Reaction of 1,2-dialkyldiaziridines with ketenes as a new approach to cyclic and linear systems containing the N-C-N fragment

Article abstract of DOI:10.1007/s11172-005-0351-z

The reaction of 1,2-dialkyldiaziridines with ketenes proceeds through the N-N bond cleavage to form three types of structures containing the N-C-N fragment, viz., 1,3-dialkylimidazolidin-4-ones, 3,5-diacyl-3,5-diazahept-1-enes, and β-lactams. The reaction

Full text of DOI:10.1007/s11172-005-0351-z

Russian Chemical Bulletin, International Edition, Vol. 54, No. 4, pp. 1021—1031, April, 2005
1021
Reaction of 1,2ꢀdialkyldiaziridines with ketenes as a new approach to
cyclic and linear systems containing the N—C—N fragment*
a
a
b
A. V. Shevtsov,a V. Yu. Petukhova, Yu. A. Strelenko, K. A. Lyssenko,
ꢀ
N. N. Makhova,a and V. A. Tartakovskya
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. Eꢀmail: mnn@ioc.ac.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. Eꢀmail: kostya@xrlab.ineos.ac.ru
The reaction of 1,2ꢀdialkyldiaziridines with ketenes proceeds through the N—N bond
cleavage to form three types of structures containing the N—C—N fragment, viz., 1,3ꢀdiꢀ
alkylimidazolidinꢀ4ꢀones, 3,5ꢀdiacylꢀ3,5ꢀdiazaheptꢀ1ꢀenes, and βꢀlactams. The reaction pathꢀ
way depends on the reaction conditions and the structures of the starting compounds.
Key words: diaziridines, ketenes, imidazolidinꢀ4ꢀones, alkenylacetamides, βꢀlactams, Xꢀray
diffraction analysis.
Diaziridines are representatives of strained threeꢀmemꢀ
bered heterocycles, which are highly prone to reactions
accompanied by a decrease in the strain energy.1—3 Most
studies of the reactions of diaziridines with electrophilic
reagents concerned with transꢀ3ꢀmonoꢀ or 3,3ꢀdisubstiꢀ
tuted derivatives, in which one or both nitrogen atoms are
unsubstituted. The introduction of an electronꢀwithdrawꢀ
ing substituent at the nitrogen atoms of such diaziridines
facilitates the diaziridine ring opening at the C—N bond
and promotes the formation of reactive intermediates, in
particular, of azomethine imineꢀtype compounds, which
are then stabilized through the formation of a new linꢀ
ear or heterocyclic system containing the N—N fragꢀ
ment. The reaction can proceed both intramolecularly
and intermolecularly through the 1,3ꢀdipolar cycloaddiꢀ
tion to an appropriate dipolarophile (see, for example,
Scheme 1).4—6
1,2ꢀDialkyldiaziridines 1 behave differently in reacꢀ
tions with electrophilic reagents, although only a few exꢀ
amples were described in the literature.7—9 In particular,
* Dedicated to Corresponding Member of the Russian Acadꢀ
emy of Sciences E. P. Serebryakov on the occasion of his
70th birthday.
Scheme 1
R´ = Alk, Ph
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 997—1006, April, 2005.
1066ꢀ5285/05/5404ꢀ1021 © 2005 Springer Science+Business Media, Inc.

1022
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Shevtsov et al.
Scheme 2
Scheme 3
the reaction of diphenyl ketene with 1,2ꢀdialkyldiaziridiꢀ
nes 1 in boiling benzene7,8 is accompanied by the N—N
bond cleavage to form 1 : 2 adducts, whose structures
depend on the substitution pattern at the carbon atom of
the starting diaziridine. The reactions of 3ꢀmonosubstiꢀ
tuted 1,2ꢀdialkyldiaziridines 1 (n ≠ 0) afford acyclic prodꢀ
uct 2, whereas the reactions with 3ꢀunsubstituted 1,2ꢀdiꢀ
alkyldiaziridines (n = 0) produce βꢀlactam derivatives 3,
which are structurally related to βꢀlactam antibiotics
(Scheme 2). The probable reaction mechanism involves
the nucleophilic attack of the nitrogen atom of diaziridine
on the spꢀhybridized carbon atom of diphenyl ketene folꢀ
lowed by the proton abstraction from the C(3) atom of
the diaziridine ring and the N—N bond cleavage to form
amidineꢀtype intermediate 4. At n = 0, this intermediate
is involved in the 1,2ꢀcycloaddition at the CH=N fragꢀ
ment with the second diphenyl ketene molecule to give
βꢀlactam 3. At n ≠ 0, the addition of the second ketene
molecule proceeds through the second aminalꢀtype interꢀ
mediate 5 to yield acyclic product 2 (see Scheme 2).
The reactions involving phenyl and benzoyl isocyanꢀ
ates were carried out only with 1,2,3ꢀtrialkyldiaziridines.8
The former reaction afforded both linear and cyclic prodꢀ
ucts (in particular, hexahydroꢀ1,3,5ꢀtriazinꢀ2ꢀone and
1,2,4ꢀtriazolidine derivatives). However, all products were
obtained in low yields, and the proposed mechanism of
their formation was not conclusively proved. The reacꢀ
tion with dimethyl acetylenedicarboxylate was studied also
only with 1,2,3ꢀtrialkyldiaziridines.9 This reaction afꢀ
forded the product of the N—N bond cleavage with a
linear structure (Scheme 3).
reactions with electrophilic reagents are scarce in the litꢀ
erature. In this connection, we thoroughly studied the
reactions of 1,2ꢀdialkyldiaziridines with electrophilic reꢀ
agents, such as ketenes with different structures.* This
approach would be expected to give both new βꢀlactam
derivatives 3 and other types of structures containing the
N—C—N fragment.
In the first step of our investigation, we reproduced
the synthesis of βꢀlactams 3 by the reactions of 1,2ꢀdiꢀ
alkyldiaziridines 1a,b with diphenyl ketene 6a to confirm
their structures, because these products have not been
sufficiently characterized in the study.8 The reaction was
carried out under the same conditions (benzene, 80 °C),
but diphenyl ketene 6a was generated in situ from diꢀ
phenylacetyl chloride 7a by adding dropwise a mixture of
the starting diaziridine and Et3N to a benzene solution
Data on the chemical transformation of 1,2ꢀdialkylꢀ
diaziridines unsubstituted at position 3 of the ring in the
* For preliminary communications, see Refs 10 and 11.

Reaction of 1,2ꢀdialkyldiaziridines with ketenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
1023
C(5)
C(31)
C(32)
of 7a heated to 60 °C. Actually, the reaction afforded 1 : 2
adducts, viz., βꢀlactams 3a,b, as the major reaction prodꢀ
ucts in 32—41% yields. Their structures were confirmed
by elemental analysis and spectroscopic methods. The
structure of βꢀlactam 3a was additionally confirmed by
Xꢀray diffraction analysis (Fig. 1, Table 1). The 1H NMR
spectra of βꢀlactams 3 are characterized by the presence
of signals at δ 2.7 corresponding to the diastereotopic
protons of the CH2 fragments of substituents bound to the
nitrogen atom of the fourꢀmembered ring and a singlet of
the cyclic CH fragment.
In the crystal of 3a, the fourꢀmembered nitrogenꢀconꢀ
taining ring is flattened; the folding angle along the
N(2)...C(3) line is 6.3°. The N(1) and N(2) atoms are
slightly pyramidalized and deviate by 0.17 and 0.07 Å
from the planes passing through the C(1), C(3),
C(4) atoms and the C(3), C(18), C(20) atoms, respecꢀ
tively. Apparently, flattening of the nitrogen atoms, as
well as shortening of the N(1)—C(1) and N(3)—C(20)
bonds (1.365(3) and 1.367(3) Å, respectively), are attribꢀ
utable to conjugation with the carbonyl group. The amide
group at the C(3) atom is located approximately in
the bisecting plane of the fourꢀmembered ring; the
O(2)—C(20)—N(2)—C(3) torsion angle is 2.0°.
C(19)
C(4)
N(1)
C(30)
C(29)
C(28)
C(21)
C(33)
C(18)
C(3)
O(1)
C(20)
N(2)
C(1)
O(2)
C(2)
C(6)
C(12)
C(13)
C(14)
C(16)
C(15)
C(22)
C(27)
C(23)
C(24)
C(17)
C(7)
C(11)
C(10)
C(26)
C(25)
C(8)
C(9)
Fig. 1. Overall view of NꢀethylꢀNꢀ(1ꢀethylꢀ4ꢀoxoꢀ3,3ꢀdiphenylꢀ
azetidinꢀ2ꢀyl)ꢀ2,2ꢀdiphenylacetamide 3a.
Table 1. Selected bond lengths (d) and bond angles (ω) in comꢀ
pound 3a
Bond
d/Å
Bond
d/Å
O(1)—C(1)
O(2)—C(20)
N(1)—C(1)
N(1)—C(3)
N(1)—C(4)
1.205(3)
1.226(3)
1.365(3)
1.453(3)
1.458(3)
N(2)—C(20)
N(2)—C(3)
N(2)—C(18)
C(1)—C(2)
C(2)—C(3)
1.367(3)
1.449(3)
1.472(3)
1.541(3)
1.585(3)
However, the reaction of diphenyl ketene 6a with
1,2ꢀdialkylaziridines 1a,b afforded not only βꢀlactams 3
but also 1 : 1 adducts, viz., 1,3ꢀdialkylꢀ5,5ꢀdiphenylꢀ
imidazolidinꢀ4ꢀones 8a,b, in low yields (8—21%). The
synthesis of the latter also proceeds through the diaziridine
ring opening at the N—N bond (Scheme 4). The strucꢀ
tures of compounds 8a,b were confirmed by elemental
analysis and spectroscopic characteristics. The structure
of compound 8a was additionally established by Xꢀray
diffraction analysis.10 An important distinguishing feature
Bond angle
ω/deg
Bond angle
ω/deg
C(1)—N(1)—C(3)
96.4(2) C(12)—C(2)—C(1) 111.7(2)
C(1)—N(1)—C(4) 129.8(2) C(6)—C(2)—C(3) 117.1(2)
C(3)—N(1)—C(4) 129.3(2) C(12)—C(2)—C(3) 115.3(2)
C(20)—N(2)—C(3) 115.4(2) C(1)—C(2)—C(3)
C(20)—N(2)—C(18) 123.7(2) N(1)—C(3)—N(2) 114.5(2)
C(3)—N(2)—C(18) 120.2(2) N(1)—C(3)—C(2) 86.9(2)
84.5(2)
1
O(1)—C(1)—N(1) 131.5(3) N(2)—C(3)—C(2) 120.5(2)
O(1)—C(1)—C(2) 136.7(3) N(1)—C(4)—C(5) 113.6(2)
91.9(2) O(2)—C(20)—N(2) 120.5(2)
C(6)—C(2)—C(12) 110.3(2) O(2)—C(20)—C(21) 121.0(2)
C(6)—C(2)—C(1) 115.9(2) N(2)—C(20)—C(21) 118.5(2)
of the H NMR spectra of compounds 8 is that the proꢀ
tons of the NCH2N fragment appear at substantially lower
field (δ 4.15) compared to the chemical shift of the analoꢀ
gous fragment of the starting diaziridine 1 characterized
by an upfield shift (δ 2.35).
N(1)—C(1)—C(2)
Scheme 4
i. C6H6, 60—80 °C
1, 3, 8: R = H (a), Me (b)

1024
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Shevtsov et al.
Scheme 5
With the aim of examining the scope of the reaction of
1,2ꢀdialkyldiaziridines 1 with ketenes, it was of interest to
perform this reaction with other aryl ketenes. As sugꢀ
gested above (see Scheme 2), the formation of products 3
is associated with the thermal [2+2]ꢀconcerted cycloadꢀ
dition of diphenyl ketene 6a to amidineꢀtype intermediꢀ
ate 4 generated upon the proton abstraction from the
C(3) atom of the diaziridine ring. The formal [3+2]ꢀcycloꢀ
addition of diphenyl ketene 6a giving rise to compounds
8a,b, which we have found in the present study, proceeds,
apparently, via a twoꢀstep mechanism involving dipolar
intermediate 9 followed by the N—N bond cleavage
and cyclization giving rise to the imidazolidine ring
(Scheme 5). The selectivity of such mixed processes is
kinetically and thermodynamically controlled. Hence, to
prepare compounds 8, the reactions of 1,2ꢀdialkylꢀ
diaziridines 1a,b with aryl ketenes 6a,c—f were performed
at low temperature. Aryl ketenes 6 were generated in situ
from arylacetyl chlorides 7 in the presence of Et3N in
anhydrous diethyl ether at –30 °C according to a standard
procedure.12 After the addition of the starting acid chloꢀ
ride to a mixture of dialkyldiaziridine 1 and Et3N, the
reaction mixture was kept at this temperature for 2 h and
then kept at room temperature for 16 h. Under these
conditions, the reactions produced only 1 : 1 adducts,
viz., 5ꢀarylꢀ1,3ꢀdialkylimidazolidinꢀ4ꢀones 8a,c—f, in
40—65% yields regardless of the acid chloride—diaziridine
molar ratio, which was varied from 1 : 2 to 2 : 1. Interestꢀ
ingly, analogous product 8a was prepared from diphenylꢀ
acetyl chloride 7a. The structures of compounds 8 were
confirmed by elemental analysis and spectroscopic charꢀ
acteristics.
The formation of imidazolidinꢀ4ꢀones 8 at low temꢀ
perature confirmed the proposed mechanism of formal
[3+2]ꢀcycloaddition. Apparently, mild temperature conꢀ
ditions are insufficient for the proton abstraction from the
carbon atom of the diaziridine ring in zwitterion 9. This
pathway would give intermediate 4 and then βꢀlactam 3
(the thermodynamically controlled process). Therefore,
zwitterion 9 is transformed into imidazolidinꢀ4ꢀones 8
(the kinetically controlled process) (see Scheme 5). Eviꢀ
dently, the reaction performed at higher temperature is
also accompanied by the partial transformation of zwitteꢀ
rion 9 into imidazolidinꢀ4ꢀones 8a,b.
In addition to the reactions with aryl ketenes, we studꢀ
ied the behavior of 1,2ꢀdialkyldiaziridines 1 in the reacꢀ
tion with parent ketene 6g 11 (Scheme 6). This reaction
can be performed only at low temperature, because ketene
6g is prone to dimerization. Ketene 6g was also generated
in situ by adding dropwise acetyl chloride to a mixture of
Et3N and the starting diaziridine in dry diethyl ether
at –40 °C.
1: R = H (a), Me (b)
8
a
c
d
e
f
R
H
H
H
Me
H
R1
Ph
H
H
H
R2
Ph
4ꢀMeC6H4
4ꢀClC6H4
4ꢀBrC6H4
2ꢀNO2C6H4
H
compounds with the simplest ketene 6g yielded comꢀ
pounds 10 with linear structures containing the 3,5ꢀdiꢀ
acetylꢀ3,5ꢀdiazaheptꢀ1ꢀene fragment (see Scheme 6) as
the major reaction products instead of the expected deꢀ
rivatives of βꢀlactams 3 or imidazolidinꢀ4ꢀones 8. The
characteristic feature of the NMR spectra (primarily, of
the 1H NMR spectra) of compounds 10 is that the signal
for one of the olefinic protons, the singlet of the NCH2N
fragment, and, in some cases, the signals of the NCH2
fragment are doubled due, presumably, to the appearance
of two rotamers (in a ratio of (7—10) : 1 depending on the
temperature, at which the spectra were recorded, and the
nature of the solvent). This phenomenon is typical of
unsymmetrical N,Nꢀdisubstituted amides and is associꢀ
ated with hindered rotation about the N—Ac bond. In the
spectra of the transformation products of diaziridines 1b,c,
the spinꢀspin coupling constants of the protons of the
CH=CH groups are ~14 Hz for both rotamers, which is
indicative of the trans configuration of the double bond.
1,2ꢀDiethylꢀ, 1,2ꢀdipropylꢀ, and 1,2ꢀbis(2ꢀphenylꢀ
ethyl)diaziridines 1a—c were used as the starting 1,2ꢀdiꢀ
alkyldiaziridines 1. In all cases, the reactions of these

Reaction of 1,2ꢀdialkyldiaziridines with ketenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
1025
Scheme 6
R = H (a), Me (b), Ph (c)
The possible mechanism of the formation of comꢀ
pounds 10 is shown in Scheme 6. The first step of the
reaction, like that in the reaction of 1,2ꢀdialkyldiaziridines
1 with aryl ketenes 6, involves the attack of the nitrogen
atom of the diaziridine ring on the central atom of ketene
6g to form zwitterionic intermediate 11, whose carbanionic
center is stabilized to a much lesser extent than those
obtained with the use of arylꢀsubstituted ketenes 6a,c—f.
Then, as expected, the negative charge of zwitterion 11
causes abstraction of one hydrogen atom bound to the
carbon atom of the diaziridine ring and the N—N bond
cleavage to give intermediate Nꢀacetylamidine 12. The
next step of the reaction should involve the [2+2]ꢀcycloꢀ
addition of the second molecule of ketene 6g at the double
bond of Nꢀacetylamidine 12 to form βꢀlactam 3c, taking
into account that the reaction of C=Nꢀcontaining strucꢀ
tures with ketenes serves as one of the most general methꢀ
ods for the preparation of βꢀlactams.13 However, it is
known13,14 that 3ꢀunsubstituted βꢀlactams can be cleaved
to give dipolar intermediates stabilized as linear products.
The structures of these compounds are determined by the
character of substituents at the other atoms of the fourꢀ
membered ring. In our case, the resulting βꢀlactam 3c is,
apparently, cleaved to form new intermediate 13, which
is stabilized as linear diamide 10. However, it cannot be
ruled out that the formation of intermediate 13 occurs
due to acylation of the nitrogen atom of Nꢀacetylamidine
12 in the reaction with ketene 6g (Scheme 6) rather than
through the formation of βꢀlactam 3c.
The data published in the literature7,8 and our reꢀ
sults10,11 suggest that βꢀlactams 3 should be prepared by
the reactions of 1,2ꢀdialkyldiaziridines 1 with ketenes at
high temperature. For this purpose, we used diaziridines
1a,b and 4ꢀchlorophenyl ketene (6d), 4ꢀbromophenyl
ketene (6e), and 4ꢀchlorophenoxyketene (6h). The reacꢀ
tion of 4ꢀchlorophenoxyketene 6h with 1,2ꢀdiethyldiꢀ
aziridine 1a at 60—80 °C produced the expected βꢀlactam
3f (Scheme 7). The 1H NMR spectrum of the crude prodꢀ
uct obtained after the treatment of the reaction mixture
without heating shows signals for the diastereotopic proꢀ
tons of the methylene units and the expected doublets for
the CH protons of the ring at δ 4.72 and 4.89. An attempt
to purify this product by passing through a SiO2 layer led
to the partial transformation of cyclic system 3f into open
form 10f. Column chromatography on SiO2 led to the
complete transformation of 3f. Under the same condiꢀ
tions, the reactions with 4ꢀchlorophenyl and 4ꢀbromoꢀ
phenyl ketenes 6d,e followed by chromatography on SiO2
afforded linear reaction products, viz., Nꢀalkenylacetꢀ
amides 10d,e, along with imidazolidinꢀ4ꢀones 8g,h.
To summarize, the investigation of the reaction of
1,2ꢀdialkyldiaziridines 1 with aryl ketenes 6 in diethyl
ether at –30 °C revealed a new pathway for the ring expanꢀ
sion in 1,2ꢀdialkyldiaziridines giving rise to 5ꢀaryl(5,5ꢀdiꢀ
aryl)ꢀ1,3ꢀdialkylimidazolidinꢀ4ꢀones 8 in 40—65% yields.
It should be noted that this reaction provides a new simple
and general approach to the synthesis of Nꢀalkylꢀsubstiꢀ
tuted imidazolidinꢀ4ꢀones. It should be emphasized that

1026
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Shevtsov et al.
Scheme 7
8g, 10d
H
4ꢀBrC6H4
8h, 10e
Me
4ꢀClC6H4
10f
H
4ꢀClC6H4O
R
R1
(0.5 mmol) and triethylamine (1.52 g, 1.5 mmol) was added
with vigorous stirring to a solution of 1,1ꢀdiphenylacetyl chloꢀ
ride (2.3 g, 1 mmol) in dry benzene (20 mL) at 60 °C under
argon, during which the temperature of the reaction mixture
increased to 80 °C. Then the reaction mixture was refluxed for
5 min and cooled to ~20 °C. Triethylamine hydrochloride that
precipitated was filtered off and washed with benzene (3×30 mL).
The solvent was distilled off in vacuo. Compounds 3a,b and 8a,b
were isolated by column chromatography on SiO2 (60 F254
0.063—0.200 mm, Merck) using a hexane—ethyl acetate mixꢀ
ture as the eluent with a gradient from 10 : 1 to 6 : 1. Compounds
3a and 8a,b were recrystallized from a hexane—ethyl acetate
mixture (1 : 1). NꢀEthylꢀNꢀ(1ꢀethylꢀ4ꢀoxoꢀ3,3ꢀdiphenylꢀ
azetidinꢀ2ꢀyl)ꢀ2,2ꢀdiphenylacetamide (3a), 1,3ꢀdiethylꢀ5,5ꢀdiꢀ
phenylimidazolidinꢀ4ꢀone (8a), NꢀpropylꢀNꢀ(1ꢀpropylꢀ4ꢀoxoꢀ
3,3ꢀdiphenylazetidinꢀ2ꢀyl)ꢀ2,2ꢀdiphenylacetamide (3b), and
1,3ꢀdipropylꢀ5,5ꢀdiphenylimidazolidinꢀ4ꢀone (8b) were obtained
in yields of 1 g (41%), 0.3 g (21%), 0.83 g (32%), and 0.13 g
(8%), respectively.
the known methods for the preparation of the latter comꢀ
pounds are based on multistep processes.15,16 An analoꢀ
gous reaction at high temperature produces a mixture of
5ꢀarylꢀ1,3ꢀdialkylimidazolidinꢀ4ꢀones 8 and a new type
of structures, viz., Nꢀalkenylacetamides 10. It was hyꢀ
pothesized (and then confirmed experimentally using one
example) that the formation of compounds 10 proceeds
through the intermediate formation of the corresponding
βꢀlactams 3. Stable 3,3ꢀdisubstituted azetidinꢀ2ꢀones 3
can be synthesized only by the reaction of
1,2ꢀdialkyldiaziridines 1 with diphenyl ketene 6a. The
reaction of 1,2ꢀdialkyldiaziridines 1 with the simplest
ketene 6g, like other known reactions of compounds 1
with substituted ketenes, is accompanied by the N—N
bond cleavage. In the latter case, only linear 3,5ꢀdiacetylꢀ
3,5ꢀdiazaheptꢀ1ꢀenes 10 were isolated.
Synthesis of 1,3ꢀdialkylꢀ5ꢀarylimidazolidinꢀ4ꢀones (8a,c—f)
(general procedure). A precooled solution of the corresponding
arylacetyl chloride 7 (0.5 mmol) in dry diethyl ether (10 mL)
was added dropwise with continuous stirring to a solution of
1,2ꢀdialkyldiaziridines 1a,b (0.5 mmol) and triethylamine
(1.52 g, 1.5 mmol) in dry diethyl ether cooled to –40—–30 °C
under argon for 10 min. The reaction mixture was kept at –30 °C
for 1 h, then slowly warmed to ~20 °C, and kept for 16 h.
Triethylamine hydrochloride that precipitated was filtered off
and washed with diethyl ether (3×40 mL). The solvent was disꢀ
tilled off in vacuo. Compounds 8a,c—f were isolated by column
chromatography on SiO2 (60 F254 0.063—0.200 mm, Merck)
using a 1 : 1 hexane—ethyl acetate mixture (for 8c—f) and a 4 : 1
hexane—ethyl acetate mixture (for 8a) as the eluent. Compound
8a was recrystallized from a hexane—ethyl acetate mixture (1 : 1).
1,3ꢀDiethylꢀ5,5ꢀdiphenylimidazolidinꢀ4ꢀone (8a), 1,3ꢀdiethylꢀ
5ꢀ(4ꢀmethylphenyl)imidazolidinꢀ4ꢀone (8c), 5ꢀ(4ꢀchloropheꢀ
nyl)ꢀ1,3ꢀdiethylimidazolidinꢀ4ꢀone (8d), 5ꢀ(4ꢀbromophenyl)ꢀ
1,3ꢀdi(nꢀpropyl)imidazolidinꢀ4ꢀone (8e), and 1,3ꢀdiethylꢀ5ꢀ
(2ꢀnitrophenyl)imidazolidinꢀ4ꢀone (8f) were obtained in yields
Experimental
The IR spectra were recorded on a URꢀ20 spectrometer in
KBr pellets (for crystalline compounds) and in a thin layer (for
oils). The H NMR spectra were measured on Bruker WMꢀ250
1
(250 MHz), Bruker AMꢀ300 (300 MHz), and Bruker DRXꢀ500
(500 MHz) spectrometers. The 13C NMR spectra were recorded
on Bruker AMꢀ300 (75.5 MHz) and Bruker DRXꢀ500 (125 MHz)
spectrometers. The chemical shifts are given in the δ scale relaꢀ
tive to the signal of Me4Si. The TLC analysis was carried out on
SilufolꢀUVꢀ254 plates; spots were visualized using a UV lamp,
with I2 vapor, and by spraying with a solution of diphenylamine
in acetone followed by heating of the plates. The melting points
were determined on a GALLENKAMP instrument (Sanyo).
Xꢀray diffraction study was carried out on a Smart 1000 CCD
diffractometer.
NꢀAlkylꢀNꢀ(1ꢀalkylꢀ4ꢀoxoꢀ3,3ꢀdiphenylazetidinꢀ2ꢀyl)ꢀ2,2ꢀ
diphenylacetamides (3a,b) and 1,3ꢀdialkylꢀ5,5ꢀdiphenylimidꢀ
azolidinꢀ4ꢀones (8a,b) (general procedure). A mixture of 1a,b

Reaction of 1,2ꢀdialkyldiaziridines with ketenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
1027
Table 2. Yields and selected physicochemical characteristics of the compounds synthesized
a
Comꢀ
pound
Yield
(%)
M.p./°C
Rf
Found
Calculated
Molecular
formula
(%)
N
C
H
Hal
3a
41
32
150—151
Oil
0.70
0.71
0.45
0.50
0.40
0.45
0.47
0.42
0.43
0.46
0.26
0.29
0.34
0.74
0.68
0.75
81.27
81.12
81.42
81.36
77.73
77.52
78.68
78.22
72.42
72.38
67.53
67.78
55.61
55.39
59.72
59.30
64.48
64.16
52.89
52.54
58.69
58.67
62.31
62.24
74.99
74.97
51.22
51.04
63.81
63.74
67.79
57.68
6.52
6.60
6.85
7.02
7.41
7.53
7.97
8.13
8.87
8.68
6.89
6.78
6.32
6.51
6.19
6.51
7.91
7.54
5.82
5.77
8.91
8.75
9.57
9.50
7.25
7.19
4.61
4.49
6.17
6.05
5.26
5.07
5.44
5.73
5.39
5.42
9.21
9.52
8.35
8.69
12.20
12.06
10.89
11.08
8.22
8.61
16.09
15.96
9.76
9.98
9.24
9.43
15.16
15.20
13.15
13.20
8.20
8.33
5.48
5.67
6.33
6.46
6.26
6.41
C33H32N2O2
C35H36N2O2
C19H22N2O
3b
8a
65
21b
8
127—128
116—118
Oil
8b
C21H26N2O
8c
40
57
46
51
23
29
33
36
44
32
31
37
C14H20N2O
8d
Oil
13.76
14.03
24.07
24.57
C13H17ClN2O
C15H21BrN2O
C13H17N3O3
C15H21ClN2O
C13H17BrN2O
C9H16N2O2
8e
Oil
8f
Oil
8g
Oil
12.09
12.63
16.47
26.89
8h
Oil
10a
10b
10с
10d
10e
10f
26—28
Oil
C11H20N2O2
C21H24N2O2
C21H22Br2N2O2
C23H26Cl2N2O2
C21H22Cl2N2O4
110—111
146—147
Oil
32.09
32.34
16.12
16.36
14.45
14.63
113—114
a A 1 : 1 hexane—ethyl acetate mixture as the eluent.
b The compound was synthesized according to Scheme 4.
of 0.95 g (65%), 0.46 g (40%), 0.72 g (57%), 0.75 g (46%), and
0.67 g (51%), respectively.
from a hexane—ethyl acetate mixture (1 : 1). 3,5ꢀDiacetylꢀ3,5ꢀ
diazaheptꢀ1ꢀene (10a), (E)ꢀ4,6ꢀdiacetylꢀ4,6ꢀdiazanonꢀ2ꢀene
(10b), and (E)ꢀ3,5ꢀdiacetylꢀ1,7ꢀdiphenylꢀ3,5ꢀdiazaheptꢀ1ꢀene
(10c) were obtained in yields of 0.30 g (33%), 0.38 g (36%), and
0.74 g (44%), respectively.
3,5ꢀDi(arylacetyl)ꢀ3,5ꢀdiazaheptꢀ1ꢀenes (10d,e) and 1,3ꢀdiꢀ
alkylꢀ5ꢀarylimidazolidinꢀ4ꢀones (8g,h). A mixture of diaziridine
1a,b (0.5 mmol) and triethylamine (1.52 g, 1.5 mmol) was added
with vigorous stirring to a solution of the corresponding arylacetyl
chloride (1 mmol) in dry benzene (20 mL) at 60 °C under argon,
during which the temperature of the reaction mixture increased
to 80 °C. Then the reaction mixture was refluxed for 10 min and
cooled to room temperature. Triethylamine hydrochloride
that precipitated was filtered off and washed with benzene
(3×30 mL). The solvent was distilled off in vacuo. Compounds
10d,e and 8g,h were isolated by column chromatography on
SiO2 (60 F254 0.063ꢀ0.200 mm, Merck) using a 7 : 3 hexꢀ
Synthesis of 3,5ꢀdiacetylꢀ3,5ꢀdiazaheptꢀ1ꢀenes (10a—c)
(general procedure). A precooled solution of acetyl chloride
(1.2 g, 1.5 mmol) in dry diethyl ether (10 mL) was added dropwise
with continuous stirring to a solution of 1,2ꢀdialkyldiaziridine
1a—c (0.5 mmol) and triethylamine (2 g, 2 mmol) in dry diethyl
ether cooled to –50—–45 °C under argon for 10 min. The reacꢀ
tion mixture was kept at this temperature for 2 h, then slowly
warmed to room temperature, and kept for 16 h. Triethylamine
hydrochloride that precipitated was filtered off and washed with
diethyl ether (3×40 mL). The solvent was distilled off in vacuo.
Compounds 10a—c were isolated by column chromatography
on SiO2 (60 F254 0.063—0.200 mm, Merck) using a 1 : 1 hexꢀ
ane—ethyl acetate mixture (for 10b), a 3 : 2 hexane—ethyl acꢀ
etate mixture (for 10c), and a 15 : 1 diethyl ether—acetone mixꢀ
ture (for 10a) as the eluent. Compound 10c was recrystallized

1028
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Shevtsov et al.
Table 3. IR, 1H and 13C NMR spectroscopic data for compounds 3 and 8
Comꢀ
pound
IR,
ν/cm–1
1H NMR
13C NMR
δ, J/Hz (CDCl3)
3a
476, 528, 612, 704,
724, 748, 776, 1032,
1056, 1084, 1112,
1176, 1212, 1224,
1320, 1352, 1392,
1416, 1456, 1496,
1600, 1648, 1764,
2940, 2980, 3028,
3060
634, 710, 745, 771,
903, 1038, 1059,
1076, 1110, 1180,
1197, 1323, 1355,
1379, 1444, 1468,
1483, 1697, 2763,
2950, 2996, 3061
1.02 (t, 3 H, NcycloCH2Me, 3J = 7.22); 1.18
(t, 3 H, NCH2Me, 3J = 7.22); 2.73 (m, 2 H,
12.14 (Me); 16.04 (Me); 36.77 (NcycloCH2);
36.91 (NCH2); 55.25 (PhCHPh); 70.03
(NCHN); 71.99 (Ccyclo); 126.97, 127.08,
127.18, 127.21, 127.50, 128.59, 128.62,
128.65, 128.70, 128.77, 129.28 (CH(Ph));
137.70, 138.23, 139.57, 140.09 (Cipso(Ph));
169.91 (COcyclo); 174.40 (CO)
N
cycloCH2Me); 2.96, 3.64 (both d.sext, 2 H,
NCH2Me, 3J = 7.22, J = 13.78, ∆δ =
168.69); 5.13 (s, 1 H, PhCHCO); 6.84
(s, 1 H, NCHN); 6.87—7.84 (m, 20 H, 4 Ph)
3b
0.89 (t, 3 H, NcycloCH2CH2Me, 3J = 7.23);
0.92 (t, 3 H, NCH2CH2Me, 3J = 7.23); 1.53
(m, 4 H, 2 CH2Me); 2.40—2.87 (m, 3 H,
11.38 (Me); 14.74 (Me); 22.97 (CH2Me);
24.04 (CH2Me); 35.32 (NcycloCH2);
35.55 (NCH2); 54.06 (PhCHPh); 68.87
(NCHN); 69.91 (Ccyclo); 126.86, 127.02,
127.09, 127.20, 127.49, 128.55, 128.62,
128.64, 128.69, 128.77, 129.29 (CH(Ph));
137.65, 138.24, 139.52, 139.98 (Cipso (Ph));
169.91 (COcyclo); 173.99 (CO)
N
cycloCH2, NCHaHb); 3.47 (m, 1 H,
NCHaHb); 5.00 (s, 1 H, PhCHCO); 6.80 (s,
1 H, NCHN); 6.83—7.87 (m, 20 Н, 4 Ph)
8a
8b
632, 704, 756, 772,
904, 1052, 1172,
1196, 1312, 1448,
1700, 2764, 2820,
2950, 3056, 3400
1.15 (t, 3 H, CONCH2Me, 3J = 7.3); 1.30
(t, 3 H, CPh2NCH2Me, 3J = 7.3); 2.18 (q,
2 H, CPh2NCH2Me, 2J = 14.5, 3J = 7.3);
13.05 (CPh2NCH2Me); 13.19
(CONCH2Me); 36.61 (CONCH2Me);
42.88 (CPh2NCH2Me); 65.12 (NCH2N);
127.53, 127.88, 128.53, 128.73, 129.07,
139.15 (Ph); 172.39 (CO)
2
3.57 (q, 2 H, CONCH2Me, J = 14.5, 3J =
7.3); 4.15 (s, 2 H, NCH2N); 7.26 (m, 10 H,
2 Ph)
639, 765, 832, 900,
980, 1016 1022,
1117, 1174, 1187,
1300, 1337, 1449,
1511, 1650, 1715,
1763, 2929, 2954,
3364
0.96 (t, 3 H, CONCH2CH2Me, 3J = 7.32);
1.04 (t, 3 H, CHNCH2CH2Me, 3J = 7.32);
1.42—1.58 (m, 4 H, 2 CH2Me); 2.50 (m,
2 H, CHNCH2CH2Me); 3.37 (t, 2 H,
CONCH2CH2Me, 3J = 7.32); 4.13 (s, 2 H,
NCH2N); 7.24 (m, 10 H, 2 Ph)
12.64 (Me); 16.96 (Me); 24.14 (CH2Me);
25.39 (CH2Me); 37.02 (NCH2); 36.52
(NCH2); 64.75 (NCH2N); 127.56, 127.74,
128.04, 128.52, 128.97, 138.88 (Ph);
171.91 (CO)
8c
804, 844, 1020,
1116, 1160, 1192,
1308, 1344, 1452,
1516, 1652, 1712,
1764, 2932, 2972,
3325
1.06 (t, 3 H, CONCH2Me, 3J = 7.5); 1.18
(t, 3 H, CHNCH2Me, 3J = 7.5); 2.33 (s,
3 H, Me); 2.50 (m, 1 H, CHNCH(H)Me);
2.76 (m, 1 H, CONCH(H)Me); 3.41 (q, 2 H,
CHNCH2Me, 2J = 13.8, 3J = 7.5); 3.93 (m,
2 H, NCHa(Hb)N, COCHcN); 4.51 (d, 1 H,
NCHa(Hb)N, 2J = 5.0); 7.12, 7.30 (both d,
2 H each, Ar, 3J = 7.5)
12.83 (Me); 12.86 (Me); 21.16 (ArMe);
36.23 (CONCH2Me); 47.16 (CHNCH2Me);
67.37 (NCH2N); 69.89 (CHAr); 128.16,
129.13, 134.67, 137.58 (Ar); 171.15 (CO)
8d
664, 764, 808, 844,
1016, 1092, 1216,
1312, 1456, 1492,
1576, 1648, 1716,
1772, 2936, 2976,
3300
1.05 (t, 3 H, CONCH2Me, 3J = 7.3); 1.17
(t, 3 H, CHNCH2Me, 3J = 7.3); 2.52 (m,
1 H, CHNCH(H)Me); 2.74 (m, 1 H,
CONCH(H)Me); 3.39 (q, 2 H,
12.81 (Me); 12.92 (Me); 36.27
(CONCH2Me); 47.29 (CHNCH2Me);
67.30 (NCH2N); 69.35 (CHAr); 128.48,
129.41, 133.62, 136.35 (Ar); 170.34 (CO)
CHNCH2Me, 2J = 15.5, 3J = 7.3); 3.93
(d.d, 1 H, NCHa(Hb)N, 2J = 4.4, 4JH ,H
=
c
b
2.2); 3.96 (s, 1 H, COCHcN); 4.50 (d,
2
1 H, NCHa(Hb)N, J = 4.4); 7.30, 7.37
3
(both d, 2 H each, Ar, J = 8.8)
(to be continued)

Reaction of 1,2ꢀdialkyldiaziridines with ketenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
1029
Table 3 (continued)
Comꢀ
pound
IR,
ν/cm–1
1H NMR
13C NMR
δ, J/Hz (CDCl3)
8e
630, 765, 815, 913,
999, 1010, 1084,
1213, 1326, 1358,
1439, 1546, 1580,
1699, 1797, 2873,
2930, 2975
0.89 (t, 3 H, CONCH2CH2Me, 3J = 7.5);
0.93 (t, 3 H, CHNCH2CH2Me, 3J = 7.5);
1.47 (m, 2 H, CONCH2CH2Me); 1.60 (m,
2 H, CHNCH2CH2Me); 2.55 (m, 2 H,
CHNCH2CH2Me); 3.31 (t, 2 H,
CONCH2CH2Me, 3J = 7.5); 3.95 (d, 1 H,
NCHa(Hb)N, 2J = 2.5); 3.98 (s, 1 H,
COCHcN); 4.51 (d, 1 H, NCHa(Hb)N,
2J = 2.5); 7.33, 7.49 (both d, 2 H each, Ar,
3J = 10.0)
12.29 (Me); 11.64 (Me); 20.90
(CONCH2CH2Me); 21.06
(CHNCH2CH2Me); 43.16
(CONCH2CH2Me) 55.31
(CHNCH2CH2Me); 68.18 (NCH2N);
69.62 (CHAr); 121.86, 129.74, 131.46,
136.95 (Ar); 170.58 (CO)
8f
668, 728, 744, 788,
1160, 1256, 1308,
1356, 1456, 1528,
1648, 1708, 2820,
2936, 2976
1.06 (t, 3 H, CONCH2Me, 3J = 7.5); 1.19
(t, 3 H, CHNCH2Me, 3J = 7.5); 2.71 (m,
2 H, CONCH2Me); 3.40 (q, 2 H,
12.69 (Me); 12.98 (Me); 36.35
(CONCH2Me); 48.11 (CHNCH2Me);
66.43 (NCH2N); 67.61 (CHAr);
124.78, 128.61, 130.18, 132.50, 133.35,
150.13 (Ar); 169.13 (CO)
CHNCH2Me, 2J = 14.5, 3J = 7.5); 4.00
(d.d, 1 H, NCHa(Hb)N, 2J = 4.4, 4JH ,H
=
b
2.2); 4.06 (s, 1 H, COCHcN); 4.52 (d, 1 cH,
NCHa(Hb)N, 2J = 4.4); 7.39—7.72 (m, 4 H, Ar)
1.05 (t, 3 H, CONCH2Me, 3J = 7.22); 1.17
(t, 3 H, CHNCH2Me, 3J = 7.22); 2.53 (m,
1 H, CHNCH(H)Me); 2.74 (m, 1 H,
8g
492, 572, 736, 804,
844, 1012, 1072,
1160,1312, 1488,
1540, 1592, 1652,
1704, 1768, 1908,
2812, 2876, 2936,
2976, 3064
12.86 (Me); 12.98 (Me); 36.32
(CONCH2Me); 47.65 (CHNCH2Me);
67.41 (NCH2N); 69.33 (CHAr);
128.52, 129.51, 133.74, 136.52 (Ar);
170.44 (CO)
CONCH(H)Me); 3.39 (q, 2 H, CHNCH2Me,
2J = 14.4, 3J = 7.22); 3.94 (br.s, 3 H,
NCHa(Hb)N, COCHcN); 4.51 (d, 1 H,
2
NCHa(Hb)N, J = 2.63); 7.32, 7.47 (both d,
2 H each, Ar, 3J = 8.53)
8h
665, 674, 754, 812,
845, 989, 1023,
1110, 1223, 1309,
1476, 1499, 1581,
1648, 1706, 1777,
2942, 2979, 3310
0.86 (t, 3 H, CONCH2CH2Me, 3J = 7.22);
0.93 (t, 3 H, CHNCH2CH2Me, 3J = 7.22);
1.42 (m, 2 H, CONCH2CH2Me); 1.57 (m,
2 H, CHNCH2CH2Me); 2.52 (m, 2 H,
CHNCH2CH2Me); 3.28 (t, 2 H,
11.17 (Me); 11.29 (Me); 20.79
(CONCH2CH2Me); 20.96
(CHNCH2CH2Me); 43.05
(CONCH2CH2Me) 55.19
(CHNCH2CH2Me); 68.11 (NCH2N);
69.48 (CHAr); 128.41, 129.35,
133.52, 136.49 (Ar); 170.62 (CO)
CONCH2CH2Me, 3J = 7.22); 3.91 (d, 1 H,
NCHa(Hb)N, 2J = 3.90); 3.95 (s, 1 H,
2
COCHcN); 4.47 (d, 1 H, NCHa(Hb)N, J =
3
3.90); 7.30, 7.37 (both d, 2 H each, Ar, J = 8.5)
Table 4. IR, 1H and 13C NMR spectroscopic data for compounds 10
Comꢀ
pound
IR,
ν/cm–1
1H NMR
13C NMR
δ, J/Hz (CDCl3)
10aa
628, 780, 800, 864,
912, 968, 996, 1036,
1104, 1164, 1204,
1240, 1288, 1340,
1368, 1392, 1424,
1460, 1632, 1668,
2924, 2976
1.18 (t, 3 H, CH2Me, 3J = 7.4); 2.14 (s,
3 H, CH3CH2NCOMe); 2.31 (s, 3 H,
CH2=CHNCOMe); 3.19, 3.28 (10 : 1)
13.45 (NCH2Me); 21.66
(CH3CH2NCOMe); 22.83
(CH2=CHNCOMe); 40.14
(CH2Me); 47.61 (NCH2N);
96.82 (CH=CH2); 130.79
(CH=CH2); 171.03
3
(both q, 2 H, CH2Me, J = 7.4); 4.40, 4.56
(10 : 1) (both d, 1 H, NCHa=CHаHb,
3JH ,H = 9.6); 4.92 (d, 1 H, NCHa=CHаHb,
a
a
3JH ,Hb = 15.0); 5.16, 5.46 (10 : 1) (both s,
(CH2CH2NCO); 171.10
(CH2=CHNCO)
a
2 H, NCH2N); 6.66, 7.07 (10 : 1) (both dd,
1 H, CH=, 3JH ,H = 9.6, 3JH ,Hb = 15.0)
a
a
a
(to be continued)

1030
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Shevtsov et al.
Table 4 (continued)
Comꢀ
pound
IR,
1H NMR
13C NMR
ν/cm–1
δ, J/Hz (CDCl3)
0.88 (t, 3 H, CH2Me, 3J = 7.2); 1.59 (m,
11.39 (CH2Me); 16.16 (CHMe);
2 H, MeCH2CH2); 1.68 (d, 3 H, СН=СНMe, 21.49 (CH2CH2NCOMe); 21.50
3J = 6.6); 2.09 (s, 3 H, CH2CH2NCOMe);
2.19 (s, 3 H, CH=CHNCOMe); 3.11, 3.22
(8 : 1) (both q, 2 H, NCH2, J = 7.2); 5.06,
5.35 (8 : 1) (both s, 2 H, NCH2N); 5.42 (m,
1 H, NCHa=CHbMe); 6.14, 6.28 (8 : 1)
(both d, 1 H, NCHa=CHbMe, 3JH ,Hb = 13.8)
10bb
620, 664, 736, 796,
824, 896, 960, 1000,
1036, 1076, 1108,
1160, 1200, 1232,
1264, 1288, 1352,
1376, 1400, 1428,
1656, 1680, 2876,
2932, 2964
(MeCH2CH2); 22.99
(CH=CHNCOMe); 47.12
(CH2CH2N); 49.00 (NCH2N);
110.20 (CH=CHMe); 125.87
(CH=CHMe); 170.71
3
(CH2CH2NCO); 171.01
a
(CH=CHNCO)
10сb
572, 612, 692, 704,
752, 956, 996, 1032,
1076, 1164, 1200,
1240, 1268, 1336,
1396, 1424, 1492,
1576, 1600, 1636,
1640, 1668, 3000,
3024
2.01 (s, 3 H, CH2CH2NCOMe); 2.38
(s, 3 H, CH=CHNCOMe); 2.92 (t, 2 H,
21.42 (CH2CH2NCOMe); 22.68
(CH=CHNCOMe); 34.95
(CH2CH2N); 47.79 (CH2CH2N);
49.75 (NCH2N); 114.95
(CH=CHPh); 126.31 (CH=CHPh);
125.62, 125.81, 125.99, 126.70,
126.87, 128.47, 128.69, 128.74,
128.90, 129.02, 136.31, 138.10
(Ph); 170.99 (CH2CH2NCO);
171.14 (CH=CHNCO)
13.91 (NCH2Me); 39.76 (CH2);
39.95 (CH2); 40.60 (CH2); 49.55
(NCH2N); 99.32 (CH=CH2);
130.62, 130.68, 131.63, 131.76,
131.83, 132.21, 132,45, 132.49 (Ar);
131.45 (CH=CH2); 170.92
(CH2CH2NCO); 171.13
3
CH2Ph, J = 7.3); 3.41, 3.56 (7 : 1) (both t,
3
2 H, NCH2CH2, J = 7.3); 5.12, 5.65 (7 : 1)
(both s, 2 H, NCH2N); 6.45 (d, 1 H,
3
NCHa=CHbPh, JH ,Hb = 14.0); 6.90, 7.01
(7 : 1) (both d, 1 H, aNCHa=CHbPh,
3JH ,Hb = 14.0); 7.21—7.36 (m, 10 H, Ph)
a
3
10d
10e
10f
488, 728, 776, 864,
1012, 1068, 1088,
1120,1208, 1268,
1344, 1360, 1432,
1492, 1632, 1648,
1676, 2920, 2980
1.13 (t, 3 H, CH2Me, J = 7.22); 3.23
3
(q, 2 H, CH2Me, J = 7.22) 3.64 (s, 2 H,
COCH2N(Et)); 3.80 (s, 2 H,
COCH2N(CH=CH2)); 4.49 (d, 1 H,
NCHa=CHаHb, 3JH ,Ha = 9.2); 4.97 (d,
a
1 H, NCHa=CHаHb, 3JH ,Hb = 14.4); 5.48
a
(s, 2 H, NCH2N); 6.69 (dd, 1 H, CH=,
3JH ,H = 9.2, 3JH ,Hb = 14.4); 7.09, 7.45
(CH2=CHNCO)
a
a
(both m, 8 H, Ar)a
3
634, 651, 745, 876,
898, 923, 976, 1065,
1090, 1112, 1134,
1167, 1234, 1265,
1298, 1300, 1354,
1391, 1418, 1432,
1658, 1695, 2866,
2923, 2954, 3028
0.86 (t, 3 H, CH2Me, J = 7.3); 1.62 (m,
2 H, MeCH2CH2); 1.72 (d, 3 H,
12.56 (CH2Me); 17.20 (CHMe);
22.53 (MeCH2CH2); 39.79 (CH2);
39.97 (CH2); 41.01 (CH2); 50.0
(NCH2N); 111.98 (CH=CHMe);
131.67(CH=CHMe); 130.87,
130.89, 131.21, 131.42, 131.78,
132.08, 132,76, 132.57 (Ar);
171.13 (CH2CH2NCO); 171.24
(CH2=CHNCO)
13.98 (NCH2Me); 39.20 (CH2);
49.92 (NCH2N); 66.82 (OCH2);
67.21 (OCH2); , 100.40 (CH=CH2);
116.02, 116.06, (Ar); 126.60 (Cipso);
126.99 (CH=CH2); 129.40, 129.52
(Ar); 156.15, 156.51 (OCipso);
167.87 (CH2CH2NCO); 168.06
(CH2=CHNCO)
СН=СНMe, 3J = 6.8); 3.27 (m, 2 H, NCH2);
3.62 (s, 2 H, COCH2N(Pr)); 3.77 (s, 2 H,
COCH2N(CH=CHMe)); 5.03 (both s, 2 H,
NCH2N); 5.47 (m, 1 H, NCHa=CHbMe);
6.25 (d, 1 H, NCHa=CHbMe, 3JH ,H
=
a
b
13.8); 7.15 (m, 8 H, Ar)
3
508, 668, 800, 832,
1060, 1104, 1136,
1228, 1240, 1288,
1328, 1428, 1492,
1584, 1596, 1640,
1672, 1704, 2924,
2972
1.21 (t, 3 H, CH2Me, J = 7.35); 3.26
(q, 2 H, CH2Me, 3J = 7.35); 4.56 (d, 1 H,
NCHa=CHаHb, 3JH ,Ha = 8.8); 4.68 (both s,
a
1 H, OCH2CON(Et)); 4.82 (s, 1 H,
OCH2CON(СН=СН2)); 5.00 (d, 1 H,
NCHa=CHаHb, 3JH ,Hb = 16.18); 5.49
a
(s, 2 H, NCH2N); 6.63 (dd, 1 H, CH=,
3JH ,H = 8.8, 3JH ,Hb = 16.18); 6.85, 7.23
a
a
(both m, 8 H, Ar)a
a 1H and 13C NMR (CDCl3, –30 °C).
b 13C NMR (CDCl3, –30 °C).
ane—ethyl acetate mixture (for 10d, 8g) and 1 : 1 hexane—ethyl
acetate mixture (for 10e, 8h) as the eluent. Compound 10d was
recrystallized from a hexane—ethyl acetate mixture (20 : 1).
3,5ꢀDi[(4ꢀbromophenyl)acetyl]ꢀ3,5ꢀdiazaheptꢀ1ꢀene (10d),
5ꢀ(4ꢀbromophenyl)ꢀ1,3ꢀdiethylimidazolidinꢀ4ꢀone
(8g),
(E)ꢀ4,6ꢀdi[(4ꢀchlorophenyl)acetyl]ꢀ4,6ꢀdiazanonꢀ2ꢀene (10e),

Reaction of 1,2ꢀdialkyldiaziridines with ketenes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
1031
and 5ꢀ(4ꢀchlorophenyl)ꢀ1,3ꢀdipropylimidazolidinꢀ4ꢀone (8h)
were obtained in yields of 0.79 g (32%), 0.34 g (23%), 0.67 g
(31%), and 0.4 g (29%), respectively.
References
1. E. Schmitz, Dreiringe mit zwei Heteroatomen, Springerꢀ
Verlag, Berlin—Heidelberg—New York, 1967.
2. H. W. Heine, Diaziridines, 3HꢀDiazirines, Diaziridinones and
Diaziridinimines, Small Ring Heterocycles, 1983, Part 2,
Chapter IV, 547—629, Ed. A. Hassner, WileyꢀInterscience.
3. R. G. Kostyanovsky, R. Murugan, and M. Sutharchanadevi,
in Diaziridines and Diazirines, Comp. Heterocycl. Chem., II,
Int. Ed., 1996, 1a, Chapter 1.11, 347—364, Eds A. R.
Katrizky and C. W. Rees, Pergamon Press, Oxford—New
York—Tokyo.
4. A. Nabeya, J. Saito, and H. Koyama, J. Org. Chem., 1979,
44, 3935.
5. H. W. Heine, R. Henrie, L. Heitz, and S. R. Kovvali, J. Org.
Chem., 1974, 39, 3187.
6. R. G. Kostyanovskii, K. S. Zakharov, M. Zaripova, and
V. F. Rudchenko, Izv. Akad. Nauk SSSR, Ser. Khim., 1975,
875 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1975, 24, 791
(Engl. Transl.)].
7. M. Komatsu, N. Nishikaze, M. Sakamoto, Y. Ohshiro, and
T. Agawa, J. Org. Chem., 1974, 22, 3198.
8. M. Komatsu, S. Tamabuchi, S. Minakata, and Y. Ohshiro,
Heterocycles, 1999, 50, 67.
9. B. Carboni, L. Toupet, and R. Carric, Tetrahedron, 1987,
43, 2293.
10. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, K. A.
Lyssenko, I. V. Fedunin, and N. N. Makhova, Mendeleev
Commun., 2003, 221.
11. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, and
N. N. Makhova, Mendeleev Commun., 2005, 29.
12. L. Fieser and M. Fieser, Reagents for Organic Synthesis,
J. Wiley and Sons, Inc., New York—London—Sydney, 1972.
13. D. E. Davies and R. C. Storr, Comp. Heterocycl. Chem., Int.
Ed., Ed. W. Lwowsky, Pergamon Press, Oxford—New York—
Toronto—Sydney, 1984, 7, Chapter 5.09, 237—284.
14. G. S. Rosenfeld, Antibiotics and Medical Biothechnology,
1986, 302.
3,5ꢀDi[(4ꢀchlorophenoxy)acetyl]ꢀ3,5ꢀdiazaheptꢀ1ꢀene (10f).
A mixture of compound 1a (0.5 mmol) and triethylamine (1.52 g,
1.5 mmol) was added with vigorous stirring to a solution of
4ꢀchlorophenoxyacetyl chloride (2.05 g, 1 mmol) in dry benꢀ
zene (20 mL) at 60 °C under argon, during which the temperaꢀ
ture of the reaction mixture increased to 80 °C. Then the reacꢀ
tion mixture was refluxed for 10 min and cooled to ~20 °C.
Triethylamine hydrochloride that precipitated was filtered off
and washed with benzene (3×30 mL). The solvent was distilled
off in vacuo. The residue was extracted with hot hexane
(3×50 mL) and triturated with cooling to 0 °C. The precipitate
that formed was filtered off and dried in air. 2ꢀ(4ꢀChloroꢀ
phenoxy)ꢀNꢀ[3ꢀ(4ꢀchlorophenoxy)ꢀ1ꢀethylꢀ4ꢀoxoazetidinꢀ2ꢀ
yl]ꢀNꢀethylacetamide (3f) was obtained in a yield of 0.9 g
(~85% purity). 1H NMR (CDCl3), δ: 1.13 (t, 3 H, NcycloCH2Me,
3J = 7.3 Hz); 1.19 (t, 3 H, NCH2Me, 3J = 7.3 Hz); 2.31 and 3.45
(both d.sext, 4 H, NCH2Me + NcycloCH2Me); 4.41 (s, 2 H,
CH2CO); 4.72 and 4.89 (both d, 1 H each, NCHN and
(COCH)cyclo,
3J = 4.5 Hz); 6.70—7.42 (m, 8 H, 2 Ar). An
attempt to purify compound 3f by chromatography on SiO2
(hexane—ethyl acetate, 7 : 3, as the eluent) led to the cleavage
of the cyclic system to give compound 10f in a yield of
0.80 g (37%).
Xꢀray diffraction study. Crystals of 3a (C33H32N2O2) are
monoclinic, at 120 K: a = 18.467(3), b = 8.600(1), c =
18.035(3) Å, β = 115.033(4)°, V = 2595.1(7) Å3, dcalc
=
1.251 g cm–1, space group P21/n, Z = 4. The intensities of
12248 reflections were measured on an automated Smart
1000 CCD diffractometer at 110 K (MoꢀKα radiation, graphite
monochromator, ω scanning technique, 2θ
= 54°), of which
max
6227 observed reflections (Rint = 0.0857) were used in calculaꢀ
tions. The structure was solved by direct methods and refined by
the fullꢀmatrix leastꢀsquares method with anisotropic/isotropic
displacement parameters against F 2. The hydrogen atoms were
revealed from difference electron density syntheses and refined
using a riding model. The final reliability factors were as follows:
wR2 = 0.0784, GOOF = 0.868 for all reflections (R1 = 0.0538
was calculated for 1982 reflections with I > 2σ(I )) using the
SHELXTL PLUS program package.17
15. H. C. Carrington, C. H. Vasey, and W. S. Waring, J. Chem.
Soc., 1953, 3105.
16. J. T. Edward and I. Lantos, Can. J. Chem., 1967, 45, 1925.
17. G. M. Sheldrick, SHELXTL Plus, PC Version, a. System of
Computer Programs for the Determination of Crystal Structure
from Xꢀray Diffraction Data, Rev. 502, Siemens Analytical
XꢀRay Instruments Inc., Germany, 1994.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ32799)
and the Russian Academy of Sciences (Program of the
Presidium of the Russian Academy of Sciences "Fundaꢀ
mental Sciences for Medicine").
Received November 29, 2004;
in revised form January 21, 2005