Reactions of 3-alkylsulfanyl-2-arylazo-3-(1-azacycloalk-1-yl)acrylonitriles with maleimide

Article abstract of DOI:10.1007/s11172-010-0169-1

Reactions of 2-arylazo-3-(1-azacycloalk-1-yl)-3- methylsulfanylacrylonitriles with male-imide in benzene gave octahydropyrrolo[3,4-a]pyrrolizines 2a-c, decahydro-2,7a-diaza-cyclopenta[a] indene 2e, and decahydro-5-oxa-2,7a-diazacyclopenta[a]indene 2f as a result of 1,3-dipolar cycloaddition. In a similar reaction with 3-allylsulfanyl-2-arylazo- 3-(1-azacycloalk-1-yl)acrylonitriles 3, dipolar cycloaddition and intramolecular cyclization competed to give a mixture of compounds 2 (major products) and 1,4,6,7,8,8a-hexahydropyrrolo[2,1-c]-1,2,4-triazines 4b-d, 1,6,7,8,9,9a- hexahydro-4H-pyrido[2,1-c]-1,2,4-triazine 4e, and 1,4,6,7,9,9a-hexahydro-1,4- oxazino[3,4-c]-1,2,4-triazine 4f (minor products).

Full text of DOI:10.1007/s11172-010-0169-1

Russian Chemical Bulletin, International Edition, Vol. 59, No. 4, pp. 833—837, April, 2010
833
Reactions of 3ꢀalkylsulfanylꢀ2ꢀarylazoꢀ
3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)acrylonitriles with maleimide
N. P. Belskaya,a A. V. Koksharov,a T. G. Deryabina,b O. S. Eltsov,a P. A. Slepukhin,b and V. A. Bakuleva
aFirst Russian President B. N. El´tsin Ural State Technical University,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Fax: +7 (343) 374 5483. Eꢀmail: belska@mail.ustu.ru
bI. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
20 ul. S. Kovalevskoi, 620041 Ekaterinburg, Russian Federation
Reactions of 2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)ꢀ3ꢀmethylsulfanylacrylonitriles with maleꢀ
imide in benzene gave octahydropyrrolo[3,4ꢀa]pyrrolizines 2a—c, decahydroꢀ2,7aꢀdiazaꢀ
cyclopenta[a]indene 2e, and decahydroꢀ5ꢀoxaꢀ2,7aꢀdiazacyclopenta[a]indene 2f as a result of
1,3ꢀdipolar cycloaddition. In a similar reaction with 3ꢀallylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ
1ꢀyl)acrylonitriles 3, dipolar cycloaddition and intramolecular cyclization competed to give
a mixture of compounds 2 (major products) and 1,4,6,7,8,8aꢀhexahydropyrrolo[2,1ꢀc]ꢀ1,2,4ꢀ
triazines 4b—d, 1,6,7,8,9,9aꢀhexahydroꢀ4Hꢀpyrido[2,1ꢀc]ꢀ1,2,4ꢀtriazine 4e, and 1,4,6,7,9,9aꢀ
hexahydroꢀ1,4ꢀoxazino[3,4ꢀc]ꢀ1,2,4ꢀtriazine 4f (minor products).
Key words: 1,2ꢀdiazaꢀ1,3ꢀbutadienes, pyrrolidine, piperidine, morpholine, maleimide,
1,3ꢀdipolar cycloaddition, intramolecular cyclization.
Scheme 1
1,2ꢀDiazabutaꢀ1,3ꢀdienes easily react with various diꢀ
enophiles to give pyridazines (heteroꢀDiels—Alder reacꢀ
tion).1 Earlier,2,3 we have found that the presence of terꢀ
minal Sꢀalkylꢀ and 1ꢀazacycloalkyl groups in a diazadiene
system radically changes the chemical properties of these
compounds. 3ꢀAlkylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(pyrrolidinꢀ1ꢀ
yl)acrylonitriles react as latent dipoles to give products of
intramolecular and intermolecular cyclization. The goal
of the present work was to study the influence of the strucꢀ
ture of the starting compounds on their tendency toward
1,3ꢀdipolar cycloaddition with maleimide, determine the
scope of the earlier discovered transformations, and obꢀ
tain new heterocyclic compounds.
Reactions of 2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)ꢀ3ꢀmeꢀ
thylsulfanylacrylonitriles 1a—e with an excess of maleimꢀ
ide were carried out in benzene at 50 °C (Scheme 1). The
products were isolated by filtration or by liquid chromaꢀ
tography. Structures 2 were determined from spectroscopic
and Xꢀray diffraction data.
The IR spectra of tricyclic compounds 2a—c,e show
absorption bands at 2200 cm–1 (CN) and 1705—1710 cm–1
(stretching vibrations of two CO groups). The H NMR
spectra of the pyrrolo[3,4ꢀa]pyrrolizines 2 obtained conꢀ
tain a double set of signals of all protonꢀcontaining groups.
The most characteristic signals indicating the formation
of cycloadducts 2a—c,e are two doublets at δ 4.7—5.20
(1 H, J = 8.5—8.8 Hz), two doublets of doublets at δ 3.6—3.8
(J = 8.5—8.8 Hz, J = 10.0—10.3 Hz), a doublet of triplets
at δ 4.4—4.8, and a broadened singlet at δ 11.52—11.7
Comꢀ
pound
1a, 2a
1b, 2b CH2
1c, 2c CH2
X
Ar
Comꢀ
pound
1d, 2d
1e, 2e
X
Ar
4ꢀMeOC6H4
1
CH2
4ꢀNO2C6H4
2ꢀCF3C6H4
4ꢀClC6H4
CH2
(CH2)2 4ꢀNO2C6H4
Reagents and conditions: benzene, 50 °C.
(NH proton of the pyrrole ring). The number of the proꢀ
tons of the azacycloalkane fragment is reduced by unity,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 816—820, April, 2010.
1066ꢀ5285/10/5904ꢀ0833 © 2010 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
Belskaya et al.
N(3)
C(18)
all the signals for this fragment being shifted downfield.
Their multiplicity and positions suggest the participation
of this fragment in the transformation under study. The
structures of products 2 were convincingly confirmed, and
some of their structural features were revealed, by singleꢀ
crystal Xꢀray diffraction study of product 2b. The general
view of its molecule is shown in Fig. 1; selected bond
lengths and bond angles are listed in Table 1.
The presence of a system of conjugated double bonds
in structure 2b results in substantial deviations of
their lengths from standard values. For instance, the
length of the formally single N(2)—C(8) bond is nearly
equal to the length of the double C(8)—C(16)
bond (1.3859(16) and 1.3864(17) Å); the single bonds
C(9)—C(8) and C(1)—N(1) are close in length (1.4264(19)
and 1.4242(17) Å, respectively) and are substantially shortꢀ
er than normal single bonds. The conjugation system
N(4)C(9)C(16)C(8)N(2)N(1) is planar: the deviations of
the atoms from the meanꢀsquare plane do not exceed
0.01 Å. The benzene ring makes an angle of 24.4° with the
conjugation plane. According to Xꢀray diffraction data,
1,3ꢀdipolar cycloaddition yields an endoꢀadduct, namely,
the Eꢀisomer of pyrrolopyrrolizine 2b.
The presence of a double set of signals for the protonꢀ
containing groups in the 1H NMR spectra of tricyclic cyꢀ
cloadducts 2 suggest that these compounds exist as two
isomers about the exocyclic double C=C bond. The 2D
NOESY spectrum of compound 2a shows a cross peak of
the orthoꢀproton of the aromatic ring and a proton at the
C(6) atom of the pyrrolidine fragment, which is possible
only in the Zꢀisomer of this compound.
It should be noted that the yields of cycloadducts 2
decrease considerably with strengthening of the electronꢀ
donating properties of the substituent in the aromatic ring.
We failed to isolate a product of a reaction of maleimide
O(2)
C(5)
O(1)
C(4)
C(17)
C(14)
C(12)
C(6)
C(1)
C(3)
C(15)
N(2)
C(13)
C(16)
C(2)
F(2)
C(8)
C(9)
N(5)
C(10)
N(1)
F(1)
C(7)
C(11)
F(3)
N(4)
Fig. 1. Structure 2b with atomic thermal displacement ellipsoids
(50% probability) from Xꢀray diffraction data.
with compound 1d containing the electronꢀdonating
methoxy group (Table 2).
Reactions with Sꢀallyl derivatives of 2ꢀarylazoꢀ3ꢀ(1ꢀ
azacycloalkꢀ1ꢀyl)acrylonitriles (3a—f) gave minor products
along with pyrrolo[3,4ꢀa]pyrrolizines 2a—f (Scheme 2,
see Table 1). The compounds obtained were separated by
liquid chromatography and identified as pyrrolotriazines
4b—d, 1,6,7,8,9,9aꢀhexahydroꢀ4Hꢀpyrido[2,1ꢀc]ꢀ1,2,4ꢀ
triazine 4e, and 1,4,6,7,9,9aꢀhexahydroꢀ[1,4]oxazino[3,4ꢀc]ꢀ
1,2,4ꢀtriazine 4f using spectroscopic techniques.
The formation of bicyclic triazines 4 in the transforꢀ
mations of 3ꢀallylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀ
yl)acrylonitriles in various solvents have been noted earliꢀ
er.3 With strengthening of the electronꢀdonating properꢀ
ties of the substituent in the aromatic ring of the starting
reagents 3a—d, the content of intramolecular cyclization
products 4 in the reaction mixture increases, while the
Table 1. Selected bond lengths (d) and bond angles (ω) in
structure 2b
Bond length
d/Å
Angle
ω/deg
N(1)—N(2)
N(1)—C(1)
N(2)—C(8)
1.2675(14) C(16)—N(5)—C(10) 132.64(11)
1.4242(17) N(1)—N(2)—C(8)
1.3859(16) N(2)—N(1)—C(1)
115.55(11)
112.11(11)
N(5)—C(16) 1.3143(15) N(2)—C(8)—C(16) 116.68(11)
N(5)—C(10) 1.4670(17) N(2)—C(8)—C(9) 120.43(11)
N(5)—C(13) 1.4654(17) N(5)—C(10)—C(11) 102.84(11)
N(4)—C(9) 1.1434(16) N(5)—C(16)—C(8) 128.19(12)
O(2)—C(17) 1.1977(17) N(5)—C(16)—C(15) 108.61(11)
O(1)—C(18) 1.1952(17) N(4)—C(9)—C(8) 177.62(15)
N(3)—C(18) 1.3719(19) O(1)—C(18)—N(3) 124.47(15)
N(3)—C(17) 1.371(2)
O(1)—C(18)—C(15) 128.77(14)
O(2)—C(17)—N(3) 124.96(16)
O(2)—C(17)—C(14) 127.58(15)
C(2)—C(7)
F(3)—C(7)
F(2)—C(7)
F(1)—C(7)
C(8)—C(16)
C(8)—C(9)
1.484(2)
1.334(2)
1.3233(17) N(3)—C(18)—C(15) 106.75(13)
1.327(2)
1.3864(17)
1.4264(19)
N(3)—C(17)—C(14) 107.44(13)

Reactions of 3ꢀalkylsulfanylacrylonitriles
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
835
Scheme 2
ylmaleimides. However, the cycloaddition with maleimꢀ
ide proceeds more slowly than that with its Nꢀsubstituted
derivatives; the reaction rate becomes comparable with
the rate of an alternative reaction (intramolecular cyclizaꢀ
tion). The structures of the starting reagents 1 and 3 are
crucial for the efficiency of 1,3ꢀdipolar cycloaddition. Inꢀ
troduction of electronꢀdonating substituents into the aroꢀ
matic ring or replacement of the pyrrolidine substituent by
the piperidine/morpholine fragment lowers the yields of
cycloadducts but is favorable for the intramolecular cyꢀ
clization of 3ꢀallylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀ
yl)acrylonitriles, thus increasing the yields of the correꢀ
sponding fused 1,2,4ꢀtriazines 4.
Experimental
1
H and 13C NMR spectra were recorded on Bruker WMꢀ250
and Bruker AVANCE II 400 instruments (250.13 and 400.00 MHz
(1H) and 100.00 MHz (13C)) in DMSOꢀd6 with Me4Si as the
internal standard. IR spectra were recorded on a URꢀ20 specꢀ
trometer (in KBr pellets). Mass spectra were measured on
a Varian MAT 311A instrument (EI, 70 eV). The course of the
reactions was monitored and the purity of the compounds obꢀ
tained was checked by TLC on Sorbfil UVꢀ254 plates in ethyl
acetate, chloroform—acetone (30 : 1), and chloroform—hexꢀ
ane—acetone (5 : 4 : 1). Products were separated and purified by
liquid chromatography on silica gel (0.035—0.070 mm, 60 Å,
Acros Organics).
3ꢀAlkylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)acrylonitꢀ
riles 1 and 3 were prepared as described earlier.1 The structures of
pyrrolotriazines 4b—d were confirmed by comparing their physicoꢀ
chemical characteristics with those of authentic samples.3
Preparation of compounds 2a—f (generat procedure). A soluꢀ
tion of 3ꢀalkylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)acryloꢀ
nitrile 1 or 3 (0.5 mmol) and maleimide (0.145 g, 1.5 mmol) in
benzene was kept at 50 °C for 7—40 h (TLC). The solvent was
removed under reduced pressure and the residue was separated
by liquid chromatography with chloroform—hexane—acetone
(5 : 4 : 1) as an eluent.
Comꢀ
X
Ar
Comꢀ
X
Ar
pound
3a, 4a
3b, 4b
3c, 4c
pound
3d, 4d
3e, 4e
CH2
CH2
CH2
4ꢀNO2C6H4
2ꢀCF3C6H4
4ꢀClC6H4
CH2
4ꢀMeOC6H4
(CH2)2 4ꢀNO2C6H4
4ꢀNO2C6H4
2f, 3f, 4f OCH2
Reagents and conditions: benzene, 50 °C.
yields of pyrrolopyrrolizines 2 decrease (see Table 2). As
with the Sꢀmethyl derivative, we did not isolate a cycloadꢀ
duct of 3ꢀallylsulfanylꢀ2ꢀ(4ꢀmethoxyphenylazo)ꢀ3ꢀ(pyrꢀ
rolidinꢀ1ꢀyl)acrylonitrile 3d with maleimide (the correꢀ
sponding pyrrolopyrrolizine 2d).
Thus, the reactions of 3ꢀalkylsulfanylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀ
azacycloalkꢀ1ꢀyl)acrylonitriles 1 and 3 with maleimide
follow the 1,3ꢀdipolar cycloaddition mechanism leading
to octahydropyrrolo[3,4ꢀa]pyrrolizines 2a—d, 1,3ꢀdiꢀ
oxodecahydroꢀ2,7aꢀdiazaꢀ and 1,3ꢀdioxodecahydroꢀ5ꢀ
oxaꢀ2,7aꢀdiazacyclopenta[a]indenes 2e,f, similar to the
earlier discovered reactions with Nꢀmethylꢀ and Nꢀphenꢀ
2ꢀ(1,3ꢀDioxooctahydropyrrolo[3,4ꢀa]pyrrolizinꢀ4ꢀylidene)ꢀ
2ꢀ(4ꢀnitrophenylazo)acetonitrile (2a), m.p. 236—238 °C, Rf 0.26
(ethyl acetate). IR, ν/cm–1: 2960 (CH2); 2200 (CN); 1720 (CO).
1H NMR, δ: 11.76, 11.66 (both s, 1 H, NH); 8.29, 7.70, 8.28,
7.91 (AA´XX´ and AA´XX´, 4 H, Ar, J = 9.3 Hz); 5.19, 4.85
(both d, 1 H, CH, J = 8.4 Hz); 4.65—4.56 (m, 1 H, CH); 3.92—3.76
(m, 2 H, CH); 3.73, 3.70 (both dd, 1 H, CH, J = 8.4 Hz, J = 9.7 Hz);
2.31—2.13 (m, 2 H, CH2); 2.08—1.98 (m, 1 H, CH); 1.57—1.39
(m, 1 H, CH). The mixture of the cisꢀ and transꢀisomers in
a ratio of 1 : 1. 13C NMR, δ: 176.6 (CO); 174.7 (CO); 174.6 (CO);
173.8 (CO); 161.3 (CAr); 158.0 (CAr); 157.7 (C(4)); 157.1 (C(4));
146.5 (CAr); 146.4 (CAr); 136.1 (CAr); 125.9 (CAr); 125.6 (CAr);
123.0 (CAr); 122.7 (CAr); 115.2 (CN); 114.9 (CN); 105.9 (C(2´));
104.5 (C(2´)); 72.0 (C(8a)); 71.6 (C(8a)); 60.0 (C(3a)); 59.9
(C(3a)); 50.1 (C(6)); 46.8 (C(6)); 42.3 (C(8b)); 41.9 (C(8b));
27.9 (C(7)); 27.7 (C(7)); 27.3 (C(8)); 27.1 (C(8)). MS, m/z (Irel (%)):
366 [M]+ (25.5). Found (%): C, 55.69; H, 3.79; N, 22.75.
C17H14N6O4. Calculated (%): C, 55.74; H, 3.85; N, 22.94.
2ꢀ(1,3ꢀDioxooctahydropyrrolo[3,4ꢀa]pyrrolizinꢀ4ꢀylidene)ꢀ
2ꢀ(2ꢀtrifluoromethylphenylazo)acetonitrile (2b), m.p. 296—298 °C,
Table 2. Yields of the products of the reactions of 3ꢀalkylsulfaꢀ
nylꢀ2ꢀarylazoꢀ3ꢀ(1ꢀazacycloalkꢀ1ꢀyl)acrylonitriles 1 and 3 with
maleimide
1, 3
Yield (%)
1, 3
Yield (%)
2
4
2
4
1d
3d
1e
3e
3f
TLC*
TLC*
44
22
38
0
30
0
40
16
1a
3a
1b
3b
1с
3с
70
75
57
54
55
35
0
0
0
TLC*
0
20
* These products were detected using TLC: for compound 2d,
Rf 0.35 (ethyl acetate); for compound 4b, Rf 0.65 (chloroꢀ
form—acetone, 30 : 1).

836
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
Belskaya et al.
Rf 0.30 (ethyl acetate). IR, ν/cm–1: 2960 (CH2); 2195 (CN);
1710 (CO). 1H NMR, δ: 11.80, 11.65 (both s, 1 H, NH); 7.98
(d, 1 H, Ar, J = 7.8 Hz); 7.77 (dd, 1 H, Ar, J = 8.4 Hz, J = 9.7 Hz);
7.68 (dd, 1 H, Ar, J = 7.8 Hz, J = 15.6 Hz); 7.53 (d, 1 H, Ar,
J = 7.8 Hz); 7.45 (dd, 1 H, Ar, J = 7.8 Hz, J = 15.6 Hz); 5.17,
4.81 (both d, 1 H, CH, J = 8.3 Hz); 4.61—4.52 (m, 1 H, CH);
3.88—3.65 (m, 3 H, CH); 2.30—2.13 (m, 2 H, CH2); 2.07—1.97
(m, 1 H, CH); 1.51—1.38 (m, 1 H, CH). The mixture of the cisꢀ
and transꢀisomers in a ratio of 5 : 6. MS, m/z (Irel (%)): 389 [M]+
(15.7). Found (%): C, 55.47; H, 3.57; N, 17.79. C18H14F3N5O2.
Calculated (%): C, 55.53; H, 3.62; N, 17.99.
2ꢀ(4ꢀChlorophenylazo)ꢀ2ꢀ(1,3ꢀdioxooctahydropyrrolo[3,4ꢀa]ꢀ
pyrrolizinꢀ4ꢀylidene)acetonitrile (2c), m.p. 273—275 °C, Rf 0.36
(ethyl acetate). IR, ν/cm–1: 2960 (CH2); 2195 (CN); 1720 (CO).
1H NMR, δ: 11.70, 11.50 (both s, 1 H, NH); 7.74 (d, 1 H, Ar,
J = 8.6 Hz); 7.53 (d, 1 H, Ar, J = 8.6 Hz); 7.45—7.34 (m, 2 H,
Ar); 5.09, 4.76 (both d, 1 H, CH, J = 8.2 Hz); 4.59—4.45 (m, 1 H,
CH); 3.89—3.62 (m, 3 H, CH); 2.39—2.15 (m, 2 H, CH2);
2.15—1.99 (m, 1 H, CH); 1.59—1.38 (m, 1 H, CH). The mixture
of the cisꢀ and transꢀisomers in a ratio of 2 : 3. 13C NMR, δ:
175.9 (CO); 175.8 (CO); 174.0 (CO); 173.2 (CO); 159.4 (CAr);
154.9 (CAr); 151.6 (C(4)); 151.3 (C(4)); 132.2 (CAr); 131.9 (CAr);
129.2 (CAr); 128.9 (CAr); 123.2 (CAr); 122.9 (CAr); 114.8 (CN);
114.5 (CN); 103.8 (C(2´)); 102.5 (C(2´)); 70.4 (C(8a)); 69.9
(C(8a)); 58.6 (C(3a)); 58.4 (C(3a)); 48.9 (C(6)); 45.9 (C(6));
41.6 (C(8b)); 41.3 (C(8b)); 26.9 (C(7)); 26.8 (C(7)); 26.6 (C(8));
26.4 (C(8)). MS, m/z (Irel (%)): 355 [M]+ (23.5). Found (%):
C, 57.32; H, 3.91; N, 19.55. C17H14ClN5O2. Calculated (%):
C, 57.39; H, 3.97; N, 19.68.
(m, 2 H, CH2); 1.72—1.65 (m, 1 H, CH2). MS, m/z (Irel (%)):
315 [M]+ (52.1). Found (%): C, 53.57; H, 4.28; N, 22.15.
C14H13N5O2S. Calculated (%): C, 53.32; H, 4.16; N, 22.21.
1ꢀ(4ꢀNitrophenyl)ꢀ4ꢀthioxoꢀ1,4,6,7,9,9aꢀhexahydroꢀ[1,4]ꢀ
oxazino[3,4ꢀc]ꢀ1,2,4ꢀtriazineꢀ3ꢀcarbonitrile (4f), m.p. 232—234 °C,
Rf 0.6 (chloroform—acetone, 30 : 1). 1H NMR, δ: 8.29, 7.75
(AA´XX´, 4 H, Ar, J = 9.6 Hz); 6.64 (dd, 1 H, CH, J = 10.0 Hz,
J = 2.8 Hz); 5.10 (d, 1 H, CH2, J = 11.2 Hz); 4.00 (dd, 1 H,
CH2, J = 11.2 Hz, J = 10.4 Hz); 3.93—3.87 (m, 1 H, CH2); 3.83
(dd, 1 H, CH2, J = 10.8 Hz, J = 2.4 Hz); 3.76—3.68 (m, 2 H,
CH2). MS, m/z (Irel (%)): 317 [M]+ (46.3). Found (%): C, 49.43;
H, 3.57; N, 22.30. C13H11N5O3S. Calculated (%): C, 49.21;
H, 3.49; N, 22.07.
Xꢀray diffraction analysis of compound 2b was carried out
according to a standard procedure at 295(2) K on an Xcalibur 3
automatic fourꢀcircle diffractometer equipped with a CCD deꢀ
tector (λ(MoꢀK), graphite monochromator, ω scan mode, scan
step 1.0°, crystal—detector distance 50 mm). No absorption corꢀ
rection was applied because of negligible absorption. The strucꢀ
ture was solved by the direct methods with the SHELXS97 proꢀ
gram4 and refined by the SHELXL97 program5 by the leastꢀ
squares method in the anisotropic (isotropic for H atoms) fullꢀ
matrix approximation on F2. The hydrogen atoms were located
from a difference electronꢀdensity map and refined using a riding
model with dependent thermal parameters. The H(3) atom at
the N(3) atom was refined independently. The Xꢀray diffraction
Table 3. Crystallographic parameters and the data collecꢀ
tion statistics for compound 2b
2ꢀ(1,3ꢀDioxoꢀ2,7aꢀdiazadecahydrocyclopenta[a]indenꢀ8ꢀ
ylidene)ꢀ2ꢀ(4ꢀnitrophenylazo)acetonitrile (2e), m.p. 220—222 °C,
1
Parameter
Value
Rf 0.48 (ethyl acetate). H NMR, δ: 11.66, 11.58 (both s, 1 H,
NH); 8.24, 7.82, 8.24, 7.66 (AA´XX´ and AA´XX´, 4 H, Ar,
J = 8.8 Hz); 5.30, 4.89 (both d, 1 H, CH, J = 12.4 Hz); 5.20, 4.69
(both d, 1 H, CH, J = 9.2 Hz); 4.24 (dt, 1 H, CH2, J = 11.6 Hz,
J = 2.8 Hz); 3.78, 3.73 (both dd, 1 H, CH, J = 9.6 Hz, J = 10.4 Hz);
3.45—3.32 (m, 1 H, CH2); 2.17—2.08 (m, 1 H, CH2); 1.99—1.92
(m, 1 H, CH2); 1.90—1.83 (m, 1 H, CH2); 1.68—1.57 (m, 2 H,
CH2); 1.37—1.28 (m, 1 H, CH2). The mixture of the cisꢀ and
transꢀisomers in a ratio of 3 : 7. MS, m/z (Irel (%)): 380 [M]+
(10.2). Found (%): C, 56.93; H, 4.36; N, 21.99. C18H16N6O4.
Calculated (%): C, 56.84; H, 4.24; N, 22.09.
Molecular formula
Molecular weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
C18H14F3N5O2
389.34
295(2)
Monoclinic
P21/n
15.3784(17)
7.6382(8)
16.519(2)
90
116.624(12)
90
1734.6(4)
4
1.491
2ꢀ(1,3ꢀDioxoꢀ5ꢀoxaꢀ2,7aꢀdiazaoctahydrocyclopenta[a]ꢀ
indenꢀ8ꢀylidene)ꢀ2ꢀ(4ꢀnitrophenylazo)acetonitrile (2f), m.p.
γ/deg
3
V/Å
1
269—271 °C, Rf 0.35 (ethyl acetate). H NMR, δ: 11.66, 10.79
Z
(both s, 1 H, NH); 8.25, 7.88, 8.25, 7.70 (AA´XX´ and AA´XX´,
4 H, Ar, J = 8.8 Hz); 5.14, 5.01 (both d, 1 H, CH, J = 12.8 Hz);
4.69—4.59 (m, 1 H, CH2); 4.35—4.23 (m, 1 H, CH2); 4.22—4.11
(m, 1 H, CH2); 4.02—3.91 (m, 1 H, CH2); 3.83, 3.79 (both dd,
1 H, CH, J = 9.6 Hz, J = 10.0 Hz); 3.68—3.53 (m, 2 H, CH2);
3.39—3.27 (m, 1 H, CH2). The mixture of the cisꢀ and transꢀ
isomers in a ratio of 1 : 2. MS, m/z (Irel (%)): 380 [M]+ (10.2).
Found (%): C, 53.63; H, 3.76; N, 21.83. C17H14N6O5. Calculatꢀ
ed (%): C, 53.41; H, 3.69; N, 21.98.
1ꢀ(4ꢀNitrophenyl)ꢀ4ꢀthioxoꢀ1,6,7,8,9,9aꢀhexahydroꢀ4Hꢀpyꢀ
rido[2,1ꢀc]ꢀ1,2,4ꢀtriazineꢀ3ꢀcarbonitrile (4e), m.p. 132—134 °C,
Rf 0.88 (chloroform—acetone, 30 : 1). 1H NMR, δ: 8.28, 7.75
(AA´XX´, 4 H, Ar, J = 9.2 Hz); 6.49 (dd, 1 H, CH, J = 10.8 Hz,
J = 2.0 Hz); 5.05 (ddd, 1 H, CH2, J = 12.8 Hz, J = 2.4 Hz,
J = 2.0 Hz); 3.42 (dt, 1 H, CH2, J = 12.4 Hz, J = 2.8 Hz);
2.17—2.05 (m, 2 H, CH2); 2.02—1.95 (m, 1 H, CH2); 1.86—1.73
dcalc/g cm–3
μ/mm–1
0.123
2.96 ≤ θ ≤ 28.29
98.8
Scan range/deg
Scan completeness (%)
Number of measured
4257
(0.0354)
2356
257
1.000
0.0423
0.0839
0.0957
0.0922
reflections (Rint
)
Number of reflections with I > 2σ(I)
Number of parameters refined
S
R1 (for I > 2σ(I))
wR2 (for I > 2σ(I))
R1 (for all reflections)
wR2 (for all reflections)
Residual electron
density/e Å–3, ρmax/ρ
0.202/–0.172
min

Reactions of 3ꢀalkylsulfanylacrylonitriles
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
837
data obtained have been deposited with the Cambridge Crystalꢀ
lographic Data Center (CCDC No. 726 716) and can be made
available free upon request on www.ccdc.cam.ac.uk/data_request/
cifwww.ccdc.cam.ac.uk/data_request/cif. Selected crystalloꢀ
graphic parameters and the data collection statistics for comꢀ
pound 2b are summarized in Table 3. Selected bond lengths and
bond angles in structure 2b are given in Table 1.
2. T. G. Deryabina, N. P. Belskaia, M. I. Kodess, W. Dehaen,
S. Toppet, V. A. Bakulev, Tetrahedron Lett., 2006, 47, 1853.
3. N. P. Belskaia, T. G. Deryabina, A. V. Koksharov, M. I.
Kodess, W. Dehaen, A. T. Lebedev, V. A. Bakulev, Tetraꢀ
hedron Lett., 2007, 48, 9128.
4. G. M. Sheldrick, SHELXS97, Program for the Solution of Crysꢀ
tal Structure, University of Göttingen, Göttingen, Germany,
1997.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 08ꢀ03ꢀ
00376_a and 08ꢀ03ꢀ92208 GFEN_a).
5. G. M. Sheldrick, SHELXL97, Program for the Refinement of
Crystal Structure, University of Göttingen, Göttingen, Gerꢀ
many, 1997.
References
1. O. A. Attanasi, L. De Crescentini, P. Filippone, F. Mantelꢀ
Received April 1, 2009;
lini, R. Perrulli, S. Santeusanio, ARKIVOC, 2002, 274.
in revised form September 30, 2009