• Journal of the Korean Chemical Society
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• v.40 no.10
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• pp.663-669
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• 1996

The rate constants for the nucleophilic addition reactions of thioglycolic acid to vinylsulfilimine(VSI) derivatives(p-OCH3, H, p-Cl and p-Br) were determined by an ultraviolet spectrophotometric method, and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base catalysis and substituent effect, a plausible addition reaction mechanism was proposed: Below pH 3.0, the reaction was proceeded via the addition of neutral molecule to carbon-carbon double bond after protonation at the nitrogen atom of the sulfilimine, and in the pH range of 3.0 to 9.0, the neutral molecule and its anion attacked to carbon-carbon double bond competitively. Above pH 9.0, sulfide anion added to the double bond (Michael type addition).

• Journal of the Korean Chemical Society
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• v.35 no.3
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• pp.268-274
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• 1991

The rate constants for the nucleophilic addition reactions of thiourea to ${\beta}$-nitrostyrene derivatives(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$) were determined by UV spectrophotometer and rate equations which can be applied over a wide pH ranges were obtained. On the basis of substituent effect, general base catalysis and rate equations, a reaction mechanism was proposed and revealed quantitively. Above pH 9.00, sulfide anion adds to the double bond(Michael type addition) and between pH 7.00 and 9.00, the neutral molecules and its anions add to the double bond competitively. Below pH 7.00, the addition reaction to double bond is initiated by the addition of neutral thiourea molecule.

• Journal of the Korean Applied Science and Technology
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• v.14 no.1
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• pp.27-32
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• 1997

Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.109-117
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• 1986

7,9-Dideoxydaunomycinone (32), a late-stage precursor of the aglycone of antitumor antibiotic daunorubicin(2a) was prepared from 3-methoxybenzoic acid(5). Thus, 3-methoxybenzoic acid was converted to 4-methoxy-3-(phenylsulfonyl)-1(3H)-isobenzofuranone(11), which furnished trimethoxynaphthoate 16 upon ring annelation developed by Hauser and Rhee. The trimethoxynaphthoate 16 upon ring annelation developed by Hauser and Rbee. The trimethoxynaphtboate 16 was then transformed into phenylsulfonylnaphthofuranone 22, which was used to make anthracenoate 24 via Michael type reaction with 7-(ethylenedioxy)-2-octenoate(23). Conversion of anthracenoate 24 to tetracyclic product 28, followed by subsequent deprotection of the methyl groups in ring-B and C furnished 7, 9-Dideoxydaunomycinone(32).

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.120-126
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• 1989

The Kinetics of hydrolysis of styrylphenylsulfone derivatives in 50% methanol-water at 25$^{\circ}$C and ionic strength of 0.10 was investigated by UV spectrophotometry in the pH range of 0.0-14.0. The rate equations, which can be applied over a wide pH range, were obtained. The Hammett rho constants for the hydrolysis are 1.85 at pH 7.0 and 1.54 at pH 13.0, respectively. On the basis of the evidence, it is proposed that the general base-catalysis occurs in the hydrolysis of styrylphenylsulfone derivatives; above pH 11.0, Michael type nucleophilic addition take place, while below pH 9.0, the reaction is initiated by addition of water and from pH 9.0 to pH 11.0 these two reactions occur com-petitively.

• Journal of Adhesion and Interface
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• v.15 no.1
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• pp.22-30
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• 2014

Self-photoinitiating acrylate (SPIA) which can undergo self-initiation under UV irradiation was synthesized by a Michael addition in the presence of a base catalyst. The SPIA polymerizations were investigated by photo-differential scanning calorimeter (photo-DSC) and surface physical properties such as pendulum hardness and pencil hardness. The results showed that the SPIA can cure upon UV irradiation by itself without a photoinitiator. But we found out that both the curing rate and the conversion were too low for the self-curing reaction of SPIA. In order to improve the SPIA curing properties, we introduced the SPIA/cationic hybrid system and observed the effects of the addition of commercial free radical type monomer and photoinitiator on the curing behaviors. SPIA/cationic hybrid system was the best suitable to improve the SPIA curing properties. The kinetic analysis indicated that the cationic monomer and photoinitiator apparently accelerated the cure reaction and rate of the hybrid SPIA system, mostly due to the synergistic effect of cationic monomer and photoinitiator increasing the mobility of active species and the generation of reactive species (free radical, cation) during the photopolymerization process. The physical properties showed that, unlike typical free radical system, the hybrid systems did not show oxygen inhibition effect because of cationic reaction on the coating surface.

• Journal of the Korean Chemical Society
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• v.44 no.2
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• pp.120-126
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• 2000

The rate constants for the hydrolysis of 2-phenyl-4H,5H-3-methyl-3-thiazolinium perchlorate(PTP) derivatives were detemined by the use of ultraviolet visible spectrophotometer in water. The rate equations which could be applied over a wide pH ranges were obtained. On the basis of rate equation, hydrolysis product analysis, general base catalysis, and substituent effect, a plausible mechanism of the hydrolysis is proposed: Below pH 4.0, the reaction is initiated by addition of water, while above pH 9.0, Michael type nucleophilic addition takes place. In the pH range of $4.5{\sim}8.0$, these two reactions appear to occur competitively.

• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.90-94
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• 2012

The furan-2-ylidene acetates (3a-d), obtained from the furan-2,3-diones (1a-b) and methyl/ethyl (triphenylphosphoranylidene)-acetates (2a-b), were converted via the Michael type reactions with 2,3-diaminopyridine and its derivatives (4a-c) into the corresponding pyrrol-2-ylidene-acetates (5a-j) in moderate yields (45-94%). Structures of these compounds were determined by the IR, NMR, elemental analysis, and X-ray diffraction method.

• Bulletin of the Korean Chemical Society
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• v.3 no.4
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• pp.162-165
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• 1982

The rate constants of the nucleophilic addition of thioglycolic acid to the derivatives $(H,\;p-CH_3,\;p-CH_3O,\;p-Cl,\;p-NO_2)$ of ${\beta}$-nitrostyrene were determined by ultraviolet spectrophotometry. The rate equations which can be applied over a wide pH range were obtained. Therefrom a reaction mechanism was proposed. Above pH 8.5 sulfide anion adds to the double bond (Michael type addtion). However, below pH 8.5, the neutral molecule and $HSCH_2COO^{\theta}$ add to the double bond.

• Proceedings of the Korean Society For Composite Materials Conference
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• 2003.10a
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• pp.1-2
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• 2003

While aromatic polyimides and polyamides have found widespread use as high performance polymers, the present work addressed the need for organosoluble materials through the use of a hyperbranching scheme. The $AB_2$ monomers were prepared. The $AB_2$ monomers were then polymerized via aromatic fluoride-displacement and Yamazaki reactions to afford the corresponding hydroxyl-terminated hyperbranched polyimides (HT-PAEKI) and amine-terminated hyperbranched polyamides, respectively. HT-FAEKI was then functionalized with allyl and propargyl bromides as well as epichlorohydrin to afford allyl-terminated AT-PAEKI, propargyl-terminated PT-PAEKI, and epoxy (glycidyl)-terminated ET-PAEKI, in that order. All hyperbranched poly(ether-ketone-imide)s were soluble in common organic solvents. AT-PAEKI was blended with a bisphenol-A-based bismaleimide (BFA-BMI) in various weight ratios. Thermal, rheological, and mechanical properties of these blend systems were evaluated. Two characteristic hyperbranched polyamides, which the one has para-electron donating groups to the surface amine groups and the other has para-electron withdrawing groups to the surface amine groups, were selected to compare BMI curing behaviors. The electron rich polymer displayed ordinary Michael addition type exothermic reaction, while electron deficient polymer did display unusual curing behaviors. Based on analytical data, the later system provided the strong evidences to support room temperature curing of BMI by reactive intermediates instead of reactive primary amine groups on the macromolecule surface.