Synthesis of 4-aroyl-1,2,4-triazolidin-3-ones via ring extension in reactions of 1,2-di- and 1,2,3,3-tetraalkyldiaziridines with aroyl isocyanates

Article abstract of DOI:10.1007/s11172-006-0291-2

Reactions of 1,2-di-and 1,2,3,3-tetraalkyldiaziridines with aroyl isocyanates involve opening of the diaziridine ring through cleavage of the C-N bond followed by cyclization of the zwitterionic intermediate into 4-aroyl-1,2,4-triazolidin-3-one derivative

Full text of DOI:10.1007/s11172-006-0291-2

Russian Chemical Bulletin, International Edition, Vol. 55, No. 3, pp. 554—558, March, 2006
554
Synthesis of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones via ring extension in reactions
of 1,2ꢀdiꢀ and 1,2,3,3ꢀtetraalkyldiaziridines with aroyl isocyanates
a
a
b
a
A. V. Shevtsov,a V. V. Kuznetsov, S. I. Molotov, K. A. Lyssenko, and N. N. Makhova

aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 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 (495) 135 5085. Eꢀmail: kostya@xrlab.ineos.ac.ru
Reactions of 1,2ꢀdiꢀ and 1,2,3,3ꢀtetraalkyldiaziridines with aroyl isocyanates involve openꢀ
ing of the diaziridine ring through cleavage of the C—N bond followed by cyclization of the
zwitterionic intermediate into 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone derivatives.
Key words: 1,2ꢀdiꢀ, 1,2,3ꢀtriꢀ, and 1,2,3,3ꢀtetraalkyldiaziridines; aroyl isocyanates, ring
extension, 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones.
It is known1—3 that diaziridines, like other strained
Scheme 1
threeꢀmembered rings, tend toward ring extension reacꢀ
tions with electrophilic reagents. Depending on the type
of the substituent at the nitrogen and carbon atoms, as
well as on the electrophilic reagent, the diaziridine ring
can undergo opening at both the C—N and N—N bonds.
However, most reactions of this type have been carried
out with unsubstituted (at one or both N atoms) diꢀ
aziridines. Recently,4—6 we have studied in detail reacꢀ
tions of 1,2ꢀdialkyldiaziridines 1 with various ketenes and
demonstrated that these reactions involve cleavage of the
N—N bond to give three types of structures containing
the N—C—N fragment: 1,3ꢀdialkylimidazolidinꢀ4ꢀones
(1 : 1 adducts), 1ꢀalkylꢀ3,3ꢀdiarylꢀ4ꢀdiarylacetylaminoꢀ
azetidinꢀ2ꢀones (βꢀlactam derivatives), and 3,5ꢀdiacylꢀ
3,5ꢀdiazaheptꢀ1ꢀenes (1 : 2 adducts). Ring opening at the
R = Me (a), Et (b)
N—N bond also occurs in reactions of diphenylketene
with 1,2,3ꢀtrialkyldiaziridines 2, yielding, however, only
linear products.7,8 In contrast, reactions of 1,2,3ꢀtrialkylꢀ
diaziridines 2a,b with benzoyl isocyanate (3a) in boiling
benzene7 give, through opening of the diaziridine ring
at the C—N bond, 1,2,5ꢀtrialkylꢀ4ꢀbenzoylꢀ1,2,4ꢀtriꢀ
azolidinꢀ3ꢀones 4a,b. The formation of compound 4 inꢀ
volves zwitterionic intermediate 5, in which the conjuꢀ
gated anion attacks the C atom of the diaziridine ring with
simultaneous cleavage of the C—N bond (Scheme 1).7
To establish the general features of this reaction for
various substituents in the diaziridine ring, here we studꢀ
ied reactions of 1,2ꢀdialkylꢀ (1) and 1,2,3,3ꢀtetraalkylꢀ
diaziridines (6) with benzoyl and pꢀchlorobenzoyl isoꢀ
cyanates 3a,b. 1,2ꢀDiethylꢀ, 1,2ꢀdipropylꢀ, and 1,2ꢀdiꢀ
butyldiaziridines 1a—c were used. Reaction conditions
for compounds 1 and 3 were optimized with 1,2ꢀdiꢀ
i. PhCONCO (3a), 75—80 °C, C6H6
propyldiaziridine (1b) and benzoyl isocyanate (3a) as an
example: the reaction was carried out in dry CH2Cl2 at
–20 to 20 °C. The resulting suspension was kept at 20 °C
for 1 h. TLC analysis revealed no significant amounts of
chromatographed products in CH2Cl2 under these condiꢀ
tions. New compounds were detected by TLC only after
the evaporation of the solvent and the extraction of the
residue with hot hexane. For this reason, in later experiꢀ
ments, the reaction mixture was refluxed in hexane and
the products were additionally extracted with hot hexane.
The product isolated by column chromatography on
SiO2 was close to previously reported7 1,2,4ꢀtriazolidinꢀ
3ꢀone derivatives 4a,b (1H NMR data). However, the
formation of isomeric 2ꢀbenzoylꢀ1,4ꢀdipropylꢀ1,2,4ꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 534—538, March, 2006.
1066ꢀ5285/06/5503ꢀ0554 © 2006 Springer Science+Business Media, Inc.

Synthesis of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
555
C(8)
Additional heating is required probably because of the
sufficient stabilities of zwitterionic intermediates 5. Exꢀ
amples of stable zwitterionic systems have been docuꢀ
mented. For instance, the first step in reactions of the
Schiff bases with isocyanates is the formation of zwitterꢀ
ionic intermediates isolated in some cases.9 Stable salts of
diaziridinium cations (e.g., picrates) obtained in dry meꢀ
dia are also known.10 Transformation of intermediates 5
into 1,2,4ꢀtriazolidine derivatives 4 is thermodynamically
controlled. The formation of triazolidines 4 rather than
isomeric compounds 7 is probably due to thermodynamiꢀ
cally more favorable cleavage of the C—N bond of the
diaziridine ring with subsequent new C—N bonding than
cleavage of the N—N bond followed by new N—N
bonding.
C(7)
C(6)
C(15)
C(14)
C(13)
O(2)
C(16)
C(17)
C(5)
N(4)
C(3)
O(1)
N(1)
C(12)
C(18)
N(2)
C(9)
C(10)
In reactions of 1,2,3,3ꢀtetraalkyldiaziridines 6 with
aroyl isocyanates, we used 1,2ꢀdimethylꢀ3,3ꢀpentaꢀ
methylenediaziridine (6a), 1,2ꢀdiethylꢀ3,3ꢀdimethyldiꢀ
aziridine (6b), and pꢀchlorobenzoyl isocyanate (3b). It
turned out that the presence of additional alkyl substituꢀ
ents at the C atom of the diaziridine ring does not change
its behavior in reactions with aroyl isocyanates: the reacꢀ
tion products were 4ꢀbenzoylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone deꢀ
rivatives 4g,h (compound 4g has a spiran structure)
(Scheme 3).
C(11)
Fig. 1. General view of structure 4c.
triazolidinꢀ3ꢀone 7a in this reaction seemed to be not
improbable (Scheme 2, pathway a) since reactions of variꢀ
ous diaziridines with aryl(diaryl)ketenes give different
products.4—8 The NOE data for the compound obꢀ
tained were ambiguous; for this reason, its structure was
proven by Xꢀray diffraction analysis. It turned out that the
reaction of diaziridine 1b with benzoyl isocyanate 3a
yields 4ꢀbenzoylꢀ1,2ꢀdipropylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone
(4c) (Fig. 1) via cleavage of the C—N bond in the threeꢀ
membered ring. Other 1,2ꢀdialkyldiaziridines 1 were also
used in reactions with aroyl isocyanates 3a,b under these
conditions; the yields of 1,2,4ꢀtriazolidinꢀ3ꢀones 4c—f
were 34—46% (Scheme 2, pathway b).
Scheme 3
Scheme 2
i. 4ꢀClC6H4CONCO (3b)
g: R = Me, R´ + R´ = —(CH2)5—; h: R = Et, R´ = Me
The structures of all the compounds obtained were
confirmed by data from elemental analysis, 1H and
13C NMR spectroscopy, and mass spectrometry. Since
1,2,3,3ꢀtetraalkyldiaziridines have not been employed in
reactions with aroyl isocyanates, the structure of spiran 4g
was confirmed by Xꢀray diffraction analysis (Fig. 2). The
yields and selected physicochemical and spectroscopic
characteristics of the compounds obtained are given in
Tables 1 and 2. The starting diaziridines 1a—c were preꢀ
pared as described earlier.11 Diaziridines 6a and 6b have
been documented;12,13 however, the methods proposed
for their synthesis are insufficiently suitable for preparaꢀ
tive purposes (gasꢀphase chlorination or use of not easily
accessible reagents). In addition, some of the physicoꢀ
chemical and spectroscopic characteristics of compounds
6a,b have been omitted.12,13 That is why here we proꢀ
c: R = Prn, Ar = Ph; d: R = Et, Ar = 4ꢀClC6H4;
e: R = Bun, Ar = Ph; f: R = Et, Ar = Ph

556
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
Shevtsov et al.
C(11)
C(10)
1H NMR spectra were recorded on Bruker WMꢀ250 (250 MHz),
Bruker AMꢀ300 (300 MHz), and Bruker ACꢀ200 spectrometers
(200 MHz). 13C NMR spectra were recorded on Bruker AMꢀ300
(75.5 MHz) and Bruker RDXꢀ500 spectrometers (125 MHz).
Chemical shifts are given on the δ scale with reference to SiMe4.
New compounds were isolated by column chromatography on
Kieselgel 60 F254 (Merck). The course of the reactions was moniꢀ
tored and the purity of the compounds obtained was checked by
TLC on ALUGRAM® SIL GLUV254 plates (Aldrich). Spots
were visualized under UV light, in the iodine vapor, and, indeꢀ
pendently, by spraying a solution of diphenylamine in acetone
onto plates followed by their heating. Melting points were deterꢀ
mined on a GALLENKAMP instrument (Sanyo). Xꢀray difꢀ
fraction analyses were carried out on Smart 1000 CCD and
Syntex P21 diffractometers.
O(2)
Cl(1)
C(9)
C(12)
C(15)
C(8)
N(4)
C(17)
C(16)
C(13)
C(14)
C(5)
O(1)
C(19)
N(1)
C(3)
N(2)
C(18)
C(7)
C(6)
Fig. 2. General view of structure 4g.
Synthesis of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones 4 (general proꢀ
cedure). A solution of aroyl isocyanates 3a,b (4.5 mmol) in
dichloromethane (5 mL) was added dropwise under argon at
–20 °C for 20 min to a vigorously stirred solution of diaziridine
1a—c or 6a,b (5 mmol) in dry dichloromethane (10 mL). The
reaction mixture was kept at –20 °C for 1 h, warmed to room
temperature, and stirred for an additional 1 h. The solvent was
removed in water aspirator vacuum. The resulting reaction mixꢀ
ture was refluxed with hexane and the solvent was decanted.
Extraction with boiling hexane was repeated until compounds 4
disappeared from the extract (TLC monitoring). Compound 4g
precipitated from the extract on cooling to room temperature.
The combined extracts were concentrated. Products 4c—f,h
posed a simple oneꢀstep route to diaziridines 6a,b and
obtained missing spectroscopic characteristics.
Xꢀray diffraction analysis of compounds 4c and 4g
revealed that their basic geometrical parameters are virtuꢀ
ally identical; in particular, the presence of the spiran
structure in compound 4g only slightly lengthens the
N(1)—C(5) and N(4)—C(5) bonds (Table 3). In both
compounds 4c and 4g, the fiveꢀmembered ring exists in
the envelope conformation with a deviation of the C(5)
atom by 0.44 and 0.59 Å, respectively. Because of the
amide conjugation, the configurations of the N(4) and
N(2) atoms are flattened: the sums of their bond angles
are 355.6(2)—355.1(2)° and 359.3(2)—358.8(2)°, respecꢀ
tively. In contrast, the N(1) atom has a pyramidal conꢀ
figuration in both structures: the sum of its bond angles
is 322(2)—323.7(2)°.
were isolated by column chromatography on SiO2 (60 F254
,
0.063—0.200 mm, Merck) with hexane—ethyl acetate (9 : 1) as
an eluent followed by crystallization from hexane (for 4c,d,f,h).
4ꢀBenzoylꢀ1,2ꢀdipropylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone 4c was obtained
in 34% yield as colorless crystals suitable for Xꢀray diffraction
analysis; 4ꢀ(4ꢀchlorobenzoyl)ꢀ1,2ꢀdiethylꢀ1,2,4ꢀtriazolidinꢀ3ꢀ
one (4d) (43%), a colorless crystalline solid; 4ꢀbenzoylꢀ1,2ꢀdiꢀ
butylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone (4e) (46%), a light yellow oil;
4ꢀbenzoylꢀ1,2ꢀdiethylꢀ1,2,4ꢀtriazolidinꢀ3ꢀone (4f) (37%),
a white crystalline solid; 4ꢀ(4ꢀchlorobenzoyl)ꢀ1,2ꢀdimethylꢀ5,5ꢀ
pentamethyleneꢀ1,2,4ꢀtriazolidinꢀ3ꢀone (4g) (37%), colorless
Experimental
IR spectra were recorded on a URꢀ20 spectrometer in KBr
pellets (for crystalline substances) and in thin films (for oils).
Table 1. Yields and selected physicochemical characteristics of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones 4
Comꢀ
pound
Yield
(%)
M.p.
/°C
Rfa
Found
Calculated
Molecular
formula
(%)
N
C
H
Hal
—
4c
4d
4e
4f
34
43
46
37
37
21
59—61
96—97
Oil
0.55
0.50
0.59
0.48
0.45
0.49
65.86
65.43
55.73
55.42
67.51
67.30
63.25
63.14
59.97
59.72
58.24
58.16
7.90
7.69
5.84
5.72
8.47
8.31
7.01
6.93
6.36
6.26
6.74
6.51
15.07
15.26
14.67
14.91
13.73
13.85
16.87
16.99
12.98
13.06
13.42
13.56
C15H21N3O2
C13H16ClN3O2
C17H25N3O2
C13H17N3O2
C16H20ClN3O2
C15H20ClN3O2
12.36
12.58
—
89—92
138—140
124—127
—
4g
4h
10.86
11.02
11.31
11.44
a With nꢀheptane—ethyl acetate (8 : 2) as an eluent.

Synthesis of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 3, March, 2006
557
1
Table 2. IR and H and 13C NMR spectra (CDCl3) of 4ꢀaroylꢀ1,2,4ꢀtriazolidinꢀ3ꢀones 4a
Comꢀ
pound
IR,
ν/cm–1
1H NMR
13C NMR
δ (J/Hz)
4c
2968, 2936,
2844, 1736,
1664, 1472,
1348, 1248,
1108, 716
2976, 2936,
2884, 1728,
1664, 1596,
1380, 1336,
1268, 1088,
848, 760
0.91, 1.01 (both t, 3 H each, Me, 3J = 7.33);
11.04, 11.40 (Me); 19.44, 20.26
(CH2Me); 44.98, 56.71 (NCH2C);
66.28 ((CH2)cycl); 127.52, 128.40,
1.53—1.72 (m, 4 H, 2 CCH2Me); 2.84 (t, 2 H,
—(CH2)cyclNCH2, 3J = 7.33); 3.33 (br.s, 2 H,
—(CO)cyclNCH2); 4.84 (s, 2 H, (CH2)cycl);
131.60, 133.75 (Ph); 152.51 ((CO)cycl);
168.49 ((CO)exocycl
7.38—7.57 (m, 2 H, Ph); 7.67 (d, 2 H, Ph, 3J = 6.84)
1.20, 1.22 (both t, 3 H each, Me, 3J = 6.62); 2.94
)
4d
11.66, 12.89 (Me), 39.60, 50.37
3
(q, 2 H, (CH2)cyclNCH2, 2J = 13.97, J = 6.62);
(CH2Me); 66.60 ((CH2)cycl); 128.07,
129.13, 131.70, 131.84 (pꢀClPh);
152.96 ((CO)cycl); 168.49 ((CO)exocycl
3.40 (br.s, 2 H, (CO)cyclNCH2); 4.82 (s, 2 H,
(CH2)cycl); 7.38, 7.61 (both d, 2 H each, Ar, J = 8.09)
3
)
4e
4f
2960, 2932,
2872, 1740,
1668, 1452,
1344, 1232,
1108, 712
0.91, 0.97 (both t, 3 H each, Me, 3J = 7.22);
1.26—1.67 (m, 8 H, 2 CH2(Bu)); 2.86 (t, 2 H,
(CH2)cyclNCH2, 3J = 7.22); 3.37 (br.s, 2 H,
(CO) cyclNCH2); 4.82 (s, 2 H, (CH2)cycl);
13.66, 13.94 (Me); 19.85, 20.32
(CH2Me); 28.90, 29.53 (CH2CH2CH2);
43.76, 55.48 (NCH2C); 66.75
((CH2)cycl); 127.65, 129.13, 131.97,
133.49 (Ph); 152.97 ((CO)cycl);
3
7.37—7.55 (m, 3 H, Ph); 7.67 (d, 2 H, Ph, J = 6.56)
169.65 ((CO)exocycl
)
2970, 2930
2881, 2840,
1726, 1662,
1594, 1337,
1266, 1085,
1012, 836, 750
3076, 2952,
1732, 1672,
1600, 1488,
1460, 1380,
1096, 848, 772
2957, 2943,
2884, 1795,
1636, 1486,
1334, 1239,
1102, 773
1.20 (m, 6 H, 2 Me); 2.93 (q, 2 H, (CH2)cyclNCH2,
2J = 13.5, 3J = 6.2); 3.40 (br.s, 2 H,
(CO)cyclNCH2); 4.83 (s, 2 H, (CH2)cycl); 7.39—7.67
(m, 5 H, Ph)
11.57, 12.92 (Me); 39.58, 50.38
(CH2Me); 66.59 ((CH2)cycl); 127.55,
128.53, 131.64, 133.72 (Ph); 152.67
((CO)cycl); 168.58 ((CO)exocycl
)
4g
4h
1.30—2.15 (m, 10 Н, (СН2)5); 2.64, 3.04 (both s,
3 H each, Ме); 7.37, 7.54 (both d, 2 H each, Ph,
3J = 6.56)
22.51, 24.93, 27.04, 32.35 (СН2);
31.14, 36.63 (Me); 84.17 (Ccycl);
128.14, 130.27, 134.27, 138.01
(pꢀClPh); 154.21 ((CO)cycl); 169.23
((CO)exocycl
)
3
1.22, 1.24 (both t, 3 H each, СН2Me, J = 6.8);
11.76, 12.31 (СН2Me); 23.34,
1.32, 1.34 (both s, 3 H each, СMe); 2.86 (q, 2 H,
25.17 (CМe); 39.07, 48.68 (CH2Me);
82.18 (Ccycl); 128.56, 130.75, 134.96,
138.45 (pꢀClPh); 153.59 ((CO)cycl);
C
cyclNCH2, 2J = 13.5, 3J = 6.8); 3.32 (br.s, 2 H,
(CO)cyclNCH2); 7.61, 7.61 (both d, 2 H each, Ar,
3J = 8.09)
168.93 ((CO)exocycl)
1
a IR spectra were recorded in KBr pellets (for 4c,d,f—h) and in a thin film of the individual compound (4e). H NMR spectra were
recorded in CDCl3 on Bruker WMꢀ250 (250 MHz) (for 4e,f,h), Bruker ACꢀ200 (200 MHz) (4c), and Bruker AMꢀ300 spectrometers
(300 MHz) (4d,g). 13C NMR spectra were recorded in DMSOꢀd6 (for 4c) and CDCl3 (4d—h) on Bruker AMꢀ300 (75.5 MHz)
(for 4c,e—h) and Bruker RDXꢀ500 spectrometers (125 MHz) (4d).
Table 3. Selected bond lengths (d) and angles (ω) in compounds 4c and 4g
Bond
d/Å
Bond
d/Å
Angle
ω/deg
Angle
ω/deg
4с
4g
4с
4g
O(1)—C(3)
N(1)—N(2)
N(1)—C(5)
N(1)—C(6)
N(2)—C(3)
N(2)—C(9)
C(3)—N(4)
1.213(2)
1.437(2)
1.467(2)
1.477(2)
1.345(2)
1.449(2)
1.423(2)
O(1)—C(3)
N(1)—N(2)
N(1)—C(6)
N(1)—C(5)
N(2)—C(3)
N(2)—C(7)
C(3)—N(4)
N(4)—C(8)
N(4)—C(5)
1.2112(15)
1.4301(14)
1.4737(17)
1.4852(16)
1.3516(15)
1.4437(16)
1.4231(15)
1.3936(14)
1.4944(15)
N(2)—N(1)—C(5)
N(2)—N(1)—C(6)
C(5)—N(1)—C(6)
C(3)—N(2)—N(1)
C(3)—N(2)—C(9)
N(1)—N(2)—C(9)
C(12)—N(4)—C(3) 128.87(15)
C(12)—N(4)—C(5) 119.36(15)
C(3)—N(4)—C(5)
101.20(13)
109.07(14)
111.71(16)
114.16(15)
125.21(16)
119.91(14)
N(2)—N(1)—C(6) 107.31(10)
N(2)—N(1)—C(5) 101.39(8)
C(6)—N(1)—C(5) 115.00(11)
C(3)—N(2)—N(1) 113.57(10)
C(3)—N(2)—C(7) 125.48(11)
N(1)—N(2)—C(7) 119.68(10)
C(8)—N(4)—C(3) 123.98(10)
C(8)—N(4)—C(5) 124.52(10)
C(3)—N(4)—C(5) 106.63(9)
N(4)—C(12) 1.387(2)
N(4)—C(5) 1.466(2)
107.31(15)

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