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Mao, J.; Guo, J.; Ji, S. The use of bifunctional copper catalyst in
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EtOAc (2
chlorovinylsulfones 2 and 3 see Table 1.
:
1) as eluent. The properties of obtained 2-
[7]
Diffraction data were collected at –100°C on a Bruker-Nonius
KappaCCD diffractometer using graphite monochromated Mo-Kα
radiation (λ = 0.71073 Å). The crystal structure of 3 was solved by
direct methods [16] and refined by full-matrix least squares [17].
All nonhydrogen atoms were refined in anisotropical
approximation, all H-atoms were refined by riding model. Crystal
data for 3: monoclinic; a = 13.7129(3), b = 9.3599(3), c =
10.1606(3) Å, β = 126.011(1)°; V = 1054.92(5) Å3, Z = 4, µ = 0.73
mm–1; space group is Cc. A total of 2342 reflection intensities were
collected up to 2θmax
= 58°; for structure refinement 1330
independent reflections with I > 3σ(I) were used. The final R-factor
is 0.040. For further details, see crystallographic data for 3
deposited with the Cambridge Crystallographic Data Centre as
Supplementary Publication Number CCDC 827292. Copies of the
data can be obtained, free of charge, on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK.
Ābele, E.; Višņevska, J. Synthesis and Suzuki reaction of (E)-
chlorovinyl sulfides and sulfones. Latvian J. Chem., 2008, (3), 263-
267.
Typical procedure for the synthesis of enynes 1-3a-d or alkynes
3b’-d’. Mixture of (E)-2-chlorovinylsulfone 1-3 (1 mmol), alkyne
(1.5 mmol), PdCl2(PPh3)2 (0.035 g, 0.05 mmol), CuI (0.019 g, 0.1
mmol), anhydrous K3PO4 (0.425 g, 2 mmol) in dry dioxane (2 ml)
was heated at 100oC (in the synthesis of product 3a 50oC was used)
for 24 h in glass reactor under argon. Reaction mixture was filtered
and solvent was removed under reduced pressure and crude residue
was chromatographed on silica using hexane: EtOAc (2 : 1 or 4 : 1)
as eluent to obtain products 1-3a-d and 3b’-d’.
Monge, A.; del Carmen Pena, M.; Palop, J.A.; Caldero, J.M.; Roca,
J.; Garcia, E.; Romero, G.; del Rio, J.; Lasheras, B. Synthesis of 2-
piperazinylbenzothiazole and 2-piperazinylbenzoxazole derivatives
with 5-HT3 antagonists and 5-HT4 agonist properties. J. Med.
Chem., 1994, 37 (9), 1320-1325.
Prilezhaeva, E.N.; Schmonina, L.I. Synthesis on the base of 2-
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(a) Garcia Ruano, J.L.; Aleman, J., Garcia Ruano C. Oxidative
addition of Pd(0) to Ar-SO2R bonds: Heck-type reactions of
sulfones. Org. Lett., 2006, 8 (13), 2683-2686; (b) Song, R.-J., Liu,
Y., Liu, Y.-Y., Li, J.-H. Palladium catalyzed conjugate addition to
electron-deficient alkynes with benzenesulfinic acid derived from
1,2-bis(phenylsulfonyl)ethane: selective synthesis of (E)-vinyl
sulfones. J. Org. Chem., 2011, 76 (3), 1001-1004.
Vollhardt, K.P.C.; Winn, L.S. Stereospecific syntheses of cis- and
trans-1,6-bistrimethylsilyl-hex-3-ene-1,5-diyne. Tetrahedron Lett.,
1985, 26 (6), 709-712; (b) Liang, Y.; Tao, L.-M.; Zhang, Y.-H.; Li,
J.-H. Palladium-catalyzed cross-coupling reactions of 1,2-
diiodoalkenes with terminal alkynes: selective synthesis of
[8]
[9]
[6]
Typical procedure for the synthesis of (E)-2-chlorovinylsulfones 1-
3. 1,1,2-Trichloroethane (4.1 ml, 44mmol) was added under stirring
to the mixture of thiol (20 mmol), K2CO3 (8.28 g, 60 mmol), KI
(6.64 g, 40 mmol) and 18-crown-6 (528 mg, 2 mmol) in 25 ml of
xylene. Reaction mixture was refluxed 2 hours, cooled and filtered.
The solvent was evaporated under reduced pressure to obtain 2-
(2,2-dichloroethanesulfanyl)hetarenes.
2-(2,2-
Dichloroethanesulfanyl)pyridine. Yellow liquid. 1H NMR spectra
(400 MHz, δ): 3.91 (d, 2H, J = 7 Hz, CH2), 5.99 (t, 1H, J = 7 Hz,
CH), 7.02 (m, 1H, 5-H), 7.20 (d, 1H, J = 8 Hz, 3-H), 7.51 (m, 1H,
4-H), 8.42 (d, 1H, J = 5 Hz, 6-H). 13C NMR spectra: 42.12
(CH2Cl), 71.69 (CHCl2), 120.09, 122.30, 136.29, 149.52, 156.41.
MS (m/z, %): 207 (M+, 4), 172 (50), 136 (37), 124 (15), 111 (100),
78 (52), 67 (20), 51 (18). 2-(2,2-Dichloroethanesulfanyl)
benzothiazole. Yellow liquid.1H NMR spectra (400 MHz, δ): 4.07
(d, 2H, J = 7 Hz, CH2), 6.19 (t, 1H, J = 7 Hz, CHCl2), 7.31 and 7.46
(both t, 2H, J = 8 Hz, 5-H and 6-H), 7.76 (d, 1H, J = 8 Hz, 4-H),
7.87 (m, 1H, J = 8 Hz, 7-H Ph protons). 13C NMR spectra: 44.58
(CH2Cl), 70.66 (CHCl2), 121.12, 121.77, 124.68, 126.22, 135.41,
152.73, 164.12. MS (m/z, %): 263 (M+, 13), 228 (21), 192 (9), 180
(4), 167 (100), 108 (18). Finely powdered KOH (2.24 g, 20 mmol)
in 25 ml of toluene were added to reaction mixtures containing 2-
(2,2-dichloroethanesulfanyl)hetarenes. Reaction mixture was
stirred 45 minutes (GC-MS control) at room temperature, filtered
and evaporated. The residue was purified by column
chromatography using toluene as eluent to obtain intermediate 2-
chlorovinylsulfides. E-2-(2-Chlorovinylsulfanyl) pyridine. Yellow
liquid. 1H NMR spectra (400 MHz, δ): 6.45 and 7.05 (both d, 1H, J
= 13 Hz, CH=CH), 7.07 (m, 1H, 5-H), 7.18 (d, 1H, J = 8 Hz, 3-H),
7.56 (m, 1H, 4-H), 8.46 (d, 1H, J = 5 Hz, 6-H). 13C NMR spectra:
120.80, 120.53, 121.68, 122.45, 136.65, 149.85, 157.02. MS (m/z,
%): 171 (M+, 3), 136 (100), 111 (7), 92 (7), 78 (59), 67 (9), 51 (29).
[10]
[11]
[12]
[13]
unsymmetrical
Synthesis, 2008, (24), 3988-3994.
buta-1,3-diynes
and
2-ethynylbenzofurans.
[14]
[15]
[16]
Kim, S.H.; Chang, S. Highly efficient and versatile Pd-catalyzed
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1
E-2-(2-Chlorovinylsulfanyl)benzothiazole. Yellow liquid. H NMR
spectra (400 MHz, δ): 6.71 and 6.97 (both d, 1H, J = 13 Hz,
CH=CH), 7.33 and 7.45 (both t, 2H, J = 8 Hz, 5-H and 6-H), 7.78
and 7.92 (both d, 2H, J = 8 Hz, 4-H and 7-H). 13C NMR spectra:
120.60, 121.03, 122.09, 124.72, 126.32, 126.39, 135.39, 153.44,
164.42.MS (m/z, %): 227 (M+, 2), 192 (100), 148 (10), 108 (10), 96
(10), 69 (9). m-Chloroperoxybenzoic acid (15.35 g, 88.9 mmol)
was added portionwise under stirring to the mixture of (E)-2-
chlorovinylsulfides (29.8 mmol) in 50 ml of dry dichloromethane.
Reaction mixture was stirred overnight at room temperature and
filtered. The filtrate was concentrated at reduced pressure. The
residue was purified by column chromatography using hexane :
[17]
Mackay, S.; Dong, W.; Edwards, C.; Henderson, A.; Gilmore, C.J.;
Stewart, N.; Shankland, K.; Donald, A. maXus, Integrated
Crystallography Software, 2003, Bruker-Nonius and University of
Glasgow.