A Highly Stereoselective Reaction in Aminolysis of 3-Acyl-4-(S)-isopropyl-1,3-thiazolidine-2-thione with Racemic Amines

정태명,박기훈,Tae Myoung Jeong,Ki Hun Park Korean Chemical Society 1988 대한화학회지 Vol.32 No.6

키랄 보조제가 붙어있는 3-acyl-4(S)-isopropyl-1,3-thiazolidine-2-thione[4(S)-AITT]을 라세미 아민과 가아민 분해반응을 시켰을때 광학활성을 갖는 아미드(S-excess)와 아민(R-excess)이 얻어지는 입체 선택적인 반응이 관찰되었다. 이와같은 입체 선택적인 반응은 macrocyclic diamide, macrocylic sperimidine alkaloid, peptide 합성에 이용될 수 있다. 가아민 분해반응의 속도는 아민의 입체적인 영향을 많이 받았고 반응이 종료점은 노락색의 소실로 쉽게 관찰되었다. 4(S)-AITT는 4(S)-isopropyl-1,3-thiazolidine-2-thione과 carboxylic acid로부터 얻었다. A chiral recognition was observed in aminolysis of 3-acyl-4(S)-isopropyl-1,3-thiazolidine-2-thione by racemic amine to give an optically active amide (S-excess) and amine (R-excess). This procedure can be applied to synthesis of macrocyclic diamide macrocyclic spermidine alkaloid, and peptide. The rate of this aminolysis is remarkably affected by steric surrounding; completion of reaction can be easily judged by the disappearance of the original yellow color of 4(S)-AITT. These features of the aminolysis suggested a potential recognition racemic amines by a chiral 4 (S)-AITT derivative. Thus 4 (S)-AITT was synthesized from 4 (S)-isopropyl-1, 3-thiazolidine-2-thione and carboxylic acids.

미강유중(米糠油中)의 Sterol조성(組成)

정태명,양민석,하봉석,Jeong, Tae-Myoung,Yang, Min-Suk,Hah, Bong-Suk 한국응용생명화학회 1984 Applied Biological Chemistry (Appl Biol Chem) Vol.43 No.3

미강유(米糠油)의 부(不)검화물(化物)을 분석(分析)하여 sterol조성(組成)을 살펴본 결과(結果)는 다음과 같았다. 4-Desmethylsterol로서는 10개가 동정(同定)되었으며 이 중(中) sitosterol이 주성분(主成分)을 이루고 있었다. 2개의 소량성분(少量成分)인 ${\Delta}^7$-stigmastenol(3%)과 ${\Delta}^7$-avenasterol(1%)를 제외(除外)하면 모두가 ${\Delta}^5$-sterol였으며 소위(所謂) ${\Delta}^5$형(型) sterol분포(分布)를 보이고 있었다. 4-monomethylsterol fraction에서는 9개가 확인(確認)되었으나 cycloeucalenol, citrostadienol, gramisterol가 주성분(主成分)이었다. 환계(環系)의 구조가 다양(多樣)하여 sterol의 생합성경로(生合成經路)의 중간단계(中間段階)임을 보여주고 있다. 4,4-Dimethylsterol(triterpene alcohol)로서는 4개가 동정(同定)되었으나 이들은 모두 9,19-cyclopropanering을 가지고 있다. 이들중(中) sterol생합성(生合成)의 초기단계(初期段階)의 물질(物質)인 cycloartenol와 24-methylenecyclo-artenol가 이 fraction의 96%를 점(占)하고 있는 것으로 봐서 미(米)강의 4,4-dimethylsterol는 짧은 경로(經路)를 거쳐 쉽게 4-monomethylsterol로 전환(轉換)되는 것 같다. Side chain에서 E-, Z-관계(關係)인 이성체(異性體)가 4-desmethylsterol로서는 fucosterol와 ${\Delta}^5$-avenasterol가 그리고 4-monomethylsterol로서는 28-isocitrostadienol와 citrostadienol로서 각각 1쌍식이 검출(檢出)된 것으로 미루어 볼때 sterol의 생합성과정(生合成過程)에서 side chain에서 보다 환계(環系)에서 먼저 변환(變換)이 일어나는 것으로 보아진다. The unsaponifiable from rice bran oil was fractionated into 4-desmethyl-'4-monomethyl- and 4, 4-dimethylsterol (triterpene alcohol) fraction by thin layer chromatography (TLC), and sterol composition of the each fraction was analyzed by gas liquid chromatography(GLC). The sterol peaks not well separated by GLC were further fractionated by $AgNO_3-TLC$, then analyzed using GLC. Each components in the three sterol fractions were identified by GLC and gas chromatography-maps spectrometry. As the results, ten sterols were confirmed as 4-desmethylsterol, nine as 4-monomethylsterol and four as 4, 4-dimethylsterol. Such uncommon phytosterols in higher plants as fucosterol, 24-ethyllophenol, 4${\alpha}$-methylstigmasta-7, 25-dienol and 28-isocitrostadienol were detected in rice bran oil and the biosynthetic pathways of the phytosterols were deduced with all the identified sterols.

Sterol Compositions in Some Cucurbitaceae Vegetable Oils

정태명,양민석,Tae Myoung Jeong,Min Suk Yang,Taro Matsumoto Korean Chemical Society 1977 대한화학회지 Vol.21 No.3

오이, 수박, 수세미, 박, 하늘수박의 다섯가지 박과식물 종자유에서 세가지 스테롤 플랙숀을 박층 크로마토그래피로 나누고 각 플랙숀의 조성을 가스크로와 가스크로에 연결된 질량분석법으로 밝혔다. 이중 4-데스메틸스테롤 플랙숀에서 ${\alpha}$-Spinasterol, ${\Delta}^{7,22,25}$-stigmastatrienol 및 ${\Delta}^{7,25}$-stigmastadienol를 단리(單離)하여 IR, NMR 및 질량분석법으로 동정(同定)하였다. Three sterol fractions; 4-desmethyl-, 4-monomethyl-, and 4,4-dimethylsterol, separated by thin layer chromatography from the unsaponifiables of five Cucurbitaceae (cucumber, watermelon, sponge cucumber, gourd and snake gourd) seed oils were analyzed by gas liquid chromatography and combined gas liquid chromatography-mass spectrometry. ${\alpha}$-Spinasterol, ${\Delta}^{7,22,25}$-stigmastatrienol and ${\Delta}^{7,25}$-stigmastadienol isolated from the 4-desmethylsterol fraction were identified by IR, NMR and mass spectrometry.

비타민류가 곰팡이의 유지생산에 미치는 영향

손병효,정태명,김용균,이영근 ( Byung Hyo Son,Tae Myoung Jeong,Yong Gyun Kim,Young Guen Lee ) 한국유화학회 1985 한국응용과학기술학회지 Vol.2 No.2

Influence of vitamins on the felt and lipid production of Aspergilus nigher var. macrosporus, Aspergillus fumigatus and penicillium notatum were investigated after 10 days of incubation at 30℃ under static culture condition. The felt of molds were lower in the media containing vitamins than control medium. The lipids produced by each strains were highest yields in media containing vitamins. Among of these Aspergillus niger var. macrosporus and Aspergillus fumigatus produced. 4.6g and 5.28g in medium containing inositol 2.5mg/1 and 0.5mg/1, respectively; while Penicillium notatum produced 1.51g in a medium containing thiamine 10mg/1. The major fatty acid of lipids were palmitic acid, stearic acid, oleic acid and linoleic acid. Aspergillus niger var. macrosporus was lower palmitic acid in media containing vitamins than control medium, While linoleic acid was higher in media containing thiamine and inositol. Aspergillus fumigatus was lower oleic acid in media containing vitamins than control medium, While linoleic acid was higher in media containing vitamins. Peniillium notatum was lower palmitic acid, oleic acid and stearic acid in media containing vitamins but linoleic acid was higher. The composition of fatty acid of lipids changed depending on the media containing vitamins but hardly found a certain tendency except linoleic acid which was higher in a media containing thiamines and inositols. The degree of unsaturation of fatty acids in the lipids were comparatively higher in media containing vitamins than control medium.

加熱食用油에 關한 硏究(II) : 米강油의 流動性과 脂肪酸變化에 關해서

金恩愛(Eun-Ae Kim),鄭태明(Tae-Myoung Jeong),金幸子(Haeng-Ja Kim),朴載玉(Jae-Ok Park) 韓國營養學會 1978 Journal of Nutrition and Health Vol.11 No.1

無患子나무 種子의 成分에 關한 硏究

金明燦(Myung-Chan Kim),鄭泰明(Tae-Myoung Jeong),梁敏錫(Min-Suk Yang) 한국식품과학회 1977 한국식품과학회지 Vol.9 No.1

榧子의 Desmethylsterol 組成 및 構造에 관한 硏究

趙鏞桂(Yong-Goe Joh),金景子(Kyeng-Ja Kim),朴貴善(Kui-Sun Bark),鄭泰明(Tae-Myoung Jeong) 한국식품과학회 1981 한국식품과학회지 Vol.13 No.2

Prochiral 탄소를 갖는 화합물에서 광학활성체 합성(Ⅱ)

鄭泰明,朴基勳 慶尙大學校 1987 論文集 Vol.26 No.1

The chiral heterocycle groups as an auxiliary use for asymmetric synthesis, Especially C-4chiral thiazolidine -2-thione has been shown to most effective for the regioselectivity of asymmetric synthesis. In order to increase the differentiation of regioselectivity between to idential groups in prochiral symmetric dicarboxylic acids. I selected 4(S)-isopropy1-1, 3-thiazolidine-2-thione [4(S)-IPTT which was synthesized from L-valine as an auxiliary. The 3-methy[ glutaric acid was reacted with 4(S)-IPTT in presence of DCC in pyridne, to give 1,5-di[4(S)-isoprony1-2-thione-1,3-thiazolidinyl]-3-methyl-1,5-pentanedione. This diamide was subjected to aminolysis with 1 molar equivalent of piperidine in CH₂Cl₂at low temperature. As resutl, very nigh regioselectivity of the reaction was observed in case.

植物油의 불감화물 利用에 關한 硏究 : 第1報 Sterol과 Tocopherol의 定量 Quantitative Analysis of the Free Sterol and Tocopherol

鄭泰明,李富永,趙武濟 慶尙大學校 1972 論文集 Vol.11 No.-

米糠油, 大豆油, 참깨油, 들깨油, 산초 및 菜種油의 불감화물중에 存在하는 free sterol을 column chromatography法과 T.L.C法에 의해 分溜 定量하였고 total tocopherol에 對해서는 Emmeri-Engel法에 의해 定量하였다. 1. Free steol을 용출할 때는 n-hexane-20% benzenedyddor에서만 용출됨을 확인하였다. 2. 이들 植物油의 不??化物中에 存在한 free sterol와 total tocopherol의 含量은 다음과 같다. Free Sterol(㎍/g) Total Tocopherol(㎍/g) 米糠油 1300 490 大豆油 1500 565 참깨油 773 425 들깨油 516 635 산초油 520 740 菜種油 640 470 Free sterols contained in unsaponifiable matters of vegetable oils such as, rice bran oil, soybean oil, sesame oil, japanes pepe oil, rape seed oil. and perilla oil are determined by the column chromatographic and thin layer chromato raphic methods. And also total tocopherols are investigated by Emmerie-Engel Procedure 1. For the elution of free sterol, it is only eluted when the n-hexane-20% benzene solution were added on the column paked silica gel. 2. Quantities of free sterol and total tocopherol contained in unsaponifiable matters of these oils are as follow, Free Sterol Total Tocopherol (㎍/g) (㎍/g) Rice Bran Oil 1300 490 Soybean Oil 1500 565 Sesame Oil 773 425 Japanes Peper Oil 516 635 Rape Seed Oil 520 740 Perilla Oil 640 470

3종의 가지과식물종자유중(料植物種子油中)의 Sterol 조성

정태명,양민석,나효환 한국농화학회 1978 Applied Biological Chemistry (Appl Biol Chem) Vol.21 No.1

Sterol compositions of three solanaceous plant seed oils i.e., tobacco(Nicotiana tabacum L.), datum (Datura stramonium L.) and Chinese lycium (Lycium chinerise Mill.) were analyzed by thin layer chromatography, gas liquid chromatography and gas liquid chromatography-mass spectrometry. Cholesterol, cholest-7-enol, campesterol, 24-methylenecholesterol, stigmasterol, sitosterol, and 28-isofucosterot were identified in 4-des-methylsterol fraction. 31-Norlanost-8-enol, 4α-methylcholest-8-enol, lophenol, 31-norlanosterol, obtusifoliol, 31-norcycloartenol, cyloeucalenol, gramisterol (24-methylenelophenol), and citrostadienol in 4-monomethylsterol fraction, and lanost-8-enol, cycloartanol, lanosterol, β-amyrin, 24-methylenelanost-8-enol, cycloartenol, lupeol and 24-methylenecycloartanol in 4,4-dimethylsterol fraction were identified respectively.