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研究生:石裕國
研究生(外文):Shih, Yuh-Kuo
論文名稱:簡易的改良方法製備2,2-雙取代-1-硝基烯類
論文名稱(外文):An Improved and Easy Method for the Preparation of 2,2-Disubstituted-1-Nitroalkenes
指導教授:姚清發姚清發引用關係
指導教授(外文):Yao, Ching-Fa
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
中文關鍵詞:硝基烯類
外文關鍵詞:nitroalkene
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第一部份
酮類(ketones)1可與硝基甲烷(nitromethane)2在催化量的piperidine 3a存在下與trapping reagents 6(benzyl mercaptan 6a、thiophenol 6b或allyl mercaptan 6c)反應產生b-nitroalkyl sulfides(7、10或11)。在0℃條件下以CH2Cl2為溶劑,使用m-chloroperoxybenzoic acid(m-CPBA)8a 可將b-nitroalkyl sulfides(7、10或11)氧化成b-nitroalkyl sulfoxides(9、12或13),然後再以CCl4為溶劑在迴流的條件下脫去PhSOH產生2,2-雙取代-1-硝基烯類5。其合成反應機構的不可逆性,除了可以克服亨利反應(Henry reaction)中,合成2,2-雙取代-1-硝基烯類5時之不實用性(可逆反應)外,亦可由環酮類1f-h合成環外硝基烯類5f-h。由此簡易改良法可將5之產率提昇到中等至高等產率。同時發現b-nitroalkyl sulfoxides(9f、9g、12b、13f或13h)在鹼性水溶液處理下亦可得到5b與5f-h,不過產率約在25-65%之間,比上述之熱解反應之產率稍低。
第二部分
酮類(ketones)1a-l、硝基甲烷(nitromethane)2以及benzyl mercaptan 6a在piperidine 3a或ethylenediamine 3b的存在下,利用THF(tetrahydrofuran )或CH3CN(acetonitrile)作為溶劑進行反應可以生成b-nitroalkyl sulfides 7a-l。如果我們利用ClCH2CH2Cl(1,2-dichloroethane)作為溶劑,於0℃的條件下可以使用m-chloroperoxybenzoic acid(m-CPBA)8a、H2O2/AcOH 8b或H2O2 8c將分離出來的b-nitroalkyl sulfides 7a-l氧化而生成b-nitroalkyl sulfoxides 9a-l,然後在迴流條件下進行脫去反應(elimination),可以生成中等至高等產率的2,2-雙取代-1-硝基烯類(2,2-disubstituted- 1-nitroalkenes)5a-l。此原理可以應用在5a-l的一鍋到底合成上,其方法是利用1a-l、2、3和6a在CH3CN溶液中迴流進行反應而生成7a-l。然後於0℃下,利用8a、8b或8c等氧化方式,在CH3CN與ClCH2CH2Cl的混合溶液中將7a-l氧化後生成 b-nitroalkyl sulfoxides 9a-l。最後9a-l在迴流狀態下進行脫去反應,生成中等至高等產率的預期產物5a-l。此種一鍋到底的合成方式,在類似的條件之下,也可以應用到2,2-雙取代-1-硝基烯類5m、5n與5o的合成上,並且同樣具有中等至高等的產率。雖然此改良方法無法將1,4-cyclohexanedione 19製備成硝基烯類,不過此條件下卻可以觀察到合環產物20的生成。

PART 1
Ketones 1 and nitromethane 2 can react with the trapping reagents 6 (benzyl mercaptan 6a、thiophenol 6b或allyl mercaptan 6c) in the presence of catalytic amount of piperidine 3a to produce b-nitroalkyl sulfides (7, 10 or 11). By the use of CH2Cl2 as solvent and at 0 ℃, b-nitroalkyl sulfides (7, 10 or 11) can be oxidized by m-CPBA (m-chloroperoxybenzoic acid) 8a to produce b-nitroalkyl sulfoxides (9、12 or 13) and subsequently elimination to produce 2,2-disubstituted-1- nitroalkenes 5. The irreversibility of the synthetic mechanism not only could overcome the impracticability of the Henry reaction in the synthesis of 2,2-disubstituted-1-nitroalkenes 5 but also could produce the major product "exo-nitroolefins" 5f-h when cyclic ketones were used. By using this improved and easy methodology to prepare 2,2-disubstituted-1- nitroalkenes 5, medium to high yields of the products are observed. Compouds 5b and 5f-h also can be produced when b-nitroalkyl sulfoxides (9f、9g、12b、13f或13h) are treated with dilute aqueous basic solution, but the yields are lower than those under pyrolysis condition.
PART 2
Reactions of ketones 1a-l, nitromethane 2 and benzyl mercaptan 6a in the presence of piperidine 3a or ethylenediamine 3b in tetrahydrofuran (THF) or acetonitrile (CH3CN) solution generate b-nitroalkyl sulfides 7a-l. By the use of 1,2-dichloroethane (ClCH2CH2Cl) as solvent, b-nitroalkyl sulfides 7a-l can be oxidized by m-chloroperoxybenzoic acid 8a, H2O2/AcOH 8b or H2O2 8c at 0 oC to generate b-nitroalkyl sulfoxides 9a-l first and then undergo elimination to produce medium to high yields of 2,2-disubstituted-1-nitroalkenes 5a-l under refluxing condition. One-pot synthesis of 5a-l from the reactions of 1a-l, 2, 3, and 6a in CH3CN solution under refluxing condition to generate 7a-l and then 7a-l was oxidized by 8a, 8b or 8c in the CH3CN and ClCH2CH2Cl solution at 0 oC to yield 9a-l. Finally, 9a-l undergo elimination under refluxing condition to yield expected products 5a-l with medium to high yields. The application of this one-pot methodology to prepare other 2,2-disubstituted-1-nitroalkenes 5m, 5n and 5o under similar conditions also get medium to high yields. Although this methodology can’t be applied to prepare nitroalkene from 1,4-cyclohexanedione 19, however, the unexpected product 20 can be observed under these conditions.

目 錄
頁數
第一部份 1
中文摘要 2
英文摘要 3
序論
背景 4
目標 11
結果和討論 13
結論 20
實驗部份
一般介紹 21
藥品和起始物 22
實驗方法 23
第二部分 27
中文摘要 28
英文摘要 29
序論
背景 30
目標 32
結果和討論 34
結論 71
實驗部份
一般介紹 73
藥品和起始物 74
實驗方法 75
光譜資料 79
參考資料 88
光譜圖 91

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