High pressure-assisted synthesis of 1,2,3-trialkyldiaziridines from N-chloroalkylamines

Article abstract of DOI:10.1002/jhet.5570450230

(Chemical Equation Presented) New method for the preparation of 1,2,3-trialkyldiaziridines 1 in high yields, based on the transformation of N-chloroalkylamines 3 without using carbonyl compounds in the presence of primary aliphatic amines with the same alkyl fragment, potassium carbonate and a small amount of water in CHCl₃ under high pressure (500 MPa), was developed. Diaziridines 1 can be synthesized in the same conditions using a larger amount of potassium carbonate instead of primary aliphatic amines however in lower yields. The kinetic investigations on the synthesis of 1,2-diethyl-3-methyldiaziridine 1a from N-chloroethylamine 3a have shown that the reaction leading to diaziridine 1a proceeds according to the law of the second order.

Full text of DOI:10.1002/jhet.5570450230

Mar-Apr 2008
497
High Pressure-Assisted Synthesis of
1,2,3-Trialkyldiaziridines from
N-Chloroalkylamines
Vladimir V. Kuznetsov, Julia S. Syroeshkina, Dmitrii I. Moskvin, Marina I. Struchkova,
Nina N. Makhova*, and Alexey A. Zharov
N. D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences,
47 Leninsky pr., 119991 Moscow, Russian Federation. E-mail: mnn@ioc.ac.ru
Received June 28, 2007
RCH2NH2, K2CO3, CHCl3, P, 15 oC
(78-95%)
NCH2R
RCH2NHCl
R
K2CO3, CHCl3, P, 15 oC
(47-55%)
NCH2R
N
N(CH2)2
R = Me, Et, PhCH2, MeOCH2, MeCONHCH2,
New method for the preparation of 1,2,3-trialkyldiaziridines 1 in high yields, based on the
transformation of N-chloroalkylamines 3 without using carbonyl compounds in the presence of primary
aliphatic amines with the same alkyl fragment, potassium carbonate and a small amount of water in CHCl3
under high pressure (500 MPa), was developed. Diaziridines 1 can be synthesized in the same conditions
using a larger amount of potassium carbonate instead of primary aliphatic amines however in lower yields.
The kinetic investigations on the synthesis of 1,2-diethyl-3-methyldiaziridine 1a from N-chloroethylamine
3a have shown that the reaction leading to diaziridine 1a proceeds according to the law of the second
order.
J. Heterocyclic Chem., 45, 497 (2008).
chloroorganic solvents. Unexpectedly, it was found out
that a reaction of N-chloroalkylamines 3 with primary
aliphatic amines 2, containing the same alkyl fragment, in
the absence of carbonyl compounds and in the presence of
potassium carbonate and a small water amount at room
temperature resulted in 1,2,3-trialkyldiaziridines 1 where
3-alkyl fragments contained one CH2-group less than the
alkyl fragment of the initial compounds. Proceeding from
the structure of the obtained products we assumed that the
first step of this reaction should be the conversion of N-
chloroalkylamines 3 into aldimines 4 as a result of HCl
E2-elimination in the presence of amines 2. Compounds 4
are hydrolyzed to aldehydes 5 in the presence of water by
analogy with reactions reported in reference [20]. In
according to known data [21,3,4] it was assumed that a
carbonyl compounds 5 and an amines 2 were condensed
into α-aminocarbinols 6, which underwent α-amino-
alkilation of N-chloroamines 3 to give N-chloroaminals 7;
the latter underwent cyclization into diaziridines 1 due to
Sni process in the presence of a base (Scheme 1). However
a low velocity of this reaction impedes its application. For
aliphatic N-chloroalkylamines 3, the reaction ended only
INTRODUCTION
In recent years we have been interested in developing
optimal approaches to the synthesis of differently
substituted diaziridines from carbonyl compounds,
primary aliphatic amines and aminating reagents (in
paticular N-chloroalkylamines) [1-5]. These studies were
motivated by a few reasons. First, diaziridines displayed
psychotropic activity [6-9]. In addition, they include
configurationally stable nitrogen atoms under normal
conditions and thereby are usable for investigations of
nitrogen stereochemistry [10-12]. And finally they may
enter ring expansion reactions with electrophilic reagents
given a heightened tensity of the three-member ring
[13,14]. Our recent investigations of the transformations
of 1,2-di-, 1,2,3-tri- and 1,2,3,3-tetraalkyldiaziridines and
their bi-cyclic analogs 1,5-diazabicyclo[3.1.0]hexanes
under the action of heterocumulenes (ketenes, isocyanates
and isothiocyanates) resulted in new simple methods for
the synthesis of both known and new heterocyclic systems
[15-19]. Therefore, a search for new methods for the
preparation of diaziridines retains its relevance.
in several days, and for N-chloroalkylamines
3
Earlier [3], while examining the ways of optimizing of
the methods for the synthesis of 1,2-di and 1,2,3-trialkyl-
synthesized from amines 2 with lower basicity lasted for
several weeks. Anyhow the variant for the synthesis of
diaziridines 1 could be useful in the cases where carbonyl
compounds were less accessible than corresponding
amines 2.
diaziridines
1 from carbonyl compounds, primary
aliphatic amines 2 and N-chloroalkylamines 3, we studied
the behavior of N-chloroalkylamines 3 in the presence of
amine
2 in excess and (or) inorganic bases in

498
V. V. Kuznetsov, Ju. S. Syroeshkina, D. I. Moskvin, M. I. Struchkova,
N. N. Makhova, A. A. Zharov
Vol 45
The specific goal of this research was to develop a new
d[Cax ] d[CD ]
(1)
(2)
!
=
= k[CAX ][CA ]
approach to the preparation of 1,2,3-trialkyldiaziridines 1
on the basis of the transformation of N-chloroalkylamines
3 in the absence of carbonyl compounds using high
pressure methods.
dt
dt
[CAX ]0 ([CA ]0 ![CAX ]0 )
[CAX ]=
A ]0![CAX
[CA ]0 expk([C
] )t ![CAX
]
0
0
Where [CAX]0, [CA]0, [CD]0, [CAX], [CA], [CD] – initial and
current concentrations of N-chloroethylamine 3a, ethyl-
amine 2a and diaziridine 1a, accordingly; [CD]=[CAX]0 -
[CAX]. The obtained kinetic data allow the assumption that
the limiting step of the process is a bimolecular reaction
of N-chloroethylamine 3a with ethylamine 2a followed by
the elimination of the HCl molecule.
The preparation of diaziridine 1a ended with the
decrease in the reaction volume since product density was
higher than that of the initial reagents. That is why the
reaction at high pressure was considered to be most
suitable for accelerating the synthesis of diaziridine 1a
from N-chloroethylamines 3a. It should be mentioned that
common acceleration of the reaction rate by increasing the
temperature is not suitable. It gives rise to side reactions;
the key of which is the decomposition of N-chloroethyl-
amine 3а. All experiments were carried out using the
reaction block shown in Figure 2.
Scheme 1
H2O
t-BuOCl
CHCl3, 0-5 oC
2
-HCl
RCH2NH2
RCH2NHCl
RHC NH
RCHO
5
3
4
2
NHCH2R
NCH2R
2
3
-H2O
K2CO3
NCH2R
NCH2R
1
RCHNHCH2R
R
R
-KCl
OH
6
7
Cl
RESULTS AND DISCUSSION
At the first step of the research, we looked to the
regularity of the disappearance of N-chloroalkylamines 3
and accumulation of diaziridines 1 in time using the NMR
method (CDCl3, δ, ppm). For that, we examined a
possibility of preparing 1,2-diethyl-3-methyldiaziridine 1a
from N-chloroethylamine 3a and ethylamine 2a (molar
ratio 1:3) in the presence of potassium carbonate and the
trace water amount at atmospheric pressure and room
temperature. The reaction ran controlled through detecting
the disappearance of more characteristic signals of N-
chloroethylamine 3a protons (Cl-N-CH2, t, 2.85) and
arising of diaziridine 1a protons (MeC3diaz. ring, d, 1.22 and
MeCH-Ndiazir. ring, m, 2.12). The regularity of the change in
the concentrations of N-chloroethylamine 3a and
diaziridine 1a in time is shown in Figure 1.
Figure 2. Reaction block for performing chemical reactions at high
pressures: 1- Teflon ampoule for reaction mixture; 2- High-pressure
block of constructional steel with hardness HRC 40-42; 3-Steel pistons
with hardness HRC 58-60; 4- thermostatic jacket; 5- thermocouple; 6-
Press plunger; 7-Press frame support; 8- Micrometer. Reaction volume
compression comprise from: an anti-extrusion steel ring - 9а, a copper
disk - 9b, a Teflon disk - 9с.
Figure 1. Regularities of the N-chloroethylamine 3a disappearance (●)
and the 1,2-diethyl-3-methyldiaziridines 1a accumulation (▲) in time at
atmospheric pressure.
The experimental data match the curves built according
to the second order law (Equations 1 and 2).

Mar-Apr 2008
High Pressure-Assisted Synthesis of 1,2,3-Trialkyldiaziridines
from N-Chloroalkylamines
499
Reaction vessels were 12.5 cm3 Teflon ampoules placed
on corresponding high volume block. The thermostatic
jacket was put on the high-pressure block and cooled with
water from thermostat. A set of packing gaskets was used
as hermetic seal for the reaction: an anti-extrusion steel
ring with the triangular section and a Teflon-4 annealed
copper disk. With pressure increasing, the deformation of
the packing gaskets occurred, in turn, resulting in reaction
volume impermeability.
Pressure [Р] was calculated by the equation: Р = Рman
*Sr/Sp, where Рman , Р – pressure in the press cylinder and
reaction block, Sr, Sp - piston face and press plunger
correspondingly.
A correlation between the reaction rate constant of the
diaziridine 1a accumulation and pressure is shown in Fig.
4. The reaction constant was estimated at the initial slope
of the kinetic curves (see Figure 3). The curve in Figure 4
" !V ± P
was estimated using the equation
k = k0 exp
RT
where Р – pressure, Т – temperature, R – gas constant,
ΔV± = -15 cm3/mole – activation volume. It can be easily
seen that ΔV± = -15 cm3/mole found for the reaction of the
diaziridine 1a formation is located in the area of the value
ΔV± which is typical for the condensation reaction.
The reaction mixture consisting of the solution of N-
chloroethylamine 3а and ethylamine 2а in CHCl3 and
molar ratio 1:3, K2CO3 was added with 0.5 mole and a
small water amount (~1-2% by volume) and kept at 20-
22°С under the adjusted pressure and pre-given time.
Then the reaction mixture was analyzed by 1H NMR
spectroscopy. All experiment results are shown in Fig. 3.
Consumption of N-chloroethylamine 3а conforms to
second order reaction in all the cases (see Figure 3).
However, as the pressure increases accumulation of
diaziridine 1a deflects from the second order reaction
which is related to the side reaction of polymerization.
According to Figure 3 almost complete conversion of
N-chloroethylamine 3а at 300 МPa has been achieved
after over 50 h. The yield of diaziridine 1a was above
90%. At 500 МPa the reaction completed after 10 h with
the same yield. When the pressure increased further up to
700 МPa, the polymerization products were
predominantly afforded as well as diaziridine 1a in low
yield.
Figure 4. A curve of correlation between reaction rate constant of
diaziridine 1a formation from N-chloroethylamine 3а and pressure.
The temperature and reagents ratio has significant
importance for the success of this reaction. The decrease
in the temperature down to 15° C at 500 МPa proved to be
a 1.3-fold increase in the reaction time (Eact.~ 40
Kdg/mole). The decrease in the temperature down to 10°
C at 700 МPa significantly diminishes the side processes
of the polymer formation, although the yield of diaziridine
1a obtained at other pressures is not reached. To optimize
the process of the diaziridine 1a synthesis we examined
the influence of the molar ratios N-chloroethylamine 3a:
ethylamine 2a, K2CO3:N-chloroethylamine 3a as well as
of the added water amount. As a result of all the
investigations it was found that the optimal conditions for
the preparation of 1,2-diethy-3-methyldiaziridine 1a from
N-chloroethylamine 3a were: pressure 500 МPa,
temperature 15° C, molar ratio of the compounds 3a:2a =
2.5:1, K2CO3 amount – 0.5 mole per 1 mole of N-chloro-
ethylamine 3a, 2% (by volume) of water and reaction
time 12-13 hours. In these conditions, the yield of
diaziridine 1a was 95% and the formation of the side
products was not actually observed. The formation of the
side products is evidently associated with polymerization
of imines formed at the first steps of the process because
independently synthesized diaziridine 1a did not change
in the reaction conditions.
Figure 3. Kinetic curves of the diaziridine 1a formation from N-chloro-
ethylamine 3а at high pressure. Curves
1 and 3 correspond to
consumption of N-chloroethylamine 3а. Curves 2 and 4 correspond to
accumulation of diaziridine 1a. Curves 1 and 2 were recorded at 300
МPa. Curves 3 and 4 were recorded at 500 МPa.

500
V. V. Kuznetsov, Ju. S. Syroeshkina, D. I. Moskvin, M. I. Struchkova,
N. N. Makhova, A. A. Zharov
Vol 45
Scheme 4. This alternative of the synthesis of diaziridines
1 allows not only obtaining diaziridines 1 in the absence of
carbonyl compounds but also saving initial amines through
the use of K2CO3 as a base. In the absence of K2CO3
nitriles 10a,b were isolated as a result of the trans-
formation of N,N-dichloroalkylamines 9a,b (Scheme 4).
A few other N-chloroalkylamines 3b-f were used in the
analogous reaction under the identified conditions. The
conversion of initial compounds 3b-f was also controlled
by 1H NMR spectroscopy. In all the instants corre-
sponding diaziridines 1b-f were prepared in good yields
(Scheme 2, Table 1). It is interesting to note that reaction
time remarkably increased at electron withdrawing
fragments entering the substituents of initial N-chloro-
alkylamines similar to the same reactions at atmospheric
pressure.
Scheme 4
CHCl3/H2O
.
2 RCH2NHCl
RCH2NH2 + RCH2NCl2
RCN + RCH2NH2 HCl
10a,b
3a,b
2a,b
9a,b
K2CO3
NCH2R
NCH2R
a
b
R = Me
R = Et
Scheme 2
R
RCH2NH2(
2
), K2CO3, CHCl3, P, 15 o
-HCl
C
NCH2R
NCH2R
RCH2NHCl
R
1a,b
3
1
N
N(CH2)2
R = MeCONHCH2
e
f
R =
a
b
c
R = Me
R = Et
R = PhCH2
Therefore two optimal approaches to the synthesis of
1,2,3-trialkyldiaziridines 1 based on the transformation of
N-chloroalkylamines 3 in the absence of carbonyl com-
pounds at high pressure have been found. The first ap-
proach includes the interaction of N-chloroalkylamine 3
with an excess of primary aliphatic amine 2 containing the
same alkyl substituent in CHCl3 in the presence of 0.5
mole of K2CO3 and a small water amount at 500 MPa and
15° C. The second approach is based on the same reaction
but with using 1 mole of K2CO3 and without adding
primary aliphatic amine 2. The developed methods are
especially attractive where appropriate aldehydes are
hardly available.
d
R = MeOCH2
Table 1
The time of reactions and yields of 1,2,3-trialkyldiaziridines 1a-f
from N-chloroalkylamines 3a-f at temperature 15 °C and pressure
500 MPa
Time of
Yield of
Initial N-chloroalkylamines 3
reaction h diaziridines 1 (%)
EtNHCl 3a
PrNHCl 3b
12-13
12-13
46-48
46-48
1а (95)
1b (84)
1c (82)
1d (91)
PhCH2CH2NHCl 3c
MeOCH2CH2NHCl 3d
The kinetic studies of the synthesis of 1,2,3-trialkyl-
diaziridines 1 from N-chloroalkylamines 3 at high
pressure (on the example of 1,2-diethyl-3-methyl-
diaziridine 1a) have revealed that these reactions conform
to the second order law at all pressures. Assumingly, the
limiting step of the process is the bimolecular interaction
of N-chloroalkylamine 3 with primary aliphatic amine 2
followed by the elimination of the HCl molecule. As a
whole, using the synthesis of 1,2,3-trialkyldiaziridines 1
as an example, has been shown a unique possibility of
employing high pressure to stimulate chemical processes,
effectiveness of which can not be enhanced through
heating due to side reactions.
N
N(CH2)3NHCl
35-36
46-48
1e (78)
1f (57)
3e
MeCONHCH2CH2NHCl 3f
As seen from Table 1, the yields of final diaziridines 1
are rather high, except for compound 1f. The decrease in
the yield of diaziridine 1f evidently related to the
reacylation reaction which resulted in 1,2-diacetyl-
ethylenediamine 8 (Scheme 3). The latter was isolated
from reaction of the N-chloroamine 3f and characterized
(Table 1).
Scheme 3
MeCONH(CH2)2NHCl + MeCONH(CH2)2NH2
MeCONH(CH2)2NHCOMe
3f
8
2f
EXPERIMENTAL
To extend possible approaches to the diaziridine
synthesis on a basis of the N-chloroalkylamines 3
transformation we studied the behavior of compounds 3
(on the example of 3a,b) in the identified optimal
conditions though without the addition of corresponding
alkylamines 2a,b. It was found that in these cases 1,2,3-
trialkyldiaziridines 1a,b were generated as well, however
in lower yields (47-55%). The success of this reaction
depends on the known capacity of N-chloroalkylamines 3
to transform into corresponding amines 2 and N,N-
dichloroalkylamines 9 [22]. Then N-chloroalkylamine 3
and alkylamine 2 lead to diaziridines 1 according to
Elemental analysis was performed by the CHN Analyzer
Perkin-Elmer 2400. The ir spectra (ν, cm-1) were measured using
a UR-20 spectrometer. Mass spectra were measured using a
Finnigan MAT INCOS-50 instrument. All of the nmr spectra
were recorded using a Bruker AM-300 spectrometer at 300 MHz
1
for H and 75.47 MHz for 13C Spectra in CDCl3. The chemical
shifts are shown in δ and are expressed relative to the chemical
1
shifts for the CDCl3 (7.27 ppm and 77.08 ppm for H and 13C
nmr, respectively). Analytical thin-layer chromatography (TLC)
was conducted on silica gel plates (Silufol UV-254). New
compounds were isolated on Kieselgel 0.060-0200 mm, 60 A
(ACROS).

Mar-Apr 2008
High Pressure-Assisted Synthesis of 1,2,3-Trialkyldiaziridines
from N-Chloroalkylamines
501
1
2
3
General procedure for the synthesis of 1,2,3-trialkyldi-
aziridines 1 from N-chloroalkylamines 3 and corresponding
alkylamines 2 in the presence of K2CO3 under high pressure.
Solution of tert-BuOCl (0.64 ml, 5.7 mmol) in 0.5 ml of
chloroform was added dropwise to a solution of 20 mmol of
amine 2 in 10 ml of chloroform at intensive stirring and
temperature 0-5 °C. The reaction mixture, containing the
mixture of 14.3 mmol of amine 2 and 5.7 mmol of N-
chloroalkylamine 3, was put in fluoroplastic reaction ampoule
with volume 12,5 cm3, potassium carbonate (0.41 g, 3 mmol)
and two drops of water were added. Then chloroform was added
to fill whole volume of the ampoule and the latter was closed
with cover. The reaction ampoule was put in the barostate (see
Fig. 2) and kept at 500 MPa, temperature 15 °C during 12-13
hours for compounds 3a,b, 35-36 hours for compound 3e and
46-48 hours for compounds 3c,d,f. The pressure was decreased
to normal value, the ampoule was elicited from the barostate, the
precipitate was filtered, washed with 5 ml of chloroform and a
solvent was evaporated. The diaziridnes 1a and 1b were distilled
in vacuum and compounds 1c-f were isolated by chroma-
tography on Kieselgel 0.060-0.200 mm, 60Å.
cm-1; H nmr: δ 2.47, 2.53 (dt, 1H, NCH, J = 14.3 Hz, J = 3.3
Hz, ∆ν = 116.6 Hz), 2.57, 2.62 (dt, 1H, NCH, 2J = 13.2 Hz, 3J =
4.4 Hz, ∆ν = 85.8 Hz), 2.87 (m, 2H, NCH), 3.38 (s, 3H, OMe),
3.4 (s, 6H, OMe), 3,52 (m, CHdiazir. ring.), 3.62 (m, 6H, CH2O) ;
13C nmr: (δ, J13C-1H): 52.3 (t, OCH2Cdiaz.
1J = 135 Hz), 59.04
ring
1
1
(q, OMe, J = 141 Hz), 59.22 (q, OMe, J = 135 Hz), 60.38 (t,
1
NCH2, J = 140 Hz), 63.07 (t, CHdiaz. ring, J = 80 Hz), 68.95 (t,
NCH2, J = 138 Hz), 71.14, 71.59 (OMe), MS m/z: (I%): 159
(M+ - MeOCH2, 17.5%), 59 (MeOCH2CH2, 53%), 45 (MeOCH2,
100%). Anal. Calcd for C9H20N2O3 (204.31): C, 52.90; H, 9.89;
N, 13.71. Found: C, 52.75; H, 10.10; N, 14.02.
1
1
1,2-Bis[3-(imidazol-1-yl)propyl]-3-[2(imidazol-1-yl)ethyl]-
diaziridine 1e. 78% yield, nondisstilled oil, nD201.5768, Rf 0.23
(5% NH3 in CHCl3:MeOH 60:1 (v/v)), ir: 3108, 2944, 2856,
1672, 1508, 1452, 1396, 1360, 1284, 1232, 1112, 1080, 1032,
908, 820, 736, 664, 624 cm-1; 1H nmr: δ 1.85 (m, 6H,
3
CH2CH2CH2 + CH2Cdiazir. ring, J = 7 Hz, ∆ν = 61 Hz), 2.04 (m,
3
2H, NCH, J = 6.5 Hz, ∆ν1 = 61 Hz, ∆ν2 = 110 Hz), 2.23 (m,
1H, NCH, 3J = 6.23 Hz, ∆ν1 = 61 Hz), 2.32 (m, 1H, CHdiazir. ring),
2.40 (m, 1H, NCH, 3J = 6.5 Hz, ∆ν2 = 110 Hz), 4.0 (m, 6H, CH2-
Nimidaz. ring), 6.84, 6.85, 6.87 (three s, C4Himidaz. ring), 6.98, 6.99,
7.02 (three s, C5Himidaz. ring), 7.4, 7.41, 7.43 (three s, C2Himidaz. ring);
13C nmr: δ: 28.19, 30.27, 30.67 (C-CH2-C), 44.47, 44.60 (N-
CH2), 49.01, 57.10, 57.64 (CH2-Nimidaz. ring), 62.55 (Cdiaz. ring),
118.79 (C4imidaz. ring), 129.41, 129.66, 130.04 (C5imidaz. ring), 139.98,
137.19, 137.24 (C2imidaz. ring); MS m/z (I%): 232 (M+-
imid.ringCH2CH2CH2N, 23%), 123 (imid.ringCH2CH2CH2N,
51%), 107 (imid.ringCH2CH2CH2, 92%), 96 (imid.ringCH2CH2,
72%), 82 (imid.ringCH2, 100%), 68 (imid.ring, 98%). Anal.
Calcd for C18H26N8 (354.52): C, 60.98; H, 7.41; N, 31.61. Found:
C, 60.75; H, 7.62; N, 14.35.
Synthesis of 1,2,3-Trialkyldiaziridines 1a,b from N-chloro-
alkylamines 3a,b and K2CO3 under high pressure (general
procedure). Solution of tert-BuOCl (1.12 ml, 10 mmol) in 1.0
ml of chloroform was added dropwise to solution of 10 mmol of
amines 2a or 2b in 8 ml of chloroform at stirring and
temperature 0-5 °C. The reaction mixture, containing of 10
mmol of N-chloroamines 3a or 3b, was put in fluoroplastic
reaction ampoule with volume 12.5 cm3, potassium carbonate
(1.38 g, 10 mmol) and two drops of water were added. Then
chloroform was added to fill whole volume of the ampoule and
the latter was closed with cover. The reaction ampoule was put
in the barostate (see Fig. 2) and was kept at 500 MPa and
temperature 15 °C during 12-13 hours. The pressure was
decreased to normal value, the ampoule was elicited from the
barostate, the precipitate was filtered, washed with 5 ml of
chloroform and a solvent was evaporated. The diaziridnes 1a
and 1b were distilled in vacuum.
1,2- Bis(2-acetamidoethyl)-3-(acetamidomethyl)diaziridine
1f. 57% yield, nondistilled oil, Rf 0.41 (5% NH3 in
CHCl3:MeOH 15:4 (v/v)), H nmr: δ 2.02, 2.04, 2.07 (three s,
3
9H, Me), 2.62 (m, 4H, NCH2), 2.78 (t, 1H, CHdiaz. ring, J = 5.5
Hz), 3.48 (m, 6H, CON-CH2), 6.28, 6.38, 7.15 (three br. s, NH);
13C nmr: δ: 23.09, 23.28, 23.37 (Me), 36.83, 38.45, 39.15
(NHCH2), 51.58, 60.26 (CH2Ndiaz. ring), 63.36 (Cdiaz. ring), 170.78,
170.86, 171.11 (CO). Anal. Calcd for C12H23N5O3 (285.40): C,
50.50; H, 8.14; N, 24.54. Found: C, 50.25; H, 8.24; N 24,24.
1
1,2-Diethyl-3-methyldiaziridine 1a: 95% yield, bp. 43-44 °C
(20 Torr), (lit[3] 43-45 °C (20 Torr)); MS m/z (I%): 113 (M+ -1,
37%), 72 (M+ - NEt, 68%), 42 (NEt, 100%).
1,2-Di-n-propyl-3-ethyldiaziridine 1b: 84% yield, bp. 71-73
°C (12 Torr), (lit[3] 71-73.5 °C (12 Torr)).
REFERENCES
1,2-Bis(2-phenylethyl)-3-(phenylmethyl)diaziridine 1c.
82% yield, nondistilled oil, nD201.5722, Rf 0.39 (hexane:ethyl
acetate 4:1 (v/v)), ir: 3028, 3004, 2932, 2860, 2846, 1668, 1604,
1584, 1496, 1456, 1360, 1244, 1180, 1084, 1032, 984, 912, 732,
700, 644 cm-1; 1H nmr: δ 2.6-3.1 (m, 11H, PhCH2, N-CH2,
CHdiaz. ring), 7.32 (m, 15H, Ph); 13C nmr: δ 126.12 (PhCH2CH2),
126.20 (PhCH2CH2), 126.65 (PhCH2CHdiaz. ring ), 54.53
(NCH2), 62.79 (NCH2), 66.38 (Cdiaz.ring), 126.12, 126.2, 126.65,
127.92, 128.06, 128.40, 128.45, 128.70, 128.89, 129.15 (Ph);
MS m/z: (I%): 251 (M+ - CH2CH2Ph, 52%), 105 (CH2CH2Ph,
100%), 91 (PhCH2, 67%), 77 (Ph, 38%). Anal. Calcd for
C24H26N2 (342.52): C, 84.15; H, 7.67; N, 8.18. Found: C, 84.32;
H, 7.52; N, 7.96.
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