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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
Shmuilovich et al.
Table 3 (continued)
Comꢀ
pound
1Н NMR,
H (J/Hz)
19F NMR*,
IR,
ν/cm–1
δ
δ
F
5b
5с
5d
6a
6b
6c
3.49 (d, 2 Н, CН2, J = 7.0); 4.31 (br.s, 2 H, NH2); 4.60 (t, 1 Н,
CН, J1 = J2 = 7.0); 6.54 (td, 1 Harom, J1 = J2 = 8.0, J3 = 1.5);
1.93, 13.12, 21.38
(2 : 1 : 2)
1495, 1522 (C—F);
1711 (C=O);
3374, 3480 (NH2)
6.67 (dd, 1 Harom, J1 = 8.0, J2 = 1.5); 7.04—7.27 (m, 7 Harom
)
3.67 (d, 2 H, CН2, J = 7.0); 4.44 (br.s, 2 H, NH2); 5.03 (t, 1 Н,
CН, J1 = J2 = 7.0); 6.56 (t, 1 Harom, J1 = J2 = 8.0); 6.70 (d, 1 Harom
J = 8.0); 7.06 (d, 1 Harom, J = 8.0); 7.14 (t, 1 Harom, J1 = J2 = 8.0)
–0.14, 2.46, 6.69,
14.20, 20.47, 21.59
(2 : 2 : 1 : 1 : 2 : 2)
,
3.64 (d, 2 H, CН2, J = 7.0); 4.40 (br.s, 4 H, 2 NH2); 5.00 (t, 1 Н,
CН, J1 = J2 = 7.0); 6.55 (t, 1 Harom, J1 = J2 = 8.0); 6.70 (m, 3 Harom);
7.01—7.21 (m, 3 Harom); 7.54 (d, 1 Harom, J = 8.0)
–0.23, 6.79, 20.46,
21.06, 29.36
(2 : 1 : 2 : 2 : 2)
4.43 (с, 2 H, NH2); 6.63—6.75 (m, 2 Harom); 7.17 (t, 1 Harom
,
22.84, 27.75
(1 : 1)
1477 (C—F);
1671 (C=O);
3394, 3481 (NH2)
J1 = J2 = 8.0); 7.44—7.66 (m, 4 Harom); 7.99 (d, 2 Harom, J = 8.0);
7.77, 7.83 (AB system, 2 Н, СН=СН)
4.45 (br.s, 2 H, NH2); 6.55—7.65 (m, 11 Н, СН=СН, 9 Harom
)
21.15, 29.25
(1 : 1)
1469 (C—F);
1657 (C=O);
3393, 3491 (NH2)
4.40 (br.s, 4 H, 2 NH2); 6.55—7.68 (m, 10 Н, СН=СН, 8 Harom
)
21.36, 23.28,
27.62, 29.29
(1 : 1 : 1 : 1)
1469 (C—F);
1635(C=O);
3383, 3473 (NH2)
* The intensity ratio is given in parentheses.
and poured onto ice. The precipitate that formed was filtered
off, washed with water, and dried in air. According to the data of
1Н and 19F NMR spectroscopy, the isolated precipitate (0.39 g)
contained a mixture of compounds 6a and 5a in the ratio 9 : 1.
Conversion of thiaꢀadducts 5a—с. Three droplets of concenꢀ
trated HCl were added to a solution of compound 5a—с (0.3 g)
in MeOH (15 mL) and the mixture was refluxed for 3 h, cooled,
and poured onto ice. In the case of the starting compound 5а,
the precipitate that formed was filtered off, washed with water,
and dried in air. Oily residues that formed from thiaꢀadducts
5b—с were extracted with diethyl ether and the extract was dried
with CaCl2 and evaporated. The reaction products were analyzed
by 1Н and 19F NMR methods.
4с, 5с, and 5d). The product, whose molecular weight correꢀ
sponded to benzothiazepine 4е, was found in the reaction mixꢀ
ture by the LCꢀMS method.
Reactions of chalcones 1a—с with oꢀaminothiophenol zinc salt
(general procedure). oꢀAminothiophenol zinc salt (3) (380 mg,
2 mmol) was added to a suspension of chalcone 1а—с (1 mmol)
in DMF (20 mL). The mixture was magnetically stirred at room
temperature for 5 h and poured onto ice. The precipitate that
formed was filtered off and dissolved in diethyl ether. A residue
of the zinc salt was filtered off and the filtrate was dried with
MgSO4 and evaporated. The products were isolated by chromaꢀ
tography on a column with Al2O3 (benzene as eluent). 3ꢀ[4ꢀ(2ꢀ
Aminophenylthio)ꢀ2,3,5,6ꢀtetrafluorophenyl]ꢀ1ꢀphenylpropꢀ2ꢀ
enꢀ1ꢀone (6a), 1ꢀ[4ꢀ(2ꢀaminophenylthio)ꢀ2,3,5,6ꢀtetrafluoroꢀ
phenyl]ꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀone (6b), and 1,3ꢀbis[4ꢀ(2ꢀ
aminophenylthio)ꢀ2,3,5,6ꢀtetrafluorophenyl]propꢀ2ꢀenꢀ1ꢀone
(6с) were obtained.
The reaction mixture obtained in the case of compound 5b
was separated by chromatography on Al2O3: at first, column
chromatography (hexane as eluent) and then preparative TLC
(benzene—hexane (1 : 1) mixture as eluent) were used. Two fracꢀ
1
tions were obtained, which contained according to the H and
19F NMR spectral data 3ꢀ(perfluorophenyl)ꢀ1ꢀphenylpropꢀ2ꢀenꢀ
1ꢀone (1b) and 4ꢀ(perfluorophenyl)ꢀ2ꢀphenylꢀ2,3ꢀdihydroꢀ
benzo[b][1,5]thiazepine (4d) (fraction 1) and substituted in the
fluorinated ring benzothiazepine 4b and 1ꢀ[4ꢀ(2ꢀaminophenylꢀ
thio)ꢀ2,3,5,6ꢀtetrafluorophenyl]ꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀone (6b)
(fraction 2). Compounds 1b, 4b, and 6b were identified in mixꢀ
References
1. D. N. Dhar, The Chemistry of Chalcones and Related Comꢀ
pounds, WileyꢀInterscience, New York—Chichester—Brisꢀ
bane—Toronto, 1981, 285 pp.
2. N. A. Orlova, E. F. Maior, T. N. Gerasimova, Izv. Sib. Otd.
Akad. Nauk SSSR, Ser. Khim. Nauk, 1989, 3, 117 [Izv. Sib.
Otd. Akad. Nauk SSSR, Ser. Khim. Nauk, 1989, 3, 117
(in Russian)].
3. A. Lévai, Chem. Heterocycl. Comp., 1986, 22, 1161.
4. M. Kodomari, T. Noguchi, T. Aoyama, Synth. Commun.,
2004, 10, 1783.
5. G. L. Khatik, R. Kumar, A. K. Chakraborti, Synthesis, 2007,
4, 541.
1
tures by the Н and 19F NMR spectral data and by comparison
with the spectra of authentic samples. We failed to isolate thiꢀ
azepine 4d in the pure form from the reaction mixture. Two
products, whose molecular weights corresponded to compounds
1b and 4d, were found in the sample of fraction 1 by the LCꢀMS
method.
The components of the reaction mixture obtained from comꢀ
pound 5с were identified by comparison of the 1Н and 19F NMR
spectra with the spectra of authentic samples (for compounds 1с,