• YAKHAK HOEJI
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• v.38 no.4
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• pp.455-461
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• 1994

Each nitrogen and oxygen site isotope enriched the cyclophosphamide metabolite phosphoramide mustard was synthesized. Reaction of N,N-bis(2-chloroethyl)phosphoramidic dichloride$[Cl_2P(O)N(CH_2CH_2Cl)_2]$ with benzyl alcohol and ammonia gave N,N-bis(2-chloroethyl)phosphorodiamidic acid phenylmethyl ester $[BzO(H_2N)P(O)N(CH_2CH_2Cl)_2]$. Catalytic hydrogenation of this benzyl ester followed by the addition of cyclohexylamine provided PM. Incorporation of $^{15}NH_3$ into this general scheme gave PM with a $^{15}NH_2$ moiety. Glycine-$^{15}N$ was converted to bis(2-chloroethyl)amine-$^{15}N$ hydrochloride which, in turn, provided for N,N-bis(2-chloroethyl)phosphorodiamidic-$^{15}N$ dichloride. Use of this compound in the general synthetic pathway yielded PM CHA with $^{15}N$ in the mustard moiety. $^{17}O$-Enriched PM was generated through the use of benzyl alcohol-$^{17}O$. To obtain the alcohol, labelled benzaldehyde was made by exchange with $^{17}OH_2$ and was then reduced with sodium borohydride.

• Archives of Pharmacal Research
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• v.6 no.2
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• pp.115-121
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• 1983

Cholesteryl p-[3-(2-chloroethyl_-3-nitrosoureido] phenylthioaccetate (2) was synthesized : an intermediate, p-[3(2-chloroethyl_-3-nitrosoureido] phenylthioacetic acid (1) is a congener of an antitumor chlorambucil which both the -CH$_{2}$CH$_{2}$-linkage and -N(CH$_{2}$CH$_{2}$Cl)$_{2}$ group of chlorambucil molecule is doubly modified into the respective -S-linkage and -NH-CO-NNO-CH$_{2}$CH$_{2}$CL group. The attackment of cholesterol moiety as a carrier group to p-[3-(2-chloroethyl-3nitrosoureido] phenylthioacetic acid was accomplished through the esterification of cholesterol with p-[3-(2-chloroethyl-3-nitrosoureido] phenylthioacetyl chloride which was obtained from the treatment of p-[3-(2-chloroethyl)-3-nitrosourei-do] phenylthioaceticacid with SOCL$_{2}$, p-[3-(2-chloroethyl)ureido]]-phenythioacetic acid was nitrosated with NaNO$_{2}$ IN 98-100% HCOOH to give exclusively p-[3-(2-chloroethyl_-3-nitrosoureido] phenylthioacetic acid. Antitumor evaluation of compounds, 1 and 2 on L 1210 leukemia did show significant activity (ED$_{40}$ : 1.14.mu./ml and 8.4.mu.g/ml, repectively). Further studies were subjected..

• Electronic Materials Letters
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• v.14 no.6
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• pp.712-717
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• 2018

In this letter, we have introduced copper chloride ($CuCl_2$) as an additive in the $CH_3NH_3PbI_3$ precursor solution to improve the surface morphology and crystallinity of $CH_3NH_3PbI_3$ films in a single solvent system. Our optimized perovskite solar cells (PSCs) with 2.5 mol% $CuCl_2$ additive showed best power conversion efficiency (PCE) of 15.22%. The PCE of the PSCs fabricated by $CuCl_2$ (2.5 mol%) additive engineering was 56% higher than the PSC fabricated with pristine $CH_3NH_3PbI_3$.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Nuclear Engineering and Technology
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• v.5 no.4
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• pp.321-333
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• 1973

The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.961-966
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• 1994

Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.223-238
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• 1974

CNDO/2 MO theoretical studies and kinetic studies of halide exchange reactions for alkylchloroformates have been carried out in order to investigate structure-reactivity relationship of alkylchloroformates. From the result of energetics, it was concluded that the most stable configuration of alkylchloroformate is that in which alkyl group and chlorine are trans to each other, and that the hindered rotation about the bond between the carbonyl carbon and alkoxy-oxygen bond is attributed to the ${\pi}-$electron delocalization. It has been found that the large charge separation is due to -M effect of carbonyl and alkoxy oxygens and-I effect of chlorine. The order of rates in solvents studied was $(CH_3)_2 > CO > CH_3CN{\gg}MeOH.$$I^->Br^->Cl^-$ in protic solvent, and of Cl^->Br^- >I^-$ in dipolar aprotic solvents. Alkyl group contribution has the decreasing order of $CH_3-> C_2H-{\gg}i-C_3H_7-.$ The solvent effect has been interpreted on the basis of initial and final state contribution. A transition state model has been suggested, and it has been proposed that the most favorable mechanism is the addition-elimination. From the results of activation parameters and electronic properties, an energy profile has been proposed. Structural factors determining reactivities of alkylchloroformates have been shown to be charge, energy level of ${\alpha}^*LUMO$ to C-Cl bond and ${\alpha}^{\ast} $antibonding strength with respect to C-Cl bond in this MO. Charge and polarizability of nucleophile, and the interaction of these effects with solvent structures are also found to be important.

• Bulletin of the Korean Chemical Society
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• v.5 no.5
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• pp.199-201
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• 1984

It has been found that $Rh(ClO_4)(CO)(P(C_6H_5)_3)_2$ catalyzes the hydrogenation and isomerization of soybean oil at room temperature under the atmospheric pressure of hydrogen. The hydrogenation occurs at the olefinic groups to produce saturated groups leaving the ester groups intact, and the isomerization converts $-CH = CH- CH_2-CH = CH-$ units to conjugated dienes and the dienes separated by more than two $-CH_2-$ groups. The rate of the hydrogenation is faster than that of the isomerization.

• Journal of Embryo Transfer
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• v.22 no.1
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• pp.69-74
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• 2007

This study was performed to determine the estrous cycles by macroscopic observation of the ovarian changes using the laparoscopy and to make use of these results for embryo transfer in Korean black goat (Copra hircus aegagrus). Laparoscopic examinations of the ovaries were performed from 2 days after $CIDR^(R)$ removal to 22 days after ovulation. The serial morphological changes of follicles and corpus luteum (CL) were observed. CL was classified corpus hemorrhagicum(CH), corpus luteum (CL) and corpus albicans (CA) by its maturation and regression. On the day before ovulation (Day 0), Graafian follicles (GF) were found on one or both ovaries. On the day (Day 1) and $2^{nd}$day (Day 2) of ovulation, and ovulation depression (OD) and an early stage corpus hemorrhagicum $(CH_1)$ were observed at the site of GF, respectively. On Days 3 to 4, more developed and enlarged corpus hemorrhagicum $(CH_2\;and\;CH_3)$ arised from the ovulation of the GF with well vascularization. On Days 5 to 6, it was identified that mature corpus luteum $(CL_3)$ was grown on the ovary, and fully developed CL with adjacent follicles were occupied most part of the ovary on Days 17 and 18. Then the size of CL was diminished, and completely luteal regression $(CL_1\;or\;CA)$ with new large follicle was identified on Days 20 and 22. From these results, the 4 stages of the estrous cycle in Korean black goats were 1) estrus (Day 0) for 1 day, 2) metestrus $(Day\;1{\sim}4)$ for 4 days (stage of CH development), 3) diestrus $(Day\;5{\sim}16/17)$ for 12 or 13 days (luteal stage), and 4) proestrus $(Day\;17/18{\sim}20/22)$ for 4 or 5 days (stage of luteal regression and follicular growing). Laparoscopy for observation of ovarian changes was invasive than laparotomy. Additionally, it had advantages of reduced adhesion and quick operation time. It was considered that laparoscopic examination of ovarian changes will be useful for embryo transfer in the Korean black goats.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.207-214
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• 1987

Rates of solvblysis of benzyl chloride in ethanol-water mixtures have been measured at 30 and $40^{\circ}C$ under various pressures up 1.6 kbar. The plots of 1n k as a function of pressure are fitted to a second order function in p, and values of ${\Delta}V^{\neq}$and ${\Delta}{\beta}^{\neq}$ are obtained from the results. Also the values of various pseudo thermodynamic quantities were evaluated from the rate constants. The relationships of the 1n k to $Q_w$ or 1n $C_w$ indicate that the reaction proceeds through $S_N1$ mechanism. A comparison between the present and the previous results gives that the increasing order of ${\mid}{{\Delta}V_0}^{\neq}{\mid}$ and n-values are $p-Cl>p-H>p-CH_3$ and $p-CH_3>p-H.p-Cl$, respectively. From these results, it is believed substituent such as the $p-CH_3$group favors the $S_N1(1)$ character, while the p-Cl group leads to the $S_N1(2)$ character.