Synthesis and Reaction of 1,5,3,7-Diazadiphosphocine-1,5-Dicarboxylic Acids

조승환,송주현,이도훈,이용균,박유미,최순규,한정태,정대일,Cho, Seung-Hwan,Song, Ju-Hyun,Lee, Do-Hun,Lee, Yong-Gyun,Park, Yu-Mi,Choi, Soon-Kyu,Hahn, Jung-Tai,Jung, Dai-Il Korean Society of Life Science 2007 생명과학회지 Vol.17 No.7

본 연구는 MRI 조영제나 새로운 생리활성 물질을 개발키 위해 paraformaldehyde와 hypophosphorous acid를 아미노산인 glycine 혹은 glutamic acid와 함께 반응시켜 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphos-phocme-1,5-diacetic acid 1 와 3,7-dihydrexy-3,7-dioxoperhydre-1,5,3,7-diazadiphos-phocme-1,5-di- (2-glutaric acid)3을 합성하였다. 그러나 aspartic acid에 의한 2-[5-(1,2-dicarboxy-ethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7]diazadiphosphocan-1-yl]-succinic acid 2는 얻지 못했다. 합성 된 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-dia-zadiphosphocine-1,5-diacetic acid 1을 산 촉매에 의한 에스테르화반응시켜 화합물 3,7-dihydroxy-3,7-dioxoper-hydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-dia-zadiphosphocine-1,5-diacetic acid ethyl ester 5, 그리고 3,7-dihyoxy-3,74dioxoperhyo-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6을 합성하였다. 계속해서 다양한 반응을 통해 새로운 화합물을 합성할 것이며 생리활성검색도 실시할 예정이다. In order to synthesize new bioactive compounds and contrasting agents, reactions of glycine and glutamic acid as an animo acid with paraformaldehyde and hypophosphorous acid were executed. Products are 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid 1 and 3,7-dihydroxy-3,7- dioxoperhydre-1,5,3,7-diazadiphosphocine-1,5-di-(2-glu taric acid) 3. 2-[5-(1,2-Dicarboxyethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7] diazadiphosphocan-1-yl]-succinic acid 2 by using aspartic acid was not obtained. Esterification of 3,7- dihydroxy-3,7-dioxoperkydro-1,5,3,7-diaza-diphosphocine-1,5-diacetic acid 1 by treatment of methanol, ethanol, and propanol were executed. 3,7-Dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3.7-dihydroxy-3,7-dioxoperhydro-1,5,3,f-diazadiphosphocine-1.5-diacetic acid ethyl ester 5, and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6 were respectively synthesized in good yields. Continuously, we will try synthesis of novel compounds and evaluation of biological activity.

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.

산성 염료 Orange 116, Orange 127, Blue 264의 합성 공정 개발

한정태 永同工科大學校 1995 硏究論叢 Vol.1 No.1

산성 염료 Orange 116, 127 그리고 Blue 264의 대량 생산 공정에 필요한 기술들인 난용성 원료의 용해 문제. 적절한 diazotization 방법 및 수율 향상, pH 조절 문제, 촉매 선택, alkylation 문제, 여과 효율 향상 문제등이 모두 확립되었다. 산성 염료 Orange 116온 Y-acid로부터 시작했으며 alkylating agent로는 p-toluenesulfonic acid ethyl ester (TEE)를 사용했다 산성 염료 Orange 127은, diazotization과 coupling을 두번 수행한 후 TEE를 사용한 alkylation을 거쳐 합성했다. 산성 염료 Blue 264는 bromamine acid로부터 시 작했으며 촉매는 Cu_2Cl_2가 사용되었다 Processing conditions and techniques such as dissolution of slightly soluble starting material, appropriate diazotization method and improvement in yield, pH control, choice of catalyst alkylating method, and improvement of titration yield, are all established for the commercial production of C.L. Acid Orange 115, 127 and Slue 294. Acid Orange 116 was started with Y-acid, and p-toluenesulfonic acid ethyl ester (TEE) was used as an alkylating agent. Acid Orange 127 was prepared by double diazotization and coupling, and alkylation with TEE. Acid Blue 264 was started with bromamine acid and Cu_2Cl_2 was used as the catalyst.

화학공학 전공 학생의 취업을 위한 복합 STC 운영

이명섭,한정태,이근복,김노수,조찬휘 永同大學校 1997 硏究論叢 Vol.3 No.1

우리 영동대학교에서 1998년 이후 지금까지 진행하여 온 특별 주제 학습과정인 STC(Special Topics COurse)프로그램을 기존의 운영틀에서 탈피하여 한층 더 발전시킨 복합STC로 활용하고자 하였으며, 특히 이를 졸업생의 취업 및 진학의 방법으로 최대한 활용하고자 계획·운영하였다. 그 결과 취업 및 진학과 같은 진로 확립은 물론 전공지식의 확대, 자격시험 대비능력의 향상, 학생과 교수간의 유대강화 등과 같은 괄목할 만한 성과를 얻을 수 있었으며, 교수들의 산업체 방문을 통한 산학협동의 계기 마련에도 커다란 성과를 얻었다. We have upgraded the STC(Special Topics Course) program, which has been carried out in our university since 1995, to more structured program so that we could train our chemical engineering students better. This program was geared to help students find better jobs and enter well-recognized graduate schools. Consequently, we had most students successful in job searches as well as entrance exams for graduate school; besides, those who actively participated in our STC program were able to attain better professional knowledge and acquire various professional engineers certificates. On top of that, this program allowed us to build up closer relationships with our students. We also made university-industry cooperation possible through our visits to industries nearby.

Methoxide Promoted Electron-Transfer Reaction between 9-Methoxyfluorene and Cobalt(Ⅲ) Complex

Hahn, Jung-Tai,Guthrie, Robert D. 永同大學校 2001 硏究論叢 Vol.7 No.1

카르보 음이온과 전이 금속 착물간의 전자이동반응의 메카니즘을 규명하는 연구의 결과와 메톡사이드/메타놀 용액 내에서의 Co(en)33+ 이온의 안정성에 대한 조사 결과를 전자이동반응에 대한 반응속도론 연구에 앞서서 보고한다. 먼저, 코발트(III) 트리스(에틸렌다이아민) 착물의 배위권은 전자이동반응 동안 고스란히 그대로 남아 있었다. 따라서 CO(en)33+와 9-메톡시플루오렌간의 전자이동과정은 외부권 메카니즘에 의한 것이라고 믿어진다. 그리고, CO(en)33+ 이온은 반응속도론 연구에서 진행하는 실험단위시간 (보통 두 시간) 동안 광학적으로 안정하다는 것을 알게 되었다. 또한, 라세미화 반응에 대한 카르본 산의 효과에 대해서도 조사해 보았는데 그 결과 카르본 산이 많이 존재하면 존재할수록 라세미화 반응은 더 빨리 발생하는 것으로 밝혀졌다. The results of the study in the determination of the mechanism of the electron-transfer reaction between carbanions and transition metal complexes, and the examination of the stability of Co(en)33+ ion in methoxide/methanol solution are reported prior to the further study of kinetics of the electron transfer reaction. First, the coordination sphere of cobalt(III) trim(ethylenediamine) complex remained intact during the electron-transfer reaction. Thus, the electron-transfer process between Co(en)33+ and 9-methoxyfluorene is believed to be of the outer-sphere mechanism. And, we found that Co(en)33+ ion can be regarded as optically stable for the time period of the kinetic studies, usually 2 hours. The effect of carbon acid on the racemization was also examined and it revealed that the more carbon acid present the faster the racemization occurs.