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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 16, Number 7
BKCSDE 16(7)
July 20, 1995 

Formation and Reactions of α-Phosphoryl Thiocarbocations: Synthesis of α-Sulfenyl Phosphonates
Taek Hyeon Kim*, Dong Young Oh
The reaction of chloro(methylthio and arylthio)methanephosphonate (1) and Pummerer-type reaction of sulfinylmethanephosphonate (2) with nucleophiles such as aromatic compounds and thiols were examined. The direct chlorination of (methylthio and arylthio)methanephosphonate with N-chlorosuccinimide (NCS) led to the formation of monochlorinated phosphonates (1) in good yield. The reaction of 1 with aromatic compounds and thiols in the presence of stannic chloride afforded a variety of aryl(methylthio)methanephosphonates (3) and thioacetals of formylphosphonates (4), respectively. Phosphonates 3 and 4 were also obtained from the reaction of Pummerer intermediate, generated from sulfinylmethanephosphonate (2), with aromatic compounds and thiols, respectively. A versatile reaction conditions to generate Pummerer intermediate were examined. The best condition was the combination of trifluoroacetic anhydride with stannic chloride. All reactions may involve an initial formation of α-phosphoryl thiocarbocation and a subsequent nucleophilic attack of aromatic compounds and thiols.
609 - 613
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