892
Y. M. Zeng, H.-H. Zeng, and F. M. Liu
Vol 53
attributed to the methoxy protons, a singlet at d 4.12
due to 2-CH, two double singlets at d2.68 and 3.13
assigned to 3-CH2. The remaining 23 aromatic protons
resonated as multiplets in the range d 8.026–6.79. In
MS spectra, molecular ion peaks of all target com-
pounds were obtained from EI-MS, but the intensities
of molecular ion peaks were very faint.
The crystal structure of 6I is illustrated in Figure 1. An
X-ray diffraction study of the compound 6I has shown that
the title compound C38H28N3S2O2Cl crystallizes in
the monoclinic system with space grouping P21/c. The
oxadiazoline ring displays an envelope conformation. The
N1-C16 (1.282 Å) bond length is significantly shorter than
N2-C16 (1.411 Å) bond distances, which clearly indicates
the double bond nature of the N1-C16 bond and the single
bond character of N2-C16. The phenyl ring (C17-C22)
forms dihedral angles with the two phenyls (C10-C15
and C1-C6) is 88.26ꢀ and 72.73ꢀ, respectively. In addition,
the quinoline ring is nearly perpendicular to the benzene
ring C33-C38 with a dihedral angle of 87.30ꢀ.
Intramolecular hydrogen bonds of the type C-H. . .S are
found in the three-dimensional packing arrangement of 6I
(Fig. 2). Atom C7, C8, and C26 acts as a hydrogen bond
donor respectively, via H. . .S bond to generate the adjacent
molecular structures. Furthermore, the structures of 6I is
linked layer by layer, in which up and down are connected
by intermolecular hydrogen bonds(C-H. . .N, C-H. . .Cl)
and a weak intermolecular C-C. . .Cg5 p-ring interaction at
1À X, À1/2 + Y, 1/2 À Z. (Cg5 = center of gravity of a
benzene ring C10-C15). Despite the fact that these interactions
are not considered as formal hydrogen bonds, they contribute
to crystal packing connecting the adjacent molecules in the
crystal structure as illustrated in Figure 2.
appeared, which was filtered, washed with H2O, and dried. The
crude compound was then recrystallized from DMF/ethanol.
General procedure for the synthesis of (2E)-3-(2-phenylthio-
quinolin-3-yl)-1-(4-substituted-phenyl)-2-propen-1-ones (3a–c).
Aceto-phenone (20 mmol) was added to a solution of 2 (20 mmol)
in aqueous KOH (10 mL, 35% KOH) at 0ꢀC. The reaction mixture
was stirred for 2 h at ice bath. After standing overnight, the solid
was collected by filtration and washed with water. The solid was
crystallized from ethanol to give crystals 3a–c. The physical and
analytical data of compound 3 are listed in Tables 4 and 5.
General procedure for the synthesis of 2,3-dihydro-2-(2-
phenylthio-quinolin-3-yl)-4-(4-substituted-phenyl)-1,5-benzothia
zepines (4a–c). Compound 3 (10 mmol) and o-aminothiophenol
(10 mmol) were dissolved in anhydrous ethanol (25 mL) with 1 mL
acetic acid as a catalyst. The reaction mixture was heated under
reflex for 2 h, whereupon no starting materials were evident by
TLC. After cooling, the separated precipitate was collected by
filtration and crystallized from DMF/ethanol to yield compound
4a–c. The physical and analytical data of compound 4 are
presented in Tables 4 and 5.
General procedure for the synthesis of 5-(2-phenylthio-quinolin-
3-yl)-1,3a-diaryl-4,5-dihydro-3aH-[1,2,4]oxadiazolo[5,4-d]
[1,5]benzothiazepines (6a–m). To a solution of 4 (25 mmol) and
benzohydroximinoyl chlorides (1.5 mmol) in 25mL, CH2Cl2 was
added dropwise a solution of Et3N (0.5mL) in the same solvent
(10 mL) at room temperature over a period of 1 h. The reaction
mixture was stirred for an additional 2 days at the same
temperature. The solvent was evaporated under reduced pressure,
and the residue was chromatographed on a silica gel column by
using a mixture of EtOAc/petroleum ether(1:8 = v/v) as eulent to
obtain 6a–m. The physical and analytical data of compound 6a–m
are presented in Tables 6 and 7.
X-ray crystallography.
title compound was obtained from
A single crystal structure of the
solution of
a
CH3COOCH2CH3-CH3CH2OH after slow evaporation at
room temperature. All non-hydrogen atoms were assigned
anisotropic displacement parameters by full-matrix least-
squares in the refinement. All hydrogen atoms were added at
calculated positions and refined using a riding model. The
crystal data and some details of the structure determination
are summarized in Table 1. The selected bond lengths and
bond angles are given in Table 2.
CCDC-820742 contains the supplementary crystallographic
data for 6I. These data can be obtained free of charge from the di-
rector of the Cambridge Crystallographic Data Centre, 12 Union
Fax:+44(0)1223-33 6033.
EXPERIMENTAL
All melting points were recorded on an X-5 micro melting point
apparatus, and temperatures were uncorrected (Maytag, Beijing,
China). The IR spectra were recorded from KBr on a Bruker Tensor
27 spectrophotometer (Bruker Optics, Germany). MS results were
recorded on an Agilent 5975 mass selective detector (Agilent, USA).
X-ray diffraction data were obtained on a Hitachi F-4500 R-AXIS
SPIDER diffractometer (Hitachi, Japan). Element analyses were
performed on a Perkin-Elmer 240 CHN analyzer (Perkin-Elmer,
Germany). Reactions were monitored by TLC. All starting materials
and solvents were commercial materials, dried or purified by standard
methods when necessary. Compounds 1(22) and 5(23) were prepared
according to the literature methods (Tables 1–3).
REFERENCES AND NOTES
[1] Tseng, C. H.; Tzeng, C. C.; Yang, C. L.; Lu, P. J.; Chen, H. L.;
Li, H. Y.; Chuang, Y. C. J Med Chem 2002, 53, 61.
[2] Yadav, J. S.; Reddy Subba, B. V.; Premalatha, K.; Murty, M. S. R.
J Mol Catalysis A: Chemical 2007, 271, 161.
[3] Sonar, S. S.; Sadaphal, S. A.; Pokalwa, R. U.; Shingate, B. B.;
Shingare, M. S. J Het Chem 2010, 46, 435.
[4] Klingenstein, R.; Melnyk, P.; Leliveld, S. R.; Ryckebusch, A.;
Korth, C. J Med Chem 2006, 49, 5300.
[5] Suzuki, T.; Fukazawa, N.; San-nohe, K. J Med Chem 1997,
40, 2047.
General procedure for the synthesis of 2-phenylthio-3-quiniline
carboxaldehyde (2). Equimolar amounts of benzenethiol
(20 mmol) and potassium hydroxide (20 mmol) were dissolved
in dimethyl sulfoxide (25 ml). After dissolution of the
reactants, a solution of 2-chloro-3-quinilinecarboxaldehyde (1)
was added to the mixture. The resulting solution was heated for
6 h (85–90ꢀC). The reaction mixture was cooled to room
temperature, then poured into water. A pale yellow precipitate
[6] Baruah, B.; Bhuyan, P. J. Tetrahedron 2009, 65, 7099.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet