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8. General procedure for the synthesis of 4-thio-but-2-yn-1-ol: To a solution
of EtMgBr (100 mmol in 200 mL of THF) was added 100 mmol of 3-
Scheme 6. Hindrance of the group on 4-position.
For intermediate C, the intramolecular nucleophilic
attack of hydroxyl group indicates that a group on 4-posi-
tion might prevent this process, which was confirmed by
the fact that the treatment of 1-phenyl-4-(phenyl-
thio)pent-2-yn-1-ol with NIS in acetonitrile gave an
unidentified mixture instead of 3-iodo-5-methyl-2-phenyl-
4-(phenylthio)furan (Scheme 6).
In summary, we developed a facile and efficient method
for the synthesis of 2,4-dihalo-3-thio-furans. As a result of
the ready availability of starting materials and the simple
and convenient operation, this type of reaction presented
here has potential utility in organic synthesis.
thioprop-1-yne dropwise under
a nitrogen atmosphere at room
temperature for 3 h, which was followed by addition of 100 mmol of
aldehyde in ice-water bath. The mixture was stirred for 5 h and
quenched with saturated NH4Cl, extracted with dichloromethane, and
dried over anhydrous Na2SO4. After evaporation, chromatography on
silica gel (eluent: EtOAc/petroleum ether = 1:10) of the crude product
afforded 4-thio-but-2-yn-1-ol, generally in yield higher than 80%.
General procedure for the synthesis of 2,4-dihalo-3-thio-furans: To a
mixture of 3.5 mmol of K2CO3 and 3 mmol of N-halosuccinimide
(NXS) in 10 mL of CH3CN was added 1 mmol of 4-thio-but-2-yn-1-ol
(1), followed by heating at 50 °C and stirring for 3 h. Then 0.5 mmol of
NXS was added. After 3 h, the reaction mixture was quenched with
30 mL of water, extracted with dichloromethane, and dried over
anhydrous Na2SO4. After evaporation, chromatography on silica gel
(eluent: petroleum ether) of the crude product afforded 2,4-dihalo-3-
thio-furan (2).
2-(4-Chlorophenyl)-3,5-diiodo-4-(phenylthio)furan (2a). 1H NMR
(400 MHz, CDCl3) d 7.95–7.92 (m, 2H), 7.43–7.41 (m, 2H), 7.33–7.30
(m, 3H), 7.30–7.27 (m, 2H); 13C NMR (CDCl3, 100 MHz) d 155.8,
147.4, 135.1, 133.7, 129.3, 128.9, 128.7, 127.9, 127.6, 127.3, 95.6, 76.4.
MS (m/z) 411 (M+À127, 5.9), 139 (100); IR (neat, cmÀ1) 1775, 1583.
Anal. Calcd for C16H9ClI2OS: C, 35.68; H, 1.68; found: C, 36.02; H,
1.99.
Acknowledgments
Financial support was received from the Natural Science
Foundation of China (No. 20702046), the Natural Science
Foundation of Zhejiang Province (R405066), and Ministry
of Education (J20060128).
References and notes
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