• Journal of the Korean Chemical Society
• /
• v.32 no.4
• /
• pp.390-405
• /
• 1988

The chlorination of $C_7H_16,\;C_8H_18,\;C_10H_22,\;and\;(Me_2CH)_2$ with N-Chlorosuccinimide, tert-BuOCl, $CCl_3SO_2Cl,\;CCl_4,\;CCl_3SCl,\; PCl_5,\;and\;Cl_2\;in\;C_6H_6\;or\;CS_2$ which both form loose complexes with $Cl_2$ atoms yielded mixtures of isomeric monochloroalkanes which were analyzed quantitatively. An isomer ratio differing from that known for the substitution of paraffinic hydrocarbons was observed. The isomer distribution observed is the result of the combined effects of the differing C-H dissociation energies of the different types of H atoms of the alkane and of the free energy of the attacking radical with polar effects of the attacking radical as well as of the hydrocarbon.

• Archives of Pharmacal Research
• /
• v.6 no.1
• /
• pp.45-53
• /
• 1983

Novel halactolactonizations using NBS (2), NIS(3), and NSP(4) in dry DMF were found to be the most reasonable and efficient procedures. The participation of X as the cylization initiator could be clarly rationalized by experimental results and the regioselectivities of formed halolactones were reasonably elucidated by weakly bridged carbonium ion intermediate.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.1
• /
• pp.27-28
• /
• 2008

• Bulletin of the Korean Chemical Society
• /
• v.16 no.7
• /
• pp.609-613
• /
• 1995

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.