• Title/Summary/Keyword: Diethyl phosphate

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Benzotriazol-1-yl Diethyl Phosphate and Benzotriazol-1-yl Diphenyl Phosphate. New Convenient Reagents for the Peptide Synthesis

  • Kim, Sung-Gak;Chang, He-Ung;Ko, Young-Kwan
    • Bulletin of the Korean Chemical Society
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    • 제8권6호
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    • pp.471-475
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    • 1987
  • Benzotriazol-1-yl Diethyl phosphate and benzotriazol-1-yl diphenyl phosphate were conveniently prepared in essentially quantitative yields by the reaction of diethyl chlorophosphate and diphenyl chlorophosphate with equal amounts of 1-hydroxybenzotriazole and triethylamine in tetrahydrofuran at room temperature, respectively. Benzotriazol-1-yl diethylphosphate was effective for the preparation of amides from carboxylic acids amines. Young test and Anderson test for racemization studies using benzotriazol-1-yl diethyl phosphate were investigated and practically no racemization occurred. However, racemization occurred to some extent during coupling of Z-Phe-Val-OH with Pro-OBu. Several dipeptides and tripeptides were prepared without little racemization using benzotriazol-1-yl diethyl phosphate. Benzotriazol-1-yl diphenyl phosphate was less effective than benzotriazol-1-yl diethyl phosphate in terms of the degree of racemization.

O,O-Diethyl-S-Phenyl $Phosphorothiolate-^{18}O$의 산화반응기작 (Mechanistic Investigation in the Oxidation of ${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-Phenyl\;Phosphorothiolate-^{18}O$)

  • 김정한
    • Applied Biological Chemistry
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    • 제37권3호
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    • pp.210-215
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    • 1994
  • ${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$와 관련화합물들을 합성하고 MCPBA로 산화시켰다. 각 반응을 $^{31}P$ NMR로 추적하였고 반응산물을 GC-MS로 분석하였다. ${\underline{O}},{\underline{O}}-Diethyl-{\underline{S}}-phenyl\;phosphorothiolate-^{18}O$은 메탄올에서 MCPBA에 의해 diethyl methyl phosphate로 전환되며 $^{18}O$를 포함하고 있어 이 산화반응은 Segall과 Casida가 제안하였던 반응기작을 따르고 있음이 증명되었다.

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Electrostatic Interaction Between Oligopeptides and Phosphate Residues by Determination of Absolute Raman Intensities

  • Kye-Taek Lim
    • Bulletin of the Korean Chemical Society
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    • 제12권3호
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    • pp.286-289
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    • 1991
  • The changed isotropic absolute Raman intensities of the phosphate residue in the complexes of positive charge oligopeptides, lys-lys, arg-arg, lys-aromat-lys, negative charge diethyl phosphoric acid (DEP) and polyriboadenylic acid{poly(rA)} were reported and discussed. Our measurements showed that the absolute intensities of phosphate stretch vibration in complexes were different according to the reaction partners. Due to the partial electrical charge and molecular structure of oligopeptides for the complex formation lysine can interact more strongly than arginine when the reaction partners have short chain and no steric hindrance. Owing to these reasons the intensity of phosphate stretching vibration is very sensitive according to the circumstance of reaction. From our results we could suggest that we can discriminate any one of the the lysine and arginine in the complicated biological molecule during interaction between nucleotides and proteins. The activity of reaction of two basical oligopeptides is not quite similar for complex formation in aqueous solution. The activity of dipeptides depends upon the structure of molecule and environment for complex formation. Aromatic ring contributes to electrostatic interaction in complexes. The amount of the absolute intensity for pure stacking interaction is smaller than electrostatic interaction in macromolecular complexes.

인산디에틸 이소프로페닐과 초산비닐 및 아크릴로니트릴의 혼성중합 (Copolymerization of Diethyl Isopropenyl Phosphate with Vinyl Acetate and Acrylonitrile)

  • 진정일;심홍구;이수민
    • 대한화학회지
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    • 제26권6호
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    • pp.421-426
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    • 1982
  • 자유 라디칼 개시제에 의한 인산디에틸이소프로페닐(DEIPA)과 초산비닐(VAc) 및 아크릴로니트릴(An)의 혼성중합 연구를 행하여 단위체 반응성비를 얻었다. 개시제로는 과산화벤조일을 사용하였으며 중합온도는 $60^{\cric}C$이었다. 단위체 반응성비는${\gamma}_1$(VAc) = 1.56, ${\gamma}_2$(DEIPA) = 0.44: ${\gamma}_1$(AN) = 15.2, ${\gamma}_2$(DEIPA) = 0.031이었다. 이 값으로부터 DEIPA의 Alfrey-Price 상수 Q=0.015, e=0.39 및 Q=0.014, e=0.34를 얻었으며${\alpha}$ 위치에 있는 메틸기가 반응성을 감소시킴을 알았다. 공중합체중 DEIPA의 함량이 증가함에 따라 공중합체의 고유점성도 및 수평균 분자량이 감소함도 알았다.

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일부 농업인의 개인보호구 착용빈도 점수와 요 중 유기인계 농약 대사체 농도와의 연관성 (The Relationship between Frequency Score of Wearing Personal Protective Equipment and Concentration of Urinary Organophosphorus Pesticide Metabolites in Farmers)

  • 최지희;문선인;노상철
    • 한국환경보건학회지
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    • 제45권6호
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    • pp.583-593
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    • 2019
  • Objectives: The purpose of this study was to evaluate the relationship between the frequency score of wearing personal protective equipment (PPE) and concentration of urinary organophosphorus pesticide metabolites in farmers. Methods: The study was conducted in Chungcheongnam-do Province of South Korea. We collected urine samples from 308 farmers from September to December 2017 and May to July 2018. Among them, 17 farmers with urinary creatinine levels outside the normal range were excluded. Information on the frequency of wearing PPE was obtained from the farmers through face-to-face survey. Each frequency of wearing for seven types of PPE was converted into a score and expressed as a total score, which was divided into quartiles. Four types of urinary organophosphorus pesticide metabolites were analyzed using a gas chromatography mass selective detector. Multiple linear regression analysis was used to identify concentrations of urinary organophosphorus pesticide metabolites affected by the frequency of wearing PPE. Results: The average frequency score of wearing PPE was 8.0. The quartiles of frequency score of wearing PPE were divided as follows: 1st quartile (≤1), 2nd quartile (1-6), 3rd quartile (6-12), and 4th quartile (>12). Compared with subjects with a low frequency score of wearing PPE (reference), subjects with a high frequency score of wearing PPE (4th quartile) had lower concentrations of urinary diethyl phosphate (DEP) (p<0.01) and dialkyl phosphate (ΣDAP) (p<0.05), which is the sum of dimethyl phosphate (DMP), DEP, dimethyl thiophosphate (DMTP), and diethyl thiophosphate (DETP). Conclusion: Concentrations of urinary organophosphorus pesticide metabolites were associated with frequency score of wearing PPE. Particularly as the frequency score of wearing PPE increased, concentrations of urinary DMP, DEP, DETP, and ΣDAP significantly decreased. The findings of this study can contribute to the management of health effects among farmers working with pesticides.

Electron Impact Fragmentations of Chlorinated Organophosphorus Pesticides

  • 홍종기;김도균;팽기정
    • Bulletin of the Korean Chemical Society
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    • 제21권8호
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    • pp.785-792
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    • 2000
  • Mass spectral fragmentations of six chlorinated organophosphorus pesticides were investigated using electron impact mass spectrometry. Understanding the fragmentation pathways, based on the fragment ions of mass spectra, should be useful in the structural elucidation and chemical identification of these compounds. The pro-posed fragmentation pathways were verified by collision-induced dissociation B/E-linked scan spectra. ln most cases,the structures of characteristic fragment ions could be expected by the observation of the peak clusters due to 35Cl and 37Cl isotopes. According to substituted groups on phosphorus atom, phosphate and phospho-rothioate exhibited significantIy differentfragmentation patterns. Especially, phosphate and phosphorothioate with diethyl ester produced more diverse fragment ions than that with dimethyl ester.

방사성 추적자에 의한 솔잎혹파리 방제용 살충제 phosphamidon의 소나무 수간이동 구명 : II. 소나무 체내에서의 대사 (Elucidation of the translocation of phosphamidon used for the control of pine leaf gall midges (Thecodipiosis japonensis Uchida et Inouye) in the trunks of pine trees by means of a radiotracer. Part II. Metabolism in pine trees)

  • 이재구;이형래;경기성
    • Applied Biological Chemistry
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    • 제36권6호
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    • pp.469-475
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    • 1993
  • 솔잎혹파리(Thecodiplosis japonensis Uchida et Inouye) 방제용으로 소나무의 수간에 주입된 침투성 살충제 phosphamidon(2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate)의 대사를 구명하기 위하여 $[vinyl,\;carbonyl-^{14}C]phosphamidon$을 약 10년생 소나무의 수간에 주사하고 그 솔잎 추출액을 autoradiography한 결과 phosphamidon은 소나무 체내에서 신속히 분해됨을 알 수 있었다. 솔잎의 phosphate buffer 추출액 중에서 phosphamidon은 주대사산물인 ${\alpha}-chloroacetoacetic$ acid diethylamide를 비롯하여 ${\alpha}-chloroacetoacetic$ acid ethylamide, 3-hydroxy-N,N-diethylbutanamide, acetoacetamide, 그리고 trimethyl phosphate 등의 대사산물을 생성하였으며, 이 대사작용은 소나무 체내에서도 유사하리라 추정된다. 또한 주 대사경로는 구조식중 P-O-vinyl 결합의 가수분해와 관련있는 것으로 보인다.

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2008년도 아산만 해수 중 유기인계 농약 분포 (Organophosphorous Pesticide Distribution in Seawater from Asan Bay, Korea in 2008)

  • 최진영;양동범;이성규;방재현;홍기훈;신경훈
    • Ocean and Polar Research
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    • 제32권3호
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    • pp.203-212
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    • 2010
  • Distribution of organophosphorous pesticides (OPs) was studied from February to September 2008 in the seawater of Asan Bay, Korea. Among the 29 types of OPs detected during the study period, IBP(S-benzyl O,O-diisopropyl phosphorothioate), ranging from <1 ng/l to 377 ng/l, was the most abundant. Other commonly observed OPs concentrations in the study area included diazinon (Diethyl 2-isopropyl-4-methyl-6-pyrimidinyl phosphorothionate; <1~307 ng/l), azinphos ethyl (3,4-Dihydro-4-oxo-3-benzotriazinylmethyl O,O-diethyl phosphorodithioate; <1~1997 ng/l), malathion (1,2-Di(ethoxycarbonyl)ethyl O,Odimethyl phosphordithioates; <1~3013 ng/l), demeton-O (Diethyl 2-(ethylthio)ethyl phosphorothionate; <1~2403 ng/l), and DDVP (2,2-dichlorovinyl dimethyl phosphate; <1~283 ng/l). Seasonal distribution of OPs in seawater is dependent on the OP application period. In August, OPs concentrations were generally decreased with the increased salinity of seawater, implying progressive dilution of pesticides in the estuarine system. OPs were deposited into Asan Bay from Asan and Sabkyo Lakes as well as surrounding tributaries. Ten OPs, including diazinon, were detected in the suspended particles of Asan Bay.

Diethyl maleate가 N-methyl-N'-nitro-N-nitrosoguanidine에 의해서 유발되는 랫드 위암 발생에 미치는 영향에 관한 병리학적 연구 (The Effects of diethyl maleate on the N-methyl-N'-nitro-N-nitrosoguanidine induced gastric carcinogenesis in rats)

  • 박철범;이준섭
    • 대한수의학회지
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    • 제35권4호
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    • pp.793-807
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    • 1995
  • This study was carried out to investigate the effects of diethyl maleate(DEM) on the carcinogenesis of forestomach and pyloric glandular stomach in rats caused by N-methyl-N'-nitro-N-nitrosoguanidine(MNNG). A total of 60 male 6-week-old Wistar rats were given twice intragastric injection of MMNG(200mg/kg BW), then were given diets containing 5% NaCl for 3 weeks until 4th week of the experiment. And then the animals of groups of 1 and 2 were placed on diets containing 0.2% DEM for 16 weeks until the end of 20 weeks of the experiment. On the other hand, the animals of groups of 3 and 4 were placed on basal diets for the same periods. The tissues of forestomach and liver of each group were frozen in liquid nitrogen and the activities of quinone reductase(QR) were determined by measurement of the dicoumarol-sensitive reduction of dichloro-indophenol by NADPH at 600nm. All rats were sacrificed at the end of 20 weeks of the experiment. Every animal was fasted for 24 hrs prior to sacrifice. The forestomach was fixed in 10% neutral phosphate buffered formalin for histology and the pyloric gland was fixed in sublimated formalin for immunohistochemistry of pepsinogen 1 altered pyloric gland(PAPG). The final body weight of the group given MNNG and treated with 5% NaCI and DEM was significantly decreased compared with that of the group 4(p<0.05). Food and water consumption rates were not significantly changed. The preneoplastic and neoplastic lesions of the forestomach given MNNG and treated with 5% NaCI and DEM were significantly increased compared to those of the group 4(p<0.0l). The incidence of PAPG in the groups treated with 0.2% DEM was significantly increased compared with that of the group 4(group 1:p<0.01, group 2:p<0.05). The activities of QR of forestomach in the groups treated with 0.2% DEM were significanitly increased compared with those of the group 4(p<0.001), but those of liver were not significant. These results indicate that DEM exert the enhancing effect of forestomach and glandular stomach carcinogenesis in rats pretreated with MNNG and NaCl.

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