Synthesis of Acylthiocholine and its kinetic study with Acetylcholineesterase (I)

정대일,권수천,신은화,이용균,박유미 한국생명과학회 2000 한국생명과학회 학술발표회 Vol.27 No.-

Choline esters are used as substrate of BuChE-catalyzed hydrolysis. It was synthesized by two methods. First, 2-chloroethyl hexanoate and 2-chloroethyl octanoate were synthesized by the treatment for hexanoyl chloride and octanoyl chloride with ethylene surfide. Hexanoylthiocholine and octanoylthiocholine were synthesized by using 2-chloroethyl hexanoate and 2-chloroethyl octanoate with trimethylamine. Second, after reaction of ethylene surfide and dimethylamine and acylation with acid anhydride, heptanoylthiocholine and decanoylthiocholine were synthesized by the treatment of methyl iodide. The synthesized choline esters are to study for its reactivity and strength of ES complex according to increase in number of carbon. The reaction mechanism of BuChE-catalyzed hydrolysis of choline esters (HexTCh, HepTCh, OcTCh, and DoTCh) have been surmised from kinetic parameter, pH-rate profile, and solvent isotope effects.

TiO₂를 이용한 아세틸렌, 프로필렌, 프로판 가스의 광촉매 산화반응

정대일,변석인,이도훈,이용균,박유미,최순규,김동현 동아대학교 환경문제연구소 2002 硏究報告 Vol.25 No.1

Photocatalyzed degradation of acetylene, propylene, and propane gases were carried out over precoated titanium dioxide(anatase) illuminated UV light in a flow reactor. photocatalytic oxidation of acetylene, propylene, and propane gases respectively indicated high conversion rates (78.0%) to CO₂gas. And photocatalytic oxidation of three gases according to a fold, twofold, and threefold of titanium dioxide(anatase) respectively gave high conversion rate. The longer reaction time was, the higher conversion rate to CO₂gas showed.

N-아실-α-아미노숙신이미드와 N-아실-α-아미노글루탈이미드의 합성

정대일,김문주,송현애,김윤영,이용균,박유미,최순규,한정태,박민수 한국생명과학회 2004 생명과학회지 Vol.14 No.1

앞선 연구의 구조적 특성을 근거로 하여, 한 분자내에 MES 유발경련에 작용하는 cyclicimide의 구조를 포함하면, 그들의 구조가 경련 유발 수용체들에 상호 보완적으로 작용, MES및 PTZ유발 경련에 모두 작용할 수 있는 적용 범위가 넓은 항경련성 화합물이 될 수 있을 것으로 생각하여 N-acyl-$\alpha$-aminosuccinimide 1과 N-acyl-$\alpha$-aminoglutar- imide 2 유도체를 합성하였다. 먼저 (R)-2-benzyloxy carbonylamino-succinic acid 3을 출발 물질로 하여 N-acyl-a-aminosuccinimide 1 유도체인 (R)-Benzoic acid 4-benzyloxycarbonyl-amino-2-oxo-pyrrolidin-l-yl ester 6a, (R)4-nitro-benzoic acid 4-benzyloxycarbon-ylamino-2-oxo-pyrrolidin-1-yl ester 6b, (R)-4-nitro-benzoic acid 4-benzyloxycarbonylamino-2-oxo-pyrrolidin-1-yl ester 6c, 그리고 (R)-propionic acid 4-benzyloxycarbonylamino-2-oxo-pyrrolidin-1-yl ester 64를 합성하였다 또한 (R)-3-car-bobenzyloxy-aminoglutarrnic acid 7를 출발물질로 하여 N-acyl-$\alpha$-aminoglutarimide 2유도체인 (R)-(3-Benzyloxycarbonyl-amino-2,6-dioxo-piperidin-1-yloxy)-acetic acid methyl ester 10a, (R)-(3-benzyloxyarbonylamino-2,6-dioxo-piperidin-1-yloxy)-acetic acid ethyl ester l0b, 그리고 (R)-2-(3-benzylox-ycarbonylanino-2,6-dioxo-piperidin-1-yloxy)-propionic acid methyl ester l0c를 합성하였다. 합성된 화합물 6a, 6b, 6c, 6d, 10a, lOb, l0c에 대한 활성평가는 각 단계별 MES test와 PTZ test의 항경련 활성 시험 방법을 가지고 실험할 예정이다. As a part of our study on the improvement of anticonvulsant, here we report the synthesis of N-acyl-$\alpha$-aminosuc-cinimides 1 and N-acyl-$\alpha$-aminoglutarimides 2. (R)-Benzoic acid 4-benzyloxycarbonylamino-2-oxo-pyrrolidin-1-ylester 6a, (R)-4-nifro-benzoic acid 4-benzyloxycarbonylamino-2- oxo-pyrrolidin-1-yl ester 6b, (R) -4-nitro-benzoic acid 4-benzyloxycarbonylamino-2-oxo-pyrrolidin-1-yl ester 6c, and (R)-propionic acid 4-benzyloxycarbonylamino-2-oxo-pyrrolidin-1-yl ester 6d were synthesized from (R)-2-benzyloxy carbonylamino-succinic acid 3 as a starting meterial. (R)-(3- Benzyloxycarbonylamino-2,6-dioxo-piperidin-1-yloxy)-acetic acid methyl ester 10a, (R)-(3-benzyloxycarbonylamino-2,6-dioxo-piperidin-1-yloxy)-acetic acid ethy1 ester 10b, an d (R)-2-(3-benzyloxycarbonylamino-2,6- diox o-piperidin-1-yl oxy)-propionic acid methyl ester l0c were synthesized from (R)- 3-carbobenzyloxy-amino-glutarmic acid 7 as a starting meterial. The yield, mp, IR, $^1H-NMR,\; and^{13}C$- NMR spectra of the products 6a, 6b, 6c, 6d, 10a, l0b, l0c are summarized in footnote. The biological studies of these compounds are in progress and will be reported in future.

1,3-Acetonedicarboxylic acid와 2,5-dimethoxytetrahydrofuran에 의한 diamine들의 반응에 관한 연구

정대일,송주현,이도훈,이용균,최순규,박유미,한정태,Jung Dai-Il,Song Ju-Hyun,Lee Do-Hun,Lee Yong-Gyun,Choi Soon-Kyu,Park Yu-Mi,Hahn Jung-Tai 한국생명과학회 2006 생명과학회지 Vol.16 No.2

본 연구를 통해 항 경련 활성을 보이는 8-aza-bicyclo[3,2,1]octan-3-one 구조를 모체로 하여 생리활성 및 구조적 특이성을 가진 8-aza-bicyclo[3,2,1]octan-3-one 화합물을 합성하고자 하였다. 본 논문에서는 ethylenediamine 1을 2,5-dimethoxyte-trahydrofuran과 1,3-acetonedicarboxylic acid을 반응시켜 8-(2-pyrrol-1-yl-ethyl)-8-aza-bicyclo[3,2,1]octan-3-one 2(yield ; 5.0%)와 1,2-di-8-aza-bicyclo[3,2,1]octan-3-onyl)ethane 3(yield ; 17.0%)을 합성하였다. 1,3diaminopropane 4의 경우에는, 8-(3-pyrrol-1-yl-propyl)-8-aza-bicyclo[3,2,1]octan-3-one 5(yield ; 6.0%)와 1,3-di-8-aza-bicyclo[3,2,1]octan-3-onyl)propane 6 (yield; 21.0%)을, 그리고 1,8-diaminooctane 7의 경우에는 8-(-8-pyrrol-1-yl-octyl)-8-aza-bicyclo[3,2,1]octan-3-one 8(yield; 2.6%)과 1,8-di-8-aza-bicyclo[3,2,1]octan-3-onyl)octane 9(yield; 24.9%)를 합성할 수 있었다. Diaminoalkanes(1,.4, 7)의 반응에서 보면 실온에서 반응을 진행시켰기에 pyrrole 유도체보다는 8-aza-bicyclo[3,2,1]octan-3-one 유도체의 합성이 보다 유리한 결과를 나타냈다. 그리고 탄소 chain이 길수록 N 원자에 전자를 잘 밀어주어 활성이 더 좋았으며 탄소 steric effect도 작기 때문에 생성물의 yield가 더 높았다. Diaminobenzene(10, 14) 역시 diaminoalkane의 반응과 같이 p-phenylenediamine 10을 2,5-dimethoxytetrahydrofuran, 그리고 1,3-acetonedicarboxylic acid과 반응시켜 p-dipyrrolylbenzene 11(yield; 4.0%), 8-(4-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one 12(yield; 12.0%), 1,4-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)-benzene 13(yield; 59.0%)을 합성하였고, m-phynylenediamine 14의 경우에도 8-(3-pyrrol-l-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one 15(yield; 2.0%)와 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)-benzene 16(yield; 28.0%)을 합성할 수 있었다. 그러나 o-phynylenediamine 17의 경우에는 8-aza-bicyclo[3,2,1]octan-3-one ring들의 steric hindrance의 영향에 의해 1,3-di-8-aza-bicyclo[3,2,1]octan-3-onyl)benzene은 합성되지 않았다. In order to synthesize novel anticonvulsants, we researched that the reactions of diamines with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid. The reaction of ethylenediamine with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid afforded 8-(2-pyrrol-1-yl-ethyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 5.0%) and 1,2-di-(8-aza-bicyclo[3,2,1]octan3-onyl)ethane (yield; 17.0%). In case of 1,3-diaminopropane, 8-(3-pyrrol-1-yl-propyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 6.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)propane (yield; 21.0%) were obtained. In case of 1,8-diaminooctane, 8-(8-pyrrol-1-yl-octyl)-8-aza-bicyclo-[3,2,1]octan-3-one (yield; 2.6 %) and 1,8-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)octane (yield; 24.9%) were obtained. In diaminobenzene reactions, synthetic yields of 8-aza-bicyclo-[3,2,1]octan-3-one derivatives were higher than those of pyrrole derivatives because re actions were done under room temperature. The longer the carbon chain of diaminoalkane is, the more reactive N atom is due to more electron donating effect, and the less steric hindrance around the carbon gave the higher chemical yields. The reaction of p-phenylenediamine as a diaminobenzene with 2,5-dimethoxyte-trahydrofuran and 1,3-acetonedicarboxylic acid produced p-dipyrrolylbenzene (yield; 4.0%), 8-(4-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 12.0%), and 1,4-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield; 59.0%). In case of m-phenylenediamine, 8-(3-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 2.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield ; 28.0%) were obtained. But, synthesis of 1,2-di-(8-aza-bicyclo[3,2,l]octan-3-onyl)benzene by treatment of o-phenylenediamine was not successful, presumably due to the steric hindrance of 8-aza-bicyclo-[3,2,1]octan-3-one rings.

달걀껍질(생, 삶은)의 수처리에 관한 연구

정대일,정선주,김인식,최영하,류정숙,이용균,최순규 동아대학교 환경문제연구소 1999 硏究報告 Vol.22 No.2

The selective absorption ability of low density heavy metal(Pb(Ⅱ) ion or Cu(Ⅱ) ion) of eggshell(raw or boiled) is better than one of existing absorption materials in treatment ability and experimental condition. The elimination ability of chlorine of eggshell(raw or soiled) is worse than one of active carbon. In elimination of trihalomethane, the effect of treatment of eggshell is almost the same as one of pine cones. And surface of eggshell(raw or boiled) after absorption of heavy metal ion was observed by Scanning Electron Microscope(SEM). Application and availability of eggshell(raw or boiled) as absorption material need lots of experiments. The experiment on baked eggshell is proceeding.

A study on the synthesis of C-2 substituted nortropinones anticipated anticonvulsant activity

정대일,변석인,송현애,이도훈,김용환,이용균,박유미,최순규,한정태 한국생명과학회 2004 한국생명과학회 심포지움 Vol.41 No.-

북한의 공민종교 - 주체사회주의의 기원, 형성, 구조를 중심으로-

정대일 한국민족운동사학회 2003 한국민족운동사연구 Vol.36 No.-

증발량 관련 기후인자와 팬증발량의 변화 분석

정대일,강재원,Jeong, Dae-Il,Kang, Jae-Won 한국수자원학회 2009 한국수자원학회논문집 Vol.42 No.2

전지구적 기온상승으로 인해 증발량이 증가할 것으로 예견되었으나, 다양한 지역에서 관측된 팬증발량은 지난 수십 년간 뚜렷한 감소추세를 나타내고 있다. 본 연구에서는 1960년부터 2007년까지 관측된 국내 18개 기상관측소의 팬증발량과, 증발에 관련된 강수량, 온도, 상대습도, 풍속, 일조시간, 일조율에 대한 변화를 분석하였다. 분석결과 팬증발량은 뚜렷한 감소현상을 나타내었으며, 강수량과 온도는 증가추세를, 상대습도, 풍속, 일조시간, 일조율은 감소추세를 나타내었다. 특히, 일조시간과 일조율의 감소추세는 팬증발량과 지역적으로 상당히 일치하고 있음을 확인하였다. 산점도를 그려 상관관계를 확인해본 결과, 일조시간과 일조율은 팬증발량과 양의 상관관계를 강하게 나타내고 있으며, 강수량의 경우는 팬증발량과는 음의 상관관계가 존재하였다. 강릉관측소 사례연구에서 Penman공식에 의해 추정된 개방된 수면에서의 증발량은 팬증발량에서 보인 것 같은 뚜렷한 하향추세가 검증되지 않아, 기존에 팬증발량 관측값으로부터 증발량을 추정하는 것은 장기적인 증발량 변화를 검토하기 위해서는 부적절함을 확인하였다. 마지막으로 팬증발량이 실제증발량과 서로 상호보완적 관계를 갖기 때문에, 팬증발량이 감소하더라도 실제증발량은 증가할 수 있음을 설명하였다. Evaporation over the world is expected to increase owing to increase in temperature by global warming. However, pan evaporation around the world has decreased in the past few decades. This study, which has been conducted in 18 meteorological gauging stations in Korean peninsula, investigates the changes in pan evaporation and climate variables such as precipitation, temperature, relative humidity, wind speed, sunshine hours, and percentage of sunshine, which can affect evaporation processes; the changes in these variables have been recorded between 1960 and 2007. At most gauging stations, pan evaporation shows statistically significant downward trends. The relative humidity, wind speed, sunshine hours, and percentage of sunshine also show downward trends. On the other hand, precipitation and temperature show upward trends. The spatial distribution of the downward trend in sunshine hours and percentage of sunshine correspond to that of the downward trend in pan evaporation. Scatter plots imply that pan evaporation has a strong positive correlation with the sunshine hours and percentage of sunshine, while it has a negative correlation with precipitation. At the Gangneung gauging station, the open water evaporation estimated using the Penman equation does not show the significant downward trend shown by pan evaporation. This result implies that pan evaporation is not a good indicator of potential or open water evaporations during the investigation of their long-term variability. Finally, this study explains the complementary relationship between pan and actual evaporations. Decreases in the pan evaporation can act as an evidence for the ever-increasing actual evaporation.

C-2와 C-2,4 위치에 치환된 8-aza-bicyclo[3.2.1]octan-3-one 유도체 합성 및 구조분석

정대일,이도훈,송주현,이용균,최순규,박유미,한정태 동아대학교 환경문제연구소 2006 硏究報告 Vol.28 No.1

The tropane ring system is an important substructure in a number of natural products and synthetic compounds of biological and medicinal importance. As a result of the significance of the tropane ring system, the purpose of this study is the synthesis of anticonvulsant compounds of new structure anticipated anticonvulsant activity. After we first synthesized the various N- substituted 8-aza-bicyclo[3.2.1]octan-3-one derivatives. We prepared now 2-substituted nortropinones. 2-Substituted 8-aza- bicyclo [3.2.1]octan-3-ones were obtained from diluted NaOH concentration(0.01N NaOH) in similar method of synthesis of 2,4-disubstituted 8-aza-bicyclo[3.2.1]octan-3-ones 23, 24, 25 were respectively synthesized by the reaction of corresponding N-substituted 8-aza-bicyclo[3.2.1]octan-3-one with corresponding aldehyde in presence of 5N-NaOH solution in ethanol and dichloromethane at room temperature. Substantially, we tried several experiments to optimize reaction condition. Continuously, the synthesis and anticonvulsant activity evaluation of a new class of 8-aza-bicyclo[3.2.1]octan-3-one derivatives are in progress and will be reported in future.

Pyrrole유도체와 Diethyl Azodicarboxylate의 부가반응

정대일,장두옥,한치선 연세대학교 자연과학연구소 1986 學術論文集 Vol.17 No.-

N-substituted pyrrole들, 즉 1-(p-acetylphenyl)-(6a), 1-(m-acetylphenyl)-(6b), 1-(p-bromophenyl)-(6c),1-(p-nitrophenyl)-(6d), 1-(m-nitrophenyl)-(6e), 그리고 1-(p-methoxyphenyl) pyrrole(6f)을 합성하여 이들과 diethyl azodicarboxylate와의 부가반응을 논하였다. 또한 이들 치환체에 의한 감응효과에 다른 반응상의 차이점을 논하였으며, 모든 반응이 1:1 및 1:2 Michael 형태를 부가반응으로 진행됨을 생성물의 IR, UV, NMR spectra로 확인하였다. The following N-substituted pyrroles, that is, 1-(p-acetylphenyl)-(6a), 1-(m-acetylphenyl)-(6b), 1-(p-bromophenyl)-(6c), 1-(p-nitorphenyl)-(6d), 1-(m-nitrophenyl)-(6e) and 1-(p-methoxyphenyl)pyrrole(6f) were prepared by the known methods, and the addition reactions of these compounds with diethyl azodicarboxylate were examined. The difference in reactivities was discussed in terms of inductive effects of the pyrrole derivatives. Both of the 1:1 and 1:2 Michael-type adducts were synthesized by these reactions and identified by IR, UV and NMR spectra.