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Studies on Polyphosphazenes-bound Wittig Reactions (포스파젠 고분자를 이용한 Wittig반응에 관한 연구)

  • Kwon, Suk-Ky;Jun, Chang-Lim
    • Applied Chemistry for Engineering
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    • v.5 no.5
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    • pp.843-850
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    • 1994
  • Polyphosphazene-bound Wittig reagents such as $[NP(OC_6H_5)_{1.7}(OC_6H_4P(Ph)_2$=$CHCH_2CH_2CH_3)_{0.3}]_n$ were synthesized by treating $[NP(OC_6H_5)_{1.7}(OC_6H_4Br)_{0.3}]_n$ with n-butyllithium, diphenylchlorophosphine, and n-butyl iodide. Polymeric reactions were carried out according to the reaction conditions with cyclic primers such as [$N_3P_3(OC_6H_5)_5(OC_6H_4P(Ph)_2$)]. The desired alkene and polymer-bound phosphine oxide were prepared successfully by the reaction of polyphosphazene-bound Wittig reagents with benzophenone.

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Park, Young Cho;Kim, Young Sik;Kim, Soo Jong
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.597-600
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    • 2017
  • $(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Kinetics and Mechanism of the Hydrolysis of N-(p-Nitrophenyl)-benzohydrazonyl Azide Derivatives (N-(p-니트로페닐)-벤조히드라조닐아지드 유도체의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Nack-Do Sung;Ki-Sung Kwon;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.22 no.3
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    • pp.150-157
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    • 1978
  • The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

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Power Input of Pitched and Double-Stage Paddle Impeller in a Agitated Vessel (교반조에서 경사 및 2단 Impeller의 교반소요동력에 관한 연구)

  • Lee, Young-Sei;Kim, Moon-Kap;Kim, Jong-Shik
    • Applied Chemistry for Engineering
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    • v.7 no.1
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    • pp.18-25
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    • 1996
  • Power input in stirred vessel is especially important in the design of mixers, as well as the evaluation of mixing processes. A type of baffles in mechanically agitated vessels and power employed are major factors that determine the stirring efficiency in a large scale, multi-step processes. In the present study, power input in the totally baffled agitated vesseles was compared systematically in connection with several previous studies and adequate power input correlation was found to be : $Np_{(pitch)}=({\theta}/90^{\circ})Np_{(90^{\circ})}$ Power number correlation was dependent upon the distance of among the impeller in the agitated vesseles, as follows : $$Np=7.09(n_p)^{0.7}(\frac{b_(double)}{d})(\frac{H}{D})^{0.18}$$, $${n_p}^{0.7}(\frac{b_{(double)}}d)$$<2 $$Np=8.73\{(n_p)^{0.7}(\frac{b_{(double)}}{d})\}^{0.7}(\frac{H}{D})^{0.18}$$, $${n_p}^{0.7}(\frac{b_{(double)}}d)$$>2.

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Refinement of the Structure of p-Dimethylaminobenzaldehyde 4-(p-Ethoxyphenyl) Thiosemicarbazone (p-Dimethylaminobenzaldehyde 4-(p-Ethoxyphenyl) Thiosemicarbazone구조의 정밀화)

  • Seo, Il-Hwan;Seo, Chu-Myeong;Park, Yeong-Ja
    • Korean Journal of Crystallography
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    • v.2 no.1
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    • pp.12-16
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    • 1991
  • C18H22N4OS, Mr=342.47, monoclinic, P2₁/c,a=11.802(2), b=31.962(2), c=9.829(2)A, β=100.12(1)˚, V=3694.8A3,F(000)=1472, Z=8, Dx=1.246 Mg m-3, Dm=1.17Mg m-3,λ=0.71073 A, μ=0.15mm-1, T=294 K. final R=0.0856 for 3718 observed reflection (Fo>3σ(Fo)) There are two molecules in an asymmetric unit and a major difference between these molecules is in the C(9)-N(1)-C(6)-C(7) torsion angles [58.8(8)˚and 1(1)˚]. Both molecules have intramolecular N(1)-H(10)'N(3) hydrogen bonds [ 2.613(7) and 2.566(7) A] and assume V-shaped conformation with N(2) atoms at the verices. The two independent molecules are linked by the two N(2)-H(11)'S' hydrogen bonds[3.367(5) A and 3.421(4)A] and the dimergen are held together by van der Waals forces.

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Synthesis of 7-Deazapurine Derivatives (7-데아자퓨린 유도체의 합성)

  • 신관석;남재우;이창규;전종갑
    • YAKHAK HOEJI
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    • v.37 no.3
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    • pp.228-234
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    • 1993
  • A new series of 7-deazapurine derivatives[7,8] as purine antagonists was prepared. Diethyl 4-cyano-N-(diphenyimethylene)-3-arylglutamate[3] were synthesized by LDA-catalyzed Michael addition of N-(diphenylrnethylene)glycine ethyl ester with (E)-2-cyano-3-arylacrylate. Deprotection yields diethyl 4-cyano-3-arylglutamate, which were easily cyclized to 4-cyano-2-ethoxycarbonyl-5-oxo-3-arylpyrrolidine[4]. The compounds[4] were treated with NaBH$_{4}$ and then with (C$_{2}$H$_{5}$)$_{3}$OBF$_{4}$ to give 4-cyano-5-ethoxy-2H-2-ethoxymethyl-3-aryl-3,4-dihydropyrrole[6], which were converted to 7-aryl-6-amino-8-ethoxymethyl-7,8-dihydro-7(3H, 9H)-deazapurine-2-thione[7] and 7-aryl-2,6-diamino-8-ethoxymethyl-7,8-dihydro-7(9H)-deazapurine[8] with possible activity against neoplastic disease.

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The Interaction of Gallium Bromide with n-Propyl Bromide in Nitrobenzene and 1,2,4-Trichlorobenzene (니트로벤젠溶液 및 1,2,4-트리클로로벤젠溶液內에서의 브롬화갈륨과 n-브롬화프로필과의 相互作用)

  • Oh Cheun Kwun;Young Cheul Kim;Dong Sup Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.4
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    • pp.302-309
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    • 1980
  • The solubilities of n-propyl bromide in nitrobenzene and in 1,2,4-trichlorobenzene have been measured at 19, 25 and $40^{\circ}C$ in the presence and absence of gallium bromide. When gallium bromide does not exist in the system, the solubility of n-propyl bromide in nitrobenzene is greater than in 1,2,4-trichlorobenzene, indicating a stronger interaction of n-propyl bromide with nitrobenzene than with 1,2,4-trichlorobenzene. In the presence of gallium bromide, 1: 1 complex $n-C_3H_7Br\cdotGaBr_3$ is formed in the solution. The instability constant K of the complex was evaluated. $$n-C_3H_7Br\cdotGaBr_3 \rightleftarrows n-C_3H_7Br + \frac{1}{2Ga_2Br_6 }$$The change of enthalpy, free energy and entropy for the dissociation of the complex were also calculated. It seems that the stabilities of the complex, gallium bromide with alkyl bromide, are relatively concerned with the stabilities of the alkyl ion.

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Synthesis of 7-Hydroxy-4-Oxo-4H-Chromene- and 7-Hydroxychroman-2-Carboxylic Acid N-Alkyl Amides and Their Antioxidant Activities

  • Kwak, Jae-Hwan;Kang, Hae-Eun;Jung, Jae-Kyung;Kim, Hwa-Jung;Cho, Jung-Sook;Lee, Hee-Soon
    • Archives of Pharmacal Research
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    • v.29 no.9
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    • pp.728-734
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    • 2006
  • A series of 7-hydroxy-4-oxo-4H-chromene- (3a - h) and 7-hydroxychroman-2-carboxylic acid N-alkyl amides (4a - g) were synthesized and their antioxidant activities were evaluated. While compounds 3a - h were less active, compounds 4a - g exhibited more potent inhibition of lipid peroxidation initiated by $Fe^{2+}$ and ascorbic acid in rat brain homogenates. Among them, 7-hydroxychroman-2-carboxylic acid N-alkylamides (4e - g) bearing nonyl, decyl, and undecyl side chain exhibited 3 times more potent inhibition than trolox (1).

Stability Constants of First-row Transition Metal and Trivalent Lanthanide Metal Ion Complexes with Macrocyclic Tetraazatetraacetic and Tetraazatetramethylacetic Acids

  • 홍춘표;김동원;최기영;김창태;최용규
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.297-300
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    • 1999
  • The protonation constants of the macrocyclic ligands, 1,4-dioxa-7,10,13,16-tetraaza-cyclooctadecane-N,N',N",N"'-tetra(acetic acid) [N-ac4[18]aneN402] and 1,4-dioxa-7,10,13,16-tetraazacyclooctadecane-1,4-dioxa-7,10,13,16-N,N',N",N"'-tetra(methylacetic acid) [N-meac4[18]aneN4O2] have been determined by using potentiometric method. The protonation constants of the N-ac4[18]aneN4O2 were 9.31 for logK1H, 8.94 for logK2H, 7.82 for logK3H, 4.48 for logK4H and 2.94 for logK5H. And the protonation constants of the N-meac4[18]aneN4O2 were 9.34 for logK1H, 9.13 for logK2H, 8.05 for logK3H, 5.86 for logK4H, and 3.55 for logK5H. The stability constants of complexes on the divalent transition ions (Co2+, Ni2+, Cu2+, and Zn2+) and tiivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with ligands N-ac4[18]-aneN4O2 and N-meac4[18]aneN4O2 have been obtained from the potentiometric data with the aid of the BEST program. The three higher values of the protonation constants for synthesized macrocyclic ligands correspond to the protonation of nitrogen atoms, and the fourth and fifth values correspond to the protonation of the carboxylate groups for the N-ac4[18]aneN4O2 and N-meac4[18]aneN4O2. The meatal ion affinities of the two tetra-azamacrocyclic ligands with four pendant acetate donor groups or methylacetate donor groups are compared. The effects of the metal ions on the stabilities are discussed, and the trends in stability constants resulting from changing the macrocyclic ring with pendant donor groups and acidity of the metal ions.

Reactions, Hydrogenation and Isomerization of Unsaturated Esters with a Rhodium(I)-Perchlorato Complex

  • Jeong Hyun Mok;Chin Chong Shik
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.468-471
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    • 1986
  • The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.