under neutral con-
ditions, Ultrason. Sonochem. (2015), http://dx.doi.org/10.1016/j.ultsonch.2014.12.011