The mannich reaction in the synthesis of N,S-containing heterocycles 4. Aminomethylation of 6-amino-3,5-dicyano-1,4-dihydropyridine-2-thiolates: A convenient regioselective route to 3,5,7,11-tetraazatricyclo[7.3.1.0 2,7]tridec-2-ene derivatives

Article abstract of DOI:10.1007/s11172-007-0158-1

Treatment of N-methylmorpholinium 4-R-6-amino-3,5-dicyano-1,4- dihydropyridine-2-thiolates (R = 2-ClC₆H₄ and 2-MeOC ₆H₄) with primary amines in the presence of an excess of formaldehyde gave 13-R-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.0 ^2,7]tridec-2-ene-1,9-dicarbonitrile derivatives in high yields (66-95%). In a similar way, aminomethylation of 3-R-10-amino-7,11-dicyano-9-aza- 3-azoniaspiro[5.5]undeca-7,10-diene-8-thiolates (R = Me and Et) afforded 1'-alkyl-8-thioxospiro[3,5,7,11-tetraazatricyclo[7.3.1.0^2,7]tridec-2- ene-13,4'-piperidine]-1,9-dicarbonitriles in 43-91% yields. Alternatively, these compounds were obtained by multicomponent cyclocondensation of N-alkylpiperidin-4-ones, cyanothioacetamide, primary amines, and aqueous formaldehyde. The starting 3-R-10-amino-7,11-dicyano-9-aza-3-azoniaspiro[5.5] undeca-7,10-diene-8-thiolates were prepared by a new method from N-alkylpiperidin-4-ones and cyanothioacetamide. The structure of 5,11-bis(4-ethoxyphenyl)-13-(2-methoxyphenyl)-8-thioxo-3,5,7, 11-tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene-1,9-dicarbonitrile was examined by X-ray diffraction analysis.

Full text of DOI:10.1007/s11172-007-0158-1

Russian Chemical Bulletin, International Edition, Vol. 56, No. 5, pp. 1053—1062, May, 2007
1053
The Mannich reaction in the synthesis of N,Sꢀcontaining heterocycles
4.* Aminomethylation of 6ꢀaminoꢀ3,5ꢀdicyanoꢀ1,4ꢀdihydropyridineꢀ2ꢀthiolates:
a convenient regioselective route
to 3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀene derivatives
a
b
c†
V. V. Dotsenko,a S. G. Krivokolysko, A. N. Chernega, and V. P. Litvinov
ꢀ
aChemEx Laboratory, Vladimir Dal´ EastꢀUkrainian National University,
20a Molodezhnyi kv., 91034 Lugansk, Ukraine.
Fax: (+0642) 41 9151. Eꢀmail: Victor_Dotsenko@bigmir.net
bInstitute of Organic Chemistry, National Academy of Sciences of the Ukraine,
5 ul. Murmanskaya, 02094 Kiev, Ukraine.
Fax: (+044) 573 2643. Eꢀmail: iochkiev@ukrpack.net
cN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 8837
Treatment of Nꢀmethylmorpholinium 4ꢀRꢀ6ꢀaminoꢀ3,5ꢀdicyanoꢀ1,4ꢀdihydropyridineꢀ2ꢀ
thiolates (R = 2ꢀClC6H4 and 2ꢀMeOC6H4) with primary amines in the presence of an excess of
formaldehyde gave 13ꢀRꢀ8ꢀthioxoꢀ3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ1,9ꢀ
dicarbonitrile derivatives in high yields (66—95%). In a similar way, aminomethylation of
3ꢀRꢀ10ꢀaminoꢀ7,11ꢀdicyanoꢀ9ꢀazaꢀ3ꢀazoniaspiro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolates (R = Me
and Et) afforded 1´ꢀalkylꢀ8ꢀthioxospiro[3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ13,4´ꢀ
piperidine]ꢀ1,9ꢀdicarbonitriles in 43—91% yields. Alternatively, these compounds were obꢀ
tained by multicomponent cyclocondensation of Nꢀalkylpiperidinꢀ4ꢀones, cyanothioacetamide,
primary amines, and aqueous formaldehyde. The starting 3ꢀRꢀ10ꢀaminoꢀ7,11ꢀdicyanoꢀ9ꢀazaꢀ
3ꢀazoniaspiro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolates were prepared by a new method from
Nꢀalkylpiperidinꢀ4ꢀones and cyanothioacetamide. The structure of 5,11ꢀbis(4ꢀethoxyphenyl)ꢀ
13ꢀ(2ꢀmethoxyphenyl)ꢀ8ꢀthioxoꢀ3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ1,9ꢀdiꢀ
carbonitrile was examined by Xꢀray diffraction analysis.
Key words: Nꢀmethylmorpholinium 6ꢀaminoꢀ4ꢀarylꢀ3,5ꢀdicyanoꢀ1,4ꢀdihydropyridineꢀ2ꢀ
thiolates, the Mannich reaction, cyclocondensation, Xꢀray diffraction analysis, 3,5,7,11ꢀtetraꢀ
azatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ1,9ꢀdicarbonitriles, 3ꢀRꢀ10ꢀaminoꢀ7,11ꢀdicyanoꢀ9ꢀazaꢀ3ꢀ
azoniaspiro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolates, 1´ꢀalkylꢀ8ꢀthioxospiro[3,5,7,11ꢀtetraazatriꢀ
cyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ13,4´ꢀpiperidine]ꢀ1,9ꢀdicarbonitriles, cyanothioacetamide, Nꢀalꢀ
kylpiperidinꢀ4ꢀones.
The Mannich reaction is one of the most efficient and
preferred methods of designing azaheterocyclic systems.1
Aminomethylation of binucleophilic substrates, specifiꢀ
cally N,Sꢀbinucleophiles, is of particular interest for the
synthesis of nitrogenꢀcontaining heterocycles. For inꢀ
stance, reactions of dithiocarbamates, as well as a number
of other substrates containing a thioamide fragment, with
formaldehyde and primary amines are known to be a genꢀ
eral method for the synthesis of 1,3,5ꢀthiadiazine derivaꢀ
tives2 many of which exhibit a broad range of biological
activity.3 Cyclic thioamides behave in a similar way: in
recent years, the "double" Mannich cyclocondensaꢀ
tion has been successfully used to obtain derivatives
of symmꢀtriazolo[3,4ꢀb][1,3,5]thiadiazine,4—11 thiazoꢀ
lo[3´,4´:1,5][1,2,4]triazolo[3,4ꢀb][1,3,5]thiadiazine,12
imidazo[2,1ꢀb][1,3,5]thiadiazine, 1,2,4ꢀtriazino[3,2ꢀb]ꢀ
[1,3,5]thiadiazine,13 and 1,3,5ꢀthiadiazino[3,2ꢀa]benzꢀ
imidazole.14 This approach has also been employed in the
synthesis of pyrido[2,1ꢀb][1,3,5]thiadiazine15 and imidꢀ
azo[2,1ꢀb][1,3,5]thiadiazine derivatives.16 Functionalized,
partially hydrogenated 3ꢀcyanopyridineꢀ2ꢀthiolates17 can
behave abnormally under the Mannich reaction condiꢀ
tions. For instance, 3,7ꢀdiazabicyclo[3.3.1]nonane derivaꢀ
* For Part 3, see V. V. Dotsenko, S. G. Krivokolysko, E. B.
Rusanov, A. V. Gutov, and V. P. Litvinov, Khim. Geterotsikl.
Soedin., 2007, 1075 [Chem. Heterocycl. Compd., 2007 (Engl.
Transl.)].
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1014—1022, May, 2007.
1066ꢀ5285/07/5605ꢀ1053 © 2007 Springer Science+Business Media, Inc.

1054
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Dotsenko et al.
tives18 have been obtained in some cases together with the
expected N,Sꢀdiaminomethylation products, namely,
pyrido[2,1ꢀb][1,3,5]thiadiazines.15 Proceeding further in
these investigations, we studied the aminomethylation of
a number of earlier prepared Nꢀmethylmorpholinium
6ꢀaminoꢀ4ꢀarylꢀ3,5ꢀdicyanoꢀ1,4ꢀdihydropyridineꢀ2ꢀ
thiolates (1), which are promising N,Sꢀbinucleophilic subꢀ
strates.
In the aminomethylation of thiolates 1a,b
(thiolate : primary amine = 1 : 1, excess of HCHO), we
isolated only products 2a—f in low yields (13—43%) rather
than the expected pyrido[2,1ꢀb][1,3,5]thiadiazines. Comꢀ
pounds 2a—f are representatives of a novel heterocyclic
system, viz., 3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ
2ꢀene. To optimize the reaction conditions, we doubled
the amount of the starting amine; as the result, the yields
of tricyclic compounds 2 were increased to 66—95%
(Scheme 1).
3,7ꢀdiazabicyclo[3.3.1]nonane (DABCN, bispidine) deꢀ
rivatives.20 It should be noted that DABCN derivatives
are of both theoretical (because of their peculiar conforꢀ
mational structures)21 and practical interest due to the
specific ability to form strong complexes with transition
metal cations22 and a broad spectrum of biological activꢀ
ity inherent in bispidines.19,20,22,23 In the reactions with
thiolates 1, the formation of a bispidineꢀlike structure was
unexpectedly accompanied by parallel cyclocondensation
resulting in closure of a tetrahydroꢀ1,3,5ꢀtriazine ring.
At the same time, it is known that close structural analogs
of dihydropyridineꢀ2ꢀthiolates 1, viz., 3,5ꢀbis(alkoxyꢀ
carbonyl)ꢀ2,6ꢀdimethylꢀ1,4ꢀdihydropyridines (Hantzsch
dihydropyridines), do not form 3,7ꢀdiazabicyclo[3.3.1]noꢀ
nane derivatives in the Mannich reaction, undergoing
aminomethylation at the methyl group, the N(1) atom,
and either the C(3) or C(5) atom to yield derivatives of
1,6ꢀnaphthyridine and pyrimido[5,6,1ꢀij][1,6]naphthyriꢀ
dine.24 The oneꢀstep transformation of thiolates 1 into
3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀenes 2 we
describe here has no direct documented analogs.
Scheme 1
The synthesis of tricyclic structures of the type 2 under
the above conditions is not very variable since sterically
unhindered primary amines should be employed only.
For instance, we failed to carry out the reaction with
2,6ꢀdimethylaniline, tertꢀbutylamine, or 2ꢀethylꢀ6ꢀ
methylaniline. However, the corresponding tetraazatriꢀ
cyclo[7.3.1.02,7]tridecꢀ2ꢀenes 2 were easily obtained from
oꢀtoluidine and 2ꢀethylaniline. The order of mixing of the
reagents substantially did not affect the yields of the final
products. The plausible reaction mechanism is shown in
Scheme 2. It is highly probable that thiolates 1 react in the
form of imino tautomers 3, which have been reliably deꢀ
tected.25
Subsequent aminomethylation can follow alternative
pathways (see Scheme 2, pathways a and b). According to
the first, the initially formed pyridotriazine 4 is further
transformed into intermediate 5 and final product 2.
Pathway b involves the initial formation of Cꢀaminoꢀ
methylation product 6 and N,N´ꢀdiaminomethylation of
bispidine intermediate 7, giving tricyclotridecene 2. Howꢀ
ever, it is not improbable that both pathways are in fact
followed in parallel. Apparently, the formation of the
diazabicyclo[3.3.1]nonane framework begins with aminoꢀ
methylation at the C(5) atom of the dihydropyridine ring.
This is indirectly supported by the fact that 4ꢀarylꢀ5ꢀ
cyanoꢀ2ꢀoxoꢀ1,2,3,4ꢀtetrahydropyridineꢀ2ꢀthiolates,
which have only one carbon nucleophilic center
(C(3) atom), behave in the Mannich reaction like typical
N,Sꢀbinucleophiles and do not form Cꢀaminomethylation
products.15
1: Ar = 2ꢀMeOC6H4 (a); 2ꢀClC6H4 (b)
2: Ar = 2ꢀMeOC6H4, R = 4ꢀEtOC6H4 (a); Ar = 2ꢀMeOC6H4,
R = 2ꢀMeC6H4 (b); Ar = 2ꢀMeOC6H4, R = 2ꢀEtC6H4 (c);
Ar = 2ꢀClC6H4, R = 4ꢀEtOC6H4 (d); Ar = 2ꢀClC6H4, R = CH2Ph (e);
Ar = 2ꢀClC6H4, R = 3,4ꢀМе2С6Н3 (f)
Thus, model thiolates 1 under the Mannich reaction
conditions do not act as N,Sꢀbinucleophiles, undergoing
regioselective aminomethylation at the C(3) and C(5)
atoms and the N atoms of the exocyclic amino and
endocyclic imino groups. It follows from numerous litꢀ
erature data19 that the aminomethylation of piperidinꢀ4ꢀ
ones and other 3,5ꢀdinucleophilic substrates of the pyriꢀ
dine series occurs at the C(3) and C(5) atoms to give
To study the range of application of the aforemenꢀ
tioned reaction, we used structural analogs of thiolates 1:
3ꢀalkylꢀ10ꢀaminoꢀ7,11ꢀdicyanoꢀ9ꢀazaꢀ3ꢀazoniaspiꢀ
ro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolates 8. These promising

Tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
1055
Scheme 2
polyfunctional reagents can be easily prepared by threeꢀ
component cyclocondensation of Nꢀalkylpiperidinꢀ4ꢀ
ones, malononitrile, and cyanothioacetamide.26
aminomethylation of compounds containing the 6ꢀaminoꢀ
3,5ꢀdicyanoꢀ1,4ꢀdihydropyridineꢀ2ꢀthiolate structural
fragment is a general and so far sole route to derivatives of
a novel heterocyclic system, namely, 3,5,7,11ꢀtetraazaꢀ
tricyclo[7.3.1.02,7]tridecꢀ2ꢀene.
An alternative approach to the synthesis of comꢀ
pounds 9, which is however of no preparative value, inꢀ
volves reactions of Nꢀalkylpiperidinꢀ4ꢀones 10 with
cyanothioacetamide 11 followed by aminomethylation of
the in situ formed condensation product (Scheme 4).
Earlier,27 we have demonstrated that treatment
of R,Rꢀmethylenecyanothioacetamides 12 with
We found that aminomethylation of 4,4´ꢀspirobiꢀ
pyridinethiolates 8a,b with an excess of formaldehyde and
two equivalents of a primary amine gives spiro[3,5,7,11ꢀ
tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ13,4´ꢀpiperidine]ꢀ
1,9ꢀdicarbonitriles 9a—o in 43—91% yields, which are
analogous to compounds 2 (Scheme 3). Thus, as with
structurally close thiolates 1, the aminomethylation ocꢀ
curs at all accessible nucleophilic centers in compound 8,
except for the S atom. Therefore, one can state that

1056
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Dotsenko et al.
Scheme 3
in the molar ratio 1 : 1 under mild conditions, which
afford thiolates 8 in 40—45% yields. In a similar way,
when piperidones 10a,b and thioamide 11 were used in
the molar ratio 1 : 2 and a small amount of Nꢀmethylꢀ
morpholine (0.1 equiv.) was added, thiolates 8a,b were
obtained in 82—84% yields.
The structures of tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀ
enes 2 and 9 were confirmed by spectroscopic methods
and elemental analysis (Tables 1 and 2). For instance, the
IR spectra of the compounds obtained show no absorpꢀ
tion bands due to the N—H stretching vibrations and
those of the conjugated C≡N group. At the same time, a
weak broadened band at 2253—2233 cm–1 indicates the
presence of nonconjugated C≡N groups and a band at
1660—1645 cm–1 corresponds to the C=N stretching viꢀ
1
brations. The H NMR spectra of compounds 2 and 9
show four sets of signals for four methylene groups. The
C(10)H2 and C(12)H2 protons resonate at δ 3.04—4.09.
The resulting signals are either two pairs of doublets with
2J = 10.7—12.8 Hz or a complex multiplet due to partial
overlapping of the signals. The protons of the tetrahydroꢀ
1,3,5ꢀtriazine ring are also resolved as either doublets
of doublets or multiplets at δ = 4.41—5.12 (C(6)H2,
2J = 16.4—17.4 Hz) and 5.11—5.80 (C(4)H2, 2J =
12.5—13.6 Hz). The signal for the C(13)H proton in the
spectra of compounds 2 appears at δ 4.52—4.76 as a narꢀ
8: R = Me (a); Et (b)
1
row singlet. In addition, the H NMR spectra of comꢀ
9: R = R´ = Me (a); R = Me, R´ = CH2Ph (b);
R = Me, R´ = (CH2)2Ph (c); R = Me, R´ = Ph (d);
R = Me, R´ = 4ꢀMeC6H4 (e); R = Me, R´ = 4ꢀFC6H4 (f);
R = Me, R´ = 4ꢀClC6H4 (g); R = Et, R´ = Me (h);
R = Et, R´ = cyclopentyl (i); R = Et, R´ = CH2Ph (j);
R = Et, R´ = furfuryl (k); R = Et, R´ = Ph (l);
R = Et, R´ = 4ꢀMeC6H4 (m); R = Et, R´ = 3ꢀMeC6H4 (n);
R = Et, R´ = 4ꢀClC6H4 (o)
pounds 2 contain three sets of signals for the aromatic
substituents: one for the Cꢀaryl substituents and two for
the primary amine. The presence of the absorption band
due to the stretching vibrations of the N—H bond and the
conjugated C≡N group in the IR spectra of thiolates 8a,b
confirms the proposed structure and agrees with the litꢀ
erature data.26
primary amines and formaldehyde gives pyrimiꢀ
do[6,1ꢀb][1,3,5]thiadiazine derivatives 13 as the result of
a cascade reaction. When developing a multicomponent
approach to the synthesis of pyrimidothiadiazines of
the type 13, we assumed that "oneꢀpot" reactions of
piperidones 10a,b with thioamide 11 (molar ratio 1 : 1,
EtOH, 20 °C, 1 h) followed by treatment with two equivaꢀ
lents of a primary amine and an excess of 37% formalin
(reflux, 3—5 min) should yield spiroꢀfused pyrimidoꢀ
thiadiazine derivatives 14. Nevertheless, we isolated only
compounds 9 in low (15—23% with respect to cyanoꢀ
thioacetamide) yields, which were identical with those
obtained in the aminomethylation of thiolates 8. This
reaction outcome can be explained by the Knoevenagel
condensation of piperidones 10a,b with cyanothioacetꢀ
amide 11 followed by the easy Michael addition of
a second molecule of thioamide 11 to condensation prodꢀ
uct 15, thus giving thiolates 8. Obviously, the reaction is
autocatalytic because of the pronounced basic properties
of piperidones 10. This assumption was confirmed by easy
reactions of piperidones 10 with cyanothioacetamide 11
The spatial structure of compound 2a was examined
by Xꢀray diffraction analysis. The general view of strucꢀ
ture 2a with selected bond lengths and angles are shown
in Fig. 1. The geometrical parameters of the central triꢀ
cyclic system N(1)—N(4)C(1)—C(9) are close to the corꢀ
responding parameters in a structural analog of comꢀ
pounds 2 we have studied earlier.28 The conformation of
the sixꢀmembered heterocycles N(1)—N(3)C(1)—C(3)
and N(3)C(2)C(4)—C(7) is intermediate between
the halfꢀchair and the halfꢀboat: the fragment
N(2)C(2)N(3)C(3) is planar to within 0.026 Å, making
with the corner N(1)—C(1)—C(3) a dihedral angle of
50.0°; analogously, the fragment N(3)C(2)C(7)C(5)C(6)
is planar to within 0.087 Å, making with the corner
C(5)—C(6)—C(7) a dihedral angle of 49.9°. The conforꢀ
mation of the ring N(4)C(5)—C(9) is a typical chair. The
N(1) and N(4) atoms have a nearly trigonal planar bond
configuration (the sums of the bond angles at these atoms
are 341.1° and 345.0°, respectively). The bond configuraꢀ
tion of the N(3) atom is trigonal planar (the sum of
the bond angles is 359.7°). Because of an efficient

Tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
1057
Scheme 4
8—10: R = Me (a); Et (b)
C(25)
O(2)
C(24)
C(21)
C(20)
C(19)
C(22)
C(9)
C(23)
N(5)
C(34)
N(4)
C(18)
C(5)
C(26)
C(6)
C(17)
O(3)
C(33)
C(8)
C(4)
C(16)
C(28)
C(27)
C(7)
C(12)
S(1)
N(3)
C(3)
C(32)
O(1)
C(11)
N(6)
C(2)
N(2)
C(13)
C(29)
C(10)
C(31)
C(14)
C(30)
N(1)
C(15)
C(1)
Fig. 1. General view of structure 2a. Selected bond lengths: S(1)—C(4) 1.642(2) Å, N(1)—C(1) 1.459(2) Å, N(1)—C(3) 1.432(2) Å,
N(2)—C(1) 1.453(2) Å, N(2)—C(2) 1.270(2) Å, N(3)—C(2) 1.417(3) Å, N(3)—C(3) 1.506(2) Å, N(3)—C(4) 1.355(2) Å,
N(4)—C(8) 1.468(1) Å, N(4)—C(9) 1.455(2) Å.

1058
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Dotsenko et al.
Table 1. Yields and physicochemical characteristics of compounds 2 and 9
Comꢀ
pound
Yield
(%)
M.p.
/°С
Found
Calculated
Molecular
formula
(%)
(solvent)
С
H
N
2а
2b
2c
2d
2e
2f
77
72
66
84
95
72
72
75
69
59
66
43
44
87
91
58
51
69
79
78
45
207—208
(Me2CO—МеOH (1 : 1))
240—245
(decomp., Me2CO)
212—214
(Me2CO—MeOH (1 : 1))
215—217
(decomp., Me2CO)
122—124
(EtOH—Me2CO (1 : 1))
209—211
(Me2CO)
236—237
(decomp., Me2CO)
194—196
(Me2CO—EtOH (1 : 1))
155—156
66.70
67.31
71.09
70.30
71.88
71.05
65.88
64.85
68.28
67.56
67.88
68.44
57.78
58.19
69.28
68.80
69.84
69.66
67.24
67.85
69.14
68.80
63.74
63.26
60.04
59.57
59.38
59.19
65.64
65.68
69.53
69.24
62.84
62.65
68.45
68.34
69.50
69.24
69.59
69.24
60.56
60.20
5.69
5.65
5.48
5.53
6.01
5.96
5.15
5.11
5.02
4.94
5.43
5.40
6.81
6.78
6.31
6.35
6.80
6.76
5.91
5.90
6.36
6.35
5.11
5.12
4.83
4.82
7.06
7.06
7.96
7.96
6.58
6.56
6.06
6.04
6.13
6.13
6.57
6.56
6.58
6.56
5.07
5.05
13.94
13.85
15.55
15.37
14.65
14.96
13.88
13.75
15.09
15.25
14.55
14.51
26.48
26.39
18.74
18.72
17.73
17.77
19.75
19.78
18.68
18.72
18.39
18.44
17.35
17.37
25.40
25.43
19.83
19.86
18.13
18.23
18.89
18.94
19.20
19.24
18.18
18.23
18.18
18.23
17.00
16.95
C34H34N6O3S
C32H30N6ОS
C34H34N6ОS
C33H31ClN6О2S
C31H27ClN6S
C33H31ClN6S
С18H25N7S
9a
9b
9c
9d
9e
9f
С30H33N7S
С32H37N7S
(Me2CO)
179—181
(Me2CO—EtOH (1 : 1))
231—233
(decomp., Me2CO—EtOH (1 : 1))
244—245
(decomp., Me2CO—EtOH (1 : 1))
260—262
(decomp., Me2CO—EtOH (1 : 1))
229—231
(decomp., DMF—EtOH (1 : 2))
210—211
С28H29N7S
С30H33N7S
С28H27F2N7S
С28H27Cl2N7S
С19H27N7S
9g
9h
9i
С27H39N7S
(decomp., EtOH)
162—163
(Me2CO—EtOH (1 : 1))
164—166
(Me2CO—EtOH (1 : 1))
218—220
(Me2CO—EtOH (1 : 1))
219—220
9j
С31H35N7S
9k
9l
С27H31N7O2S
С29H31N7S
9m
9n
9o
С31H35N7S
(decomp., Me2CO—EtOH (1 : 1))
235—236
(decomp., Me2CO—EtOH (1 : 1))
270
С31H35N7S
С29H29Cl2N7S
(decomp., DMF—EtOH (1 : 1))
conjugation of the lone electron pair of the N(3) atom
with the πꢀsystem of the S(1)=C(4) double bond, the
N(3)—C(4) bond (1.355(2) Å) is substantially shorter than
the ordinary N(sp2)—C(sp2) bond (1.43—1.45 Å).29,30
In summary, 6ꢀaminoꢀ3,5ꢀdicyanoꢀ1,4ꢀdihydropyriꢀ
dineꢀ2ꢀthiolates in the Mannich reaction form abnormal
aminomethylation products that belong to a novel heteroꢀ
cyclic system: 3,5,7,11ꢀtetraazatricyclo[7.3.1.02,7]triꢀ
decꢀ2ꢀene.
Experimental
1
H NMR spectra were recorded on a Varian Gemini 200
instrument (200 MHz) in DMSOꢀd6 with Me4Si as the internal
standard. IR spectra were recorded on an IKSꢀ29 spectrophoꢀ
tometer (Nujol). Elemental analysis was carried out on a
Perkin—Elmer C,H,NꢀAnalyzer instrument. The purity of the
compounds obtained was checked by TLC on Silufol UV 254
plates (acetone—heptane (1 : 1), iodine vapor, UV detector).

Tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
1059
Table 2. Spectroscopic characteristics of compounds 2 and 9
Comꢀ
pound
IR,
ν/cm–1
1H NMR
(DMSOꢀd6), δ, J/Hz
2а
2b
2c
2250 (C≡N);
1660 (C=N)
1.38 (q, 6 Н, signal overlapping, 2 СН3СН2O, 3J = 7.0); 3.70—4.00 (m, 8 Н, 2 СН3СН2O,
С(10)Н2, С(12)Н2); 3.91 (s, 3 Н, МеО); 4.60 (s, 1 Н, С(13)Н); 5.03 (q, 2 Н, С(6)Н2, 2J = 16.8);
5.76 (q, 2 Н, С(4)Н2, 2J = 13.2); 6.44—7.41 (m, 12 Н, 3 Ar)
2245 (C≡N);
1655 (C=N)
1.84, 2.40 (both s, 3 H each, 2 Н3СAr); 3.55—3.99 (m, 4 Н, signal overlapping С(10)Н2 and С(12)Н2);
3.94 (s, 3 Н, МеО); 4.72 (s, 1 Н, С(13)Н); 4.95 (dd, 2 Н, С(6)Н2, 2J = 17.0);
5.68 (dd, 2 Н, С(4)Н2, 2J = 13.2); 6.70—7.40 (m, 12 Н, 3 Ar)
2248 (C≡N);
1650 (C=N)
1.07, 1.31 (both t, 3 H each, 2 СН3СН2, 3J = 7.5); 2.32, 2.74 (both q, 2 H each, 2 СН3СН2, 3J = 7.5);
2
3.49 (pseudotriplet, 2 Н, С(10)Н2 or С(12)Н2, J = 11.0); 3.91 (s, 3 Н, МеО); 3.94 (dd, 2 Н,
С(12)Н2 or С(10)Н2, 2J = 10.7); 4.76 (s, 1 Н, С(13)Н); 4.88 (dd, 2 Н, С(6)Н2, 2J = 17.2);
5.60 (dd, 2 Н, С(4)Н2, 2J = 13.1); 6.63—7.40 (m, 12 Н, 3 Ar)
2d
2e
2f
2253 (C≡N);
1653 (C=N)
1.29—1.39 (m, 6 Н, signal overlapping 2 ОСН2СН3); 3.77—3.96 (m, 8 Н, signal overlapping
2 ОСН2СН3, С(10)Н2 and С(12)Н2); 4.70 (s, 1 Н, С(13)Н); 5.06 (dd, 2 Н, С(6)Н2, 2J = 16.9);
5.80 (m, 2 Н, С(4)Н2); 6.44—7.60 (m, 12 Н, 3 Ar)
3.17—3.62 (m, 4 Н, signal overlapping С(10)Н2, С(12)Н2); 3.83 (m, 4 Н, signal overlapping
2 СH2Ph); 4.49 (dd, 2 Н, С(6)Н2, 2J = 16.8); 4.52 (s, 1 Н, С(13)Н); 5.34 (q, 2 Н, С(4)Н2, 2J = 12.9);
7.09—7.61 (m, 14 Н, 3 Ar)
1.98, 2.08, 2.15, 2.17 (all s, 3 H each, 4 Ме); 3.82, 3.99 (both d, 1 H each, С(10)Н2 or С(12)Н2,
2J = 11.9); 3.89, 4.09 (both d, 1 H each, С(12)Н2 or С(10)Н2, 2J = 12.2); 4.71 (s, 1 Н, С(13)Н);
5.12 (q, 2 Н, С(6)Н2, 2J = 17.1); 5.70 (q, 2 Н, С(4)Н2, 2J = 13.3); 6.40—7.59 (m, 10 Н, 3 Ar)
1.84, 2.20, 2.59, 2.71 (all m, 8 Н, (СН2)2N(CH2)2); 2.19, 2.25, 2.37 (all s, 3 H each, 3 NCH3);
3.04 (dd, 2 Н, С(10)Н22or С(12)Н2, 2J = 11.2); 3.16 (m, 2 Н, С(12)Н2 or С(10)Н2);
4.41 (dd, 2 Н, С(6)Н2, J = 16.7); 5.13 (dd, 2 Н, С(4)Н2, 2J = 12.8)
2240 (C≡N);
1649 (C=N)
2250 (C≡N);
1655 (C=N)
9a
9b
2237 (C≡N);
1650 (C=N)
2240 (C≡N):
1650 (C=N)
1.86, 2.20, 2.61, 2.68 (all m, 8 Н, (СН2)2N(CH2)2); 2.19 (s, 3 Н, NCH3); 2.99—3.22 (m, 4 Н,
2
С(10)Н2 and С(12)Н2, signal overlapping); 3.72 (q, 2 Н, СН2Ph, J = 13.2); 3.74 (q, 2 Н, СН2Ph,
2J = 13.4); 4.47 (dd, 2 Н, С(6)Н2, 2J = 17.0); 5.18 (dd, 2 Н, С(4)Н2, 2J = 12.9);
7.20—7.34 (m, 10 Н, 2 Ph)
9c
9d
9e
2242 (C≡N);
1650 (C=N)
1.84, 2.23, 2.58, 2.73 (all m, 12 Н, 2 NCH2CH2, (СН2)2N(CH2)2); 2.07 (m, 4 Н, 2 CH2Ph);
2.19 (s, 3 Н, NCH3); 3.04—3.26 (m, 4 Н, С(10)Н2, С(12)Н2, signal overlapping);
4.47 (dd, 2 Н, С(6)Н2, 2J = 17.1); 5.13 (dd, 2 Н, С(4)Н2, 2J = 12.7); 6.93—7.22 (m, 10 Н, 2 Ph)
1.76, 2.23, 2.35, 2.53, 2.71 (all m, 8 Н, (СН2)2N(CH2)2); 2.18 (s, 3 Н, NCH3);
3.72 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.4); 3.82 (m, 2 Н, С(12)Н2 or С(10)Н2);
5.10 (dd, 2 Н, С(6)Н2, 2J = 16.8); 5.13 (dd, 2 Н, С(4)Н2, 2J = 13.4); 6.70—7.20 (m, 10 Н, 2 Ph)
1.79, 2.33, 2.54, 2.71 (all m, 8 Н, (СН2)2N(CH2)2); 2.19 (m, 9 Н, 2 ArCH3, NCH3);
3.63 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.8); 3.74 (m, 2 Н, С(12)Н2 or С(10)Н2);
5.06 (dd, 2 Н, С(6)Н2, 2J = 16.9); 5.65 (dd, 2 Н, С(4)Н2, 2J = 13.3);
2238 (C≡N);
1658 (C=N)
2245 (C≡N);
1657 (C=N)
6.63 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.4); 6.80 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.5)
1.84, 2.33, 2.59, 2.72 (all m, 8 Н, (СН2)2N(CH2)2); 2.20 (s, 3 Н, NCH3);
3.61 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.1); 3.73 (dd, 2 Н, С(12)Н2 or С(10)Н2, 2J = 12.5);
5.09 (m, 2 Н, С(6)Н2); 5.73 (dd, 2 Н, С(4)Н2, 2J = 13.3); 6.59—6.98 (m, 8 Н, 2 4ꢀFС6Н4)
1.86, 2.32, 2.60, 2.72 (all m, 8 Н, (СН2)2N(CH2)2); 2.21 (s, 3 Н, NCH3);
3.66 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.0); 3.76 (m, 2 Н, С(12)Н2 or С(10)Н2);
5.11 (dd, 2 Н, С(6)Н2, 2J = 17.4); 5.74 (dd, 2 Н, С(4)Н2, 2J = 13.6);
9f
2233 (C≡N);
1657 (C=N)
9g
2240 (C≡N);
1656 (C=N)
6.73 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 9.0); 6.94 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.9)
0.97 (t, 3 Н, NCH2CH3, 3J = 7.0); 1.85, 2.20, 2.65, 2.76 (all m, 8 Н, (СН2)2N(CH2)2);
2.26 (s, 3 Н, NCH3); 2.37 (m, 5 Н, signal overlapping NCH3, NCH2CH3);
3.05 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 11.0); 3.20 (m, 2 Н, С(12)Н2 or С(10)Н2);
4.41 (dd, 2 Н, С(6)Н2, 2J = 16.7); 5.11 (dd, 2 Н, С(4)Н2, 2J = 12.6)
9h
2245 (C≡N);
1650 (C=N)
3
9i
9j
2238 (C≡N);
1653 (C=N)
0.97 (t, 3 Н, NCH2CH3, J = 7.0); 1.37—1.83, 2.21, 2.63—2.76 (all m, 26 Н, 2 С5Н9,
3
(СН2)2N(CH2)2); 2.37 (q, 2 Н, NCH2CH3, J = 7.0); 2.94—3.19 (m, 4 Н, С(10)Н2 and С(12)Н2,
signal overlapping); 4.55 (dd, 2 Н, С(6)Н2, 2J = 17.0); 5.35 (dd, 2 Н, С(4)Н2, 2J = 12.6)
0.98 (t, 3 Н, NCH2CH3, 3J = 7.0); 1.86, 2.22, 2.67, 2.76 (all m, 8 Н, (СН2)2N(CH2)2);
2242 (C≡N);
1645 (C=N)
3
2.38 (q, 2 Н, NCH2CH3, J = 7.0); 3.08 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 11.6);
2
3.17 (dd, 2 Н, С(12)Н2 or С(10)Н2, 2J = 11.4); 3.72 (q, 2 Н, СН2Ph, J = 13.4);
2
3.75 (q, 2 Н, СН2Ph, J = 13.3); 4.48 (dd, 2 Н, С(6)Н2, 2J = 17.1); 5.17 (dd, 2 Н,
С(4)Н2, 2J = 12.7); 7.20—7.35 (m, 10 Н, 2 Ph)
(to be continued)

1060
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
Dotsenko et al.
Table 2 (continued)
Comꢀ
pound
IR,
ν/cm–1
1H NMR
(DMSOꢀd6), δ, J/Hz
9k
2241 (C≡N);
1651 (C=N)
0.97 (t, 3 Н, NCH2CH3, 3J = 6.8); 1.83, 2.18, 2.64, 2.75 (all m, 8 Н, (СН2)2N(CH2)2);
3
2.36 (q, 2 Н, NCH2CH3, J = 6.8); 3.07 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 11.0);
3.16 (dd, 2 Н, С(12)Н2 or С(10)Н2, 2J = 11.2); 3.69 and 3.74 (both m, 2 H each, 2 СН2, furfuryl);
4.49 (dd, 2 Н, С(6)Н2, 2J = 16.8); 5.14 (dd, 2 Н, С(4)Н2, 2J = 12.5);
6.21 and 6.30 (both m, 1 H each, 2 С(3)Н, furan); 6.35 and 6.40 (both m, 1 H each, 2 С(4)Н, furan);
7.48 and 7.61 (both m, 1 H each, 2 С(5)Н, furan)
9l
2245 (C≡N);
1658 (C=N)
0.97 (t, 3 Н, NCH2CH3, 3J = 6.9); 1.75, 2.22, 2.58, 2.77 (all m, 8 Н, (СН2)2N(CH2)2);
3
2.37 (q, 2 Н, NCH2CH3, J = 6.9); 3.72 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.6);
3.83 (m, 2 Н, С(12)Н2 or С(10)Н2); 5.10 (dd, 2 Н, С(6)Н2, 2J = 16.4);
5.64 (dd, 2 Н, С(4)Н2, 2J = 13.5); 6.71—7.20 (m, 10 Н, 2 Ph)
9m
2240 (C≡N);
1650 (C=N)
0.97 (t, 3 Н, NCH2CH3, 3J = 7.0); 1.78, 2.20, 2.60, 2.76 (all m, 8 Н, (СН2)2N(CH2)2);
2.03 and 2.19 (both s, 3 H each, 2 ArCH3); 2.38 (q, 2 Н, NCH2CH3, 3J = 7.0);
3.63 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.4); 3.73 (m, 2 Н, С(12)Н2 or С(10)Н2);
5.06 (dd, 2 Н, С(6)Н2, 2J = 17.2); 5.64 (dd, 2 Н, С(4)Н2, 2J = 13.2);
6.63 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.2); 6.80 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.4)
0.97 (t, 3 Н, NCH2CH3, 3J = 7.1); 1.77, 2.22, 2.60, 2.77 (all m, 8 Н, (СН2)2N(CH2)2);
9n
9o
2245 (C≡N);
1656 (C=N)
3
1.97 and 2.15 (both s, 3 H each, 2 ArCH3); 2.38 (q, 2 Н, NCH2CH3, J = 7.1);
3.69 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.6); 3.77 (m, 2 Н, С(12)Н2 or С(10)Н2);
5.11 (dd, 2 Н, С(6)Н2, 2J = 17.2); 5.65 (br.pseudotriplet, 2 Н, С(4)Н2, 2J = 13.6); 6.45—7.05 (m, 8 Н, 2 Ar)
0.98 (t, 3 Н, NCH2CH3, 3J = 6.8); 1.84, 2.23, 2.65, 2.77 (all m, 8 Н, (СН2)2N(CH2)2);
2242 (C≡N);
1654 (C=N)
3
2.39 (q, 2 Н, NCH2CH3, J = 6.8); 3.65 (dd, 2 Н, С(10)Н2 or С(12)Н2, 2J = 12.8);
3.76 (m, 2 Н, С(12)Н2 or С(10)Н2); 5.11 (m, 2 Н, С(6)Н2); 5.64 (dd, 2 Н, С(4)Н2, 2J = 13.2);
6.73 (dd, 4 Н, 4ꢀClС6Н4, 3J = 8.6); 6.94 (dd, 4 Н, 4ꢀМеС6Н4, 3J = 8.3)
Melting points were measured on a Kofler hot stage and are
given uncorrected. The starting thiolates 1a,b were prepared
according to a known procedure.25 NꢀAlkylpiperidinꢀ4ꢀones 10
were commercial chemicals (Acros). Cyanothioacetamide 11
was synthesized from malononitrile and hydrogen sulfide.31
Thiolates 8 were prepared according to a known method26 and
as described below.
(2 C≡N). 1H NMR (DMSOꢀd6), δ: 1.17 (t, 3 H, NCH2CH3,
3J = 6.8 Hz); 1.83 (m, 4 H, C(3´)H2, C(5´)H2); 3.03 (q, 2 H,
NCH2CH3, 3J = 6.8 Hz); 3.29 (m, 4 H, C(2´)H2, C(6´)H2);
5.62 (br.s, 2 H, NH2); 8.29 (s, 1 H, NH).
3,5,7,12ꢀTetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ1,9ꢀdiꢀ
carbonitriles 2 (general procedure). An excess (4—5 mL) of 37%
HCHO was added to a suspension of an appropriate thiolate
1a,b (2.5 mmol) in EtOH (20 mL) and the mixture was heated
with stirring to complete dissolution. An appropriate primary
amine (5.0 mmol) was added in one portion to the resulting
solution. The mixture was refluxed with vigorous stirring for
3 min and then stirred at ~20 °C for 5 h. The precipitate of
compound 2 was filtered off and washed three times with EtOH
and heptane. The physicochemical characteristics of comꢀ
pounds 2 are specified in Tables 1 and 2.
5,11ꢀDisubstituted 1´ꢀalkylꢀ8ꢀthioxospiro[3,5,7,11ꢀtetraꢀ
azatricyclo[7.3.1.02,7]tridecꢀ2ꢀeneꢀ13,4´ꢀpiperidine]ꢀ1,9ꢀdiꢀ
carbonitriles 9 (general procedure). Thiolate 8 (2 mmol) was
thoroughly pulverized in a mortar, mixed with an excess of 37%
formalin (3.5—4 mL), and heated with stirring for 2 min. Then
EtOH (5—7 mL) and an appropriate primary amine (4.1 mmol)
were added. The mixture was refluxed with stirring for 3—5 min
to complete dissolution of thiolate 8, filtered through a paper
filter, and left at ~20 °C for 48 h. The crystals of compounds
9a—o were filtered off and washed with EtOH and heptane. The
physicochemical characteristics of compounds 9 are specified in
Tables 1 and 2.
9ꢀAzaꢀ3ꢀazoniaspiro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolates (8).
An appropriate piperidone 10a,b (25 mmol) and Nꢀmethylꢀ
morpholine (0.55 mL, 5 mmol) were added to a suspension of
cyanothioacetamide 11 (5 g, 50 mmol) in EtOH (40 mL). The
mixture was heated with vigorous stirring to complete homoꢀ
genization. (Caution! Hydrogen sulfide evolves!) The reaction mixꢀ
ture was stirred at ~25 °C for 6 h and left for ~14 h. Then
a double volume of acetone was added and the mixture was
stirred for 2 h. The yellowish orange precipitate of thiolate 8a,b
was filtered off, washed with acetone and ether, and used in
subsequent transformations without additional purification.
10ꢀAminoꢀ7,11ꢀdicyanoꢀ3ꢀmethylꢀ9ꢀazaꢀ3ꢀazoniaspiꢀ
ro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolate (8a). The yield was 82%,
m.p. 225—230 °C (decomp.). Found (%): C, 55.92; H, 5.81;
N, 26.73. C12H15N5S. Calculated (%): C, 55.15; H, 5.79;
N, 26.80. IR, ν/cm–1: 3410, 3310, 3200 (NH, NH2); 2158
(2 C≡N). 1H NMR (DMSOꢀd6), δ: 1.81 (m, 4 H, C(3´)H2,
C(5´)H2); 2.71 (s, 3 H, NMe); 3.29 (m, 4 H, C(2´)H2, C(6´)H2);
5.63 (br.s, 2 H, NH2); 8.29 (s, 1 H, NH).
10ꢀAminoꢀ7,11ꢀdicyanoꢀ3ꢀethylꢀ9ꢀazaꢀ3ꢀazoniaspiꢀ
ro[5.5]undecaꢀ7,10ꢀdieneꢀ8ꢀthiolate (8b). The yield was 84%,
m.p. 240—245 °C (decomp.). Found (%): C, 57.24; H, 6.26;
N, 25.30. C13H17N5S. Calculated (%): C, 56.70; H, 6.22;
N, 25.43. IR, ν/cm–1: 3420, 3320, 3195 (NH, NH2); 2163
Singleꢀcrystal Xꢀray diffraction analysis of compound 2a was
carried out on an Enraf—Nonius CADꢀ4 automatic fourꢀcircle
diffractometer (CuꢀKα radiation, λ = 1.54178 Å, scan rate ratio
2θ/ω = 1.2, θ
= 65°, sphere segment 0 < h < 10, 0 < k < 12,
max

Tetraazatricyclo[7.3.1.02,7]tridecꢀ2ꢀenes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 5, May, 2007
1061
–36 < l < 36) at ~20 °C for a single crystal with the linear
dimensions 0.19×0.32×0.56 mm. The total number of reflecꢀ
tions was 6027, out of which 5356 reflections were independent;
Rint = 0.023). The crystals of compound 2a are monoclinic: a =
9.212(2) Å, b = 11.295(3) Å, c = 30.984(8) Å, β = 95.56(2)°, V =
3208.6(1.4) Å3, M = 606.7, Z = 4, dcalc = 1.26 g cm–3, µ =
12.47 cm–1, F(000) = 1280, space group P21/n (No. 14). The
structure was solved by the direct method and refined by the
leastꢀsquares method in the fullꢀmatrix anisotropic approximaꢀ
tion with the CRYSTALS program package.32 In refinement,
3906 reflections with I > 3σ(I ) were used (397 parameters reꢀ
fined, the number of reflections per parameter was 9.8); 80% of
the H atoms were located from the electron density difference
map; the positions of the other H atoms were calculated geoꢀ
metrically. All the H atoms were refined with fixed coordinates
and thermal parameters. The Chebyshev weighting scheme33
with five parameters (1.11, –0.45, 0.33, –0.56, and –0.20)
was used in refinement. Final residuals were R = 0.048 and
Rw = 0.052, GOOF = 1.113. The residual electron densities
7. HaoꢀXin Shi, HaiꢀJian Shi, and Z. Wang, Youji Huaxue,
2000, 20, 344; Chem. Abstrs, 2000, 133, 120280c.
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A. M. Mahmoud, Z. Naturforsch., Teil B, 1997, 52, 1401;
Chem. Abstrs, 1998, 128, 88906v.
9. Haijian Shi, Haoxin Shi, and Z. Wang, J. Heterocycl. Chem.,
2001, 38, 929.
10. Haijian Shi, Z. Wang, and Haoxin Shi, Chimia, 1997,
51, 529.W
11. Haijian Shi, Z. Wang, and Haoxin Shi, Synth. Commun.,
1999, 29, 2027.
12. S. Yadav Lal Dhar, A. Vaish, and S. Sharma, J. Agric. Food
Chem., 1994, 42, 811.
13. Z. A. Hozein, J. Chem. Res. (S), 2000, 3, 99.
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from the difference Fourier synthesis were 0.32 and –0.31 e Å–3
.
Absorption correction was applied by azimuthal scanning.34 The
comprehensive Xꢀray diffraction data for compound 2a have been
deposited with the Cambridge Crystallographic Data Center
(CCDC 611690; CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: +44ꢀ1223/336ꢀ033; eꢀmail: deposit@ccdc.cam.ac.uk;
http://www.ccdc.cam.ac.uk).
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Received October 12, 2006;
in revised form February 14, 2007