1-Aryl-2-nitro-3-trichloromethylaziridines: Synthesis and structure

Article abstract of DOI:10.1007/s11172-009-0131-2

A two-step method was developed for the synthesis of new polyfunctional aziridines involving the addition of aromatic amines to 1-bromo-3, 3, 3-trichloro-1-nitropropene and the dehydro-bromination of the resulting adducts. The 1H and 13C NMR spectroscopic

Full text of DOI:10.1007/s11172-009-0131-2

Russian Chemical Bulletin, International Edition, Vol. 58, No. 5, pp. 1023—1033, May, 2009
1023
1ꢀArylꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridines: synthesis and structure
V. M. Berestovitskaya,a S. V. Makarenko,a I. S. Bushmarinov,b K. A. Lyssenko,b A. S. Smirnov,a and E. V. Stukan´ a
aHerzen State Pedagogical University of Russia,
48 nab. Moika, 191186 St. Petersburg, Russian Federation.
Fax: +7 (812) 571 3800. Eꢀmail: kohrgpu@yandex.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: bushꢀi@ya.ru
A twoꢀstep method was developed for the synthesis of new polyfunctional aziridines involving
the addition of aromatic amines to 1ꢀbromoꢀ3,3,3ꢀtrichloroꢀ1ꢀnitropropene and the dehydroꢀ
1
bromination of the resulting adducts. The H and 13C NMR spectroscopic and Xꢀray diffracꢀ
tion studies showed that 1ꢀarylꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridines are stereohomogeneous
and have the geometry, such that the nitro and aryl substituents are in the trans positions with
respect to the trichloromethyl group. The chemical bonding in the crystal and the gas phase
was investigated based on highꢀresolution Xꢀray diffraction analysis of the electron density
distribution and quantum chemical calculations.
Key words: 1ꢀarylꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridines, ethyleneimines, 1ꢀbromoꢀ3,3,3ꢀ
trichloroꢀ1ꢀnitropropene, arylamines.
Scheme 1
Due to the ability to readily undergo the cleavage in
the presence of nucleophiles, the aziridine (ethyleneimine)
ring is a good alkylating agent. This property determines
the mutagenic and toxic effects of aziridines.1 Aziridine is
involved in antitumor drugs.2—4 In particular, triethyleneꢀ
imine thiophosphoramide1 is used in the therapy for
ovarian and breast cancer. The drug Dipin is recomꢀ
mended for the treatment of lymphatic leukemia and
laryngeal cancer.4 Natural compounds of the aziridine
series were also documented. For example, mitomycin C
exhibits antibiotic and antitumor activities.1 Due to all
these facts, aziridine derivatives attract considerable
interest.5
The investigation of the dehydrobromination of
nucleophilic addition products of arylamines to the previꢀ
ously unknown 1ꢀbromoꢀ3,3,3ꢀtrichloroꢀ1ꢀnitropropene6
allowed us to synthesize a series of original 1ꢀarylꢀ2ꢀnitroꢀ
3ꢀtrichloromethylaziridines.
Ar = Ph (2,8), pꢀMeC6H4 (3,9), pꢀClC6H4 (4,10), pꢀBrC6H4 (5,11),
mꢀO2NC6H4 (6,12), αꢀnaphthyl (7,13)
The reaction of 1ꢀbromoꢀ3,3,3ꢀtrichloroꢀ1ꢀnitroꢀ
propene (1) with aromatic amines (aniline, pꢀtoluidine,
pꢀchloroaniline, pꢀbromoaniline, mꢀnitroaniline, and
αꢀnaphthylamine) in anhydrous methanol at room
temperature affords Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloroꢀ
methyl)ethyl]anilines (2—7) in 46—77% yields (Scheme 1).
Then compounds 2—7 are transformed into 1ꢀarylꢀ2ꢀniꢀ
troꢀ3ꢀtrichloromethylaziridines (8—13) in 19—37% yields
under reflux in ethanol in the presence of a oneꢀandꢀaꢀ
half excess of freshly melted potassium acetate.
The structures of Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloroꢀ
methyl)ethyl]anilines (2—7) were assigned based on the
IR and H NMR spectroscopic data (Table 1). The IR
1
spectra of compounds 2—7 shows symmetric absorpꢀ
tion bands (1350—1340 cm–1) and antisymmetric bands
(1575—1570 cm–1) of the unconjugated nitro group with
a frequency separation Δν = 220—230 cm–1 characteristic
of compounds with the geminal arrangement of the nitro
1
group and the halogen atom.7,8 The H NMR spectra of
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 998—1007, May, 2009.
1066ꢀ5285/09/5805ꢀ1023 © 2009 Springer Science+Business Media, Inc.

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Berestovitskaya et al.
Table 1. Yields and characteristics of Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]anilines 2—7
Comꢀ Yield
pound (%)
Rf
Diaꢀ
stereoꢀ
mera
1H NMR
(CDCl3, δ, J/Hz)
IR
(CHCl3), ν/cm–1
Ar (m)
HA (d)
HB (dd)
NH (d)
Ar
NO2
NH
2
77
71
67
59
52
0.64
A
B
A
B
A
B
A
B
A
B
—
6.71
(JAB = 3.7)
4.88
5.08
(JBH = 10.7)
1600,
1510
1570,
1350
3415
(JAB = 3.7,
JBH = 10.7)
5.37
(JAB = 2.7,
JBH = 11.1)
4.83
(JAB = 3.3,
JBH = 10.3)
5.29
(JAB = 1.5,
JBH = 10.3)
4.78
(JAB = 2.8,
JBH = 10.3)
5.32
(JAB = 1.9,
JBH = 10.3)
4.78
(JAB = 3.2,
JBH = 10.4)
5.33
(JAB = 2.5,
JBH = 11.0)
4.93
6.79—7.26
6.73—7.01
6.67—6.98
6.80—7.26
6.75—7.20
6.76—7.37
6.71—7.34
—
6.84
(JAB = 2.7)
4.53
(JBH = 11.1)
3b
0.55
0.43
0.55
0.50
6.67
(JAB = 3.3)
4.99
(JBH = 10.3)
1615,
1520
1570,
1350
3430
3420
3415
3415
6.83
(JAB = 1.5)
4.48
(JBH = 10.3)
4
6.75
(JAB = 2.8)
5.09
(JBH = 10.3)
1600,
1505
1575,
1350
6.86
(JAB = 1.9)
4.50
(JBH = 10.3)
5
6.74
(JAB = 3.2)
5.10
(JBH = 10.4)
1600,
1505
1570,
1340
6.85
(JAB = 2.5)
4.50
(JBH = 11.0)
6c
6.81
(JAB = 3.5)
5.54
(JBH = 10.6)
1620,
1490
1575,
1350
(JAB = 3.5,
JBH = 10.6)
5.44
7.14—7.74
6.88
4.91
(JAB = 2.7)
(JAB = 2.7,
JBH = 11.0)
(JBH = 11.0)
7
46
0.60
A
B
—
6.89
5.14
5.98
1600,
1490
1570,
1345
3455
(JAB = 3.0)
(JAB = 3.0,
JBH = 10.3)
5.68
(JBH = 10.3)
6.97—8.03
6.96
5.25
(JAB = 2.7)
(JAB = 2.7,
JBH = 10.8)
(JBH = 10.8)
a The stereoisomers of compounds 2—7 with HA and HB at higher field are marked with A; the stereoiosmers with HA and HB at lower
field are marked with B. The A : B ratio for compounds 2—4 is 1 : 2; for compounds 5—7, 1 : 1.7; 1 : 1.5, and 2 : 3, respectively.
b The protons of the methyl group at the para position of the benzene ring of compound 3 are observed at δ 2.19 and 2.21 for the
diastereomers A and B, respectively.
c The absorption bands of the nitro group in the aromatic ring of compound 6 are observed at 1540 cm–1 (ν ) and 1355 cm–1 (ν ).
as
s
compounds 2—7 contain a double set of signals, which
indicate that Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ꢀ
ethyl]anilines (2—7) exist as mixtures of erythro and threo
diastereomers.
The 1H NMR spectra of nitroaziridines 8—13 contain
signals for the protons of all structural fragments (Table 2).
Thus, the protons of the aromatic ring appear as multiꢀ
plets at δ 6.91—8.04 and the methine protons of the
aziridine ring appear as singlets at δ 5.53—5.91 (HA) and
4.18—4.45 (HB). An analysis of the data published in the
literature showed that the spinꢀspin coupling constants
3JH
in aziridines containing hydrogen atoms in
AHB
the trans positions can vary in a relatively broad range
(1—5 Hz) depending on the nature of the substituents.
For example, in the spectrum of the related 1ꢀnitroꢀ
2ꢀtrichloromethyloxirane molecule, the signals for the ring
protons HA (HCNO2) and HB (HCCCl3) are observed
without splitting at δ 5.58 and 4.03, respectively.9 The cis
spinꢀspin coupling constants in aziridines are more conꢀ
served and are generally no larger than 4 Hz.10 Therefore

1ꢀArylꢀ2ꢀnitroꢀ3ꢀtricholormethylaziridines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
1025
Table 2. Melting points, yields, and spectral characteristics of 1ꢀarylꢀ2ꢀnitroꢀ3ꢀ(trichloromethyl)aziridines
8—13
Comꢀ
pound
Yield
(%)
M.p./°С
1H NMR
(CDCl3, δ)
IR (CHCl3),
ν/cm–1
Ar (m)
HА (s) HВ (s)
NO2
Ar
CCl3
8
25
30
37
36
19
27
58—59
86—87
69—71
106—107
82—84
116—117
7.37—7.02
7.13, 6.92
7.27, 6.93
7.46, 6.91
7.31—8.04
8.04—7.40
5.58
5.55
5.53
5.56
5.65
5.91
4.24
4.21
4.18
4.20
4.29
4.45
1560, 1355
1565, 1355
1560, 1350
1560, 1350
1560, 1350
1570, 1345
1600, 1495
1600, 1510
1610, 1505
1590, 1490
1590, 1490
1600, 1510
810
815
820
815
815
810
9a
10
11
12b
13
a
The protons of the methyl group at the para position of the aromatic ring of compound 9 appear as a
singlet at δ 2.31.
b The absorption bands of the nitro group in the benzene ring of compound 12 are observed at νas 1525 and
ν 1350 cm–1
.
s
3
X = Cl(4), Br(1)
the constants JH
provide indirect evidence for the
AHB
trans arrangement of the vicinal protons in the aziridine ring.
The 13C {1H} NMR spectrum of compound 10 shows
signals for all carbon atoms (at δ 55.8 (C—CCl3), 71.2
(C—NO2), 93.7 (CCl3), 117.7, 119.7, 132.3, 141.3 (C6H4)).
The IR spectra of compounds 8—13 contain stretching
bands of the unconjugated nitro group (1570—1560 and
1355—1345 cm–1), the aromatic ring (1600—1590 cm–1),
and the CCl3 groups (820—810 cm–1).
C(8)
C(7)
C(6)
O(1)
C(9)
C(10)
O(2)
N(2)
C(5)
The UV spectra of aziridines 9—11 show intense abꢀ
sorption bands of π→π* transitions of the aromatic rings
at λmax 230—233 nm (ε 19100—23600) and weak bands of
n→π* transitions at 323—333 nm (ε 1700—1800).
N(1)
C(3)
C(2)
C(4)
Cl(3)
C(11)
Cl(2)
C(11´)
Cl(1)
Fig. 2. Molecular structures of compounds 10 and 11 with disꢀ
placement ellipsoids drawn at p = 50%.
C(8)
C(8´)
C(7)
C(6)
C(9)
O(3)
C(8)
C(7´)
C(6´)
N(3)
O(4)
C(7)
C(6)
C(5)
C(10)
O(1)
C(9)
C(10)
C(5´)
O(2)
O(1)
N(1)
O(1´)
N(2)
C(2)
N(1´)
N(2´)
N(1)
C(3)
O(2´)
N(2)
Cl(3)
O(2)
C(3)
C(2)
C(4)
Cl(2)
C(4)
Cl(1)
Cl(2)
Cl(3)
Cl(1)
Fig. 3. Molecular structure of compound 12 with displacement
ellipsoids drawn at p = 50%.
Fig. 1. Molecular structure of compound 9 illustrating the
character of disorder.

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Berestovitskaya et al.
electronꢀwithdrawing substituents in the para positions,
these compounds may be of interest in view of nonlinear
optical properties. Compound 13 crystallizes in the centroꢀ
symmetric space group P21/n with three independent
molecules A—C per asymmetric unit. Compound 12 crysꢀ
tallizes in the space group P1.
Selected geometric parameters of the common fragꢀ
ments and their mutual arrangement in molecules 10—13
are virtually identical (Tables 3 and 4). Unfortunately,
the disorder in the crystal structure of 9 (see the Experiꢀ
mental section) makes it impossible to discuss the details
of its molecular geometry.
C(10A)
C(8A)
C(11A)
C(14A)
C(7A)
C(9A)
C(6A)
O(1A)
N(2A)
C(12A)
O(2A)
C(13A)
C(5A)
N(1A)
C(2A)
C(3A)
In all the molecules under consideration, the bond
lengths in the common fragment are virtually identical.
The maximum difference in the bond lengths is 0.019(2) Å
for C(4)—Cl(1) and N(1)—C(2) (see Table 3). Therefore,
the aromatic ring is not involved in the conjugation
with the lone electron pair of the N(1) atom, because the
N(1)—C(5) bond length is independent (the maximum
change is 0.006(2) Å) of both the nature of the ring and
the substituents at the benzene ring. An analysis of
the Cambridge Structural Database11 showed that the
N(1)—C(5) bond length (1.420(1) Å) is typical of
the bonds between the aziridine nitrogen atom and the
benzene ring (see the refcodes COYMOS, COYMOS01,
JESKIC, ESIMEY, XEVDOR, IFOKUJ, and KAPBEI),
the N—Ph bond length being virtually independent of the
angle between the benzene and aziridine fragments (see
the refcode KAPBEI), which confirms the suggestion
that there is no conjugation between the aziridine nitroꢀ
gen atom and the aromatic fragment.
C(4A)
Cl(2A)
Cl(3A)
Cl(1A)
Fig. 4. Molecular structure of compound 13 with displacement
ellipsoids drawn at p = 50%.
The structures of trichloromethylꢀcontaining nitroꢀ
aziridines 8—13 were unequivocally confirmed by the
Xꢀray diffraction study of five compounds 9—13 containꢀ
ing the pꢀmethyl, pꢀchloro, pꢀbromo, mꢀnitrophenyl, and
αꢀnaphthyl substituents, respectively.
According to the Xꢀray diffraction data, the nitro group
and the aromatic moiety in compounds 9—13 are in the
trans positions with respect to the trichloromethyl moiety
(Figs 1—4).
All compounds crystallize without solvent molecules.
Compound 9 and isostructural aziridines 10 and 11
crystallize in the noncentrosymmetric space group Pna21.
Taking into account the fact that compounds 9—11
contain the aromatic ring with electronꢀdonating and
Unlike the electronic properties of the aromatic ring,
its steric volume leads to a change in the angle of rotation
of the aromatic moiety and the nitro group about the
N(1)—C(2) bond. Actually, the corresponding torsion
angles for the aromatic ring and the NO2 group are
Table 3. Selected bond lengths in molecules 10—13 in the crystal structures
Bond
d/Å
10
11
12
13A
13B
13C
Xa—C(8)
1.7385(6)
1.7620(6)
1.7663(5)
1.7791(6)
1.2216(6)
1.2246(6)
1.4198(6)
1.4401(6)
1.4406(6)
1.4908(6)
1.4917(7)
1.5180(7)
1.9012(19)
1.7665(19)
1.7692(17)
1.7787(19)
1.225(2)
1.229(2)
1.425(2)
1.441(2)
1.446(2)
1.489(2)
1.488(2)
1.511(2)
—
—
—
—
Cl(1)—C(4)
Cl(2)—C(4)
Cl(3)—C(4)
O(1)—N(2)
O(2)—N(2)
N(1)—C(5)
N(1)—C(3)
N(1)—C(2)
N(2)—C(2)
C(2)—C(3)
C(3)—C(4)
1.7700(11)
1.7684(11)
1.7733(11)
1.2276(14)
1.2246(13)
1.4213(13)
1.4422(13)
1.4506(14)
1.4923(15)
1.4899(14)
1.5175(15)
1.7733(16)
1.7635(16)
1.7775(16)
1.2209(19)
1.2323(18)
1.4275(19)
1.4400(19)
1.4467(19)
1.485(2)
1.7668(16)
1.7620(15)
1.7797(16)
1.2284(17)
1.2242(17)
1.4287(19)
1.4421(19)
1.4479(19)
1.4853(18)
1.488(2)
1.7615(16)
1.7640(16)
1.7836(16)
1.2234(18)
1.2228(18)
1.4264(19)
1.4433(19)
1.4549(19)
1.492(2)
1.494(2)
1.518(2)
1.488(2)
1.516(2)
1.518(2)
a Х stands for Cl(4) in compound 10 and for Br(1) in compound 11.

1ꢀArylꢀ2ꢀnitroꢀ3ꢀtricholormethylaziridines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
1027
Table 4. Selected bond angles in molecules 9—13 in the crystal structures
Angle
ω/deg
9
10
12
13A
13B
13C
C(5)—N(1)—C(3)
C(5)—N(1)—C(2)
C(3)—N(1)—C(2)
O(2)—N(2)—O(1)
O(2)—N(2)—C(2)
O(1)—N(2)—C(2)
N(1)—C(2)—C(3)
N(1)—C(2)—N(2)
C(3)—C(2)—N(2)
N(1)—C(3)—C(2)
N(1)—C(3)—C(4)
C(2)—C(3)—C(4)
C(3)—C(4)—Cl(1)
C(3)—C(4)—Cl(2)
Cl(1)—C(4)—Cl(2)
C(3)—C(4)—Cl(3)
Cl(1)—C(4)—Cl(3)
Cl(2)—C(4)—Cl(3)
122.51(4)
126.19(4)
62.37(3)
125.41(5)
115.98(4)
118.61(4)
58.80(3)
119.64(4)
114.68(4)
58.83(3)
118.83(4)
122.39(5)
112.53(4)
108.27(3)
109.77(3)
107.01(4)
109.31(3)
109.89(3)
122.22(14)
125.82(14)
62.05(11)
125.04(16)
116.14(14)
118.82(14)
59.12(11)
119.40(14)
114.65(14)
58.83(11)
118.57(15)
122.24(15)
112.65(12)
108.45(12)
109.33(10)
107.31(13)
109.20(10)
109.87(9)
123.11(9)
123.85(9)
62.00(7)
125.38(11) 125.18(15)
115.83(10) 119.12(13)
118.77(9)
58.73(7)
118.39(9)
114.93(9)
59.28(7)
118.25(9)
121.31(9)
107.68(7)
112.49(7)
110.08(6)
108.58(7)
109.02(6)
108.91(6)
123.41(12)
125.12(12)
62.35(10)
122.24(12)
124.69(12)
61.99(10)
124.94(13)
119.05(12)
116.00(12)
118.69(12)
58.81(9)
122.46(12)
124.45(12)
61.80(10)
125.22(14)
116.32(13)
118.43(13)
58.72(9)
117.72(12)
115.01(13)
59.48(9)
117.92(13)
123.16(13)
113.42(11)
109.24(11)
109.30(8)
107.01(11)
108.85(8)
108.91(8)
115.64(15)
117.60(13)
58.61(9)
116.42(14)
59.04(9)
116.19(13)
121.69(14)
109.65(11)
112.41(11)
108.95(9)
108.07(11)
109.37(8)
108.34(8)
116.51(12)
59.19(9)
116.16(12)
121.19(13)
108.93(10)
112.15(11)
109.45(8)
107.87(10)
109.77(8)
108.64(8)
112.7(2)—117(2)° and 40.4(2)—46.6(2)° in the case of
the naphthyl substituent and 128.9(1)—130.1(1)° and
31.9(1)—32.9(1)° in the case of the paraꢀhalophenyl subꢀ
stituent.
in the gas phase increase to 1.786—1.802 Å, but the C—Cl
bonds antiperiplanar to the C—C and C—N bonds of the
aziridine moiety remain elongated. The orbital populaꢀ
tion analysis at the NBO level12,13 (the wave function was
obtained from the calculations for compound 10 by the
DFT method (B3LYP/6ꢀ311G*)) showed that the elonꢀ
gation of the C(4)—Cl(2) and C(4)—Cl(3) bonds is
associated with the stereoelectronic interactions between
the “banana” bonds of the aziridine ring and the antiꢀ
periplanar C—Cl bonds. The energy of the charge transfer
from the banana bond to the σ*(C—Cl) bond is 3.67 and
2.44 kcal mol–1 for the C(2)—C(3) and C(1)—N(1) bonds,
respectively.
In addition to the NBO analysis, the chemical bondꢀ
ing in compound 10 was studied by the Bader theory of
Atoms in Molecules.14 As has been demonstrated previꢀ
ously,15 this theory makes it possible to reveal finer details
compared to the commonly recognized NBO localization
procedure.
An analysis of the electron density distribution funcꢀ
tion (ρ(r)) based on the results of MP2 calculations
revealed the bond critical points (3,–1) (CP (3,–1)) not
only for all expected bonds but also for the intramolecular
C(10)—H(10)...Cl(3) contact (H...Cl, 3.105 Å; CHCl,
137.9°). In spite of the low value of ρ(r) at CP (3,–1) for
the H...Cl contact (0.03 eÅ–3), the substantial distance
between CP (3,–1) and CP (3,+1) of the attached ring
(0.40 Å) indicates that the molecular graph is sufficiently
stable. The ellipticity of CP (3,–1) corresponding to the
N(1)—C(5) bond is 0.02, which unambiguously indicates
that there is no conjugation between the nitrogen lone
pair and the benzene ring. The estimation of the energy of
Although there are no steric factors, which could fix
the conformation of the CCl3 group, the latter is arranged
in all compounds so that the C(4)—Cl(2) and C(4)—Cl(3)
bonds are antiperiplanar to the C(2)—C(3) and C(2)—N(1)
bonds of the aziridine ring, and the C(4)—Cl(1) bond lies
in the bisecting plane of the C(2)—C(3)—N(1) angle (see
Figs 1—4). As opposed to the nitro group, the arrangeꢀ
ment of the CCl3 group with respect to the aziridine
moiety is independent of the nature of the aromatic subꢀ
stituent. A slight change in the Cl(1)—C(4)—C(3)—N(1)
torsion angle (31.6(1)—43.2(1)°) is apparently determined
by the crystal packing effects. Interestingly, the C—Cl
bonds in the CCl3 group have different lengths in all the
molecules under study. The difference between the longest
and shortest C—Cl bonds varies from 0.01 to 0.02 Å
depending on the molecule (see Table 3). The ratio
between the C(4)—Cl(1), C(4)—Cl(2), and C(4)—Cl(3)
bond lengths has a common trend in all the molecules in
the crystal structures of 10—13. In five of the six molecules,
the C(4)—Cl(3) bond is the longest one and its length is
larger than the other two bonds by 0.01—0.02 Å.
This difference in the bond lengths can be attributed
to both the stereoelectronic effects in the molecules and
the influence of intermolecular interactions in the crystal
structures. To analyze the stereoelectronic effects, we
carried out ab initio calculations for molecule 10 in the
isolated state by the MP2 method with the 6ꢀ311G* basis
set. The calculations showed that the C—Cl bond lengths

1028
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
Berestovitskaya et al.
this interaction in terms of the Espinosa correlation
scheme16,17 gave 0.67 kcal mol–1. Therefore, in addition
to the steric factors, the invariable mutual arrangement of
the aryl substituent and the CCl3 group is attributed also
to the binding interactions between these moieties. The
charges on the chlorine atoms of the CCl3 group, which
were evaluated by the integration over the corresponding
atomic basins, are –0.152, –0.172, and –0.176 e for the
Cl(1), Cl(2), and Cl(3) atoms, respectively. These values
are in qualitative agreement with the dependences
revealed previously for the stereoelectronic N—C—S
interactions.15 Thus, the Cl(2) and Cl(3) atoms acquire
an additional negative charge. It should be noted that the
higher charge is observed for the chlorine atom involved
in the interaction with the more donor (NBO data) C—C
bond of the aziridine moiety. This atom is characterized
also by the longer (by 0.005 Å) C—Cl bond. However, the
change in the energy for the Cl(2) and Cl(3) atoms
estimated by the integration of the local electron energy
density (he(r)) over the atomic basins appeared to be oppoꢀ
site to the change in the charge (+2.4 and +2.8 kcal mol–1
with respect to the energy of Cl(1)) for the Cl(2) and
Cl(3) atoms, respectively), which is inconsistent with the
correlations found for the N—C—S system.15 This can be
attributed to the fact that the stereoelectronic interaction
is very weak and, consequently, the relative energies of
the Cl(2) and Cl(3) atoms are influenced by other factors,
for example, by the polarization of the Cl(1) atom caused
by the density of the aziridine ring, as well as to the fact
that the interaction with the banana bond can differ in
nature from the interaction with the lone pair and, conseꢀ
quently, can have a different effect on the integrated propꢀ
erties of the atoms.
C—Cl—O angle is close to 180° and the Cl—N—O angle
is virtually equal to 120°), it is reasonable to suggest that
these contacts correspond to the charge transfer from the
oxygen lone pair of the NO2 group to the antibonding
orbital of the Cl—C bond.
In the crystals, molecules 10 and 11 are arranged in
layers through Hal...O2N interactions, where Hal = Cl
or Br (Fig. 5, a). These contacts can be considered as
structuring interactions, because the CCl3...NO2 contacts
remain unchanged upon the replacement of the chlorine
substituent in the para position at the benzene ring (in the
crystal of 10) by the bromine atom (in the crystal of 11).
The only considerable difference is observed for the
Br...O2N contact of the para substituent; the elongation
of the latter by 0.015 Å compared to the Cl...O2N contact
in the crystal of 10 corresponds to the difference in the
van der Waals radii of these halogen atoms. The differꢀ
ence in the X—O—N angles is within experimental error.
In the crystal of compound 9, in which the halogen atom
at the benzene ring is replaced by the methyl group, shortꢀ
ened Cl...O2N contacts (Cl...O, 2.83 Å) are also observed.
In the crystal structure, molecules 9 are linked together by
these contacts to form chains. In turn, the character of
a
The rotation barrier can serve as another independent
estimate of the energy of stereoelectronic interactions. The
potential surface scan along the Cl(1)—C(4)—C(3)—N(1)
torsion angle coordinate by the density functional theory
at the B3LYP/6ꢀ311g(d) level gave the rotation barrier
of the CCl3 group equal to 4.1 kcal mol–1. Taking into
account the fact that the steric barriers to rotation of the
CCl3 group are virtually absent, this energy can serve as
an indirect estimate for the stereoelectronic interaction
between the trichloromethyl group and the aziridine ring.
As for the experimental bond lengths, it should be
noted that the C(4)—Cl(1) bond, which is not involved
in stereoelectronic interactions, is not the shortest bond,
at least in molecules 13A and 13C. This is apparently
attributed to the crystal packing effect. Actually, in all
the crystals under study, the CCl3 groups are involved in
the formation of relatively strong Cl...O contacts with the
NO2 groups. The O...Cl distance varies in the range of
2.92—3.25 Å. The Cl—O—N angles are 175.6—100.8°.
The geometry of these contacts is typical of Cl...O2N
interactions.18 Since the shortest Cl...O2N contacts are
characterized by a pronounced directionality (i.e., the
Cl
Br
O
N
b
Cl
O
N
Fig. 5. Fragments of the layers in the crystal structures of comꢀ
pounds 11 (a) and 12 (b).

1ꢀArylꢀ2ꢀnitroꢀ3ꢀtricholormethylaziridines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
1029
the crystal packing changes in the presence of the metaꢀ
nitrophenyl substituent at the aziridine fragment. In the
crystal of 12, the molecules form layers through Cl...NO2
and Cl...Cl interactions (Cl...Cl, 3.271(3)—3.444(3) Å)
(see Fig. 5, b), and the layers are linked only by weak
C—H...Cl contacts.
C(3)
Therefore, the contribution of the X...O2N interacꢀ
tions (X = Cl or Br) to the stability of the crystals of
1ꢀarylꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridines is relatively
high. Hence, it can be concluded that it is these contacts
that determine the preferable crystal packing of the comꢀ
pounds under consideration.
C(2)
N(1)
In the crystal structure of 13, both Cl...O contacts and
NO2...NO2 interactions are observed. Thus, the O(2B)
atom forms a shortened contact with the NO2 group of
13C (O(2B)...N(2C), 2.794(5) Å; N(2B)—O(2B)—N(2C),
164.2(2)°), which corresponds to the interaction between
the oxygen lone pair and the antibonding orbital of the
nitro group.
Fig. 6. Deformation electron density map in the plane of the
aziridine ring in the crystal structure of 10 contoured at 0.05 eÅ
intervals; dashed lines indicate the negative values and the zero
contour.
–3
To study in more detail the nature of intermolecular
interactions and the influence of these interactions on the
charge distribution, we studied the electron density distriꢀ
bution in the crystal structure of 10 based on highꢀresoluꢀ
tion Xꢀray diffraction data (Fig. 6). The static function
ρ(r) was determined by the multipole refinement (see the
Experimental section).
orbital of the N—O bond (see Fig. 7, a) or the back
donation from the oxygen atom to the C—Cl σ*ꢀbond
(see Fig. 7, b). In this case, such interaction will lead to
a substantial charge redistribution predominantly at the
chlorine atoms and the NO2 group compared to the isolated
molecule.
As in the isolated molecule, in the crystal of 10 there is
the intramolecular C(10)—H(10)...Cl(3) contact with ρ(r)
at CP (3,–1) equal to 0.04 eÅ–3 and the energy of the
contact Econt equal to 0.72 kcal mol–1. Therefore, even the
presence of intermolecular interaction has virtually no
effect on this intramolecular contact.
Indeed, the ratio of the charges on the chlorine atoms
of the CCl3 group in the crystal structure differs from that
a
It should be expected that the banana bonds in the
threeꢀmembered ring would be distorted compared to
single covalent bonds in unconjugated structures. Indeed,
the maximum in the deformation electron density map
for the aziridine ring (Fig. 7) deviates from the bond line.
Moreover, an analysis of the topological parameters at
CP (3,–1) for the bonds of the aziridine ring showed that
they are characterized by unusually high degrees of ellipꢀ
ticity (from 0.64 for the N(1)—C(3) bond to 1.31 for the
C(2)—C(3) bond), which is characteristic of banana
bonds, π bonds, and threeꢀmembered rings in carboranes.19
An analysis of the bond paths in the aziridine ring in both
the crystal and the isolated molecule showed that, unlike
cyclopropanes, the deviation of the bond path from the
line between the nuclei of the atoms is small and has
the maximum value (0.02 Å) for the N(1)—C(2) bond in
the crystal.
Cl(2)
N(2)
O(1)
b
Cl(4)
O(2)
Based on the deformation electron density distribuꢀ
tion in the corresponding planes, it can be concluded
that, depending on the geometry of the interaction (to be
more precise on the angle at the chlroine atom), the charꢀ
acter of Cl...NO2 interactions can be interpreted as either
the transfer of the chlorine lone pair to the antibonding
Fig. 7. Deformation electron density distribution in the region of
the O(1)...Cl(2) (a) and O(2)...Cl(4) (b) contacts in the crystal
structure of 10 contoured at 0.1 eÅ intervals; dashed lines
–3
indicate the negative values and the zero contour.

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Berestovitskaya et al.
Table 5. Topological parameters* at the critical points (3,–1) for Cl...O2N interactions in the crystal structure of 10
2
Interaction
Symmetry
operation
d/Å
ρ(r)
∇ ρ(r)
/eÅ–5
V(r)
/a.u.
Econt
/kcal mol–1
/eÅ–3
Cl(2)—O(1)
Cl(1)—O(2)
Cl(1)—O(1)
Cl(1)—O(2)
Cl(4)—O(2)
2 – x, 1 – y, –1/2 + z
3/2 + x, –1/2 – y, z
x – 1, y, z
2.964(1)
3.306(1)
3.408(1)
3.209(1)
3.044(1)
0.08
0.04
0.03
0.05
0.06
1.13
0.56
0.48
0.69
0.85
–0.00716
–0.00292
–0.00240
–0.00382
–0.00505
2.2
0.9
0.8
1.2
1.6
x – 1, y, z
x, y, z + 1
2
* ∇ ρ(r) is the Laplacian of the electron density, V(r) is the potential energy density, and Econt is the energy of
intermolecular interactions calculated in terms of the Espinosa correlation scheme.
observed in the isolated molecule. Thus, the absolute
values of the charges on the Cl(1) (–0.35 e) and Cl(2)
(–0.38 e) atoms are substantially higher than the charge
on the Cl(3) atom (–0.26 e).
the substituents at the aziridine ring and gave estimates
for the stereoelectronic interactions between the banana
bond and the σ*(C—Cl) bond and the influence of the
crystal packing on the character of charge distribution in
the molecules.
An analysis of the experimental electron density disꢀ
tribution function ρ(r) revealed the presence of the bond
critical points (3,–1) for all Cl...O2N contacts, whose
lengths are smaller than the sums of the van der Waals
radii of the corresponding atoms, and also for two other
Cl...O2N contacts, whose lengths are only slightly larger
than the sum of the van der Waals radii of the Cl and O
atoms (Table 5). The positive values of the Laplacian and
h(r) at these points indicate that the Cl...O2N interactions
correspond to the closed shells. According to the estiꢀ
mates of the strength of intermolecular contacts in terms
of the Espinosa correlation scheme,16,17 the energies of
interactions between the trichloromethyl group and the
nitro groups characterized by the Cl...O distances smaller
than the sum of the van der Waals radii (Cl(2)...O(1) and
Cl(1)...O(2)) are 2.2 and 1.2 kcal mol–1, respectively,
which suggests that these interactions play a structureꢀ
forming role in the crystal of compound 10. The Cl...O2N
interaction involving the Cl(4) atom bound to the
benzene ring has a comparable energy (1.58 kcal mol–1).
It should be noted that of the three chlorine atoms of the
CCl3 group, only the Cl(1) and Cl(2) atoms are linked
to the NO2 groups by intermolecular interactions. As can
be seen from Table 5, the total energy of the interactions
is comparable and is 2.87 and 2.25 kcal mol–1, respecꢀ
tively. On the contrary, the Cl(3) atom is not involved in
the aboveꢀmentioned interactions, which is apparently
responsible for such a substantial difference of its charge
in the crystal.
Experimental
The IR spectra were recorded on an InfraLyum FTꢀ02 Fourierꢀ
transform spectrometer in chloroform (c 0.1—0.001 mol L–1).
The electronic absorption spectra were measured in ethanol
on a Shimadzu UV2401PC spectrophotometer in quartz cells
(l 0.1 cm, c 0.00037—0.00046 mol L–1). The H and 13C NMR
1
spectra were recorded on Bruker WMꢀ400, Bruker ACꢀ200, and
Jeol JNMꢀECX400A spectrometers operating at 400.13 MHz
(1H), 50.323 MHz (13C) and 399.78 MHz (1H), 100.525 MHz
(13C) in CDCl3 and DMSOꢀd6 with the use of the residual signal
of the nondeuterated solvent as the internal standard. The chemiꢀ
cal shifts were measured with an accuracy of 0.5 Hz on the
δ scale. The mass spectra were obtained on a MX 1321 mass
spectrometer using a direct inlet system; the ionization voltage
was 70 V; the temperature of the ionization chamber was 180 °C.
Crystals of compounds 9—13 suitable for the Xꢀray diffracꢀ
tion study were grown from diethyl ether.
The Xꢀray diffraction study of compounds 8—13 was carried
out on a SMART APEX II CCD diffractometer (MoꢀKα radiaꢀ
tion, graphite monochromator, ωꢀscanning technique). The
structures were solved by direct methods and refined anisotropiꢀ
cally by the fullꢀmatrix leastꢀsquares method based on F2hkl. An
analysis of the temperature factors and difference Fourier maps
revealed a superposition of two mirrorꢀsymmetric isomers in the
crystals of 9, such that the CCl3 group and the C(9)—C(10) and
C(2)—C(3) bonds are common. The reciprocal space analysis
revealed no twinning. In turn, the structure refinement in the
monoclinic system on the assumption that the orthorhombic
system is determined by the systematic twinning did not elimiꢀ
nate the disorder (BASF 0.0) as well. Based on this fact, the final
structure refinement was carried out in the space group Pna21
and some atoms were refined isotropically. The hydrogen atoms
were located in difference Fourier maps and refined isotropically
for the structures of 10—13 and using a riding model for the
structure of 9. Principal crystallographic data and the Xꢀray data
collection and structure refinement statistics are given in Table 6.
All calculations were carried out using the SHELXTL PLUS
program package.20
To sum up, we developed the preparative procedure
for the synthesis of 1ꢀarylꢀ2ꢀnitroꢀ3ꢀtrichloromethylꢀ
aziridines. The structures of these compounds were conꢀ
1
firmed by IR, UV, and H and 13C NMR spectroscopy,
mass spectrometry, and Xꢀray diffraction. The Xꢀray difꢀ
fraction studies, including the analysis of the electron
density distribution in the crystals, and quantum chemical
calculations for the molecules in the gas phase revealed
the factors stabilizing the observed mutual arrangement of

1ꢀArylꢀ2ꢀnitroꢀ3ꢀtricholormethylaziridines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
1031
Table 6. Principal crystallographic parameters and the Xꢀray data collection and refinement statistics for compounds 9—13
Parameter
9
10
11
12
13
Molecular formula
Molecular weight
T/K
C10H9Cl3N2O2
295.54
100
C9H6Cl4N2O2
315.96
100
C9H6BrCl3N2O2
360.42
100
C9H6Cl3N3O4
326.52
C13H9Cl3N2O2
331.57
100
100
Crystal system
Space group
Z (Z´)
Orthorhombic
Pna21
Orthorhombic
Pna21
Orthorhombic
Pna21
Triclinic
Pꢀ1
Monoclinic
P21/n
4
4
4
2
12 (3)
a/Å
b/Å
c/Å
α/deg
33.404(4)
6.1528(7)
6.1514(6)
90.00
90.00
90.00
1264.3(2)
1.553
7.15
7.9594(5)
14.9116(9)
10.4502(6)
90.00
90.00
90.00
7.9345(7)
14.9026(14)
10.5952(9)
90.00
90.00
90.00
1252.83(19)
1.911
8.6497(3)
8.8089(4)
9.2167(5)
106.2612(9)
94.9897(8)
107.9308(6)
629.79(5)
1.722
8.4810(4)
16.3054(7)
30.4277(14)
90.00
94.3931(9)
90.00
4195.4(3)
1.575
6.56
β/deg
γ/deg
V/Å3
1240.31(13)
1.692
dcalc/g cm–3
μ/cm–1
9.43
39.1
7.40
F(000)
600
632
704
328
2016
2θmax/deg
54
110
60
65
58
Number of measured
reflections
Number of independent
reflections
Number of reflections
with I > 2σ(I)
Number of refined
parameters
R1
12818
69669
10708
29098
50692
2840
1978
146
15539
13537
179
3583
3357
155
4555
3953
196
11146
9383
542
0.0594
0.1327
0.0269
0.0672
0.0204
0.0491
0.0286
0.0711
0.0338
0.0788
wR2
GOOF
1.025
1.016
0.874
1.000
1.034
Residual electron
density/eÅ–3 (dmax/dmin
0.550/–0.452
0.747/–0.466
0.278/–0.380
0.593/–0.308
0.556/–0.373
)
The multipole refinement of compound 10 was carried out
in terms of the Hansen—Coppens model21 with the use of the
XD program package.22 Before the refinement, all C—H disꢀ
tances were normalized to the ideal distance determined by neuꢀ
tron diffraction (1.08 Å).23 The refinement was performed based
on Fhkl; the final R factors were R = 0.0194, Rw = 0.0202,
GOOF = 0.9227 for 6386 reflections with I > 2σ(I). The validity
solvents.28 The course of the reactions was monitored and the
individuality of the reaction products was checked by thinꢀlayer
chromatography on Silufol UVꢀ254 plates using a hexane—
acetone mixture (2 : 1, v/v); the visualization was carried out
with iodine vapor and on a chromascope.
The starting 1ꢀbromoꢀ3,3,3ꢀtrichloroꢀ1ꢀnitropropene was
synthesized according to a known procedure.6
2
of the refinement was checked from the difference (Δ < 0.001 Å )
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]aniline (2).
A solution of freshly distilled aniline (0.323 mL, 0.331 g,
3.55 mmol) in anhydrous methanol (5 mL) was added dropwise
to a solution of 1ꢀbromoꢀ3,3,3ꢀtrichloroꢀ1ꢀnitropropene (1)
(0.958 g, 3.55 mmol) in anhydrous methanol (5 mL). The reacꢀ
tion mixture was kept at room temperature for 1 h and then
poured into ice crumbs. The resulting emulsion was extracted
with diethyl ether (2×30 mL), and the ethereal solution was
dried with MgSO4. After removal of the solvent, an oily subꢀ
stance was obtained in a yield of 1.090 g. The substance was
chromatographed on a silica gel column. Oily compound 2
was isolated in a yield of 1.00 g (77%), Rf 0.64, from the fracꢀ
tions eluted with hexane and carbon tetrachloride. Found (%):
C, 30.08; H, 2.63; N, 7.85. C9H8BrCl3N2O2. Calculated (%):
C, 29.83; H, 2.22; N, 7.73.
between the meanꢀsquare vibration amplitudes for bonded
atoms (Hirshfeld rigidꢀbond test). The topological analysis of
the experimental electron density distribution function was
carried out with the use of the WinXPRO program package.24
The quantum chemical calculations for compound 10 at the
B3LYP level of theory were performed using the Gaussian 03
program package.25 The potential energy surface was scanned
along the Cl(1)—C(4)—C(3)—N(1) torsion angle coordinate in
the range of 0—360° with a step of 5°. The calculations for
compound 10 were performed by the MP2 method with the
use of the PCꢀGAMESS program package.26 The topological
analysis of the wave function was carried out using the AIMAll
program package.27
The reaction products were purified and separated by recrystalꢀ
lization and column chromatography on Chemapol 100/250 LD
silica gel, 100/400 (Czech Republic) with a substance to support
weight ratio of 1 : 10 — 1 : 20 using Trappe’s eluotropic series of
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀpꢀtoluidine
(3) was synthesized analogously to compound 2 starting from
pꢀtoluidine (the reaction mixture was kept for 2 h). Oily comꢀ

1032
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
Berestovitskaya et al.
pound 3 was isolated in 71%, Rf 0.50, from the fraction
eluted with nꢀhexane. Found (%): C, 32.03; H, 2.86; N, 7.53.
C10H10BrCl3N2O2. Calculated (%): C, 31.90; H, 2.68; N, 7.44.
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ4ꢀchloroꢀ
aniline (4) was synthesized analogously to compound 2 starting
from pꢀchloroaniline (the reaction mixture was kept for 3.5 h).
Oily compound 4 was isolated in 67% yield, Rf 0.45, from
the fraction eluted with nꢀheptane. Found (%): N, 7.19.
C9H7Cl4BrN2O2. Calculated (%): N, 7.05.
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ4ꢀbromoꢀ
aniline (5) was synthesized analogously to compound 2, starting
from pꢀbromoaniline (the reaction mixture was kept for 2 h).
Oily compound 5 was isolated in 59% yield, Rf 0.65, from the
fraction eluted with nꢀhexane. Found (%): C, 24.87; H, 1.93;
N, 6.62. C9H7Br2Cl3N2O2. Calculated (%): C, 24.49; H, 1.60;
N, 6.35.
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ3ꢀnitroaniline
(6) was synthesized analogously to compound 2 starting from
mꢀnitroaniline (the reaction mixture was kept for 2 h). Oily
compound 6 was isolated in 52% yield, Rf 0.50, from the fraction
eluted with carbon tetrachloride. MS, m/z: 407 [M]+.
Nꢀ[2ꢀBromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ1ꢀnaphthylꢀ
amine (7) was synthesized analogously to compound 2 starting
from 1ꢀnaphthylamine (the reaction mixture was kept for 1.5 h).
Oily compound 7 was isolated in 46% yield, Rf 0.60, from the
fraction eluted with carbon tetrachloride. Found (%): N, 6.73.
C13H10BrCl3N2O2. Calculated (%): N, 6.79.
2ꢀNitroꢀ1ꢀphenylꢀ3ꢀtrichloromethylaziridine (8). A hot soluꢀ
tion of potassium acetate (0.362 g, 3.69 mmol) was added to a
boiling solution of Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ꢀ
ethyl]aniline (2) (0.891 g, 2.46 mmol) in ethanol (25 mL). After
refluxing for 6 h, the reaction mixture was poured into a beaker
with ice crumbs. The resulting emulsion was extracted with
diethyl ether (2Ѕ30 mL), and the ethereal solution was dried
with MgSO4. After removal of the solvent, a dark oily substance
was obtained in a yield of 0.546 g. The substance was chromatoꢀ
graphed on silica gel. Crystalline compound 8 was isolated in a
yield of 0.173 g (25%), m.p. 58—59 °C (from an ethanol—water
mixture, 4 : 1), from the fraction eluted with nꢀhexane.
Found (%): C, 38.51; H, 2.69; N, 9.86. C9H7Cl3N2O2. Calcuꢀ
lated (%): C, 38.40; H, 2.51; N, 9.95. 13C {1H} NMR (CDCl3),
δ: 56.4 (Cl3CC), 71.9 (O2NC), 94.5 (Cl3C), 142.7, 129.8, 125.3,
118.5 (Ar).
1ꢀ(pꢀBromophenyl)ꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridine (11)
was synthesized analogously to compound 8 starting from
Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ4ꢀbromoaniline
5 and potassium acetate (the reaction mixture was kept for
4 h). Crystalline compound 11 was isolated in 36% yield,
m.p. 106—107 °C (from petroleum ether), from the fraction
eluted with nꢀhexane. Found (%): C, 30.19; H, 2.06; N, 7.88.
C9H6BrCl3N2O2. Calculated (%): C, 29.99; H, 1.68; N, 7.77.
MS, m/z: 360 [M]+. 13C NMR (CDCl3), δ: 55.8 (d, Cl3CCH,
J = 182.3 Hz), 71.2 (d, O2NCH, J = 220.5 Hz), 93.7 (Cl3C),
141.3, 132.3 (d, J = 167.8 Hz), 119.6 (d, J = 160.4 Hz),
1
117.7 (Ar). H NMR (DMSOꢀd6), δ: 4.92 (d, 1 H, CHCCl3,
1,3J = 0.9); 6.03 (d, 1 H, O2NCH, 1,3J = 0.9 Hz); 7.52 and 7.08
(both d, 2 H each, Ar). 13C {1H} NMR (CDCl3), δ: 55.8 (Cl3CC),
71.2 (O2NC), 93.7 (Cl3C), 141.3, 132.3, 119.6, 117.7 (Ar).
2ꢀNitroꢀ1ꢀ(mꢀnitrophenyl)ꢀ3ꢀtrichloromethylaziridine (12)
was synthesized analogously to compound 8 starting from
Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ3ꢀnitroaniline 6
and potassium acetate (the reaction mixture was kept for 4.5 h).
Crystalline compound 12 was isolated in 19% yield, m.p. 82—84 °C
(from petroleum ether), from the fraction eluted with carbon
tetrachloride. MS, m/z: 327 [M]+. 13C {1H} NMR (CDCl3), δ:
56.4 (Cl3CC), 71.4 (O2NC), 93.7 (Cl3C), 149.6, 144.0, 130.8,
124.4, 120.1, 113.8 (Ar).
1ꢀNaphthylꢀ2ꢀnitroꢀ3ꢀtrichloromethylaziridine (13) was
synthesized analogously to compound 8 starting from Nꢀ[2ꢀbromoꢀ
2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ1ꢀnaphthylamine 7 and potasꢀ
sium acetate (the reaction mixture was kept for 5 h). Crystalline
compound 13 was isolated in 27% yield, m.p. 116—117 °C (from
an ethanol—water mixture, 2 : 1), from the fraction eluted with
nꢀhexane. Found (%): N, 8.42. C13H9Cl3N2O2. Calculated (%):
N, 8.45.
This study was financially supported by the Council
on Grants of the President of the Russian Federation
(Program for State Support of Leading Scientific Schools
of the Russian Federation, Grant MDꢀ172.2008.3),
the Russian Foundation for Basic Research (Project
No. 06ꢀ03ꢀ32557ꢀa), and the Government of Saint Petersꢀ
burg (Grant MKN 30ꢀ04/108).
References
2ꢀNitroꢀ1ꢀ(pꢀtolyl)ꢀ3ꢀtrichloromethylaziridine (9) was synꢀ
thesized analogously to compound 7 starting from Nꢀ[2ꢀbromoꢀ
2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀpꢀtoluidine 3 and potassium
acetate (the reaction mixture was kept for 2 h). Crystalline comꢀ
pound 9 was isolated in 30% yield, m.p. 86—87 °C (from an
ethanol—water mixture, 4 : 3), from the fraction eluted with
nꢀhexane. Found (%): C, 40.85; H, 3.36; N, 9.54. C10H9Cl3N2O2.
Calculated (%): C, 40.64; H, 3.07; N, 9.47. MS, m/z: 294 [M]+.
13C {1H} NMR (CDCl3), δ: 20.8 (CH3) 56.4 (Cl3CC), 72.0
(O2NC), 94.5 (Cl3C), 140.2, 135.0, 130.3, 118.3 (Ar).
2ꢀNitroꢀ1ꢀ(pꢀchlorophenyl)ꢀ3ꢀtrichloromethylaziridine (10)
was synthesized analogously to compound 8 starting from
Nꢀ[2ꢀbromoꢀ2ꢀnitroꢀ1ꢀ(trichloromethyl)ethyl]ꢀ4ꢀchloroaniline
4 and potassium acetate (the reaction mixture was kept for 4 h).
Crystalline compound 10 was isolated in 37% yield, m.p. 69—71 °C
(from an ethanol—water mixture, 3 : 1), from the fraction eluted
with nꢀhexane. Found (%): C, 34.80; H, 2.05; N, 8.95. C9H6Cl4N2O2.
Calculated (%): C, 34.58; H, 1.90; N, 8.86.
1. T. L. Gilchrist, Heterocyclic Chemistry, 2nd ed., Longman
Group UK Ltd, London, 1992.
2. M. D. Mashkovskii, Lekarstvennye sredstva [Drugs], Novaya
Volna, Moscow, 2005, p. 973 (in Russian).
3. Registr lekarstvennykh sredstv Rossii. Entsiklopediya lekarstv
[Register of Drugs in Russia. Encyclopedia of Drugs], OOO
RLSꢀ2002, Moscow, 2002, Issue 9, p. 836 (in Russian).
4. A. T. Soldatenkov, N. M. Kolyadina, I. V. Shendrik, Osnovy
organicheskoi khimii lekarstvennykh veshchestv [Foundations
of Organic Chemistry of Medicines], Khimiya, Moscow, 2001,
p. 75 (in Russian).
5. G. S. Singh, M. D´hooghe, N. De Kimpe, Chem. Rev., 2007,
107, 2080.
6. J. A. Durden, D. L. Heywood, A. A. Sousa, H. W. Spurr,
J. Agr. Food Chem., 1970, 18, 1, 50.
7. V. I. Slovetskii, Usp. Khim., 1971, 40, 4, 740 [Russ. Chem.
Rev. (Engl. Transl.), 1971, 40, 4, 393].

1ꢀArylꢀ2ꢀnitroꢀ3ꢀtricholormethylaziridines
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 5, May, 2009
1033
8. V. I. Slovetskii, Izv. Akad. Nauk SSSR, Ser. Khim., 1970,
2215 [Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.),
1970, 19, 2215].
9. N. A. Sokolov, Yu. G. Chernov, Yu. V. Glazkov, Zh. Org.
Khim., 1972, 8, 2325 [J. Org. Chem. USSR, 1972, 8, 2325].
10. L. D. Vitis, S. Florio, C. Granito, L. Ronzini, L. Troisi,
V. Capriati, R. Luisi, T. Pilati, Tetrahedron, 2004, 60, 1175.
11. (a) Cambridge Structural Database, ver. 5.29 (November
2007, updates January 2008); (b) F. H. Allen, Acta Crystallogr.
B, 2002, 58, 380.
12. A. E. Reed, F. Weinhold, J. Chem. Phys., 1983, 78, 4066.
13. A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem. Phys.,
1985, 83, 735.
14. R. F. W. Bader, Atoms in Molecules. A Quantum Theory,
Clarendron Press, Oxford, 1990.
23. J. E. Worsham Junior, W. R. Busing, Acta Crystallogr. B,
1969, 25, 572.
24. A. Stash, V. Tsirelson, WinXPRO, A program for Calculation
of the Crystal and Molecular Properties Using the Model Elecꢀ
tron Density, 2001; A. Stash, V. G. Tsirelson, Acta Crystallogr.,
2002, 35, 371.
25. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr.,
T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S.
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi,
G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji,
M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross,
C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann,
O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador,
J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels,
M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck,
K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G.
Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu,
A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J.
Fox, T. Keith, M. A. AlꢀLaham, C. Y. Peng, A. Nanayakkara,
M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen,
M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, Reviꢀ
sion B.02, Gaussian, Inc., Pittsburgh PA, 2003.
15. I. S. Bushmarinov, M. Yu. Antipin, V. R. Akhmetova, G. R.
Nadyrgulova, K. A. Lyssenko, J. Phys. Chem. A, 2008, 112,
5017.
16. E. Espinosa, E. Molins, C. Lecomte, Chem. Phys. Lett.,
1998, 285, 170.
17. E. Espinosa, I. Alkorta, I. Rozas, J. Elguero, E. Molins,
Chem. Phys. Lett., 2001, 336, 457.
18. F. H. Allen, J. P. M. Lommerse, V. J. Hoy, J. A. K. Howard,
G. R. Desiraju, Acta Crystalllogr. B, 1997, 53, 1006.
19. (a) I. V. Glukhov, K. A. Lyssenko, A. A. Korlyukov, M. Yu.
Antipin, Izv. Akad. Nauk, Ser. Khim., 2005, 541 [Russ. Chem.
Bull., Int. Ed., 2003, 52, 547]; (b) K. A. Lyssenko, M. Y.
Antipin, V. N. Lebedev, Inorg. Chem., 1998, 37, 5834.
20. G. M. Sheldrick, SHELXTLꢀ97, Version 5.10, Bruker AXS
Inc., Madison, WIꢀ53719, USA.
26. A. A. Granovsky, PC GAMESS version 7.1 (http://classic.
chem.msu.su/ gran/gamess/index.html), 2007.
27. T. A. Keith, AIMAll Version 08.01.25 (http://aim.tkgristmill.com),
2008.
21. N. K. Hansen, P. Coppens, Acta. Crystallogr. A, 1978, 34,
909.
28. Organikum. Organischꢀchemisches Grundpraktikum, Wissenꢀ
schaften, Berlin, 1964.
22. T. S. Koritsansky, S. T. Howard, T. Richter, P. Macchi,
A. Volkov, C. Gatti, P. R. Mallinson, L. J. Farrugia, Z. Su,
N. K. Hansen, XD — A Computer Program Package for Multiꢀ
pole Refinement and Topological Analysis of Charge Densities
from Diffraction Data, 2003.
Received July 17, 2008;
in revised form January 21, 2009