公开(公告)号：KR100519715B1

公开(公告)日：2005-10-10

申请号：KR1020030018239

申请日：2003-03-24

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  장문호 ,  고훈영 ,  배애님 ,  차주환 ,  전보경

IPC: C07C17/272

Abstract: 본 발명은 인듐할라이드(III)염을 사용하여 알렌올에서 2-할로-1,3-다이엔을 제조하는 방법에 관한 것으로, 인듐할라이드(III)염 (화학식 1)을 사용하여 알렌올(화학식 2)에서 화학식 4의 반응을 통하여 2-할로-1,3-다이엔(화학식 3)을 제조하는 것을 특징으로 한다.
(화학식 4)

(상기 화학식 1 ∼ 화학식 4에서, R
1 , R
2 , R
3 , R
4 는 수소, 알킬기, 방향족 화합물, 고리화합물 치환기를 말하며, X는 Cl, Br, I와 같은 할로겐 원소를 말한다.)

公开(公告)号：KR100478901B1

公开(公告)日：2005-03-28

申请号：KR1020020002789

申请日：2002-01-17

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  김유승 ,  고훈영 ,  최경일 ,  배애님 ,  차주환

IPC: C07D307/12

Abstract: 본 발명은 베일리스-힐만 생성물 및 이의 제조방법에 관한 것으로, 구체적으로는 베타위치가 치환된 베일리스-힐만 생성물 및 인듐을 이용하여 통상적인 방법으로는 제조하기 어려운 상기 베일리스-힐만 생성물을 온화한 조건과 용이한 방법으로 제조하는 방법에 관한 것이다.

公开(公告)号：KR1020040097444A

公开(公告)日：2004-11-18

申请号：KR1020030029741

申请日：2003-05-12

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  장문호 ,  고훈영 ,  배애님 ,  차주환

IPC: C07D309/32

Abstract: PURPOSE: 3,4-Diexomethylene tetrahydropyrane derivatives and a process for preparing the same derivatives are provided, which derivatives are useful as intermediate for preparing two or three cyclic compounds through Diels-Alder reaction. CONSTITUTION: The 3,4-diexomethylene tetrahydropyrane derivatives represented by formula (1) are provided, wherein R1 and R2 are selected from hydrogen, C1-C10 optionally saturated linear, branched chain or cyclic alkyl, and aromatics. The process for preparing the 3,4-diexomethylene tetrahydropyrane derivatives of formula (1) comprises reacting 1-substituted-3-trimethylsilanylmethyl-3,4-pentadiene-1-ol derivatives of formula (2) with aldehyde derivatives of formula (3) in solvent in the presence of Lewis acid catalyst at -100 deg. C to room temperature, wherein the Lewis acid catalyst is selected from trimethylsillyl trifluoromethanesulfonate(TMSOTF), aluminium halide, indium(III) halide, boron halide and titanium(IV) halide; and the solvent is selected from dimethylether, diethylether and tetrahydrofuran.

Abstract translation: 目的：提供3,4-二亚甲基四氢吡喃衍生物和制备相同衍生物的方法，该衍生物可用作通过Diels-Alder反应制备两种或三种环状化合物的中间体。 构成：提供由式（1）表示的3,4-阴离子亚甲基四氢吡喃衍生物，其中R 1和R 2选自氢，C 1 -C 10任选饱和的直链，支链或环烷基和芳族。 制备式（1）的3,4-二甲基四氢吡喃衍生物的方法包括使式（2）的1-取代-3-三甲基硅烷基甲基-3,4-戊二烯-1-醇衍生物与式（3）的醛衍生物反应， 在溶剂中，在-100度的路易斯酸催化剂存在下进行。 其中路易斯酸催化剂选自三甲基甲硅烷基三氟甲磺酸酯（TMSOTF），卤化铝，卤化铟（III），卤化硼和卤化钛（IV）; 溶剂选自二甲醚，二乙醚和四氢呋喃。

公开(公告)号：KR1020040083678A

公开(公告)日：2004-10-06

申请号：KR1020030018240

申请日：2003-03-24

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  장문호 ,  고훈영 ,  배애님 ,  차주환 ,  전보경

IPC: C07C17/02

Abstract: PURPOSE: Provided is a method for preparing various types of allyl halide compounds from allyl alcohols with ease by a one-step process at a high yield. CONSTITUTION: The method for preparing an allyl halide represented by formula 3 from an allyl alcohol represented by formula 2 comprises treating the allyl alcohol with an indium(III) halide salt represented by the formula of InX3 (wherein X is Cl, Br or I), through the reaction route of the following formula 4. In formulas 2 to 4, each of R1 to R3 represents H, Si, a halogen atom, an alkyl group, an aromatic substituent or a cyclic substituent. In the method, the reaction solvent is selected from acetonitrile and benzene.

Abstract translation: 目的：提供通过一步法以高收率容易地从烯丙醇制备各种烯丙基卤化物的方法。 构成：由式2表示的烯丙醇制备由式3表示的烯丙基卤的方法包括用式InX 3（其中X为Cl，Br或I）表示的卤化铟（III）处理烯丙醇， 在式2〜4中，R 1〜R 3各自表示H，Si，卤素原子，烷基，芳香族取代基或环状取代基。 在该方法中，反应溶剂选自乙腈和苯。

公开(公告)号：KR100419592B1

公开(公告)日：2004-02-19

申请号：KR1020010074837

申请日：2001-11-29

Applicant: 한국과학기술연구원

Inventor： 한예선 ,  고훈영 ,  임혜원 ,  차주환 ,  김욱현 ,  백정호

IPC: C12N15/53

CPC classification number: C12N9/0036

Abstract: The invention is a gene coding for a quinone oxidoreductase from Kluyveromyces marxianus and a protein having an amino acid sequence expressed therefrom, which can be advantageously used in a reduction reaction of a quinone compound and synthesis of intermediates for a biologically active compound.

Abstract translation: 本发明是编码来自马克斯克鲁维酵母的醌氧化还原酶的基因和具有由其表达的氨基酸序列的蛋白质，其可以有利地用于醌化合物的还原反应和用于生物活性化合物的中间体的合成。

公开(公告)号：KR1020030062542A

公开(公告)日：2003-07-28

申请号：KR1020020002789

申请日：2002-01-17

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  김유승 ,  고훈영 ,  최경일 ,  배애님 ,  차주환

IPC: C07D307/12

Abstract: PURPOSE: Provided is a method of making β-methyl substituted Baylis-Hillman product represented by the formula(1) with indium easily under mild condition. The product is useful as precursor for the synthesis of carbapenem antibiotics. CONSTITUTION: A method of preparation of making β-methyl substituted Baylis-Hillman product comprises the steps of: making a compound of the formula (IV) by mixing and reacting a compound of the formula (II) with a compound of the formula(III) in a solvent, followed by addition of indium, stirring, reacting with acid and extraction; and adding the compound of the formula(IV) and base. In the formula (IV), R is alkyl, cycloalkyl, aryl or heterocyclic compound; R1 is alkyl, aryl or heterocyclic compound.

Abstract translation: 目的：提供在温和条件下容易地用铟制备由式（1）表示的β-甲基取代的Baylis-Hillman产品的方法。 该产品可用作合成碳青霉烯类抗生素的前体。 构成：制备β-甲基取代的Baylis-Hillman产品的方法包括以下步骤：通过将式（II）化合物与式（III）的化合物混合和反应来制备式（Ⅳ）化合物 ），然后加入铟，搅拌，与酸反应并萃取; 并加入式（IV）和碱的化合物。 在式（Ⅳ）中，R是烷基，环烷基，芳基或杂环化合物; R1是烷基，芳基或杂环化合物。

公开(公告)号：KR1020030058742A

公开(公告)日：2003-07-07

申请号：KR1020010089276

申请日：2001-12-31

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  고훈영 ,  배애님 ,  강경호 ,  김상희

IPC: C07D223/16

Abstract: PURPOSE: Benzoazepine derivatives and a preparation process thereof using indium are provided, thereby rapidly and easily preparing the benzoazepine derivatives using an appropriate amount of indium powder. CONSTITUTION: Benzoazepine derivatives are represented by the formula IV, wherein X is H, F, Cl, Br, I, alkyl or alkoxy. The benzoazepine derivatives represented by the formula III are also provided, wherein R is methyl, ethyl or hydrogen; and X is H, F, Cl, Br, I, alkyl or alkoxy. A process for preparing benzoazepine derivatives of the formula IV comprises the steps of: (1) stirring 2-nitro benzaldehyde derivatives of the formula I and methyl 2-(bromomethyl) acrylate or ethyl 2-(bromomethyl) acrylate in water or aqueous organic solvent, together with indium coil or indium thin layer and acid to prepare a compound of the formula III; and (2) reacting the compound of the formula III with base in an organic solvent, wherein the aqueous organic solvent in the step (1) is tetrahydrofuran solution, acetonitrile solution, N,N-dimethylformamide solution, methylalcohol solution or ethylalcohol solution; the base in the step (2) is sodium hydride, potassium butoxide, sodium bicarbonate, sodium carbonate, potassium carbonate or cesium carbonate; and the organic solvent in the step (2) is tetrahydrofuran, N,N-dimethylformamide, methylsulfoxide, dimethylsulfoxide or dichloromethane.

Abstract translation: 目的：提供苯并氮杂衍生物及其使用铟的制备方法，由此使用适量的铟粉快速且容易地制备苯并氮杂衍生物。 构成：苯并氮杂衍生物由式IV表示，其中X是H，F，Cl，Br，I，烷基或烷氧基。 还提供了由式III表示的苯并氮杂衍生物，其中R是甲基，乙基或氢; 且X为H，F，Cl，Br，I，烷基或烷氧基。 制备式Ⅳ的苯并吖庚因衍生物的方法包括以下步骤：（1）将式I的2-硝基苯甲醛衍生物和2-（溴甲基）丙烯酸甲酯或2-（溴甲基）丙烯酸乙酯在水或含水有机溶剂中搅拌 ，与铟线圈或铟薄层和酸一起制备式III化合物; 和（2）使式III化合物与碱在有机溶剂中反应，其中步骤（1）中的有机有机溶剂是四氢呋喃溶液，乙腈溶液，N，N-二甲基甲酰胺溶液，甲醇溶液或乙醇溶液; 步骤（2）中的碱为氢化钠，丁醇钾，碳酸氢钠，碳酸钠，碳酸钾或碳酸铯; 并且步骤（2）中的有机溶剂是四氢呋喃，N，N-二甲基甲酰胺，甲基亚砜，二甲基亚砜或二氯甲烷。

公开(公告)号：KR1020030058741A

公开(公告)日：2003-07-07

申请号：KR1020010089275

申请日：2001-12-31

Applicant: 한국과학기술연구원

Inventor： 조용서 ,  김유승 ,  고훈영 ,  최경일 ,  강경호 ,  배애님

IPC: C07D209/36

Abstract: PURPOSE: Indol derivatives and a preparation process thereof are provided, thereby rapidly preparing indol derivatives under mild conditions in higher yield. CONSTITUTION: Indol derivatives are represented by the formula 6, wherein R is H, or halogen selected from Cl, F, Br and I; and Y is -Ts(tosyl), -Ms(mesyl) or -Ac(acetyl). A process for preparing the indol derivatives of the formula 6 comprises the steps of: reacting a compound of the formula 1 with a compound of the formula 2 in the presence of indium metal and acid to simultaneously perform allylation of aldehyde and reduction of nitro group, thereby preparing a compound of the formula 3; protecting amine group of the compound of the formula 3 to prepare a compound of the formula 4; oxidizing secondary alcohol of the compound of the formula 4 to prepare a compound of the formula 5; and cyclization of the compound of the formula 5 in the presence of organic base, wherein the oxidation of secondary alcohol uses pyridinium chlorochromate(PCC) or pyridinium dichromate(PDC) or Swern's oxidation or Dess-Martin periodinane oxidation; and the organic base is diisopropylethylamine, DBU (1,8-diazabicyclo£5.4.0|undec-7-ene), DBN (1,5-diazabicyclo£4.3.0|non-5-ene), triethylamine or pyridine.

Abstract translation: 目的：提供吲哚衍生物及其制备方法，从而在温和条件下以更高的收率快速制备吲哚衍生物。 构成：吲哚衍生物由式6表示，其中R是H，或选自Cl，F，Br和I的卤素; 和Y是-T（甲苯磺酰基），-Ms（甲磺酰）或-Ac（乙酰基）。 制备式6的吲哚衍生物的方法包括以下步骤：在铟金属和酸的存在下使式1的化合物与式2的化合物反应，以同时进行醛的还原和烯基的还原， 从而制备式3的化合物; 保护式3化合物的胺基以制备式4的化合物; 氧化式4化合物的仲醇制备式5的化合物; 在有机碱的存在下环化式5的化合物，其中仲醇的氧化使用氯铬酸吡啶鎓（PCC）或重铬酸吡啶鎓（PDC）或Swern的氧化或Dess-Martin氧化氧化; 有机碱是二异丙基乙胺，DBU（1,8-二氮杂双环{5.4.0 |十一-7-烯），DBN（1,5-二氮杂双环{4.3.0 |非-5-烯），三乙胺或吡啶。

公开(公告)号：KR1020030056992A

公开(公告)日：2003-07-04

申请号：KR1020010087362

申请日：2001-12-28

Applicant: 한국과학기술연구원

Inventor： 고훈영 ,  최경일 ,  조용서 ,  배애님 ,  차주환 ,  한예선 ,  이종수 ,  윤홍철

IPC: C07D209/48

CPC classification number: C07D209/48

Abstract: PURPOSE: Carbonyl compounds and a preparation process thereof using carbonyl reductase isolated from Kluyveromyces marxianus are provided. The carbonyl compounds are useful as intermediates for preparing beta-lactam family antimicrobial agents. CONSTITUTION: Carbonyl compounds represented by the formula(Ia) and (Ib) are provided, wherein R is methyl, ethyl, propyl, isopropyl, isobutyl and allyl containing saturated or unsaturated alkyl, or phenyl containing aryl; R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen, halogen atoms including Br, Cl, F and I, methyl and ethyl containing C1-C4 alkyl, hydroxy, C1-C4 alkoxy, acetoxy containing ester, and phenyl. A process for preparing the carbonyl compound of the formula(Ia) and (Ib) comprises the steps of: mixing a compound of formula(VI) with β-NADPH and a pH 5.0 to 8.0 buffer solution; adding carbonyl reductase isolated from Kluyveromyces marxianus into the mixture; and reacting the mixture at 20 to 40 deg. C for 5 hours to 5 days.

Abstract translation: 目的：提供羰基化合物及其使用从马克斯克鲁维酵母分离的羰基还原酶的制备方法。 羰基化合物可用作制备β-内酰胺家族抗微生物剂的中间体。 构成：提供由式（Ia）和（Ib）表示的羰基化合物，其中R是含有饱和或不饱和的烷基或含苯基的芳基的甲基，乙基，丙基，异丙基，异丁基和烯丙基; R 1，R 2，R 3和R 4独立地选自氢，包括Br，Cl，F和I的卤素原子，含有C 1 -C 4烷基，羟基，C 1 -C 4烷氧基，含乙酰氧基的酯和苯基的甲基和乙基 。 制备式（Ia）和（Ib）的羰基化合物的方法包括以下步骤：将式（VI）化合物与β-NADPH和pH 5.0-8.0缓冲溶液混合; 将从马克斯克鲁维酵母分离的羰基还原酶加入到混合物中; 并使混合物在20至40℃下反应。 C为5小时至5天。

公开(公告)号：KR1020030044179A

公开(公告)日：2003-06-09

申请号：KR1020010074837

申请日：2001-11-29

Applicant: 한국과학기술연구원

Inventor： 한예선 ,  고훈영 ,  임혜원 ,  차주환 ,  김욱현 ,  백정호

IPC: C12N15/53

CPC classification number: C12N9/0036

Abstract: PURPOSE: A quinone oxidoreductase gene from Kluyveromyces marxianus is provided to be used for the reduction reaction of the quinone compounds and for the intermediate synthesis of the biologically active compounds by way of the excellent quinone reduction activity thereof. CONSTITUTION: A gene codes the amino acid sequence of Kluyveromyces marxianus quinone oxidoreductase(kmQOR) presented at the sequence No. 2. The kmQOR has a molecular weight of about 42kDa. A recombinant vector contains the gene coded with the kmQOR, and is determined to be plasmid pQOR22b. An E. coli is transformed into the recombinant vector. In a method of preparing the kmQOR, the transformed E. coli is first cultured, and β-D-isopropyl-D-thiogalactopyranoside (IPTG) is then added to the cultured E. coli to induce the expression of kmQOR therefrom. The expressed kmQOR is collected, and purified.

Abstract translation: 目的：提供马克斯克鲁维酵母的醌氧化还原酶基因，用于醌类化合物的还原反应和生物活性化合物的中间合成，其优异的醌还原活性。 构成：A基因编码序列号2中提供的马克斯基黄酮醌氧化还原酶（kmQOR）的氨基酸序列。kmQOR的分子量约为42kDa。 重组载体含有用kmQOR编码的基因，并确定为质粒pQOR22b。 将大肠杆菌转化入重组载体。 在制备kmQOR的方法中，首先培养转化的大肠杆菌，然后将β-D-异丙基-D-硫代吡喃半乳糖苷（IPTG）加入到培养的大肠杆菌中以诱导其表达KmQOR。 收集并纯化表达的kmQOR。