• Journal of the Korean Chemical Society
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• v.44 no.3
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• pp.229-236
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• 2000

The reaction of 6-chloro-2-hydrazinoquinoxaline 4.oxide(10) with acetylacetone or dibenzoylmethane gave 6-chloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxaline 4-oxides (11) through the intramolecular·cyclization.The chlorination of compound 11 with phosphoryl chloride afforded 3,6-dichloro-2-(3,5-disubstituted pyrazol-1-yl)quinoxalines (12), whose reaction with hydrazine hydrate provided 6-chloro-3-hydrazinodehydes, benzenesulfonyl chloride, substituted benzoyl chlohdes or acyl chlorides gave novel pyrazolylquinoxalines (14-17).

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.2109-2112
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• 2011

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2805-2808
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• 2011

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.709-712
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• 2011

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.309-312
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• 2012

• Journal of the Korean Chemical Society
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• v.24 no.6
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• pp.457-462
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• 1980

Phosphates and phosphoric amides were synthesized by the reaction of phosphoryl chloride with allyl alcohol, 2,3-dibromopropanol, 2-pyrrolidone and ethylenimine. All of these compounds were thermally very unstable. Allyl phosphorodichoridate and diallyl phosphorochloridate gave significant amount of polymeric products when they were distilled. IR spectra showed characteristic P=O stretching bands between 1300 and $1200 cm^{-1}$ and NMR spectra were very complicated due to the long range coupling effect of phosphorus atom. And mass spectrum of 2,3-dibromopropyl phosphorodichloridate gave no indication of molecular ion peak.

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

• Textile Coloration and Finishing
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• v.20 no.6
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• pp.75-81
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• 2008

This paper dealt with the synthesis and characterization of the polymeric product by the reaction of the water-soluble poly(vinyl alcohol)[PVA] nonwoven fabrics and the phosphoryl chloride ($POCl_3$), which has been applied to prepare water-proofing materials or intermediates for increasing water-proofing or fire-proofing ability of commercially available water-soluble PVA support layer. $POCl_3$ was reacted with PVA nonwoven fabrics under non-aqueous condition, and their reactivity, and chemical structure were checked and discussed. PVA was reacted with $POCl_3$ under the reaction condition of 1:1, or 1:2 mole ratios at 70, 80 and $90^{\circ}C$, and the reaction products were further hydrolyzed. The structure of the resulting products from water soluble PVA nonwoven fabrics reacted with $POCl_3$ were identified by FT-IR or X-ray fluorescence spectrophotometer, and they indicated the PVA polymer chains to have phosphorous and chlorine moieties.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1945-1950
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• 2011

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4361-4365
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• 2011

The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.