558
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Shevtsov et al.
Table 4. Selected crystallographic parameters and a summary of
data collection and refinement for compounds 4c and 4g
second distillation being carried out over K2CO3. Fractions with
b.p. 71—75 °C (12 Torr) for 6a and b.p. 47—50 °C (12 Torr)
for 6b were collected. The final yields of compounds 6a and 6b
were 6.4 and 6.9 g (isolation losses were 36 and 37%, reꢀ
spectively). 1,2ꢀDimethylꢀ3,3ꢀpentamethylenediaziridine 6a.
1H NMR (CDCl3), δ: 1.43 (m, 2 H, CH2); 1.49 (m, 8 H, CH2);
2.37 (s, 6 H, NMe); nD20 1.4687. The 13C NMR spectrum agrees
with the literature data.12 1,2ꢀDiethylꢀ3,3ꢀdimethyldiaziriꢀ
dine 6b. 1H NMR (CDCl3), δ: 1.07 (t, 6 H, CH2Me, 3J =
7.18 Hz); 1.23 (s, 6 H, CcyclMe); 2.36, 2.50 (both m, 2 H each,
NCH2). 13C NMR (CDCl3), δ: 13.8 (CH2Me); 19.4 (CcyclMe);
47.4 (NCH2); 60.6 (Ccycl).
Xꢀray diffraction analysis. Structures 4c and 4g were solved
by the direct method and refined by the leastꢀsquares method in
the anisotropic fullꢀmatrix approximation on F 2hkl. Hydrogen
atoms were located from the electron density difference maps
and refined isotropically. All calculations were performed with
the SHELXTL PLUS program package. Selected bond lengths
and angles are listed in Table 3. A summary of data collection
and refinement is given in Table 4.
Parameter
4c
4g
Molecular formula
T/K
C15H21N3O2
120
C16H20ClN3O2
193
Diffractometer
Scan mode
Crystal system
Space group
a/Å
Smart CCD
ω
Monoclinic
Syntex P21
θ/2θ
Orthorhombic
P21/c
Pbca
12.573(2)
5.525(1)
21.242(4)
102.290(5)
1441.8(5)
29.711(6)
11.309(2)
9.337(2)
b/Å
c/Å
β/deg
V/Å3
3137.2(11)
8(1)
321.80
2.55
Z(Z´)
M
µ/cm–1
4(1)
275.35
0.86
F(000)
ρ
592
1.268
1360
1.363
calc/g cm–3
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ
32799).
2θmax/deg
56.00
60.00
Number of measured
6650 (0.0302)
4538 (0.00)
reflections (Rint
)
References
Number of independent
reflections
Number of
reflections with I > 2σ(I )
Number of parameters refined
R1
wR2
3298
2032
4538
3487
1. E. Schmitz, Dreiringe mit zwei Heteroatomen, Springerꢀ
Verlag, Berlin—Heidelberg—New York, 1967.
2. H. W. Heine, Diaziridines, 3HꢀDiazirines, Diaziridinones and
Diaziridinimines, in Small Ring Heterocycles, Ed. A. Hassner,
WileyꢀInterscience, 1983, Part 2, Chapter IV, 547—629.
3. R. G. Kostyanovsky, R. Murugan, and M. Sutharchanadevi,
Comprehensive Heterocyclic Chemistry, II, Eds A. R. Katrizky
and C. W. Rees, Pergamon Press, Oxford—New York—
Tokyo, 1996, 1a, Chapter 1.11, 347—364.
265
0.0511
0.1226
279
0.0393
0.1143
GOOF
ρ/e Å–3 (max/min)
0.969
1.004
0.199/–0.204
0.310/–0.343
crystals suitable for Xꢀray diffraction analysis; 4ꢀ(4ꢀchloroꢀ
benzoyl)ꢀ1,2ꢀdiethylꢀ5,5ꢀdimethylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone (4h)
(21%), a colorless crystalline solid.
4. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, K. A.
Lyssenko, I. V. Fedunin, and N. N. Makhova, Mendeleev
Commun., 2003, 221.
Synthesis of 1,2ꢀdimethylꢀ3,3ꢀpentamethylenediaziridine (6a)
and 1,2ꢀdiethylꢀ3,3ꢀdimethyldiaziridine (6b). A solution of NaOCl
(0.15 mol) prepared from NaOH (12.6 g, 0.315 mol) and Cl2
(10.65 g, 0.15 mol) in water (60 mL) was added dropwise at
0—5 °C to a 20% aqueous solution of methylꢀ or ethylamine
(0.15 mol), respectively, in the presence of dissolved NaHCO3
(3 g) at the same temperature. The reaction mixture was satuꢀ
rated with NaCl and the organic material was extracted with
chloroform (3×30 mL). The extract was dried with a small
amount of K2CO3 for 5—10 min. The yields of MeNHCl and
EtNHCl were 0.11 mol (73%) and 0.12 mol (80%), respectively
(from iodometric data). Finely divided K2CO3 (0.3 mol, 41.5 g),
methylamine (0.11 mol) or ethylamine (0.12 mol) as a 20—25%
solution in chloroform, and cyclohexanone (0.11 mol, 11.3 mL)
or acetone (0.12 mol, 8.8 mL), respectively, were added to the
stirred extract. The reaction mixture was stirred at 18—20 °C
for 24—28 h. The inorganic precipitate was filtered off and
thoroughly washed with chloroform and the solvent was reꢀ
moved. The yields of diaziridines 6a (0.0714 mol, 65%) and 6b
(0.0853 mol, 71%) were determined by iodometric titration in
the presence of catalytic amounts of CuCl2 (or Cu(OAc)2). The
products were twice distilled in water aspirator vacuum, the
5. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, and
N. N. Makhova, Mendeleev Commun., 2005, 29.
6. A. V. Shevtsov, V. Yu. Petukhova, Yu. A. Strelenko, K. A
Lyssenko, N. N. Makhova, and V. A. Tartakovsky, Izv. Akad.
Nauk, Ser. Khim., 2005, 997 [Russ. Chem. Bull., Int. Ed.,
2005, 54, 1021].
7. M. Komatsu, N. Nishikaze, M. Sakamoto, Y. Ohshiro, and
T. Agawa, J. Org. Chem., 1974, 39, 3198.
8. M. Komatsu, S. Tamabuchi, S. Minakata, and Y. Ohshiro,
Heterocycles, 1999, 50, 67.
9. B. Carboni, L. Toupet, and R. Carrié, Tetrahedron, 1987,
43, 2293.
10. H. Ulrich, Acc. Chem. Res., 1969, 2, 186.
11. N. N. Makhova, A. N. Mikhailyuk, V. V. Kuznetsov,
S. A. Kutepov, and P. A. Belyakov, Mendeleev Commun.,
2000, 182.
12. H. Alper, D. Daniele, K. Masayuki, and R. Dominique,
Organometallics, 1990, 9, 762.
13. Ger. Pat. 1 127 907 (1962); Chem. Abstr., 1962, 57, 9665.
Received November 11, 2005;
in revised form March 2, 2006