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Synthesis of Chloroacetamide Compounds and their Herbicidal Activities (Chloroacetamide형(型) 화합물(化合物)의 합성(合成)과 제초활성(除草活性))

  • Hong, Moo-Ki;Jeong, Young-Ho;Oh, Se-Mun
    • Applied Biological Chemistry
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    • v.31 no.3
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    • pp.234-240
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    • 1988
  • Some chloroacetamide derivatives were synthesized from 2,6-dialkyl, aniline 4-chloroaniline, or 3,4-dichloroaniline with alkyl 2-bromopropionate and chloroacetyl chloride and identified by elemental analyses, NMR, and GC/MS spectra as N-(1'-methoxycarbonylethyl)-N-chloroacetyl-2,6-dimethylaniline(ACRI-S-8609), etc. These compounds synthesized were subjected to the test for pre-emergence herbicidal effecs on some grass weeds(Digitaria adscendens, Setaria viridis, Echinochloa crus-galli) and broad leaf weeds(Portulaca oleracea, Amaranthus lividus, Chenopodium album) in pots applied as wettable powder formulations. It was found that N-(1'-ethoxycarbonylethyl)-N-chloroacetyl-2,6-dimethylaniline(ACRI-S-8701) has the highest herbicidal effect on grass weeds, which corresponds to a 95% control effect at an application of 200g a.i/10a. Whereas, some chloroacetamide derivatives derived from 4-chloroaniline or 3,4-dichloroaniline had very weak herbicidal effects on grass and broad leaf weeds.

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Comparative molecular field analysis (CoMFA) and holographic quantitative structure-activity relationship (HQSAR) on the growth inhibition activity of the herbicidal 3-phenyl-5-(3,7-dichloro-8-quinolinyl)-1,2,4-oxadiazole derivatives (제초성 3-Phenyl-5-(3,7-dichloro-8-quinolinyl)-1,2,4-oxadiazole 유도체들의 생장 저해활성에 관한 비교 분자장 분석 (CoMFA)과 분자 홀로그램 구조-활성관계 (HQSAR))

  • Sung, Nack-Do;Lee, Sang-Ho;Song, Jong-Hwan;Kim, Hyoung-Rae
    • The Korean Journal of Pesticide Science
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    • v.7 no.2
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    • pp.108-116
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    • 2003
  • A series of new quinclorac family, herbicidal 3-phenyl-5-(3,7-dichloro-8-quinolinyl)-1,2,4-oxadiazole derivatives as substrate were synthesized and their growth inhibition activity $(pI_{50})$ against root and shoot of rice plant (Oryza sativa L.) and barnyard grass (Echinochloa crus-galli) were determined. And then comparative molecular field analysis (CoMFA) and molecular holographic quantitative structure- activity relationship (HQSAR) were compared in terms of their potential for predictiability. The statistical results were suggested that HQSAR based model had better predictability than CoMFA model. The selective factors to remove barnyard grass take electron withdrawing groups which can be created positive charge and steric bulky on the phenyl ring. Results revealed that the unknown 2,6-dichloro-substituent, U5 and 2,4,6-trichloro-substituent, U6(${\Delta}pI_{50}$=CoMFA: 1.18 & HQSAR: 1.82) were predicted as compound with higher activity and selectivity.

Synthesis of a series of cis-diamminaedichloro-platinum (II) Complexes Linked to Uracil and Uridine as Candidate An-titumor Agents.

  • Kim, Jack-C.;Kim, Mi-Hyang;Kim, Seon-Hee;Choi, Soon-Kyu
    • Archives of Pharmacal Research
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    • v.18 no.6
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    • pp.449-453
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    • 1995
  • The search for patinum (II)-based compounds with improved therapeutic properties was prompted to design and synthesize a new family of water-soluble, third generation cis-diamminedichlorplatinum (II) complexes linked to uracil and uridine. Six heretofore undescribed uracil and uridine-platinum (II) complexes are ; [N-(2-aminoethyl)uracil-5-carboxamide]dichloroplatinum (II)(3a), [N-2(2-aminoethyl)uracil-6-carboxmide]dichloroplatinum (II) (3b),[5-(2-aminorthyl)carbamoyl-2',3',5',-tri-O-acetyluridine] dichloroplatinum (II) (6b), [5-(2-aminoethyl)-carbamoyl]-2',3',5',-tri-O-acetyluridine] dichloroplatinum (II) (6b), [5-(2-aminoethyl)carbamoylu-ridine]dihloroplatinum (II) (7a), [6-(2-aminoethyl)carbamoyluridine]dichloroplatinum (II) (7b). These analogues were prepared from the key starting materials, 5-carboxyuracil (1a) and 6-carboxyuracil (1b) which were reacted with ethylenediamine to afford the respective N-(2-aminoethyl)uracil-5-carboxmide (2a) land N-(2-aminoethyl)uracil-6-carboxamide (2b). The cisplatin complexes 3a and 3b were obtained through the reaction of the respective 2a and 2b ficiently introduced on the .betha.-D-ribose ring via a Vorbruggen-type nucleoside coupling procedure with hexamethyldisilazane, trimethylchlorosilane and stannicchloride under anhydrous acetonitfile to yield the sterospecific .betha.-anomeric 5-carboxy-2',3',5'-tri-O-acetyluridine (4a) and 6-carboxy-2',3',5'-tri-O-acetyluridine (4b), respective 5-(2-aminoethyl)carbamoyl-2',3',5'-tri-O-acetyluridine (5a) and 6-(2-aminoethyl)carbamoyl-2',3',5'-tri-O-acetyluridine (5b). The diamino-uridines 5a and 5b were reacted with potassium tetrachloroplatinate (II) to give the novel nucleoside complexes, 6a and 6b respectively which were deacetylated into the free nucleosides, 7a and 7b by the treatment with CH/sub 3/ONa. The antitumor activities were evaluated against three cell lines (K-562, FM-3A and P-388).

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Studies of Solvolyses of Biphenyl-4-carbonyl Chloride by Extended Grunwald-Winstein Equation (확장된 Gruwald-Winstein 식에 의한 Biphenyl-4-carbonyl chloride의 가용매분해 반응대한 연구)

  • Choi, Hojune;Koh, HanJoong;Yang, Kiyull;Koo, InSun
    • Journal of the Korean Chemical Society
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    • v.60 no.1
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    • pp.16-20
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    • 2016
  • The solvolysis rate constants of biphenyl-4-carbonyl chloride (C6H5C6H5COCl, 1) in 19 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale, YCl solvent ionizing scale, and I aromatic ring parameter with sensitivity values of 0.31±0.10, 0.46±0.05, and 0.96±0.20 for l, m, and h, respectively. These l, m, and h values can be considered to support a dissciative SN2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH (15.3~16.1 kcal/mol) values and large negative ΔS (−17.2~−20.0 cal/mol·K) values.

Crystal Structure of Dehydrated Partially Cobalt(II)-Exchanged Zeolite X, $Co_{41}Na_{10}-X$ (부분적으로 $Co^{2+}$ 이온으로 치환된 제올라이트 X, $Co_{41}Na_{10}-X$를 탈수한 결정구조)

  • Jang, Se-Bok;Jeong, Mi-Suk;Han, Young-Wook;Kim, Yang
    • Korean Journal of Crystallography
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    • v.6 no.2
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    • pp.125-133
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    • 1995
  • The crystal structure of dehydrated, partially Co(II)-exchanged zeolite X, stoichiometry Co2+Na+-X (Co41+Na10Si100Al92O384) per unit cell, has been determined from three-dimensional X-ray diffraction data gathered by counter methods. The structure was solved and refined in the cubic space group Fd3:α=24.544(1)Å at 21(1)℃. The crystal was prepared by ion exchange in a flowing stream using a solution 0.025 M each in Co(NO3)2 and Co(O2CCH3)2. The crystal was then dehydrated at 380℃ and 2×10-6 Torr for two days. The structure was refined to the final error indices, R1=0.059 and R2=0.046 with 211 reflections for which I > 3σ(I). Co2+ ions and Na+ ions are located at the four different crystallographic sites. Co2+ ions are located at two different sites of high occupancies. Sixteen Co2+ ions are located at the center of the double six-ring (site I; Co-O = 2.21(1)Å, O-Co-O = 90.0(4)°) and twenty-five Co2+ ions are located at site II in the supercage. Twenty-five Co2+ ions are recessed 0.09Å into the supercage from its three oxygen plane (Co-O = 2.05(1)Å, O-Co-O = 119.8(7)°). Na+ ions are located at two different sites of occupandies. Seven Na+ ions are located at site II in the supercage (Na-O = 2.29(1)Å, O-Na-O = 102(1)°). Three Na+ ions are statistically distribyted over site III, a 48-fold equipoint in the supercages on twofold axes (Na-O = 2.59(10)Å, O-Na-O = 69.0(3)°). Seven Na+ ions are recessed 1.02Å into the supercage from the three oxygen plane. It appears that Co2+ ions prefer sites I and II in order, and that Na+ ions occupy the remaining sites, II and III.

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The Early Experience with a Laparoscopy-assisted Pylorus-preserving Gastrectomy: A Comparison with a Laparoscopy-assisted Distal Gastrectomy with Billroth-I Reconstruction (복강경 보조 유문부보존 위절제술의 초기 경험: 복강경 보조 원위부 위절제술 후 Billroth-I 재건술과의 비교)

  • Park, Jong-Ik;Jin, Sung-Ho;Bang, Ho-Yoon;Chae, Gi-Bong;Paik, Nam-Sun;Moon, Nan-Mo;Lee, Jong-Inn
    • Journal of Gastric Cancer
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    • v.8 no.1
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    • pp.20-26
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    • 2008
  • Purpose: Pylorus-preserving gastrectomy (PPG), which retains pyloric ring and gastric function, has been accepted as a function-preserving procedure for early gastric cancer for the prevention of postgastrectomy syndrome. This study was compared laparoscopy-assisted pylorus-preerving gastrectomy (LAPPG) with laparoscopy-assisted distal gastrectomy with Billroth-I reconstruction (LADGB I). Materials and Methods: Between November 2006 and September 2007, 39 patients with early gastric cancer underwent laparoscopy-assisted gastrectomy in the Department of Surgery at Korea Cancer Center Hospital. 9 of these patients underwent LAPPG and 18 underwent LADGBI. When LAPPG was underwent, we preserved the pyloric branch, hepatic branch, and celiac branch of the vagus nerve, the infrapyloric artery, and the right gastric artery and performed D1+$\beta$ lymphadenectomy to the exclusion of suprapyloric lymph node dissection. The distal stomach was resected while retaining a $2.5{\sim}3.0\;cm$ pyloric cuff and maintaining a $3.0{\sim}4.0\;cm$ distal margin for the resection. Results: The mean age for patients who underwent LAPPG and LADGBI were $59.9{\pm}9.4$ year-old and $64.1{\pm}10.0$ year-old, respectively. The sex ratio was 1.3 : 1.0 (male 5, female 4) in the LAPPG group and 2.6 : 1.0 (male 13, female 5) in the LADGBI group. Mean total number of dissected lymph nodes ($28.3{\pm}11.9$ versus $28.1{\pm}8.9$), operation time ($269.0{\pm}34.4$ versus $236.3{\pm}39.6$ minutes), estimated blood loss ($191.1{\pm}85.7$ versus $218.3{\pm}150.6\;ml$), time to first flatus ($3.6{\pm}0.9$ versus $3.5{\pm}0.8$ days), time to start of diet ($5.1{\pm}0.9$ versus $5.1{\pm}1.7$ days), and postoperative hospital stay ($10.1{\pm}4.0$ versus $9.2{\pm}3.0$ days) were not found significant differences (P>0.05). The postoperative complications were 1 patient with gastric stasis and 1 patient with wound seroma in LAPPG group and 1 patient with left lateral segment infarct of liver in the LADGB I group. Conclusion: Patients treated by LAPPG showed a comparable quality of surgical operation compared with those treated by LADGBI. LAPPG has an important role in the surgical management of early gastric cancer in terms of quality of postoperative life. Randomized controlled studies should be undertaken to analyze the optimal survival and long-term outcomes of this operative procedure.

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The Variation of Natural Population of Pinus densiflora S. et Z. in Korea -Characteristics of Needle and Wood of Wangsan, Bonghwa and Yangju Populations- (소나무 천연집단(天然集團)의 변이(變移)에 관(關)한 연구(硏究)(VII) -왕산(旺山), 봉화(奉化), 양주집단(楊州集團)의 침엽(針葉) 및 재질형질(材質形質)-)

  • Yim, Kyong Bin;Lee, Kyong Jae
    • Journal of Korean Society of Forest Science
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    • v.40 no.1
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    • pp.1-18
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    • 1978
  • Three Pinus densiflora populations as shown in location map (Fig. 1) were studied in 1977. These succeed the population numbers 10, 11 and 12 after the preceeding populations. Following the previous study methods, 20 trees were chosen from each population and the morphological characteristics such as tree forms, branching habit, needle and wood properties were investigated. The results are summerized as follows; 1. The mean stand ages were ranged from 40 to 45. The growth performances of trees of population 10 and 11 was similar, but 12 seemed to be inferior more or less. 2. The ratios of clear bole length was 0.53 in population 12 as the highest but 0.43 for population 10 as the lowest. 3. The population 12 was considered to be a stand of the coarser branching habit having the crown index (The maximum crown diameter/the crown length) 1.65 though the mean branching angle indicates almost horizontal. 4. The differences were observed in the clear bole length ratios and crown-indices between populations as shown in Fig. 3 and 4. 5. No inter-population differences in serration density of needle was shown but significant inter and intra-population and individual differences (within population) in number of stomata rows and resin duct. 6. Population 12 shown 0.119 of resin duct index as the maximum. 7. The pattern of diameter growth, analyses based on the width of 10-year-ring segment unit (for example, the 1st segment denotes the width between pith center and 10th year ring and the 2nd one is from 11th to 20th year ring and so on.), was alike among populations as shown in Fig. 9. 8. No significant differences between population in mean summer wood percentages as well as in wood specific gravity was observed. The values of wood specific gravity were increased with the increase of ages in population 10 and 11 however vice versa in population 12. 9. The fiber length was increased with the increase of age but no differences between populations as shown in Fig. 12.

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The Variation of Natural Population of Pinus densiflora S. et Z. in Korea (IX) -Needle and Wood Characteristics of Six Populations- (소나무천연집단(天然集團)의 변이(變異)에 관(關)한 연구(硏究)(IX) -광주(廣州), 제천(堤川), 보은(報恩), 무주(茂朱), 구례(求禮), 제주집단(濟州集團)의 침엽(針葉) 및 재질형질(材質形質)-)

  • Yim, Kyong Bin;Lee, Kyong Jae
    • Journal of Korean Society of Forest Science
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    • v.44 no.1
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    • pp.1-25
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    • 1979
  • Six natural populations of Pinus densiflora S. et Z. as shown in the location map (Flg 1) were studied during 1978. The numerial pouplation codes, 13 to 18. The results of populations 1 to 12 were reported in previous papers. Following the study methods described before, 20 trees were sampled from each population and morpological characteristics such as stem forms, branching habit needle and wood properties investigated. The results are summerized as follows; 1. The mean stand ages were ranged from 36 to 97 of years. The growth performances of trees of population 14. 15 and 18 was similar, but 13, 16, and 17 seemed to be inferior more or less. 2. The ratios of clear bole length were 0.70 in population 18 as the highest but 0.28 for population 16 as the lowest. 3. The population 17 was considered to be a stand of the coarser branching habit having the crown index (The maximum crown diameter/the crown height) 158 though the branching angles were almost horizontal. 4. The differences were observed in the clear bole length ratios and crown-indices between population as shown In Fig. 3 and 4. 5. As to the serration density, number of stomata row and resin duct; the significant differences exist between individual trees within population and also between populations. 6. Population 18 shown resin duct index 0.119 as the maximum. 7. The patterns of diameter growth, based on the width of 10-year-ring segment unit(for example, the 1st segment denotes the with between pith center and 10th year ring and the 2nd one is from 11th to 20th ring and so on.), were alike among populations as shown in Fig 9. 8. Significant differences between population in mean summer wood percentage as well as in wood specific gravity was observed. The values of wood specific gravity were increased with the increase of ages in population 14, 18 however vice versa in population 13, 15, and 17. 9. The fiber length was mereased with the increased of age but no differences between populations as shown in Fig. 12.

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Influence of substituted phenoxy group on the fungicidal activities of 2-N-benzyl-5-phenoxy-3-isothiazolone derivatives (2-N-benzyl-5-phenoxy-3-isothiazolone 유도체의 살균활성에 미치는 치환-phenoxy기의 영향)

  • Sung, Nack-Do;Kim, Ki-Hyun
    • The Korean Journal of Pesticide Science
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    • v.5 no.3
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    • pp.36-40
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    • 2001
  • A series of new 2-N-benzyl-5-phenoxy-3-isothiazolone derivatives were synthesized and their in vitro antifungal activities against resistant Phytophthora capsici (RPC) & sensitive Phytophthora capsici (SPC) with metalaxyl fungicide have been measured. In addition, influence of substituted 5-phenoxy group on the -antifungal activities ($pI_{50}$) and the reactivity of substrates were investigated. From the results, reactivity of none substituted substrate showed tendency displaying orbital-controlled reaction. The substituents on the 5-phenoxy ring showed selective fungicidal activity between SPC and RPC. Especially, the 4-fluoro substituent, 6 in the RPC and 4-nitro substituent, 3 in SPC exhibited strongly selective antifungal activity among them. The activities on the SPC would depend largely on the optimal molar refractivity ($MR_{(opt.)}=7.37cm^3/mol$) whereas the activities on the RPC would depend largely on the optimal highest occupied molecular orbital energy ($HOMO_{(opt.)}=-9.2137e.v.$) and weak electron donating (${\sigma}<0$) group. And Free-Wilson analyses revealed that the antifungal activity against RPC depends on the methoxy and bromo-substituent and all of the substituents contribute to antifungal activities against SPC.

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Interpretation of Dispersion Phenomena in Grunwald-Winstein Correlation for Solvolyses of Naphthoyl Chloride

  • Ryu, Zoon-Ha;Ju, Chang-Suk;Sung, Dae-Dong;Sung, Nak-Chang;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.123-131
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    • 2002
  • Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).