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3789
under a positive pressure of argon. Air- and moisture sensitive re-
agents and solvents were transferred via syringe, and were intro-
duced into reaction vessels through a rubber septum. All the
reactions were monitored by thin layer chromatography (TLC) car-
ried out using Merck 60 F254 plates with a 0.25 mm thickness. Col-
umn chromatography was carried out using Merck silica gel 60
(230–400 mesh).
Hept-1-en-2-yl(phenyl)sulfide (5g) [43]: 1H NMR (200 MHz,
CDCl3) d 0.88 (t, J = 7.0 Hz, 3H); 1.15–1.38 (m, 4H); 1.55 (qui,
J = 7.2 Hz, 2H); 2.22 (t, J = 7.4 Hz, 2H); 4.87 (s, 1H); 5.14 (s, 1H);
7.29–7.46 (m, 5H). 13C NMR (50 MHz, CDCl3) d 14.0, 22.4, 28.1,
31.1, 36.5, 112.4, 127.5, 127.6, 129.0, 133.2, 146.1.
(E)-Phenyl(styryl)selenide (6a) [44]: 1H NMR (200 MHz, CDCl3)
d 6.84 (d, J = 15.6 Hz, 1H); 7.15 (d, J = 15.6 Hz, 1H); 7.20–7.29 (m,
8H); 7.48–7.60 (m, 2H). 13C NMR (100 MHz, CDCl3) d 119.3,
125.9, 127.2, 127.4, 128.5, 129.1, 130.1, 132.3, 134.9, 136.8.
(E)-(4-Chlorostyryl)(phenyl)selenide (6b) [37]: 1H NMR
(200 MHz, CDCl3) d 7.05 (d, J = 16.4 Hz, 1H); 7.50 (d, J = 16.4 Hz,
1H); 7.15–7.35 (m, 8H); 7.72–7.75 (m, 2H). 13C NMR (100 MHz,
CDCl3 d 120.7, 127.1, 127.6, 128.7, 129.4, 129.6, 132.8, 133.0,
133.1, 135.4.
3.2. General procedure for the uncatalyzed preparation of vinylic
chalcogenides
To a two-necked 50 mL round-bottomed flask equipped with a
Dean–Stark and a reflux condenser were added diphenyl dichalc-
ogenides (2.5 mmol), ethanol (10 mL), sodium borohydride
(0.270 g, 7.5 mmol) and the mixture was stirred at room tempera-
ture. After the mixture was clear (ca. 10 min), DMF (15 mL) and the
vinylic halide (5 mmol) were added. Then the mixture was stirred
at reflux temperature for 2 h while the ethanol was collected in a
Dean–Stark apparatus. The reaction mixture was cooled to room
temperature and extracted with ethyl acetate (3 Â 50 mL). The or-
ganic layer was washed with NH4Cl saturated aqueous solution
(50 mL) and water (100 mL), and dried over MgSO4. The solvent
was removed and the residue was purified by silica-gel chromatog-
raphy eluting with hexanes.
(Z)-Phenyl(styryl)selenide (6c): m.p. 43–45 °C (Lit. [45] 44–
45 °C).
(Z)-(4-Chlorostyryl)(phenyl)selenide (6d): m.p. 80–82 °C. 1H
NMR (400 MHz, CDCl3)
d 6.79 (d, J = 10.4 Hz, 1H); 6.89 (d,
J = 10.4 Hz, 1H); 7.28–7.32 (m, 7H); 7.53–7.58 (m, 2H). 13C NMR
(100 MHz, CDCl3) d 124.9, 127.8, 128.6, 128.8, 129.4, 129.5,
131.3, 132.8, 132.9, 135.7. MS: m/z = 296.0, 295.1, 294.3, 214.0,
179.1, 156.3, 136.0, 101.0, 89.0, 77.1, 51.3. Anal. Calc. for
C14H11ClSe: C: 57.26; H: 3.75. Found: C: 56.83; H: 3.67%.
(Z)-(4-Methylstyryl)(phenyl)selenide (6e) [37]: m.p. 45–47 °C
1H NMR (200 MHz, CDCl3) d 6.69 (d, J = 10.4 Hz, 1H); 6.91 (d,
J = 10.4 Hz, 1H); 7.13–7.31 (m, 8H); 7.52–7.55 (m, 2H). 13C NMR
(50 MHz, CDCl3) d 21.2, 122.7, 127.5, 128.2, 129.0, 129.2, 130.1,
131.7, 132.6, 134.4, 137.1.
3.3. General procedure for the preparation of vinylic chalcogenides
catalyzed by Ni(PPh3)2Cl2
To a two-necked 50 mL round-bottomed flask equipped with a
Dean–Stark and a reflux condenser were added diphenyl dichalc-
ogenides (2.5 mmol), ethanol (10 mL), sodium borohydride
(0.270 g, 7.5 mmol) and the mixture was stirred at room tempera-
ture. After the mixture was clear (ca. 10 min), DMF (15 mL) was
added. After 10 min the vinylic halide (5 mmol) and Ni(Ph3P)2Cl2
(0.170 g; 0.25 mmol) were added. Then the mixture was stirred
at 60 °C (for diphenyldisulfide), at 70 °C (for diphenyldiselenide)
or 110 °C (for diphenylditelluride) for 2 h. After that, was cooled
to room temperature and extracted with ethyl acetate
(3 Â 50 mL). The organic layer was washed with NH4Cl saturated
aqueous solution (50 mL) and water (100 mL), and dried over
MgSO4. The solvent was removed and the residue was purified
by silica-gel chromatography eluting with hexanes.
Phenyl-(1-phenylvinyl)selenide (6f) [46]: 1H NMR (200 MHz,
CDCl3) d 5.37 (s, 1H); 5.90 (s, 1H); 7.21–7.30 (m, 8H); 7.50–7.59
(m, 2H). 13C NMR (100 MHz, CDCl3) d 117.8, 127.3, 127.7, 128.2,
128.3, 129.2, 131.5, 134.1, 140.1, 141.9.
Hept-1-en-2-yl(phenyl)selenide (6g) [47]: 1H NMR (400 MHz,
CDCl3) d 0.86 (t, J = 7.0 Hz, 3H); 1.20–1.32 (m, 4H); 1.49 (qui,
J = 7.2 Hz, 2H); 2.31 (t, J = 7.4 Hz, 2H); 5.42 (s, 1H); 5.96 (s, 1H);
7.20–7.30 (m, 3H); 7.77–7.79 (m, 2H). 13C NMR (100 MHz, CDCl3)
d 14.0, 22.4, 29.1, 30.9, 42.1, 113.1, 124.3, 127.9, 129.3, 130.7,
139.3.
(E)-Phenyl(styryl)telluride (7a) [48]: 1H NMR (400 MHz, CDCl3)
d 7.08 (d, J = 16.4 Hz, 1H); 7.52 (d, J = 16.4 Hz, 1H); 7.18–7.28 (m,
8H); 7.71–7.73 (d, J = 8.3Hz, 2H). 13C NMR (100 MHz, CDCl3) d
101.5, 113.5, 126.0, 127.7, 127.8, 128.4, 129.4, 137.7, 138.0, 143.1.
(E)-(4-Chlorostyryl)(phenyl)telluride (7b) [49]: 1H NMR
(400 MHz, CDCl3) d 6.98 (d, J = 16.4 Hz, 1H); 7.51 (d, J = 16.4 Hz,
1H); 7.15–7.32 (m, 7H); 7.67–7.78 (m, 2H). 13C NMR (100 MHz,
CDCl3) d 102.8, 113.1, 127.2, 128.1, 128.7, 129.5, 133.4, 136.5,
138.1, 141.1.
(E)-Phenyl(styryl)sulfide (5a) [36]: 1H NMR (200 MHz, CDCl3) d
6.70 (d, J = 15.4 Hz, 1H); 6.86 (d, J = 15.4 Hz, 1H); 7.19–7.34 (m,
8H); 7.37–7.42 (m, 2H). 13C NMR (50 MHz, CDCl3) d 123.2, 125.9,
126.7, 127.4, 128.5, 129.0, 129.6, 131.6, 135.1, 136.3.
(E)-(4-Chlorostyryl)(phenyl)sulfide (5b) [37]: 1H NMR
(200 MHz, CDCl3) d 6.51 (d, J = 15.6 Hz, 1H); 6.86 (d, J = 15.6 Hz,
1H); 7.23–7.43 (m, 9H). 13C NMR (50 MHz, CDCl3) d 124.6, 127.3,
127.2, 128.8, 129.2, 129.7, 130.2, 133.1, 134.7, 135.0.
(Z)-Phenyl(styryl)telluride (7c) [50]: m.p. 40–42 °C; 1H NMR
(200 MHz, CDCl3) d 7.06 (d, J = 10.6 Hz, 1H); 7.43 (d, J = 10.6 Hz,
1H); 7.13–7.37 (m, 8H); 7.70–7.75 (m, 2H). 13C NMR (50 MHz,
CDCl3) d 109.15, 115.3, 127.3, 127.4, 128.0, 128.4, 129.3, 136.8,
137.9, 138.8.
(Z)-Phenyl(styryl)sulfide (5c): m.p. 39–41 °C (Lit. [38] 39–42 °C;
Lit. [39] 43–44 °C).
(Z)-(4-Chlorostyryl)(phenyl)sulfide (5d) [40,41]: m.p. 84–86 °C.
1H NMR (400 MHz, CDCl3) d 6.49 (d, J = 10.8 Hz, 1H); 6.46 (d,
J = 10.8 Hz, 1H); 7.18–7.32 (m, 5H); 7.40–7.43 (m, 4H). 13C NMR
(100 MHz, CDCl3) d 125.8, 126.9, 127.3, 128.4, 129.1, 129.9,
130.1, 132.6, 134.9, 135.7.
(Z)-(4-Chlorostyryl)(phenyl)telluride (7d): m.p. 72–74 °C (Lit.
[51] 72.5–74 °C).
(Z)-(4-Methylstyryl)(phenyl)telluride (7e): m.p. 54–56 °C (Lit.
[51] 54.5–55.5 °C).
Phenyl-(1-phenylvinyl)telluride (7f): 1H NMR (200 MHz, CDCl3)
d 5.6 (s, 1H); 6.28 (s, 1H); 7.12–7.30 (m, 6H); 7.60–7.80 (m, 4H). 13C
NMR (100 MHz, CDCl3) d 114.4, 125.2, 127.5, 128.0, 128.1, 129.4,
137.9, 139.1, 142.8. MS: m/z = 310.0, 308.0, 206.9, 180.0, 130.0,
103.3, 77.2, 51.0. Anal. Calc. for C14H12Te: C: 54.62, H: 3.93; Found:
C: 54.82, H: 3.85%.
(Z)-(4-Methylstyryl)(phenyl)sulfide (5e) [41]: m.p. 51–53 °C. 1H
NMR (200 MHz, CDCl3) d 2.36 (s, 3H); 6.43 (d, J = 10.6 Hz, 1H); 6.57
(d, J = 10.6 Hz, 1H); 7.17–7.47 (m, 9H). 13C NMR (50 MHz, CDCl3) d
21.3, 124.8, 127.0, 127.4, 128.7, 129.0, 129.1, 130.0, 133.7, 136.4,
137.0.
Phenyl(1-phenylvinyl)sulfide (5f) [42]: 1H NMR (200 MHz,
CDCl3) d 5.27 (s, 1H); 5.65 (s, 1H); 7.20–7.70 (m, 10H). 13C NMR
(50 MHz, CDCl3) d 115.7, 127.0, 127.3, 128.2, 128.4, 129.0, 131.9,
133.8, 138.7, 144.4.
Hept-1-en-2-yl(phenyl)telluride (7g): 1H NMR (200 MHz,
CDCl3) d 0.86 (t, J = 7.0 Hz, 3H); 1.20–1.35 (m, 4H); 1.49 (qui,
J = 7.2 Hz, 2H); 2.31(t, J = 7.4 Hz, 2H); 5.42 (s, 1H); 5.96 (s, 1H);
7.17–7.27 (m, 3H); 7.76–7.80 (m, 2H). 13C NMR (100 MHz, CDCl3)