1,5- Diazabicyclo[3.1.0]hexanes and 1,6-diazabicyclo[4.1.0]heptanes: A new method for the synthesis, quantum-chemical calculations, and X-ray diffraction study

Article abstract of DOI:10.1023/A:1023962907733

A new method was developed for the synthesis of 6-substituted 1,5-diazabicyclo[3.1.0]hexanes and 7-substituted 1,6-diazabicyclo[4.1.0] heptanes by condensation of N-monohalotrimethylene- and N- monohalotetramethylenediamines with carbonyl compounds in the presence of bases. X-ray diffraction studies and quantum-chemical B3LYP/6-31G* calculations demonstrated that the conformations of the resulting bicyclic systems are stabi-lized by stereoelectronic interactions. As a result, a boat conformation prevails in 1,5-diazabicyclo[3.1.0]hexanes, whereas the energies of chair, half-chair, and boat conformations of 1,6-diazabicyclo[4.1.0]heptanes are equalized.

Full text of DOI:10.1023/A:1023962907733

Russian Chemical Bulletin, International Edition, Vol. 52, No. 3, pp. 665—673, March, 2003
665
1,5ꢀDiazabicyclo[3.1.0]hexanes and 1,6ꢀdiazabicyclo[4.1.0]heptanes:
a new method for the synthesis, quantumꢀchemical calculations,
and Xꢀray diffraction study*1,*2
a
a
b
a
V. V. Kuznetsov,a S. A. Kutepov, N. N. Makhova, K. A. Lyssenko, and D. E. Dmitriev
ꢀ
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@xray.ineos.ac.ru
A new method was developed for the synthesis of 6ꢀsubstituted 1,5ꢀdiazabiꢀ
cyclo[3.1.0]hexanes and 7ꢀsubstituted 1,6ꢀdiazabicyclo[4.1.0]heptanes by condensation of
Nꢀmonohalotrimethyleneꢀ and Nꢀmonohalotetramethylenediamines with carbonyl compounds
in the presence of bases. Xꢀray diffraction studies and quantumꢀchemical B3LYP/6ꢀ31G*
calculations demonstrated that the conformations of the resulting bicyclic systems are stabiꢀ
lized by stereoelectronic interactions. As a result, a boat conformation prevails in 1,5ꢀdiꢀ
azabicyclo[3.1.0]hexanes, whereas the energies of chair, halfꢀchair, and boat conformations of
1,6ꢀdiazabicyclo[4.1.0]heptanes are equalized.
Key words: 1,5ꢀdiazabicyclo[3.1.0]hexanes, 1,6ꢀdiazabicyclo[4.1.0]heptanes, synthesis,
Xꢀray diffraction analysis, stereoelectronic effects, conformation.
It is known that diaziridine derivatives exhibit neuroꢀ
tropic activity1,2 associated with inhibition of monoamine
oxidase.2,3 In this connection, a search for new simple
general procedures for the synthesis of compounds of this
class, including bicyclic diaziridines, is an urgent problem.
1,5ꢀDiazabicyclo[3.1.0]hexanes 1 are among rather readily
accessible and wellꢀstudied compounds. Earlier,4,5a,6 these
compounds have been synthesized by halogenation of
1,3ꢀdiazacyclohexanes 2 with NaOCl in water followed
by intramolecular cyclization of monohalo derivatives 3.
Recently,7 we have modified a procedure for the synthesis
of compounds 1 by performing the process in aprotic
organic solvents with the use of ButOCl as the halogenatꢀ
ing reagent and K2CO3 as the basic and dehydrating reꢀ
agent. This made it possible to substantially simplify the
isolation of the final products and perform the reactions
with waterꢀinsoluble carbonyl compounds. Earlier,5a the
simplest representative of 1,6ꢀdiazabicyclo[4.1.0]heptaꢀ
nes 4, viz., compound 4a, has been synthesized through
1,3ꢀdiazacycloheptane 5a and monochloro derivative 6a.
The starting diazacyclanes 2 and 5 were prepared by conꢀ
densation of the carbonyl compound with the correspondꢀ
ing diaminoalkanes and then used in the subsequent reacꢀ
tions without isolation (Scheme 1).
However, known procedures for the synthesis of comꢀ
pounds 1 and 4 appeared to be unsuitable for these reacꢀ
tions, if substituents in carbonyl compounds are sensitive
to strong halogenating reagents, such as NaOCl or ButOCl.
To overcome this limitation, we examined the possibility
of performing preꢀhalogenation of 1,3ꢀ and 1,4ꢀdiaminoꢀ
alkanes to form monochloro derivatives 7 and 8, respecꢀ
tively, followed by condensation with the carbonyl comꢀ
pound to produce 1,3ꢀ or 1,4ꢀdiazaꢀ1ꢀchlorocycloalkaꢀ
nes 3 and 6 and the subsequent transformation into biꢀ
cyclic compounds 1 and 4, respectively, under the action
of bases (Scheme 2). Diaminoalkanes were halogenated
to monochloro derivatives 7 and 8 with an equimolar
amount of ButOCl in methanol or chloroform depending
on the solubility of the starting carbonyl compound. Then
the corresponding carbonyl compound and base (B) were
added and the reaction mixture was kept at 0—20 °C,
*1 Dedicated to Academician I. P. Beletskaya on the occasion of
her anniversary.
*2 Preliminary results were published in the Abstracts of Papers
of the I AllꢀRussian Conference on Chemistry of Heterocycles
Dedicated to the Memory of A. N. Kosta (V. V. Kuznetsov,
S. A. Kutepov, and N. N. Makhova, Suzdal´, September 19—23,
2000, p. 243 (in Russian)) and in the Abstracts of Papers of the
I International Conference "Nitrogen Heterocycles and Alkaꢀ
loids" (V. V. Kuznetsov, S. A. Kutepov, N. N. Makhova, and
K. A. Lyssenko, Moscow, October 9—12, 2001, 2, p. 173 (in
Russian)).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 638—645, March, 2003.
1066ꢀ5285/03/5203ꢀ665 $25.00 © 2003 Plenum Publishing Corporation

666
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Kuznetsov et al.
Scheme 1
Y (%)
65
60
55
50
100
150
200
250
∆C (%)
Fig. 1. Yield (Y) of 6ꢀ(3ꢀnitrophenyl)ꢀ1,5ꢀdiazabicycꢀ
lo[3.1.0]hexane (1c) in the presence of an excess (∆C) of
1,3ꢀdiaminopropane.
on the yield of the final product was studied using the
synthesis of 6ꢀphenylꢀ and 6ꢀ(3ꢀnitrophenyl)ꢀ1,5ꢀdiazaꢀ
bicyclo[3.1.0]hexanes (1b and 1c), respectively, as exꢀ
amples. It was demonstrated that all the aboveꢀmentioned
bases are suitable for this purpose, but the best results
were obtained when an equimolar excess of the starting
1,3ꢀdiaminopropane was used (Fig. 1). Apparently, inꢀ
tramolecular αꢀaminoalkylation of amino alcohols 9 and
10 giving rise to 1ꢀchlorodiazacycloalkanes 3 and 6, reꢀ
spectively, is a more favorable process than the intermoꢀ
lecular reaction. The reactions of aminocarbinols 11 and
12 with the corresponding Nꢀchlorodiaminoalkanes 7 and
8 through intermediate Nꢀchloroaminals 13 and 14 would
afford diaziridines 15 and 16, respectively (Scheme 3).
1, 2, 3: n = 3, m = 1; 4, 5, 6: n = 4, m = 2;
4a, 5a, 6a: R = R´ = H
after which the target bicyclic compound was isolated.
The formation of compounds 3 and 6 can be represented
as the result of intramolecular αꢀaminoalkylation of inꢀ
termediate amino alcohols 9 and 10, respectively (see
Scheme 2).
Scheme 3
Scheme 2
1, 3, 7, 9: n = 3, m = 1; 4, 6, 8, 10: n = 4, m = 2
The effect of the nature of the base (Et3N, K2CO3, or
starting diaminoalkane), whose addition is necessary to
neutralize the acid liberated in the course of the reaction,

1,5ꢀDiazabicyclo[3.1.0]hexanes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
667
The new procedure developed by us for the synthesis
of bicyclic compounds 1 and 4 consists in keeping the
reaction mixture without stirring in MeOH at 0—5 °C or
in CHCl3 at 5—20 °C. The reactions were carried out
with a broad spectrum of various aldehydes, including
those containing substituents sensitive to NaOCl and
ButOCl (for example, the cyclopropyl, thiophene, or fuꢀ
ran groups). As a result, we prepared a series of not only
known8,9 but also of new 6ꢀsubstituted 1,5ꢀdiazabiꢀ
cyclo[3.1.0]hexanes 1 and previously unknown 7ꢀsubstiꢀ
tuted 1,6ꢀdiazabicyclo[4.1.0]heptanes 4, including those
based on glyoxal (Table 1).
Hence, in the present study we performed Xꢀray diffracꢀ
tion analysis of one of the compounds synthesized, viz.,
of compound 4b (and of 1d compound for comparison
purposes), and carried out quantumꢀchemical calculaꢀ
tions of the energetically most favorable conformations of
the simplest representatives of compounds of both types.
Xꢀray diffraction study demonstrated that both molꢀ
ecules 1d and 4b in the crystals have the approximate
symmetry Cs, i.e., the pseudoplane m passing through the
C(6) and C(3) atoms in 1d and through the C(7) atom
and the midpoint of the C(3)—C(4) bond in 4b (Fig. 2;
Tables 2 and 3).
In the crystal of diaziridine 1d, like in the crystal of
6,6´ꢀbis(1,5ꢀdiazabicyclo[3.1.0]hexane) 1g,10 the pyrazolꢀ
idine ring adopts an envelope conformation (dihedral
angle (α) between the C(2)—C(3)—C(4) and
N(1)—N(5)—C(2)—C(4) planes is 26.5°). In compound
1d, the angle of the bend of the diaziridine ring from the
base of the envelope (β) is 74.9°. Therefore, the overall
conformation of the sixꢀmembered ring in the crystal of
1d can be described as a flattened boat. In such a conforꢀ
mation, the lone electron pairs (n) of the N atoms are
antiperiplanar to the C(2)—C(3) and C(3)—C(4) bonds
of the ring, which can give rise to the n(N)—σ*(C—C)
interaction and, according to the earlier data,5a—c to staꢀ
bilization of this conformation.
1
Earlier, analysis of H and 13C NMR spectra,5a—d
semiempirical quantumꢀchemical calculations, and Xꢀray
diffraction study10 have demonstrated that 1,5ꢀdiazaꢀ
bicyclo[3.1.0]hexanes 1 adopt predominantly a boat conꢀ
formation. By contrast, no unambiguous conclusion about
the conformation of 1,6ꢀdiazabicyclo[4.1.0]heptane 4a
can be made due to a rapid interconversion between two
twist conformations, which persists even at –80 oC.5a
Table 1. Yields and melting (boiling) points of 6ꢀRꢀ1,5ꢀdiazaꢀ
bicyclo[3.1.0]hexanes 1 and 7ꢀRꢀ1,6ꢀdiazabicyclo[4.1.0]hepꢀ
tanes 4
Comꢀ
pound
R
Yield
(%)
M.p. (b.p.)/°C
[p/Torr]
By contrast, the bicyclic moiety in the crystal of comꢀ
pound 4b adopts a chairꢀlike conformation. This is
1a
1b
1c
cycloꢀC3H5
Ph
3ꢀNO2C6H4
73
89
63
(110—111) [25]
93—94 (cf. lit. data8: 93—94)
106, with decomp.
(cf. lit. data9: 105,
with decomp.)
C(9)
C(8)
C(7)
C(10)
1d
4ꢀClC6H4
59
103—105, with decomp.
(cf. lit. data9: 104—105,
with decomp.)
Cl(1)
C(6)
N(1)
1e
1f
2ꢀClꢀ5NO2C6H3
85
63
134
C(11)
C(3)
C(4)
85.0—85.5
N(5)
C(2)
C(12)
1g
69
214—215, with decomp.
(cf. lit. data10: 215,
with decomp.)
90.0—91.5
1d
4b
4c
4d
Ph
4ꢀClC6H4
4ꢀBrC6H4
59
60
95
65
95—96
C(10)
C(9)
C(8)
C(7)
4e
4f
87
47
92—93
N(6)
N(1)
C(11)
C(12)
C(4)
C(3)
Oil unstable under
standard conditions
C(5)
C(2)
C(13)
4g
4h
31
51
Oil unstable under
standard conditions
4b
204—206
Fig. 2. Overall views of molecules 1d and 4b according to the
results of Xꢀray diffraction analysis.

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Kuznetsov et al.
Table 2. Principal bond lengths (d) and bond angles (ω) in
1,5ꢀdiazabicyclo[3.1.0]hexanes according to the results of Xꢀray
diffraction study of compound 1d and quantumꢀchemical
(B3LYP/6ꢀ31G*) calculations of molecule 1h
Table 3. Principal bond lengths (d) and bond angles (ω) in
1,6ꢀdiazabicyclo[4.1.0]heptanes according to the results of Xꢀray
diffraction study of compound 4b and quantumꢀchemical
(B3LYP/6ꢀ31G*) calculations of molecule 4a
Parameter
1d
1h (boat)* 1h (chair)*
d/Å
Parameter
4b
4a
(chair)* (boat)* (hꢀchair)**
Bond
N(1)—N(5)
N(1)—C(2)
N(1)—C(6)
N(5)—C(4)
N(5)—C(6)
C(2)—C(3)
C(3)—C(4)
Angle
N(5)—N(1)—C(2)
N(5)—N(1)—C(6)
N(1)—N(5)—C(4)
N(1)—N(5)—C(6)
C(2)—N(1)—C(6)
C(6)—N(5)—C(4)
N(1)—C(2)—C(3)
C(4)—C(3)—C(2)
N(5)—C(4)—C(3)
N(1)—C(6)—N(5)
1.517(2)
1.488(2)
1.456(2)
1.485(2)
1.458(2)
1.533(2)
1.531(2)
1.509
1.482
1.449
—
1.527
1.488
1.447
—
ꢁ —
1.538
1.538
Bond
d/Å
N(1)—N(6)
N(1)—C(2)
N(6)—C(5)
N(1)—C(7)
N(6)—C(7)
C(2)—C(3)
C(3)—C(4)
C(4)—C(5)
Angle
N(6)—N(1)—C(7) 58.7(1) 58.2
C(2)—N(1)—C(7) 116.2(1) 116.2
N(1)—N(6)—C(7) 58.1(1)
C(5)—N(6)—C(7) 115.0(1)
1.528(2) 1.521
1.478(2) 1.476
1.477(2)
1.452(2) 1.445
1.461(2)
1.501
1.477
—
1.448
—
1.539
1.554
—
1.515
1.474
1.490
1.438
1.450
1.534
1.529
1.531
—
—
1.542
1.542
ω/deg
—
1.516(2) 1.536
1.539(2) 1.554
107.1(1) 107.5
58.71(9) 58.6
107.0(1)
58.56(9)
111.7(1) 112.5
111.2(1)
107.7(1) 108.1
102.4(1) 102.1
108.0(1)
107.3
58.1
—
—
112.6
—
105.9
103.3
—
1.518(2)
—
ω/deg
—
—
58.8
117.2
—
115.2
117.8
—
112.6
—
62.4
58.7
117.7
58.0
—
—
—
—
N(1)—C(2)—C(3) 108.8(1) 109.0
N(6)—C(5)—C(4) 109.3(1)
C(2)—C(3)—C(4) 111.5(1) 111.3
C(3)—C(4)—C(5) 111.1(1)
N(1)—C(7)—N(6) 63.2(1) 63.5
117.3
115.3
108.5
110.0
63.3
—
—
62.73(9) 62.7
63.7
—
* The geometry of the molecule was optimized within the symꢀ
metry Cs.
* The geometry of the molecule was optimized within the symꢀ
metry Cs.
** The geometry of the molecule was optimized within the symꢀ
the only of all possible conformations, in which the
n(N)—σ*(C—C) interaction cannot occur (see Fig. 2).
The sixꢀmembered ring in molecule 4b adopts a boat conꢀ
formation (C(2) and C(5) atoms deviate from the
N(1)—N(6)—C(3)—C(4) plane by 0.67 Å) instead
of the expected twist conformation,5a and the diꢀ
aziridine ring forms an angle (γ) of 72.7° with the
N(1)—N(6)—C(2)—C(5) plane (see Fig. 2). Apparently,
the observed elongation of the N(1)—N(6) bond (1.528(2)
Å) in molecule 4b compared to the N(1)—N(5) bond
(1.517(2) Å) in the structure of 1d is attributable to an
increase in the contribution of the р orbital of the N
atom, because there is no n(N)—σ*(C—C) interaction in
compound 4b.
Since the N atoms in compound 4b are involved in the
intermolecular N(1)...H(12´)—C(12´) contacts (1/2 – x,
2 – y, –0.5 + y) (N(1)...H(12´), 2.47 Å; N(1)...C(12´),
3.488(3) Å; N(1)—H(12´)—C(12´), 160°), the conforꢀ
mation of the bicyclic moiety (chair) observed in molꢀ
ecule 4b may be attributed to the crystal packing effect.
With the aim of determining the energetically most
favorable conformation and estimating the influence of
the stereoelectronic effects on the preferable conformaꢀ
tions of 1,5ꢀdiazabicyclo[3.1.0]hexanes 1 and 1,6ꢀdiazaꢀ
bicyclo[4.1.0]heptanes 4, quantumꢀchemical calculations
(B3LYP/6ꢀ31G*)11 were carried out for model comꢀ
pounds 1h (Fig. 3) and 4a (Fig. 4) with R = R´ = H.
metry C1.
In the isolated molecule, the energy of the boat conꢀ
formation (1h (boat)) with consideration for the zeroꢀ
point energy (ZPE) is 3.4 kcal mol–1 lower than the enꢀ
ergy of the chair conformation (1h (chair)). The geometry
of 1h (boat) rather adequately reproduces the correspondꢀ
ing experimental values for 1d, except for a slight shortenꢀ
ing of the N(1)—N(5) bond to 1.509 Å (see Table 2). The
transformation from the boat conformation to the chair
conformation in 1h is accompanied by an increase in the
N(1)—N(5) bond length to 1.527 Å, an increase in the
C(2)—C(3)—C(4) bond angle from 102.1° to 105.9°,
and an increase in the α angle from 24.9° to 31.3°.
These changes are consistent with the presence of the
n(N)—σ*(C—C) interaction in 1h (boat). To estimate the
contribution of the n(N)—σ*(C—C) interaction to stabiꢀ
lization of 1h (boat), we carried out the NBO analysis,12
which has earlier been successfully applied to the investiꢀ
gation of anomeric and related interactions (see, for exꢀ
ample, Refs. 13a,b). In line with the published data5a—d
and the observed variations in the geometric parameters,
the NBO analysis demonstrated that the nꢀelectrons of
the N(1) and N(5) atoms in 1h (boat) interact with the
σ* orbitals of the C(2)—C(3) and C(3)—C(4) bonds. The
contribution of these interactions to the charge deloꢀ
calization is 4 kcal mol–1. Both conformations of 1h

1,5ꢀDiazabicyclo[3.1.0]hexanes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
669
H(6A)
H(2A)
H(5A)
H(3A)
C(3)
H(6B)
H(3B)
C(2)
H(2B)
C(6)
H(4A)
C(4)
H(4B)
C(3)
H(2A)
N(1)
N(5)
C(5)
H(5B)
C(4)
N(6)
H(3B)
C(2)
N(1)
H(3A)
H(4B)
H(2B)
H(4A)
H(7B)
C(7)
H(7A)
1h (boat)
4a (boat)
H(3B)
H(6A)
H(6B)
H(4B)
H(3A)
H(2B)
N(1)
C(7)
C(3)
C(6)
H(4A)
C(2)
H(7B)
H(2A)
N(6)
C(4)
H(5B)
N(5)
C(4)
H(3A)
C(5)
H(4A)
H(2A)
C(2)
N(4)
H(7A)
C(3)
H(4B)
H(5A)
H(2B)
4a (chair)
H(3B)
H(4B)
H(2B)
1h (chair)
H(5A)
Fig. 3. Overall views of conformations 1h (boat) and 1h (chair)
C(4)
C(2)
(calculated data).
N(6)
H(4A)
N(1)
H(3A)
C(5)
are characterized by the presence of not only the
n(N)—σ*(C—C) interactions but also of the
n(N)—σ*(C(6)—H(6A)) interactions comparable in
energy (3.5 kcal mol–1) to the former interactions (see
Fig. 3). Apparently, the latter interactions are responsible
for the constancy of the dihedral angle β (73.7 and 73.9°
in 1h (boat) and 1h (chair), respectively).
C(3)
H(2A)
C(7)
H(5B)
H(3B)
H(7B)
H(7A)
4a (hꢀchair)
The geometry optimization of 4a revealed three conꢀ
formations of this bicyclic compound with close energies.
In two of these conformations, the sixꢀmembered ring
adopts a boat conformation, but the overall conformation
of the bicyclic moiety in these two cases can be described
as a boatꢀlike conformation (4a (boat)), in which the
diaziridine ring and the C(3)—C(4) bond are on the same
side of the N(1)—N(6)—C(2)—C(5) plane, and a chairꢀ
like conformation (4a (chair)), in which the diaziridine
ring and the C(3)—C(4) bond, on the contrary, deviate in
opposite directions. In another chairꢀlike conformation
Fig. 4. Overall views of conformations 4a (boat), 4a (chair), and
4a (hꢀchair) (calculated data).
of bicyclic compound 4a, the sixꢀmembered ring adopts a
halfꢀchair conformation (4a (hꢀchair)) with the C(3) and
C(4) atoms deviating from the N(1)—N(6)—C(2)—C(5)
plane by 0.36 and –0.41 Å, respectively (see Fig. 4).
Although 4a (boat) is characterized by the lowest energy,
this conformation is only 0.45 kcal mol–1 more stable
than 4a (hꢀchair) taking account of ZPE. The energy of

670
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Kuznetsov et al.
the latter conformation is, in turn, only 1.35 kcal mol–1
lower than the energy of 4a (chair). Such insignificant
differences in the energy of the conformations of molꢀ
ecule 4a agree well with the efficient flattening of the sixꢀ
membered ring observed from the NMR spectra.5a
1,5ꢀdiazabicyclo[3.1.0]hexanes 1 and, which is more
unusual, the energies of chair, halfꢀchair, and boat
conformations in 1,6ꢀdiazabicyclo[4.1.0]heptanes are
equalized.
In spite of the fact that three conformations of 4a are
close in energy, their geometric parameters and, primaꢀ
rily, the N(1)—N(6) bond lengths are substantially differꢀ
ent and (like those in molecule 1h) are determined by the
presence and strength of the n(N)—σ*(C—C) interacꢀ
tions (see Table 3). Thus, the shortest N—N bond
(1.501 Å) is observed in conformation 4a (boat), in which
the contribution of the n(N)—σ*(C—C) interaction to
the charge delocalization is 6.8 kcal mol–1 (according to
the results of the NBO analysis). To the contrary, 4a
(chair), in which this interaction is a priori absent, has the
longest N—N bond (1.521 Å). Conformation 4a (hꢀchair)
is, in turn, characterized by the intermediate value of the
N—N bond length (1.515 Å) as well as by the differences
in the bond angles at the C(2) and C(5) atoms, which is
associated with the fact that only one N atom in this
conformation is involved in the n(N(6))—σ*(C(5)—C(4))
Experimental
The IR spectra were recorded on a URꢀ20 spectrometer in
KBr pellets. The H NMR spectra of compounds 1a,c—e,g and
1
4b—d,g were measured on a Bruker DRXꢀ500 spectrometer
(500 MHz). The 1H NMR spectra of compounds 1b,f and 4e,f,h
were recorded on a Bruker AMꢀ300 spectrometer (300 MHz).
The assignment of the signals in the spectrum of compound 1a
was made based on the COSY 2D homonuclear correlation
spectrum. The spin system of compound 1a was analyzed with
the use of the CALM program for iterative analysis. This proꢀ
1
gram allowed us to calculate the H NMR spectra of this comꢀ
pound based on the spinꢀspin coupling constants, which were
roughly determined from the experimental spectrum, as the iniꢀ
tial approximation and then to perform an iterative search for
the parameters of the spin system (proton chemical shifts and
spinꢀspin coupling constants) to achieve the best fit of the calcuꢀ
lated spectrum to the experimental data. For the remaining
compounds 1 and 4, the spinꢀspin coupling constants were calꢀ
culated manually. The 13C NMR spectrum of compound 4h was
recorded on a Bruker DRXꢀ500 spectrometer (125.8 MHz). The
13C NMR spectra of compounds 1a and 4c,e were measured on
a Bruker AMꢀ300 spectrometer (75.5 MHz). The 13C NMR
spectra of compounds 1b,f and 4b,d were recorded on a Bruker
WMꢀ250 spectrometer (62.9 MHz). The chemical shifts are given
in the δ scale with respect to the residual signals of the protons of
the deuterated solvent. The mass spectra were obtained on an
MSꢀ30 spectrometer. The TLC analysis was carried out on Silufol
UVꢀ254 plates; visualization was carried out with iodine vapor
and independently by spraying with a solution of diphenylamine
in acetone followed by heating of the plates (CHCl3—MeOH,
10 : 1, as the eluent).
6ꢀCyclopropylꢀ1,5ꢀdiazabicyclo[3.1.0]hexane (1a). A soluꢀ
tion of ButOCl (2.2 mL, 16.5 mmol) in MeOH (3 mL) was
added dropwise to a solution of 1,3ꢀdiaminopropane (2.4 g,
33 mmol) in MeOH (15 mL) at 0 °C and then formylcycloꢀ
propane (1.2 g, 16.6 mmol) was added. The reaction mixture
was kept at this temperature for 1 h and then at 20 °C for 1 h.
The precipitate that formed was filtered off and the yield of
compound 1a (73%) was determined by iodometric titration.
The solvent was evaporated in vacuo, the residue was distilled
off, and the fraction with b.p. 110—111 °C (25 Torr) was colꢀ
lected. Compound 1a was obtained in a yield of 1.4 g (68%),
interaction with the energy of 6.4 kcal mol–1
.
Since the remaining bond lengths in both molecules
1h and 4a depend only slightly on the conformation, the
observed correlation between the N—N bond length and
the strength of the n(N)—σ*(C—C) interaction can serve
as a reliable criterion in studies of stereoelectronic interꢀ
actions in such systems. For example, the N—N bond in
transꢀexoꢀ2,4,6ꢀtrimethylꢀ1,3,5ꢀtriazabicyclo[3.1.0]hexꢀ
ane, in which the n(N)—σ*(C—N) interaction has a
higher energy, is shortened to 1.511 Å.14
Apparently, the observed variations in the angle of the
bend (γ) of the diaziridine ring (71.9—75.2°) in comꢀ
pound 4a, in contrast to the constancy of the correspondꢀ
ing dihedral angle β in molecule 1h, result from the
difference in the energy (3.8—4.8 kcal mol–1) of the
n(N)—σ*(C(7)—H(7A)) interactions.
The character of the 1H NMR spectra of compounds 1
and 4 is consistent with the data from Xꢀray diffraction
analysis and quantumꢀchemical calculations. For exꢀ
ample, the NMR spectra of compounds 1 at 20 °C have
multiplets with fine splitting patterns, which indicates that
the molecules in solution occur predominantly in a single
conformation stable within the NMR time scale. By conꢀ
trast, the spectra of compounds 4 both at 20 and –80 °C
have broadened poorly resolved multiplets, which indiꢀ
cates that several conformations with close energies occur
in dynamic equilibrium in solution.
20
20
d4 1.02, nD 1.490, Rf 0.56. Found (%): C, 67.5; H, 9.7;
N, 22.5. C7H12N2. Calculated (%): C, 67.7; H, 9.7; N, 22.6.
To summarize, Xꢀray diffraction analysis, NMR
spectroscopic studies, and quantumꢀchemical calculaꢀ
tions demonstrated that the stereoelectronic interactions
play the main role in stabilization of the conformations of
the nitrogenꢀcontaining bicyclic compounds under conꢀ
sideration. As a result, a boat conformation prevails in

1,5ꢀDiazabicyclo[3.1.0]hexanes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
671
IR, ν/cm–1: 630, 670, 840, 950, 1020, 1220, 1250, 1440,
2890, 2940, 2990, 3110. H NMR (CDCl3), δ: 0.17 (m, 2 H,
N, 17.5. IR, ν/cm–1: 2926, 1538, 1354, 1076, 831, 747. 1H NMR
1
(DMSOꢀd6), δ: 1.95 (m, 1 H, Hax(3)); 2.00 (m, 1 H, Heq(3),
3
3
Ht(8), Ht(9), JH (8)—H (9) = 9.23 Hz); 0.23 (m, 2 H, Hc(8),
2J = –12.0 Hz); 3.10 (m, 2 H, Hax(2(4)), JH
=
(2(4))—H (3)
eq
ax
t
t
3
2
Hc(9), JH (8)—H (9) = –9.40 Hz, JH (8(9))—H (8(9)) = –4.51 Hz,
8.5 Hz); 3.53 (s, 1 H, HCring(6)); 3.61 (m, 2 H, Heq(2(4)),
2J = –12.1 Hz, 3JH
= 8.8 Hz); 7.61 (d, 1 H,
3JH (9)—H (9(8)) =c5.96 Hz, 3JH (8)—H (9) = 9.40cHz); 0.68 (m, 1 H,
c
t
(2(4))—H (3)
ax
eq
t
c
c
c
3
3
3
H(7), JH(7)—H (8(9)) = 4.82 Hz, JH(7)—H (8(9)) = 8.56 Hz); 1.50
HCAr(3)); 8.11 (d, 1 H, HCAr(4), J = 7.8 Hz); 8.15 (s, 1 H,
t
c
3
(m, 1 H, Heq(3), JH
H(6), JH(6)—H(7) = 4.87 Hz); 2.72 (m, 2 H, Heq(2), Heq(4),
= –13.16 Hz); 2.00 (d, 1 H,
HCAr(6)).
(3)—H (3)
ax
eq
3
6ꢀ(2ꢀPyridyl)ꢀ1,5ꢀdiazabicyclo[3.1.0]hexane
(1f).
3
3JH
= 8.18 Hz, JH
(3) = 11.03 Hz); 3.13
= –12.07 Hz,
eq
Found (%): N, 25.8. C9H11N3. Calculated (%): N, 26.1. IR,
ν/cm–1: 3025, 1672, 1204, 1067, 712. 1H NMR (DMSOꢀd6), δ:
1.80 (m, 2 H, Hax(3), Heq(3), 2J = –11.8 Hz); 3.08 (m,
(2(4))—H (3)
ax eq
(m, 2 H, Heq(2), Heq(4)eq, 2JH
(2(4))—H
ax
ax
(2(4))—H (2(4))
ax
3JH
= 8.92 Hz). 13C NMR (CDCl3), δ: –0.2
(2(4))—H (3)
ax
eq
3
3
(C(8), C(9)); 9.5 (C(7)); 20.6 (C(3)); 50.0 (C(2), C(4));
2 H, Hax(2(4)), JH
= 8.3 Hz, JH
=
(2(4))—H (3)
ax ax
(2(4))—H (3)
eq
ax
56.3 (C(6)).
11.1 Hz); 3.30 (s, 1 H, HCPy(6)); 3.56 (m, 2 H, Heq(2(4)),
6ꢀArylꢀ and 6ꢀheteroarylꢀ1,5ꢀdiazabicyclo[3.1.0]hexanes (1),
7ꢀarylꢀ and 7ꢀheteroarylꢀ1,6ꢀdiazabicyclo[4.1.0]heptanes (4)
(general procedure). A solution of ButOCl (0.022 mol) in MeOH
or CHCl3 (3 mL) was added dropwise with active stirring to a
solution of diaminoalkane (0.04 mol) in MeOH (30 mL) for
1b,c,e—g and 4b,e—h or in CHCl3 (30 mL) for 1d and 4c,d at
–5—0 °C. Then a solution of aldehyde (0.02 mol) in the correꢀ
sponding solvent (4—6 mL) was added. The reaction mixture
was kept for 24 h at 0—5 °C (with the use of MeOH) or at
20—25 °C (with the use of CHCl3) and filtered through a thin
layer (1.5—2.0 cm) of silica gel. The solvent was evaporated in
vacuo and water (50 mL) was added to the residue. The reaction
mixture was saturated with NaCl, extracted with ether or CH2Cl2
(3×30 mL), and dried with K2CO3. The solvent was evaporated
in vacuo and the residue was recrystallized from acetone or
ether. The spectroscopic characteristics of the compounds are
given in Table 2.
3JH
=
8.9 Hz); 7.13 (t,
1
H, HCPy(5),
= 5.3 Hz);
Py
(2(4))—H (3)
ax
eq
3
3JH(C
= 6.8 Hz, JH(C
(5))—H(C (4))
Py
(5))—H(C (6))
Py
Py
3
7.26 (d, 1 H, HCPy(3), JH(C
= 7.8 Hz); 7.58 (t,
(3))—H(C (4))
Py
Py
1 H, HCPy(4)); 8.40 (d, 1 H, HCPy(6)). 13C NMR (DMSOꢀd6),
δ: 21.50 (Cring(3)); 52.35 (Cring(2(4)); 57.39 (Cring(6)); 121.13
(CPy(3)); 123.46 (CPy(5)); 136.79 (CPy(4)); 148.52 (CPy(6));
157.07 (CPy(2)).
7ꢀPhenylꢀ1,6ꢀdiazabicyclo[4.1.0]heptane (4b). Found (%):
N, 15.6. C11H14N2. Calculated (%): N, 16.1. IR, ν/cm–1: 2938,
1
1568, 1325, 1052, 858, 745. H NMR (DMSOꢀd6), δ: 1.61 (m,
4 H, Hax(3), Heq(3), Hax(4), Heq(4)); 2.90 (m, 2 H, Hax(2),
Hax(5)); 3.30 (m, 2 H, Heq(2), Heq(5), 2JH
=
(2(5))—H (2(5))
ax
eq
–13.5 Hz); 3.79 (s, 1 H, HCring(7)); 7.30 (m, 5 H, HCAr).
13C NMR (DMSOꢀd6), δ: 7.41 (Cring(3(5))); 37.04 (Cring(2(4)));
57.71 (Cring(7)); 118.34 (CAr(2(6))); 118.75 (CAr(3(5))); 124.03
(CAr(4)); 127.19 (CAr(1)).
7ꢀ(4ꢀChlorophenyl)ꢀ1,6ꢀdiazabicyclo[4.1.0]heptane (4c).
Found (%): N, 13.0. C11H13ClN2. Calculated (%): N, 13.4. IR,
ν/cm–1: 3084, 2953, 1594, 1336, 1070, 796, 762. 1H NMR
(DMSOꢀd6), δ: 1.72 (m, 4 H, Hax(3), Heq(3), Hax(4), Heq(4));
2.88 (m, 2 H, Hax(2), Hax(5)); 3.42 (m, 2 H, Heq(2), Heq(5),
6ꢀPhenylꢀ1,5ꢀdiazabicyclo[3.1.0]hexane (1b). The IR specꢀ
trum is identical with the published data.9 1H NMR (CDCl3), δ:
2
1.90 (m, 1 H, Hax(3)); 1.95 (m, 1 H, Heq(3), J = –12.0 Hz);
3.18 (m, 2 H, Hax(2), Hax(4), 3JH
= 8.5 Hz,
(2(4))—H (4)
eq
= 11.3 Hz); 3.59 (m, 2 H, Heq(2), Heq(4),
ax
3JH
2JH
= –13.1 Hz); 3.49 (s, 1 H, HCring(7));
(2(5))—H (2(5))
ax
(2(4))—H (3)
ax
ax
eq
2J = –12.1 Hz, JH
= 1.3 Hz, JH
=
7.28 (q, 4 H, HCAr, 3J = 11.2 Hz). 13C NMR (DMSOꢀd6),
δ: 7.41 (Cring(3(5))); 37.04 (Cring(2(4))); 57.71 (Cring(7));
118.34 (CAr(3(5))); 118.75 (CAr(2(6))); 124.03 (CAr(4));
127.19 (CAr(1)).
3
3
(2(4))—H (3)
eq eq
(2(4))—H (3)
ax
eq
8.8 Hz); 3.59 (s, 1 H, HCring(6)); 7.33 (m, 5 H, HCAr). 13C NMR
(CDCl3), δ: 21.6 (Cring(3)); 52.2 (Cring(2(4))); 56.6 (Cring(6));
127.2 (CAr(2(6))); 128.16 (CAr(3(5))); 128.4 (CAr(4)); 137.0
(CAr(1)). Partial mass spectrum (EI, 70 eV), m/z (Irel (%)): 160
[M]+ (24.8), 159 [M – H]+ (100), 83 [M – Ph]+ (15), 65
[Ph]+ (28.8).
7ꢀ(4ꢀBromophenyl)ꢀ1,6ꢀdiazabicyclo[4.1.0]heptane (4d).
Found (%): N, 10.8. C11H13BrN2. Calculated (%): N, 11.1. IR,
ν/cm–1: 2914, 1585, 1340, 1105, 858, 740. 1H NMR (CDCl3), δ:
1.71 (m, 4 H, Hax(3), Heq(3), Hax(4), Heq(4)); 2.85 (m, 2 H,
Hax(2), Hax(5)); 3.40 (m, 2 H, Heq(2), Heq(5)); 3.49 (s, 1 H,
HCring(7)); 7.30 (q, 4 H, HCAr, AB system, ∆ν = 80.0, 3J =
8.2 Hz). 13C NMR (CDCl3), δ: 17.63 (Cring(3(4))); 47.31
(Cring(2(5))); 67.97 (Cring(7)); 122.45 (CAr(1)); 129.29
(CAr(3(5))); 131.49 (CAr(2(6))); 137.88 (CAr(4)).
6ꢀ(3ꢀNitrophenyl)ꢀ1,5ꢀdiazabicyclo[3.1.0]hexane (1c). The
IR spectrum is identical with the published data.9 1H NMR
(DMSOꢀd6), δ: 1.85 (m, 1 H, Hax(3)); 1.90 (m, 1 H, Heq(3),
2J = –12.2 Hz); 2.95 (m, 2 H, Hax(2), Hax(4), 3JH
=
(2(4))—H (3)
ax eq
8.4 Hz, 3JH
Heq(4), 2JH
= 11.1 Hz); 3.51 (m, 2 H, Heq(2),
(2(4))—H (3)
ax
ax
ax
= –12.3 Hz, 3JH
=
(2(4))—H (2(4))
eq
(2(4))—H (3)
eq
eq
3
1.4 Hz, JH
= 8.8 Hz); 3.59 (s, 1 H, HCring(6));
H, HCAr(6),
7ꢀ(2ꢀPyridyl)ꢀ1,6ꢀdiazabicyclo[4.1.0]heptane
(4e).
(2(4))—H (3)
ax
eq
7.61 (t,
1
H, HCAr(5)); 7.75 (d,
1
Found (%): N, 23.5. C10H13N3. Calculated (%): N, 24.0. IR,
3JH(CAr(6))—H(CAr(5)) = 7.8 Hz); 8.11 (d, 1 H, HCAr(4), 3J =
5.6 Hz); 8.15 (s, 1 H, HCAr(2)).
ν/cm–1: 1658, 1186, 1032, 710. H NMR (CDCl3), δ: 1.69 (m,
1
4 H, Hax(3), Heq(3), Hax(4), Heq(4)); 2.92 (m, 2 H, Hax(2),
6ꢀ(4ꢀChlorophenyl)ꢀ1,5ꢀdiazabicyclo[3.1.0]hexane (1d). The
IR spectrum is identical with the published data.9 1H NMR
Hax(5)); 3.45 (m, 2 H, Heq(2), Heq(5), 2JH
=
(2(5))—H (2(5))
ax
eq
–13.0 Hz); 3.78 (s, 1 H, HCring(7)); 7.13 (d, 1 H, HCPy(3), 3J =
2
3
(DMSOꢀd6), δ: 1.85 (m, 2 H, Hax(3), Heq(3), J = –12.0 Hz);
7.8 Hz); 7.25 (t, 1 H, HCPy(5), JH(C
= 6.9 Hz,
(5))—H(C (4))
Py
Py
2.91 (m, 2 H, Hax(2), Hax(4), 3J
= 8.5 Hz);
3JH(C
= 5.0 Hz); 7.68 (t, 1 H, HCPy(4)); 8.48 (d,
(5))—H(C (6))
Py
H
(2(4))—H (3)
eq
ax
Py
3.47 (m, 2 H, Heq(2), Heq(4), 2J = –12.1 Hz, 3JH
=
1 H, HCPy(6)). 13C NMR (CDCl3), δ: 17.23 (Cring(3(4))); 47.24
(Cring(2(5))); 68.82 (Cring(7)); 120.96 (CPy(3)); 123.50 (CPy(5));
136.87 (CPy(4)); 148.71 (CPy(6)); 157.59 (CPy(2)).
(2(4))—H (3)
eq
ax
8.7 Hz); 3.37 (s, 1 H, HCring(6)); 7.35 (q, 4 H, HCAr, AB
system, ∆ν = 25, 3J = 12.0 Hz).
6ꢀ(2ꢀChloroꢀ5ꢀnitrophenyl)ꢀ1,5ꢀdiazabicyclo[3.1.0]hexane
(1e). Found (%): N, 17.1. C10H10ClN3O2. Calculated (%):
7ꢀ(2ꢀFuryl)ꢀ1,6ꢀdiazabicyclo[4.1.0]heptane (4f). Found (%):
N, 16.6. C9H12N2O. Calculated (%): N, 17.1. 1H NMR

672
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 3, March, 2003
Kuznetsov et al.
(CDCl3), δ: 1.66 (m, 4 H, Hax(3), Heq(3), Hax(4), Heq(4)); 3.46
for 12 h and filtered through a thin layer (1.5—2.0 cm) of silica
gel. The solvent was concentrated in vacuo. The residue was
dissolved in water (50 mL), saturated with NaCl, extracted with
ether or CH2Cl2 (3×30 mL), and dried with K2CO3. The solvent
was concentrated in vacuo and the mixture was recrystallized
from acetone or ether. The yields of compounds 1b and 1c
prepared with the use of Et3NH were 21 and 25%, respectively.
The yields of these compounds obtained with the use of K2CO3
were 33 and 31%, respectively.
Xꢀray diffraction study. All Xꢀray data were collected on a
SMART CCDꢀ1000 diffractometer (ω scanning technique,
frames were exposed for 10 s). The Xꢀray data were processed
with the use of the SAINT PLUS program package. The empiriꢀ
cal absorption correction was applied based on equivalent reꢀ
flections with the use of the SADABS program. The principal
crystallographic data and details of the refinement are given in
Table 4. The structures were solved by direct methods and reꢀ
fined by the fullꢀmatrix leastꢀsquares method based on F 2 with
anisotropic and isotropic thermal parameters. The H atoms were
revealed from difference electron density syntheses and included
in the final refinement with isotropic thermal parameters. All
calculations were carried out on a personal computer with the
use of the SHELXTL PLUS ver. 5.0 program package.
(m, 2 H, Hax(2), Hax(4)); 3.56 (m, 2 H, Heq(2), Heq(5)); 3.59 (s,
3
1 H, HCring(7)); 6.30 (d, 1 H, HCHet(3), J = 2.0 Hz); 6.36 (t,
1 H, HCHet(4), 3J H(C
(5)) = 1.75 Hz); 7.45 (d, 1 H,
(4))—H(C
Het
Het
HCHet(5)).
7ꢀ(5ꢀBromoꢀ2ꢀthienyl)ꢀ1,6ꢀdiazabicyclo[4.1.0]heptane (4g).
Found (%): N, 10.6. C9H11BrN2S. Calculated (%): N, 10.8.
1H NMR (CDCl3), δ: 1.69 (m, 4 H, Hax(3), Heq(3), Hax(4),
Heq(4)); 2.85 (m, 2 H, Hax(2), Hax(5)); 3.47 (m, 2 H, Heq(2),
2
Heq(5), J = –11.5 Hz); 3.75 (s, 1 H, HCring(7)); 6.91 (d, 1 H,
HCHet(3)); 7.19 (d, 1 H, HCHet(4), 3J = 1.5 Hz).
7,7´ꢀBis(1,6ꢀdiazabicyclo[4.1.0]heptane) (4h). Found (%):
S, 61.5; H, 9.1; N, 28.7. C10H18N4. Calculated (%): S, 61.8;
1
H, 9.3; N, 28.8. H NMR (CDCl3), δ: 1.59 (m, 4 H, Hax(3),
Hax(3´), Hax(4), Hax(4´)); 1.69 (m, 4 H, Heq(3), Heq(3´), Heq(4),
2
Heq(4´), J = –12.3 Hz); 2.41 (s, 2 H, HCring(7), HCring(7´));
2.68 (m, 4 H, Hax(2), Hax(2´), Hax(5), Hax(5´)); 3.39 (m, 4 H,
2
Heq(2), Heq(2´), Heq(5), Heq(5´), J = –12.0 Hz). 13C NMR
(CDCl3), δ: 17.04 (Cring(3), Cring(3´) (Cring(4), Cring(4´));
46.78 (Cring(2), Cring(2´) (Cring(5), Cring(5´)); 68.48 (Cring(7),
C
ring(7´)).
6ꢀPhenylꢀ (1b) and 6ꢀtrinitrophenylꢀ1,5ꢀdiazabicycꢀ
lo[3.1.0]hexane (1c) in the presence of Et3NH or K2CO3.
A solution of ButOCl (0.04 mol) in MeOH (6 mL) was added
dropwise with stirring to a solution of 1,3ꢀdiaminopropane
(0.04 mol) in MeOH (30 mL) at –5—0 °C. Then Et3NH or
K2CO3 (0.04 mol) and the corresponding aldehyde (0.02 mol)
were added dropwise. The reaction mixture was stirred at 0—5 °C
We thank Prof. N. Allinger (University of Georgia,
Athens, USA) for help in performing quantumꢀchemical
calculations.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ32807)
and INTAS (Grant 99ꢀ0157).
Table 4. Principal crystallographic parameters of compounds 1d
and 4b
Parameter
C10H11ClN2 (1d) С11H14N2 (4b)
References
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F(000)
194.66
816
174.24
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µ(MoꢀKα)/cm–1
Space group
Diffractometer
Scanning mode
ω Scan step/deg
Exposition time
per frame/s
T/К
a/Å
b/Å
c/Å
V/Å3
3.57
Pbca
0.78
P212121
«SMART CCDꢀ1K»
ω Scan technique
0.3
10
110
14.255(5)
7.669(1)
10.350(2)
12.087(2)
959.4(3)
4
1.310
52
6189
8.935(2)
14.779(4)
1882.3(8)
8
1.374
58
Z
dcalc/g cm–3
2θmax/deg
Number of measured
reflections
Number of independent
reflections
wR2 based on F 2
for all reflections
R1, based on F for
reflections with I > 2σ(I )
GOF
6345
2463
(Rint = 0.0201)
0.1562
1862
(Rint = 0.0320)
0.0935
0.0532 (1990
reflections)
1.075
0.0372 (1610
reflections)
1.042

1,5ꢀDiazabicyclo[3.1.0]hexanes
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in revised form December 18, 2002