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.

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