CROSS-COUPLING OF 2,5-BIS(CHLOROMETHYLIDENE)-1,4-DITHIANE
1721
S
C22H16S2. Calculated, %: С 76.79; H 4.68; S 18.62. Di-
phenyldiacetylene III, mass spectrum, m/z (Irel, %): 202
(100) [M] +, 150 (9), 101 (9).
2
Ph
+
Cl
Cl
S
The main results were obtained on the equipment of
the Baikal analytical center in general use of the Siberian
Branch of the Russian Academy of Sciences. 1H (400.13
МHz) and 13С (100.61 МHz) NMR spectra were reg-
istered on a spectrometer Bruker DPX-400 in CDCl3,
internal reference TMS (1H, 13C). Mass spectra were
obtained on a GC-MS instrument Shimadzu QP5050A
(EI, 70 eV), column SPB-5 ms (60 m).
I
Pd(PPh3)4,
S
Ph
Ph
Ph
CuI, Et NH
2
S
II
Ph
+
ACKNOWLEDGME
III
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grant
no. 11-03-00810).
bridge included in the 1,4-dithiane ring. In contrast to the
known bis(1-buten-3-ynyl) sulfide where the triple bond
is located in the cis-position with respect to the sulfide
bridge [4], in heterocycle II a trans-structure is present.
REFERENCES
2,6-Bis[(E)-3-phenylprop-2-ynylidene]-1,4-dithi-
ane (II). To 116 mg (0.10 mmol) of Pd(PPh3)4 and 29 mg
(0.15 mmol) of CuI in 2 mL of dioxane under an argon
atmosphere was added a solution of 290 mg (4.0 mmol)
of Et2NH in 0.5 mL of dioxane, the mixture was stirred
for 15 min, and then a solution of 107 mg (0.50 mmol)
of dithiane in 2.5 mL of dioxane was added, and 30 min
later was introduced a solution of 306 mg (3.0 mmol) of
phenylacetylene in 1 mLof dioxane. The reaction mixture
was stirred at room temperature for 24 h, diluted with 15
mL of water, extracted with chloroform, the extract was
dried with CaCl2. On removing chloroform in a vacuum
the residue (0.526 g) was chromatographed on silica gel,
eluents hexane, then chloroform. We obtained 0.118 g
of diphenyldiacetylene III, fine white crystals, mp 89°С
(87–88ºС [8]) and 0.160 g of a mixture of heterocycle
II and diphenyldiacetylene in the 1 : 1 ratio according to
1H NMR data (calculated yield of heterocycle II 58%].
The obtained mixture of heterocycle II and 1,4-diphenyl-
butadiyne was separated by thin layer preparative chroma-
tography on silica gel, eluent hexane–chloroform, 1 : 1.
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Dithiane II. Yield 66 mg (38%), light yellow plate
4. Volkov, A.N., Kudyakova, R.N., and Trofimov, B.A., Zh.
Org. Khim., 1979, vol. 15, p. 1554.
1
crystals, mp 132–134°С, Rf 0.10–0.28. H NMR spec-
5. Martynov, A.V., Larina, L.I., and Amosova, S.V., Tetrahe-
dron Lett., 2012, vol. 53, p. 1218.
trum, δ, ppm: 3.91 s (4H, CH2), 5.87 s (2H, =CH),
7.31–7.36 m (6H), 7.41–7.47 m (4H). 13С NMR spectrum,
6. Stothers, J.B., Carbon-13 Nuclear Magnetic Resonance
Spectro-scopy, New York: Academic Press, 1972.
7. Metal-Catalyzed Cross-Coupling Reactions, Diedirich, F.,
Stang. P.J., Weinheim, et al., Wiley-VCH, 1998.
8. Kakusawa, N., J. Organometal. Chem., 2005, vol. 690,
p. 2956.
1
δ, ppm: 31.79 t.m (CH2, J 147.1 Hz), 85.16 s (С≡),
96.03 m (C≡), 107.06 d.t (SC=CH, 1J 167.4, 3J 4.4 Hz),
1
123.10 s (Сi), 128.57 d (С3arom, J 160.0 Hz), 128.69 d
1
1
(С4arom, J 161.4 Hz), 131.63 d (С2arom, J 162.6 Hz),
143.26 m (=C–S). Found, %: C 76.98; H 4.64; S 18.38.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013