• Title/Summary/Keyword: Product Substitution

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Photochemical Studies of Schiff Base Cu(II) Complex: (1) UV-Irradiation of N,$N^{\prime}$-bis(salicylidene)ethylenediamine copper(II)

  • An, Byeong Tae
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.202-204
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    • 1995
  • The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

Kinetic Studies of Nucleophilic Substitution Reaction of para-Substituted Benzoyl Compounds with Pyridines (파라치환 벤조일화합물과 피리딘의 친핵성치환반응에 대한 속도론적 연구)

  • Jeong Wha Kim;Tae Sup Uhm;Ik Choon Lee;In Sun Koo
    • Journal of the Korean Chemical Society
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    • v.29 no.1
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    • pp.15-22
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    • 1985
  • Kinetic studies of nucleophilic substitution reaction of substituted benzoyl cyanides and benzoyl chlorides with pyridines were conducted at 25$^{\circ}C$ in pure acetone solvent. Results showed that (ⅰ) magnitudes of $_{\rho}_S$, $_{\rho}_N$ and ${\beta}$ associated with a change of substituent in the nucleophile indicate relatively advanced bond-formation in the transition state, (ⅱ) the potential energy surface model is able to predict the reaction mechanism, but it is unable to predict the transition state variation to a more product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with better leaving ability (ⅲ) the quantum mechanical model predicted the product-like transition state and slightly better leaving ability of CN- as compared with Cl-.

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Photochemical Reactions of Pseudosaccharin Pyridinemethyl Ethers (Pseudosaccharin Pyridinemethyl Ether들의 광화학반응)

  • Yoon, Ung Chan;Kim, Jeong Hie;Lee, Sang Jin;Kim, Hyun Jin;Oh, Sun Wha;Park, Won Woo
    • Journal of the Korean Chemical Society
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    • v.41 no.12
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    • pp.666-671
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    • 1997
  • Photoreactions of pseudosaccharin pyridinemethyl ethers have been investigated. Pseudosaccharin 2-pyridinemethyl ether, pseudosaccharin 4-pyridinemethyl ether and pseudosaccharin 3-pyridinemethyl ether all undergo a facile photoreaction via reaction pathways involving homolysis of the bond between pseudosaccharyl oxygen and pyridinemethyl carbon, and excited nucleophilic substitution of pyridinemethoxy group by solvent, methanol which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution.

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Kinetic Studies on Nucleophilic Substitution Reaction of Phenacyl Halides with Pyridines in MeOH-MeCN Mixtures (메탄올-아세토니트릴 혼합용매계에서 할로겐화 펜아실과 피리딘유도체와의 친핵성 치환반응에 대한 속도론적 연구)

  • 구인선;양기열;박종근;이익춘
    • Journal of the Korean Chemical Society
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    • v.41 no.1
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    • pp.22-46
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    • 1997
  • Kinetic studies on nucleophilic substitution reaction of phenacyl bromide and phenacyl chloride with pyridines were conducted at 25℃ and 35℃ in methanol-acetonitrile solvents mixtures. It was shown that the reaction proceeds via an SN2 reaction mechanism based on the transition state parameters, ΔH≠ and ΔS≠ and Bro nsted β values. Quantum mechanical model predicted a product-like transition state, where bond-formation is much more progressed than bond breaking, upon changing the leaving group to that with a better leaving ability.

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A Study on the Formation of Octanenitrile as a Precursor for Synthesis of Carboxylic Acid (카르복실산 합성전구체(合成前驅體)로서의 옥탄니트릴의 생성반응(生成反應)에 관(關한) 연구(硏究))

  • Kim, Yong-In;Oh, Yang-Hwan;Kim, Kwang-Sik;Lee, Dong-Woo
    • Journal of the Korean Applied Science and Technology
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    • v.6 no.2
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    • pp.29-37
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    • 1989
  • Using the quarternary ammonium salts as phase transfer catalyst, the nucleophilic substitution reaction of 1-chlorooctane with sodium-cyanide was investigate kinetically with respect to the formation of octanenitrile. The product was analyzed with gas chromatograph, and quantity of octanenitrile was measured. The reaction condition was considered by the effect of the reaction temperature, of the species and the amount of catalyst, of the speed of strirring, and of the concentration of reactants. The reaction was carried out in the first order on the concentration of 1-chlorooctane and sodium cyanide, respectively. The over-all order was 2nd. The activation energies for the nucleophilic substitution reaction of 1-chlorooctane and 1-bromooctane under tetrabutylammonium hydrogen-sulfate were calculated as 2.05 and 10.08kcal/mol, respectively. The effect of various caltalysts was decreased in the order of tetrabutylammonium bromide, terabutylammonium, tetrabutylammonium hydrogensulfate, and tetrabutylammonium iodide. The reaction rate was dependent on the concentration of sodium-cyanide dissolved in the aqueous phase, and the good result was shown when the mol ratio between 1-chlorooctane and sodium cyanide was one per three.

Role of Val289 Residue in the $\alpha$-Amylase of Bacillus amyloliquefaciens MTCC 610: An Analysis by Site Directed Mutagenesis

  • Priyadharshini, R.;Hemalatha, D.;Gunasekaran, P.
    • Journal of Microbiology and Biotechnology
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    • v.20 no.3
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    • pp.563-568
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    • 2010
  • The Val289 residue in the $\alpha$-amylase of Bacillus amyloliquefaciens, which is equivalent to the Ala289 and Val286 residues in the $\alpha$-amylases of B. stearothermophilus and B. licheniformis, respectively, was studied by site-directed mutagenesis. This residue was substituted with 10 different amino acids by random substitution of the Val codon. In these mutant $\alpha$-amylases, Val289 was substituted with Ile, Tyr, Phe, Leu, Gly, Pro, Ser, Arg, Glu, and Asp. Compared with the wild-type $\alpha$-amylase, the mutant $\alpha$-amylase Val289Ile showed 20% more hydrolytic activity, whereas Val289Phe and Val289Leu showed 50% lesser activity. On the other hand, the mutant $\alpha$-amylases Val289Gly, Val289Tyr, Val289Ser, and Val289Pro showed less than 15% activity. The substitution of Val289 with Arg, Asp, or Glu resulted in complete loss of the $\alpha$-amylase activity. Interestingly, the mutant $\alpha$-amylase Val289Tyr had acquired a transglycosylation activity, which resulted in the change of product profile of the reaction, giving a longer oligosaccharide.

Effect of Changes of Bubble-based Leavening Agent and Bubble Mixing Ratio on Quality of Lightweight Concrete (기포계팽창재 및 기포혼입율 변화가 경량기포 콘크리트의 품질에 미치는 영향)

  • Kim, Min-Sang;Cha, Cheon-Soo;Park, Do-Yeong;Park, Yong-Kyu;Kim, Hyun-Woo;Han, Cheon-Goo
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2016.05a
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    • pp.189-190
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    • 2016
  • Lightweight concrete is currently used at apartment buildings or housing construction sites causes some uneconomical problems due to excessive cracks and subsidences. So, it is in the situation that it is necessary to set up countermeasures against such subsidences. Therefore, in this study, it is intended to analyze the prevention of a subsidence inducing the expansion of the aluminum components depending on the changes of substitution rate and bubble mixing ratio by using the bubble-based Leavening Agent that Aluminum slag as an industrial by-product is substituted into some desulfurized plaster. As the results, it was found that the blending ratios, such as, the substitution ratio of bubble-based leavening agent (1%) and the bubble mixing ratio (65%) are appropriate while the flow property, subsidence depth and compression strength are considered.

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PREPERATION OF AMPHOTERIC STARCHS AND STUDY ON WET END CHEMISTRY IN PAPERMAKING

  • Shan, Chen-Fu;Su, Xie-Lai;Yi, Wang-Hai;Quan, Long-Yan
    • Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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    • 1999.04b
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    • pp.386-389
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    • 1999
  • Amphoteric polymers have brought to papermakers' attention gradually. In this paper, a series of amphoteric starches with different cationic and anionic degree of substitution (DS) are prepared. Better product has been selected and used under different condition. As retention and drainage aids, amphoteric starches were used in shorter fiber length, weak strength and poor drainage bleached AQ-Soda wheat straw pulp. In neutral and alkaline papermaking system, when amphoteric starches contain 0.024-0.026 anionic degree of substitution (DS), it is shown that the higher the cationic degree of substitution (DS) in amphoteric starches, the better the filler retention. The filler retention is improved 12.5%, 30.3%, and 35.1% and 32.5% respectively by adding 1% amphoteric starch LS-L2 -1 (0.034), LS-L2-2 (0.040), LS-L2-3 (0.047) and LS-L2-4 (0.052). But the strength of handsheets if affected a little. By adding 2% Al2 (SO4)3 and 1.5% LS-L2-3 at pH 7.5, filler retention can be improved from 38% to 80%, and breaking length of sheet only decreases 3.2%. As dry strengthening aids, amphoteric starches were used in eucalyptus APMP. Amphoteric starches are used in eucalyptus APMP. The amphoteric starch LS-L2-2 is better dry strength aid. Adding 1% LS-L2-2 can improve breaking length 24.5%, burst index 42.9%, tear index 38.8%, folding endurance and density of the handsheets.

Catalytic Properties of Borosilicate in Methanol Conversion (메탄올의 전환반응에서 보로실리케이트의 촉매성질)

  • Lee, Gye Su;Jo, Min Su;Jeong, Byeong Gu;Seo, Gon
    • Journal of the Korean Chemical Society
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    • v.34 no.4
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    • pp.360-369
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    • 1990
  • Borosilicate, HZSM-5 zeolite and iron-substituted borosilicate and HZSM-5 zeolite were prepared and their catalytic properties in methanol conversion were studied. The effects of strength and amount of acid site determined from TPD spectra of ammonia on the product distribution was examined. Selectivity to propylene was high over borosilicate with small amount of strong acid site, but selectivity to aromatic compound was high over HZSM-5 zeolite with large amount of the strong acid site. The participation of weak acid site on the conversion did not confirmed, and the product distribution could be explained in terms of the amount of the strong acid site. Although the amount of the weak acid site was increased by substitution of iron, there was no meaningful change in the product distribution.

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Syntheses and Reactions of Iridium Complexes Containing Mixed Phosphine-Olefin Ligand: (3-(Diphenylphosphino)propyl)(3-butenyl)phenylphosphine

  • Young-ae W. Park;Devon W. Meek
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.524-528
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    • 1995
  • The reaction of [IrCl(cod)]2 with ppol ligand, Ph2PCH2CH2CH2P(Ph)CH2CH2CH=CH2, in ethanol gives an iridium complex, whose structure is converted from an ionic form, [Ir(cod)(ppol)]Cl·2C2H5OH (1),in polar solvents (ethanol, methanol and acetonitrile), to a molecular form, [IrCl(cod)(ppol)], in non-polar solvents (benzene and toluene). The cationic complexes, [Ir(cod)(ppol)]AsF6·1/2C2H5OH and [Ir(cod)(ppol)]PF6·1/2CH3CN, were prepared to compare with the ionic form by 31P NMR spectroscopy. When carbon monoxide is introduced to 1, cod is replaced by CO to give the 5-coordinated complex, [IrCl(CO)(ppol)]. Hydrogenation of 1-octene was not successful in the presence of 1. In order to verify the reason for 1 not behaving as a good catalyst for hydrogenation, electrophilic reactions with HCl, I2 and HBF4·etherate were performed, which yielded the oxidative addition product, [IrHCl2(ppol)], the substitution product, [IrI(cod)(ppol)], and another cationic product, [Ir(cod)(ppol)]BF4, respectively. Thus, the iridium complex is not sufficiently basic to activate hydrogen atoms or the olefin of the ppol ligand.