• Journal of the Korean Applied Science and Technology
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• v.8 no.1
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• pp.59-67
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• 1991

The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• Journal of the Korean Chemical Society
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• v.55 no.4
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• pp.594-602
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• 2011

The effect of ${\alpha}$-, ${\beta}$- and ${\gamma}$-picolines on the stereochemistry of the coordination compounds of lanthanide(III) nitrates derived from 4[N-(furfural)amino]antipyrine semicarbazone (FFAAPS) has been studied. The general composition of the present coordination compounds is [Ln(FFAAPS)$(NO_3)_3$Pic] (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy or Ho and Pic=${\alpha}$-, ${\beta}$- or ${\gamma}$-picolines). All these coordination compounds have been characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies suggest that the FFAAPS behaves as a neutral tridentate ligand with N, N, O donor while ${\alpha}$-, ${\beta}$- or ${\gamma}$-picoline is coordinated to the lanthanide(III) ions via heterocyclic N-atom. Nitrates are bicovalently bonded in these compounds. From the electronic spectral data, nephelauxetic effect (${\beta}$), covalence factor ($b^{1/2}$), Sinha parameter (${\delta}%$) and the covalence angular overlap parameter (${\eta}$) have been calculated. Thermal stabilities of these complexes have been studied by thermogravimetric analysis. The coordination number of lanthanide(III) ions in the present compound is found to be ten. The antibacterial studies screening of the primary ligand FFAAPS and the complexes showed that the present complexes have moderate antibacterial activities.

• Archives of Pharmacal Research
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• v.25 no.3
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• pp.250-257
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• 2002

A series of benzimidazole derivatives carrying different heterocycles such as 1,2,3-thiadiazole, 1,3,4-thiadiazole, thiazolidine, 2,3-dihydro-thiazole, 1,3,4-oxadiazole, semicarbazone and substituted thiosemi-carbazones were synthesized. Also a series of 1-methylbenzimidazole carrying hydroxy ethyl-amide, substituted sulfonyl hydrazide and benzoyl hydrazide from aminobenzoyl group at position 2 of 1-methylbenzimidazole were synthesized. The antimicrobial evaluation of some of the new compounds was carried out.

• Journal of the Korean Chemical Society
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• v.53 no.2
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• pp.159-165
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• 2009

The synthesis of 2-amino-5-substituted-1,3,4-oxadiazoles 4 were carried out from the electrooxidation of semicarbazone 3 at the platinum electrode under controlled potential electrolysis in an undivided cell. This is an environmentally benign method in the field of synthetic organic chemistry. The non-aqueous solvents acetic acid and acetonitrile and a supporting electrolyte lithium perchlorate were used for the electrolysis in the electrooxidation. The products were structurally charecterised by IR, $^1H$-NMR, $^{13}C$-NMR and elemental analysis.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.435-439
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• 2019

An efficient one pot multicomponent synthesis of pyrimidinone derivatives of Biginelli type is described. 4-amino-6-aryl-pyrimidine-5-carbonitrile molecules were synthesized efficiently via three-component Biginelli-type condensation of aldehyde, malononitrile, and semicarbazone as urea substituent in the presence of a catalytic amount of PEG-400 as green medium under microwave irradiation. The reactions proceeded efficiently in the presence of microwave radiation to afford the desired products in good to excellent yields. Products have been confirmed by IR, and NMR spectral analysis. All the molecules were tested for their antimicrobial activity against E. coli, S. aureus, P. aeruginosa and C. tropicalis. Some of the compounds have shown moderate to good inhibition efficiency against both gram-positive and gram-negative bacteria. The potent activity was observed against the fungal species with minimum inhibition concentration 12.5 ㎍/mL.

• Archives of Pharmacal Research
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• v.23 no.2
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• pp.128-138
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• 2000

In continuation of the previous work (Fathalla, 1992) on the synthesis of some heterocycles containing uracil moiety, we report herein the incorporation of uracil moiety into cyan-opyridine thione, thiosemecarbazone, semicarbazone, cyanopyridine, ami nocyano pyridine, isoxazoline, pyrazoline, pyrimidine, triazolo pyrimidine, pyran, selena and thiazole derivatives which might modify their biological activities. The biological studies revealed that the chemical compound III f showed high molluscicdal activity than other compounds. The profile of the nucleoprotein extracted from chemically (compound IIIc, e, f and g) treated or UV-irradiated B.alexandrina snails did not show appreciable differences when compared to non-treated (native) snails by using SDS-PAGE, where no obvious qualitative or quantitative differences were observed. Immunization of experimental animals with the nucleoprotein extracted from native, chemically (compound III f ＆ g) treated or physically treated B.alexandrina snails induced significant protection against challenge with normal S.mansoni cercariae, as compared to the non-immunized challenged control. As well as , a decrease in the number of granuloma formation and the size range of granuloma was also observed in immunized animals. It is concluded that, compounds III f and g have a potent molluscicidal activity. They also induced chemical modification comparable to that induced by physical treatment in the snail's nucleoprotein, which could possibly be used in immunization against S. mansoni infection.

• Archives of Pharmacal Research
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• v.28 no.11
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• pp.1205-1212
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• 2005

2-Thiouracil-5-sulphonic acid N-(4-acetylphenyl) Amide (1) was reacted with a series of aromatic aldehydes giving chalcones 2 (Claisen-Schemidt reaction), some of these chalcones were reacted with urea and thiourea giving pyrimidine-2-one and pyrimidine-2 thione derivatives respectively of the type 3a,b and 4a,b. In addition many chalcones were reacted with hydroxylamine hydrochloride giving isoxazoline derivatives 5a,b. They could also reacted with phenylhydrazine to give pyrazoline derivatives 5a,b, chalcones also were reacted withethylcyano acetate and/or malononitryl in pyridine giving pyran derivatives 7a,c and 8a,c. In another pathway chalcones were epoxidised by $H_{2}O_{2}$ giving epoxides 9a,c which in turn were reacted with phenylhydrazine giving 4-hydroxypyrazoline derivatives 10a,c. In another reaction chalcones were reacted with ethylcyanoacetate in presence of amm.acetate giving pyridone derivatives 11a,d which could be prepared also in exellent yield from compound 1 by its reaction with certain aromatic aldehydes and ethylcyanoacetate in presence of ammonium acetate. Finally, compound 1 was reacted with semicarbazide giving semicarbazone intermediate 12 which in turn was reacted with thionyl chloride giving thiadiazole derivative 13. The biological effects of some of the new synthesized compounds were also investigated.

• Korean Journal of Food Science and Technology
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• v.37 no.3
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• pp.334-338
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• 2005

Method was developed to efficiently analyze semicarbazide (SEM) in foods. Although SEM is produced by thermal decomposition of blowing agent azodicarbonamide, it is too small to be activated by ultraviolet light or fluorescence. When 2-nitrobenzaldehyde semicarbazone, derivatization of SEM, was analyzed by HPLC with triple column system, coefficient correlation over 0.9997 and detection limit of 0.48 ng/g were observed. SEM level in commercial bottle cap gasket was 812.20-5771.30ng/g. Recoveries for SEM in food and PVC gasket were 83.45-97.33% and 92.12-98.71%, respectively. SEM level in plastic seals of press twist-off metal lids was ND-5771.330ng/g.

• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.13-24
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• 1990

2-N,N,N-trimethyl ammonia decanoate, 2-N,N,N-trimethyl ammonio dodecanoate, 2-N,N,N-trimethyl ammonia tetradecanoate and 2-N,N,N-hexadecanoate with in straight long chain alkyl carboxybetaines, and N-decyl N,N-dimethyl ammonio ethanoate, N-dodecyl N,N-dimethyl ammonia ethanoate, N-tetradecyl N,N-dimethyl ammonia ethanoate and N-hexadecyl N,N-dimethyl ammonia ethanoate with in nitrogen-straight long chain alkyl carboxy betaines measured respectively surface tensions by the stalagmometer method at various temperature, also their critical micelle concentration were evaluated. In micellization, the contribution of standard free energy change(${\Delta}G^{\circ}m$), standard enthalpy change(${\Delta}H^{\circ}m$) and standard entropy change (${\Delta}S^{\circ}m$), have been calculated, with increasing temperature. ${\Delta}H^{\circ}m$ changes from negative, and a similar change in the sign of ${\Delta}H^{\circ}m$ is observed with increasing chain length at $25^{\circ}C$, while the entropy of micellization, ${\Delta}S^{\circ}m$ is positive over the temperature range studied, it becomes less so at higher temperatures. Estimates of the enthalpy and entropy contribution attributable to the ion head group and alkyl chain have been made. The enthalpy and entropy change, per methylene group increase respectively with increasing chain length the result are discussed in terms of current theories of micellization.