• Title/Summary/Keyword: Thiocarbonyl

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Synthetic Applications of Di-2-pyridyl Thionocarbonate As a Dehydration, a Dehydrosulfuriation, and a Thiocarbonyl Transfer Reagent

  • Kim, Sung-Gak;Yi, Kyu-Yang
    • Bulletin of the Korean Chemical Society
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    • v.8 no.6
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    • pp.466-470
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    • 1987
  • Di-2-pyridyl thionocarbonate, prepared from thiophosgene and 2-hydroxypyridine in the presence of triethylamine in dichloromethane, was found to be very effective for dehydration, dehydrosulfurization, and thiocarbonyl transfer reactions. Di-2-pyridyl thionocarbonate was successfully for the esterification of carboxylic acids, dehydration of aldoximes into nitriles, preparation of isothiocyanates from amines, and preparation of cyclic thionocarbonates from 1,2- and 1,3-diols.

Macroalkoxyamines and macroRAFT agents based on polyethylene for the syntheses of polyolefin based polar block copolymers

  • Lopez R. Godoy;Boisson C.;D'Agosto F.;Spitz R.;Boisson F.;Gigmes D.;Bertin D.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.377-377
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    • 2006
  • Alkoxyamine and thiocarbonyl thio end capped polyethylene (PE) chains were synthesized using a direct and simple approach consisting in reacting di(polyethylenyl)magnesium (PE-Mg-PE) chains with a range of nitroxides and disulfides of thiocarbonyl thio compounds. PE-Mg-PE compounds were prepared by a catalyzed chain growth reaction of ethylene on nbutyloctylmagnesium (BOMg) with a neodymocene complex $(C_{5}Me_{5})_{2}NdCl_{2}Li(OEt_{2})_{2}$. Complete characterizations confirm the introduction of the desired end groups. The controlled radical polymerization (NMP and RAFT) of butyl acrylate mediated by these functional polyethylenes was successful.

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Kinetics and Mechanism of the Reactions of S-Phenyl Dithiobenzoates with Benzylamines in Acetonitrile

  • 오혁근;신철호;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.657-661
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    • 1995
  • Kinetic studies are carried out on the reaction of S-phenyl dithiobenzoates with benzylamines in acetonitrile at 30.0 ℃. Small magnitude of ρX (βX) as well as ρZ (βZ) obtained suggests rate-limiting nucleophilic attack of the thiocarbonyl carbon. This is supported by the unusually small magnitude of ρXY and ρYZ, albeit their signs do not agree with those expected. Moreover, the inverse secondary kinetic isotope effects (kH/kD<1.0) involving deuterated benzylamine nucleophiles are also in line with the proposed mechanism.

Studies of Pharmacological Activity on New Oral Cephalosporins (새로운 경구용 세팔로스포린의 약효평가)

  • La, Sung-Bum;Kim, Wan-Joo;Jee, Ung-Kil
    • YAKHAK HOEJI
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    • v.38 no.2
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    • pp.140-148
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    • 1994
  • ${\beta}-Lactamase$ stability, chemotherapeutic activity, and pharmacokinetics of 7-[(Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonylthiomethyl-3-cephem-4-carboxylic acid(CEN1), 7-[(Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyrimidyl)piperazinyl]thiocarbonylthiomethyl-3-cephem-4-carboxylic acid(CEN2), pivaloyloxymethyl-7-[(Z)-2-(2-aminothizaole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonyl-thiomethyl-3-cephem-4-carboxylate(CEN1P), and pivaloyloxymethyl-7-{(Z)--2-(2-aminothizaole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl]thiocarbonyl-thiomethyl-3-cephem-4-carboxylate(CEN2P) were examined. CEN1, CEN2, CEN1P, and CEN2P were very stable to the ${\beta}-lactamase$ obtained from three strains(Enterobacter cloacae P99, Escherichia coli TEM, and Citrobacter freundii). Chemotherapeutic activities$(ED_{50})$ of CEN2 and CEN2P against experimental systemic infections due to Streptococcus pyogenes 77A and Escherichia coli 078 were superior to those of CEN1 and CEN1P, respectively. The $ED_{50}$ values of CEN1, CEN2 were 5.82 mg/kg, 0.89 mg/kg(s.c., S. pyogenes 77A) while those of CEN1P, CEN2P were 14.56mg/kg, 6.40mg/kg(p.o., S. pyogenes 77A), respectively. The pharmacokinetics of CEN1, CEN2, CEN1P, and CEN2P were investigated in mice and rats. In mice, peak blood levels of $1.25\;{\mu}g/ml$ were recorded within 20 min after oral administration of a single dose equivalent to 40 mg/kg CEN1P. Cmax of CEN1P was much higher than that of CEN1 in mice and rats. Oral absorption of CEN2P was much higher than that of CEN2.

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Synthesis and iNOS Inhibitory Activities of Thioflavones

  • Dao Tran Thanh;Tuyen Truong Ngoc;Park Haeil
    • Archives of Pharmacal Research
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    • v.28 no.6
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    • pp.652-656
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    • 2005
  • A number of thioflavones has been synthesized and evaluated for their iNOS inhibitory activities. Thiowogonin (6) was obtained from naturally occurring chrysin in 5 steps. Other thioflavones were prepared from the corresponding flavones in a single step by the reaction with Lawesson's reagent. The biological activities of thioflavones were not enhanced by the functional group conversion from carbonyl to thiocarbonyl. Compounds 11 and 13 showed potent. NO inhibitory activity at high concentration (40 uM), leading to the possible development of novel neuroprotective agents based on wogonin.

Determination of Reactivity by MO Theory (XX). An MO Theoretical Study on Mechanism of Thiocarbonyl Addition.

  • Lee, IK-Choon;Yang, Ki-Yull
    • Bulletin of the Korean Chemical Society
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    • v.2 no.4
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    • pp.132-138
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    • 1981
  • Ab initio molecular orbital calculations have been performed in an effort to determine which types of chemical interactions play essential roles for the system, , $H_2O+CH_2SH^+$, and $H_2O+ CH_2S$. The most important contribution to the interaction energy in controlling reaction path is the exchange repulsion energy, EX, which is largely responsible for the shape of the total interaction energy curve. In the ion-molecule reaction, prior protonation of thioformaldehyde or prior deprotonation of water leads to formation of the corresponding ionic adducts ($H_2O+CH_2SH$ and $HOCH_2S^-$), with no barrier to reaction, simulating specific acid and base catalysis, respectively, as in the case of formaldehyde. Otherwise, approach of water to thioformaldehyde gives rise to a completely repulsive interaction.

From the synthesis of functional RAFT agents to the design of functional latex particles

  • Bathfield M.;D'Agosto F.;Spitz R.;Charreyre M.T.;Delair T.;Dos Santos A.M.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.319-319
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    • 2006
  • RAFT polymerization can produce under controlled conditions polymer chains incorporating well-defined chain ends. By designing a simple way of producing functional RAFT agents, a variety of ${\Box}-end$ groups was successfully introduced onto hydrophilic polymer chains. The ${\Box}-end$ group being a thiocarbonyl thio function was used as efficient chain transfer agent in dispersion or emulsion polymerization to produce original functional latex particles.

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Physicochemical Properties and Degradation of New Oral Cephalosporins (새로운 경구용 세팔로스포린류의 물리화학적 성질 및 분해특성)

  • La, Sung-Bum;Kim, Wan-Joo;Jee, Ung-Kil
    • YAKHAK HOEJI
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    • v.38 no.2
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    • pp.123-130
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    • 1994
  • Physicochemical properties and hydrolysis kinetics of new some oral cephalosporins were examined in buttered solution and human plasma or rat liver homogenate. The test cephalosporins were 7-[(Z)-2-(2-aminothiazole-4-yl)-2- methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazinyl] thiocarbonylthhiomethyl-3-cephem-4-carboxylic acid (CEN1), 7-[(Z)-2-(2-aminoth iazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyrimidyl)piperazinyl]th iocarbonylthiomethyl-3-cephem-4-carboxylic acid (CEN2), pivaloyloxymethyl-7-[ (Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[4-(2-pyridyl)piperazi nyl]thiocarbonylthiomethy1-3-cephem-4-carboxylate (CEN1P), and pivaloyloxymethyl-7-[(Z)-2-(2-aminothiazole-4-yl)-2-methoxyiminoacetamido]-3-[ 4-(2-pyrimidyl)piperazinyl]thiocarbonyl-thiomethyl-3-cephem-4-carboxylate (CEN2P). The partition coefficient(Ko/w) of CEN1P, CEN2P were higher than those of CEN1, CEN2. The calculated pKa values of CEN1, CEN2, CEN1P, and CEN2P were 7.09, 7.75, 4.92, and 5.39, respectively. The hydrolysis of CEN1P and CEN2P were not depend on the composition of pH of the test medium except weak alkaline buffered solution (pH 8.00). CEN1 and CEN2 were very stable in pH 6.80 and 8.00 buffer solutions. CEN1P and CEN2P were rapidly deesterified to CEN1 and CEN2 in human plasma and in rat liver homogenate. Half-lives$(t_{1/2})$ of CEN1 and CEN2 were 3.49 and 4.93 hr in human plasma, 1.47 and 1.26 hr in rat liver homogenate, respectively.

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