Isothiazole Ring Formation using O-Mesitylenesulfonyl hydroxyl amine (MSH);Synthesis of 5-methylsufany1-3, 4-dihydro-2-H-pyrano[3,2-c]quinolin-4-one

다국어 초록 (Multilingual Abstract)

A. Isothiazole Ring Formation using O-Mesitylenesulfonyl hydroxyl amine (MSH).
다양한 치환체를 가진 2-alkylthio-3-acyl-4-quinolinone에 aminating agent 인 O-mesitylenesulfonylhydroxylamine(MSH) 를 이용하여 isothiaz-ole 골격을 형성하였다. 주 생성물로써 알킬기가 전이된 3-methyl-9-alkyl-4, 9-dihydroisothiazolo[5,4-b]quinolin-4-one 을 얻고, 부 생성물로써 알킬기가 제거된 3-methyl-4, 9-dihydroisothiazolo[5,4-b]quinolin-4-one을 얻었다. K2CO3를 사용하지 않고 과량의 MSH (2equiv.)를 사용하여 부 생성물로 얻어진 알킬기가 제거된 3-methyl-4, 9-dihydroisothiazolo[5,4-b]quinolin-4-one를 정량적으로 얻어냈다.
B. Synthesis of 5-methylsulfanyl-3, 4-dihydro-2-H-pyrano[3,2-c]quinolin-4-one.
다양한 치환기를 가진 3-acetyl-2-methylsulfanyl-1, 4-dihydro-4-quinolinone를 trimethylsulfoxonium iodide와 sodium hydride를 사용하여 DMSO용매하에서 반응하여 5-methylsulfanyl-3,4-dihydro-2-H- pyrano[3,2-c]quinolin-4-one 를 합성하였다.

다국어 초록 (Multilingual Abstract)

A. Isothiazole Ring Formation using O-Mesitylenesulfonyl hydroxyl amine (MSH).
Isothiazole ring skeleton was formed by treatment of substituted 2-alkylthio-3-acyl-4-quinolinone with O-mesitylenesulfonylhydroxylamine(MSH). A mixture of alkyl transferred 3-methyl-9-alkyl-4, 9-dihydroisothiazolo[5,4-b]quinolin-4-one as a major product and dealkylated 3-methyl-4, 9-dihydroisothiazolo[5,4-b]quinolin-4-one as a minor product was obtained from unsubstituted 2-alkylthio-3-acyl-4-quinolinone. Excess amount of MSH (2 equiv.) has been employed in the absence of K2CO3, under same reaction condition. The reaction proceeded to afford dealkylated 3-methyl-4, 9-dihydroisothiazolo[5,4- ]quinolin-4-one quanti-tatively.
B. Synthesis of 5-methylsulfanyl-3, 4-dihydro-2-H-pyrano[3,2-c]quinolin-4-one.
Reaction of 3-acetyl-2- methylsulfanyl-1, 4-dihydro -4- quinolinone with trimethylsulfoxonium iodide in the presence of sodium hydride in DMSO provided 5-methylsulfanyl-3, 4-dihydro-2-H-pyrano[3,2-c]quinolin-4-one.

목차 (Table of Contents)

• Contents = 1
• ABSTRACT = 4
• Ⅰ. INTRODUCTION = 7
• A. General reviews = 7
• 1. Quinolones = 7
• 2. Isothiazoles = 14
• B. Previous works = 21
• 1. Using the Hydroxylamine-O-sulfonic acid (HOSA) = 21
• 2. Various synthesis of Isothiazoles = 25
• Ⅱ. RESULTS AND DISCUSSION = 35
• A. Synthesis of Isothiazolo quinolone = 35
• 1. Synthesis of ketene dithioacetals = 35
• 2. Cyclization of ketene dithioacetal α-anilides = 37
• 3. Synthesis of O-mesitylenesulfonylhydroxylamine (MSH) = 40
• 4. Synthesis of isothiazolo quinolone = 43
• 5. Plausible Mechanism = 44
• 6. Confirmation of mechanism = 49
• 7. Scope and limitation = 58
• B. Synthesis of 5-methylsulfanyl-3, 4-dihydro-2-H-pyrano[3,2-c]quinolin-4-one = 69
• 1. Epoxidation of a carbonyl compound using the trimethylsulfoxoniu-m iodide = 69
• 2. Synthesis of 5-methylsulfanyl-3, 4-dihydro-2-H-pyrano[3,2- c]quino-c]quinolin-4-one = 70
• Ⅲ. EXPERIMENTAL SECTION = 75
• A. Instruments and measurements = 75
• B. Materials = 76
• C. Synthesis of ketene dithioacetal α-anilides = 77
• D. Synthesis of quinolinones = 82
• E. Synthesis of Ethyl O-(mesitylsulfonyl)acetohydroxamate = 86
• F. Ethyl O-(mesitylenesulfonyl)acethydroxamate(68) = 87
• G. Synthesis of isothiazoloquinolinones 71 and 72. = 89
• H. Synthesis of 2,4,6-trimethyl-benzenesulfonic acid methyl ester(74) = 101
• I. Synthesis of 2,4,6-trimethyl-benzenesulfonic acid(75) = 102
• J. Synthesis of N-Methoxy-2,4,6-trimethyl-benzenesulfonamide(76) = 103
• K. Synthesis of O-Mesitylenesulfonylhydroxylamine(77) = 104
• L. Synthesis of 3-Methyl-isothiazolo[5,4-b]quinoline(89). = 105
• M. Sythesis of 3-methyl-9-oxa-1-thia-2-aza-cyclopenta[b]naphthalen-4-one. = 108
• N. Synthesis of 3-acyl-2-methyltionaphthalene. = 110
• O. Synthesis of 1-(4-Methoxy-2-methylsulfanyl-quinolin-3-yl)-ethanone. = 116
• P. Synthesis of 5-Methylsulfanyl-2, 3-dihydro-pyrano[3,2-c]quinolin-4-one. = 118
• Ⅳ. References = 120