1532
Can. J. Chem. Vol. 84, 2006
δ: 134.5, 132.8, 128.7, 59.9, 28.8, 11.5. Anal. calcd. for
C15H16S2: C 69.18, H 6.19; found: C 69.04, H 6.32.
Typical procedure for the microwave-assisted reaction
of thiol with polychloroalkane
A 5.0 mL process vial was charged with polychloroalkane
(2 mL), thiol (0.5 mmol), and DBU (1.0 mmol). The vial
was then capped with a Teflon septum and irradiated with
microwave to 150 °C for 20 min. After cooling, the reaction
mixture was poured into water and extracted with dichloro-
methane (3 × 5 mL). The combined organic phase was dried
over MgSO4 and then filtered. The solvent was evaporated,
and the residue was purified by flash chromatography to
give the desired dithioacetals or sulfides in good to excellent
yields (72%–95%).
1-Chloro-2-phenylthioethane (3ac) (25)
1
Colorless oil; yield 89%. H NMR (400 MHz, CDCl3) δ:
7.40–7.24 (m, 5H), 3.61 (t, J = 4.2 Hz, 2H), 3.21 (t, J =
4.2 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ: 134.3, 130.5,
129.3, 127.1, 42.1, 35.9.
1,2-Di(phenylthio)ethane (3ac′) (26)
White solid; mp 92–93 °C; yield 91%. 1H NMR
(400 MHz, CDCl3) δ: 7.32–7.21 (m, 10H), 3.08 (d, J =
2.4 Hz, 4H). 13C NMR (100 MHz, CDCl3) δ: 135.0, 130.0,
129.0, 126.5, 33.4.
Di(phenylthio)methane (3aa) (22)
White solid; mp 30–34 °C; yield 95%. 1H NMR
(400 MHz, CDCl3) δ: 7.43–7.27 (m, 10H), 4.34 (s, 2H). 13C
NMR (100 MHz, CDCl3) δ: 135.1, 130.8, 129.1, 127.2, 40.5.
Tris(phenylthio)methane (3ad)
1
Pale yellow oil; yield 72%. H NMR (400 MHz, CDCl3)
δ: 7.49–7.30(m, 15H), 5.41 (s, 1H). 13C NMR (100 MHz,
CDCl3) δ: 134.1, 133.1, 129.1, 128.5, 64.9. Anal. calcd. for
C19H16S3: C 67.02, H 4.74; found: C 67.30, H 4.86.
Di(p-tolylthio)methane (3ba) (23)
White solid; mp 40–42 °C; yield 94%. 1H NMR
(400 MHz, CDCl3) δ: 7.34–7.32 (d, J = 6.4 Hz, 4H), 7.13–
7.11 (d, J = 6.8 Hz, 4H), 4.26 (s, 2H) 2.33 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ: 137.4, 131.5, 131.3, 129.7,
41.9, 21.1.
1,1-Di(4-bromophenylthio)propane (3eb)
1
Colorless oil; yield 95%. H NMR (400 MHz, CDCl3) δ:
7.43–7.28(m, 8H), 4.28 (t, J = 6.6 Hz, 1H), 1.84 (m, 2H),
1.12 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ:
137.4, 133.1, 132.0, 122.1, 60.3, 28.8, 11.8. Anal. calcd. for
C15H14Br2S2: C 43.08, H 3.37; found: C 43.29, H 3.30.
Di(4-methoxyphenylthio)methane (3ca)
White solid; mp 66–67 °C; yield 95%. 1H NMR
(400 MHz, CDCl3) δ: 7.40 (dd, J = 2.4, 6.4 Hz, 4H), 6.85 (d,
J = 9.2 Hz, 4H), 4.15 (s, 2H), 3.81 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ: 159.6, 134.4, 125.2, 114.6, 55.3, 44.5.
Anal. calcd. for C15H16O2S2: C 61.61, H 5.52; found: C
61.69, H 5.48.
1-Chloro-2-(4-bromophenylthio)ethane (3ec)
White solid; mp 134–136 °C; yield 92%. 1HNMR
(400 MHz, CDCl3) δ: 7.45–7.23 (m, 4H), 3.60 (m, 2H), 3.20
(m, 2H). 13C NMR (100 MHz, CDCl3) δ: 133.5, 132.3,
132.0, 121.1, 42.1, 36.2. Anal. calcd. for C8H8BrClS: C
38.19, H 3.21; found: C 38.07, H 3.33.
Di(4-chlorophenylthio)methane (3da) (23)
White solid; mp 42–43 °C; yield 90%. 1H NMR
(400 MHz, CDCl3) δ: 7.33 (d, J = 6.8 Hz, 4H), 7.12 (d, J =
6.8 Hz, 4H), 4.26 (s, 2H). 13C NMR (100 MHz, CDCl3) δ:
133.6, 133.0, 132.4, 129.1, 41.2.
1,4-Dithiane (3gc) (27)
1
White solid; yield 81%. H NMR (400 MHz, CDCl3) δ:
2.90 (s, 8H). 13C NMR (100 MHz, CDCl3) δ: 29.1
4-Bromophenylthiopentane (3ee)
Colorless oil; yield 94%. H NMR (400 MHz, CDCl3) δ:
7.40–7.16 (m, 4H), 2.89 (t, J = 7.4 Hz, 2H), 1.67–1.25 (m,
6H), 0.91 (t, J = 5.4 Hz, 3H). 13C NMR (100 MHz, CDCl3)
δ: 136.3, 131.8, 130.3, 119.3, 33.6, 30.9, 28.7, 22.2, 13.9.
Anal. calcd. for C11H15BrS: C 50.97, H 5.83; found: C
51.04, H 5.77.
1
Di(4-bromophenylthio)methane (3ea)
White solid; mp 70.5–72.0 °C; yield 93%. 1H NMR
(400 MHz, CDCl3) δ: 7.3 (d, J = 8.4 Hz, 4H), 7.26 (d, J =
8.4 Hz, 4H), 4.28 (s, 2H). 13C NMR (100 MHz, CDCl3) δ:
133.6, 132.5, 132.1, 121.5, 40.8. Anal. calcd. for
C13H10Br2S2: C 40.02, H 2.58; found: C 40.21, H 2.61.
Di(octylthio)methane (3fa) (15a)
Colorless oil; yield 86%. H NMR (400 MHz, CDCl3) δ:
Acknowledgment
1
3.64 (t, J = 1.2 Hz, 2H), 2.62 (t, J = 6.8 Hz, 4H), 1.55–1.60
(m, 4H), 1.27–1.38 (m, 20H), 0.88 (t, J = 7.2 Hz, 6H). 13C
NMR (100 MHz, CDCl3) δ: 35.4, 31.8, 30.8, 29.2, 29.2,
28.9, 22.6, 14.0.
We are grateful to the National Key Project for Basic Re-
search of China (2004CCA00100), the Natural Science
Foundation of China (20472021 and 20672040), the Hubei
Province Science Fund for Distinguished Young Scholar
(2004ABB011), and Central China Normal University for
the financial support of this research.
1,3-Dithiolane (3ga) (24)
Colorless oil; yield 72%. H NMR (400 MHz, CDCl3) δ:
1
3.86 (d, J = 0.4 Hz, 2H), 3.16 (d, J = 0.8Hz, 4H). 13C NMR
(100 MHz, CDCl3) δ: 8.0, 34.3.
References
1. (a) R.J. Gremlyn. An introduction to organosulfur chemistry.
Wiley, New York. 1996; (b) A. Thuillier and P. Metzner. Sulfur
reagents in organic synthesis. Academic Press, New York.
1994; (c) T.-Y. Luh and C.-F. Lee. Eur. J. Org. Chem. 3875
(2005).
1,1-Di(phenylthio)propane (3ab)
Pale yellow oil; yield 79%. H NMR (400 MHz, CDCl3)
1
δ: 7.47–7.24 (m, 10H), 4.35 (t, J = 6.4 Hz, 1H), 1.88 (m,
2H), 1.13 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3)
© 2006 NRC Canada