Benzodiazepinone과 1,5-Benzodiazepine 유도체의 합성 연구

정대일,이용균,박유미,최태원,정일수,김인식,김윤영 東亞大學校 1997 東亞論叢 Vol.34 No.-

The reaction of o-phenylenediamine 5 with acrylic acid 11 in the presencce of P₂O5+H₃PO₄afforded benzodiazepinone 13 and pyridobenzodiazepinono 17. The reactions of o-phenylenediamine 5 with acrylic acid 11 in the presence of PPA or SiO₂afforded only benzodiazepinone 13. But the reaction of O-phenylenediamine 5 with acrylic acid 11 in the presence of acetonedicarboxylic acid 18 or acetonedicarboxylic acid 18 and PPA or acetonedicarboxylic acid 18 and SiO₂was respectively synthesized 2,4,4,-trimethyI-3H-5-hydro-1.5-benzodi-azepine 23 as new cyclic imine compound. We propose that formation of 2-(2`-imine)propyI-N-isopropylidene aniline proceed though 2-amino, N-isopropylidene aniline intermediate C and 2-(N-a-methylethyI) amino, N-isopropylidene aniline intermediate G. The reaction of o-phenylenediamine 5 with acetonedicarboxylic acid 18 in the presence of PPA or SiO₂or HCI gave 2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23. Using acetone 19 instead of acetonedicarboxylic acid 18, the reaction of o-phenylenediamine 5 in the presence of PPA or SiO₂or acrylic acid 11 was synthesized 2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23 as same product. And also the reaction of o-phenylenediamine 5 with acetone 19 and acrylic 11 in the presence of PPA or SiO₂was obtained 2,4,4-trimethyI-3H-5-hydro-1,5-benzodiazepine 23. In case of acetophenone 21 in stead of acceton 19, the reaction of o-phenylenediamine 5 in presence of PPA or SiO₂at 40~45℃ were obtained 2,4-diphenyI-4methyI-3H-5-hydro-1,5-benzodiazepine 24. The reaction of o-phenylenediamine 5 with crotonic acid 25 in the presence of PPA or P₂O5+H₃PO₄or SiO₂at 100~110℃ afforded respectively 4-methybenzodiazepinone 26 as 1:1 cycloadduct.

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.

1,2-Benzisothiazol-3-one-1,1-Dioxide 유도체의 합성

정대일,정희철,변석인,이용균,박유미,최순규,한정태 東亞大學校附設基礎科學硏究所 2002 基礎科學硏究論文集 Vol.19 No.1

사카린 유도체는 제초제, 항독성, 살균제 등에 광범위하게 연구되어져 오고 있다. 새로운 농략 활성을 가진 물질을 합성하기 위해 먼저 선도물질로 사카린 1을 산화, 염소화 시킨 3-chloro-1,2-benzisothiazol-1,1-dioxide(BID-CI) 2와2cholromethy-1,2-benzisohizol-3-one1,1-dioxide 4를 합성하였다. 선도물질, amines, imidazoles, trones등과 반응시켜 다음과 같은 물질들을 얻었다. ; 3-cyclohexylamino-1,2-benzisothiazol-1,1-dioxide 6, 3-furylamino-1,2-benzisothiazol-1,1-dioxide 8, 3-(3-imidazol)-1,2-benzisothiazol-1,1-dioxide 10, 3-(2-methy-3-imidazol)-1,2-benzisothaizol-1,1-dioxide 12, 2-(3-imidazol)methy-1-1,2-benzisothiazol-3-one-1,1-dioxide 13, and 2-(-3-imidazol)methyl- 1,2-benzisothiazol-1,1-dioxide 14.

흥미로운 구조를 가진 Dipyrrolylbenzene들의 합성에 관한 연구

정대일,김인식,정두희,박철우,김윤영 東亞大學校 大學院 1996 大學院論文集 Vol.21 No.-

1-(2-Aminophenyl)pyrrole 20a and 1,2-dipyrrolylbenzene 17a were synthesized by using 1,2-phenylenediamine 16a with 2,5-dimethoxytetrahydrofuran 12 in glacial acid. 1-(3-Aminophenyl)pyrrole 20b and 1,3-dipyrrolylbenzene 17b were obtained by using 1,3-phenylenediamine 16b with 2,5-dimethoxytetrahydrofuran 12 in glacial acetic acid. 1,4-Dipyrrolybenzene 17c was synthesized by using 1,4-phenylenediamine 16c with 2,5-dimethoxytetrahydrofuran 12 in glacial acetic acid. Aminophenylpyrroles 20 and dipyrrolylbenzenes 17 were respectively synthesized by the treatment of 1,2-phenylenediamine 16a, 13-phenylenediamine 16b, 1,4-phenylenediamine 16c and 2,5-dimethoxytetrahydrofuran 12 in no solvent, acrylic acid, silica-gel, acrylic acid + silica-gel + acetic acid instead of glacial acetic acid. In case of silica-gel + acetic acid among various methods reactivity about synthesis of dipyrrolylbenzene 17 was best. 9-Phenylcarbazole 15 was synthesized by treatment of 1-phenylpyrrole 13 with 2,5-dimethoxytetrahydrofuran 12 in glacial acetic acid.

3-Cyano 및 3-Carbomethoxy Chromone과 Allenylstannane과의 반응

鄭大一,宋有淨,崔舜圭,李龍均,安賢淑,윤구식 東亞大學校附設基礎科學硏究所 1998 基礎科學硏究論文集 Vol.15 No.2

t-Butyldimethylsilyl triflate 존재에서 3-Cyano 및 3-Carbomethoxy Chromone(1a,b)과 Allenylstannane(2) 과의 반응에서 Chromone의 C-2위치에 propargyl기가 도입된 유도체(3a,b)를 합성하였다. 합성한 유도체의 상대적 구조는 ¹H-NMR을 통해 분석하였으며, T.S구조의 모델을 통하여 가능한 메카니즘을 제시하였다. Reaction of 3-Cyano and 3-Carbomethoxy Chromone(1a,b) with Allenylstannane(2) in the presence of tert-butyldimethylsilyl triflate afforded the corresponding the propargylation product(3a,b) in the moderate yield. The relative stereochemistry of 3a,b are obtained on the basis of ¹H-NMR analysis. And the possible reaction mechanism are suggested by the molecular models in the transition state.

TiO₂를 이용한 프로필렌 가스의 광촉매 산화반응

정대일,이동희,김용환,김현숙,이용균,박유미,최순규,김동현 동아대학교 환경문제연구소 2001 硏究報告 Vol.24 No.1

Photocatalyzed degradation of propylene gas was carried out over precoated titanium dioxide(anatase) illuminated W light in a flow reactor. photocatalytic oxidation of propylene gas indicated high conversion rates (78.0%) to CO₂ gas. And photocatalytic oxidation of gas 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 CO₂ gas showed.

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.

Thioamide와 Benzothiazole 유도체의 합성

정대일,신규하,김인식,김윤영,정두희,이용균 東亞大學校 1998 東亞論叢 Vol.35 No.-

The thioamides; {N-(6-methyl-2-pyridinecarbothionyl)-3-methoxyaminobenzene (27), N-(6-methyl-2-pyridinecarbothionyl)-4-methoxyaminobenzene (29), N-(6-methyl-2-pyridine-carbothionyl)-3-ethoxyaminobenzene (31), N-(6-methyl-2-pyridinecarbothionyl)-4-ethoxyamion-benzene (33), N-(6-methyl-2-pyridinecarbothionyl)-3-bromoaminobenzene (35), N-(6-methyl-2-pyridinecarbothionyl)4-bromoaminobenzene (37), N-(6-methyl-2-pyridinecarbothionyl)-3-chloroaminobenzene (39), N-(6-methyl-2-pyridinecarbothionyl)-4-chloroaminobenzene (41)} were synthesized by the treatment of 2,6-lutidine(22) with sulfur in aniline derivatives (23). The benzothiazole derivatives; {5-methoxy-2-(6-methylpyridy)benzothiazole (46) and 6-ethoxy-2-(6-methylpyridyl)benzothiazole (47)} were respecively synthesized by the treatment of synthesized thioamides; N-(6-methyl-2-pyridinecarbothionyl)-3-methoxy-aminobenzene (27) and N-(6-methyl-2-pyridinecarbothionyl)-4-ethoxyaminobenzene (33) with zirconium (Ⅳ) oxide catalyst in sodium carbonate solution.

Nortropinone 유도체로부터 Nortropane Spirohydantoin 유도체의 합성

정대일,박유미,박종훈,김윤영,정두희,김인식 東亞大學校 1998 東亞論叢 Vol.35 No.-

The nortropinones 11 (tropinone lla, N-isopropylnortropinone 11b, N-Carbethoxynortropinone 11c, N-furfurylnortropinone 11d, N-(p-methoxyphenyl)nortropinone 11e) were respectively synthesized by the treatment of acetonedicarboxylic acid 8 with, 2, 5-dimethoxytetrahydrofurane 9 in various amines 10 (methylamine 10a, N-isopropylamine 10b, ethylcarbamate 10c, furfurylamine 10d, p-anisidine 10e). The nortropane spirohydantoins 14 (tropane spirohydanttoin 14a, N-isopropylnortropane spirohydantoin 14b, N-Carbethoxynortropane spirohydantoin 14c, N-furfurylnortropane spirohydantion 14d, n_(p-methoxyphenyl) nortropane spirohydantoin 14e) were respectively synthesized by the treatment of synthesized nortropinones 11 (tropinone 11a 54%, N-isopropylnortropinone 11b 50%, N-Carbethoxynortropinone 11c 58%, N-furfurylnortropinone 11d 31%, N-(p-methoxyphenyl) nortropinone 11e, 70%) with potassium cyanide 12, ammonium carbonate 13.

Hofmann 전이 반응을 이용한 N-(L-Aspartyl)-1,1-Diaminoethane의 합성

정대일,이용균,정일수,김윤영,김선영,박민수 東亞大學校 1998 東亞論叢 Vol.35 No.-

Some retroisomeric peptide showed an agonistic or antagonistic effect of the parent peptides. So the studies on their synthesis and their structure-activity relationship are currently being investigated. In general, the synthesis of the retroisomeric peptide required N,N'-diacylated gem-diamino compound as an important synthetic intermediate, in which those diacylated group could be removed selectively in different condition. In connection with the development of facile synthetic method for retroisomeric peptide, we tried the synthesis of N-benzoyl-1. l-diaminoethane, intermediate of 1, 1-diaminoethane based Sweetener, from N-benzoyl alanine aimde 28 using improved Hofmann rearrangement as a key step. In this procedure, the N-benzoyl-N'-Cbz-1,1-diaminoethane 29 could be prepared in high yield without any bypreducts. And also this compound was converted to N-benzoyl-1, 1-diaminoethane 30 by hydrogenolysis successfully. From the above result, this method thought to be very convenient synthetic method for these N-acyl-l, l-diamino typed compounds, a intermediate of retroisomeric peptides. And also β-benzyl aspartate, another intermediate of these sweetener, could be prepared from aspartic acid via dibenzylation and selective hydrolysis.