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한호규,장기혁,이화석,마혜덕,Hahn, Hoh Gyu,Chang, Kee Hyuk,Lee, Wha Suk,Ma, He Duck 대한화학회 1996 대한화학회지 Vol.40 No.5
아세톡시 1,3-옥사티올란 1의 이성체들의 입체화학을 두 가지 방법에 의해 결정하였다. 첫째, 산촉매하에서 디히드로옥사티인 2로의 전환되는 반응속도 차이에 의해 알파이성체 7과 베타이성체 9의 구조를 결정하였다. 이탈기인 아세톡시기가 황원자와 트랜스 위치에 있을 때 1,3-옥사티올란 고리에 대한 입체장애가 적은 이성체가 알파이성체 7이며 반응속도가 느린 이성체가 베타이성체 9이었다. 둘째, 술폭시드의 각각의 diastereomer들의 중수소 치환반응에서, methine 수소가 중수소로 치환된 화합물은 시스이성체 15, 17, 그리고 메틸기의 수소가 중수소로 치환된 화합물은 트랜스이성체 16, 18이었다. Methine 또는 메틸기의 수소의 중수소로의 치환은 [2,3] 시그마트로픽 전위에 의한 입체특이적 개환 및 폐환의 결과였다. Stereochemistries of acetoxy 1,3-oxathiolane 1 were determined by two methods. First, the structures of $\alpha$ isomer 7 and $\beta$ isomer 9 were confirmed by the difference of their conversion rates to dihydrooxathiin 2 under acid catalysis. When the acetoxy leaving group is located in trans relationship to sulfur, a isomer in which carboxanilide is less hindered sterically against the 1,3-oxathiolane ring is $\beta$ isomer 7, and the other isomer of which the reaction rate is slower than 7 is $\beta$ isomer 9. Second, in the deuterium reactions of diastereomeric sulfoxides, the isomers of which methine hydrogen is substituted to deuterium were cis isomers 15 and 17, and another isomers of which methyl hydrogen is substituted to deuterium were trans isomers 16 and 18. Substitution of either methine or methyl hydrogen to deuterium resulted from stereospecific ring opening followed by recyclization by [2,3] sigmatropic rearrangement.
황원자의 인접기 참여에 의한 카르복신의 경제적 합성과 그 반응기전
한호규(Hoh-Gyu Hahn),남기달(Kee Dal Nam),장기혁(Kee Hyuk Chang) 한국농약과학회 2000 농약과학회지 Vol.4 No.2
New convenient and economical synthesis of 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 1 and the plausible reaction mechanism were described. Reaction of α-chloroacetoacetanilide 4(1 molar equivalent) with 2-mercaptoethanol(1.2 molar equivalent) in the presence of p-toluenesulfonic acid monohydrate (0.05 molar equivalent) as a catalyst in refluxing toluene with water trap yielded carboxin 1. The proposed mechanism is that α-chloro l,3-oxathiolane 8 which is a hemithioketal of 4 was converted to unisolable sulfonium ion 9 through neighboring group participation of sulfur followed by rearrangement to more stable oxonium ion 12 and then release acidic proton to produce the carboxin 1.
Trifluoromethylated Dihydro-1,4-dithiin carboxanilide 유도체의 합성 및 살균활성
한호규(Hoh-Gyu Hahn),남기달(Kee Dal Nam),장기혁(Kee-Hyuk Chang),이선우(Seon-Woo Lee),조광연(Kwang Yun Cho) 한국농약과학회 2001 농약과학회지 Vol.5 No.2
α, β-Unsaturated carboxamides 12 with trifluromethylated dihydro-1,4-dithiins were synthesized for the purpose of development of new agrochemical fungicide. Chlorination of trifluoromethylated β-keto ester 4 followed by the reaction with l,2-ethanedithiol gave intermediate 1,4-dithiane 9. Without purification of 9 substitution of hydroxy by chlorine followed by dehydrochlorination in the presence of triethylamine afforded trifluoromethylated dihydro-l,4-dithiin ethyl ester 7. Activation of the hydroxy of the carboxylic acid 10 obtained from the hydrolysis of 7 and then reacted with various amines gave the corresponding trifluoromethylated dihydro-l,4-dithiin carboxamides. Antifungal screening (in vivo) against typical plant diseases, Rice Blast, Rice Sheath Blight, Cucumber Gray Mold, Tomato Late Blight, Wheat Leaf Rust, and Barley Powdery Mildew of the synthesized compounds was carried out. As a result, most of the compounds showed weak antifungal activities and some compounds in which isopropyl group was substituted in meta of the phenyl showed antifungal activity (99%) at 250 ppm against the disease Wheat Leaf Rust.
성낙도,유성재,남기달,장기혁,한호규 충남대학교 생물공학연구소 1999 생물공학연구지 Vol.7 No.-
기질(S) 화합물로 30종의 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide 유도체들을 합성하고 벼 잎집무늬 마름병균(Rhizoctonia solani)과 밀 붉은 녹병균(Puccinia recondita)에 대한 항균활성(in vivo) 값(pI_50)을 측정하였다. (S)는 잘록병균보다 밀 붉은녹병균에 대하여 보다 큰 항균활성을 나타내었으며 두 종의 균에 대하여 3-methoxy, 11, 3-iso-propyloxy, 13 및 3-iso-propyl 치환체, 25가 제일 큰 활성을 보였다. 그리고 치환(X)-phenylcarbamoyl group의 변화에 따른 물리-화학 파라미터와 항균활성(pI_50)으로부터 구조-활성관계(SAR)를 검토 한 결과, 벼 잎집무늬 마름병균에 대하여는 공명효과에 따른 전자밀게(R<0)의 소수성이 큰(π>0) m-alkyl 치환기(X)가, 그리고 밀 붉은녹병균에 대하여는 분자 분극율(Sp.Po1.)과 분자의 음하전(ABSQ<0)을 위시하여 HOMO에너지(e.v.)가 클수록(HOMO<0) 높은 항균활성을 나타내었다. 또한, 전하-조절 반응에 의한 수용체-(S)간의 상호작용과 높은 활성발현 조건들이 검토되었다.(1998년 2월 3일 접수, 1998년 12월 1일 수리) New thirty derivatives of 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide as substrate(S) were synthesized and their fungicidal activities in vivo against rice sheath blight(Rhizoctonia solani) and wheat leaf rust(Puccinia recondita) were examined. The structure activity relationships(SAR) between the activities(pI_50) and a physicochemical parameters of substituents(X) at the phenylcarbamoyl group were analyzed using the adaptive regression analysis method. The 3-methoxy, 11, 3-isopropyloxy, 13 and 3-isopropyl substituent, 25 as X on the phenylcarbamoyl group exhibited the most highest fungicidal activity against the two fungi. The fungicidal potency of the (S) against Puccinia recondita was higher than Rhizoctonia solani. In case of Rhizoctonia solani, the molecular hydrophobicity(π>0) and resonance effect(R<0) by meta-alkyl substitutents with electron donating were important factors in determining fungicidal activity. And the HOMO energy(HOMO>0), ABSQ, sum of absolute values of the atomic charges on each atom and specific polarizability(Sp.Pol<0) of (S) were significantly influential towards fungicidal activity against Puccinia recondita. The interaction between (S) and receptor against from the based on SAR studies proceeds through charge-control reaction, and conditions to show higher activity has been also discussed.