臺灣博碩士論文加值系統

本研究論文其內容包括合成及反應機制探討，分為六大類簡述：一、合成本研究所需使用之單環及雙環雜環1,2,4-triazine鹼基。 二、實驗得知由單環3-amino-2-benzyl-6-hydrazino-1,2,4-triazin-5(2H)-one (12)與二硫化碳於水/吡啶中進行反應，其反應機制乃經由分子內重排爾後再環合得到雙環6-amino-3-benzylmercaptor-1,2,4-triazolo[3,4-f] [1,2,4]triazin-8(7H)-one(18)之產物。 三、化合物3-amino-1,2,4-triazin- 5(2H)-one(2)及其6-bromo衍生物3各別經由偶氮化(diazotization)，再氧化成1,2,4-triazin-3,5(2H,4H)-dione(5)及其6-bromo衍生物6。此氧化機制則需經過環內芳香化才能進行。溴取代基之共振效應可幫助偶氮化更易進行，又溴基的誘導效應會幫助水的加成與氮的離去。
四、化合物5和6經矽化進行取代反應主要為N-2單取代產物29、30、31及32。若以一當量碳酸鉀與一當量溴化物進行反應則為2, 4-N,N對稱雙取代產物33、34、35、36及N-4單取代之主產物37、38、39、40。因此N-2或N-4單取代之產物再以一當量碳酸鉀與一當量溴化物進行反應，可得到不對稱雙取代產物41、42、43、44。 五、本研究證明3-amino-2-benzyl-1,2,4-triazin-5(2H)-one(10)之溴化反應不需經由環內芳香化。並於不同的反應時間可各別得到溴化產物11、45、46。 六、雙環雜環化合物3-alkyl-6-amino-1,2,4-triazolo[3,4-f] [1,2,4]triazin-8(7H)-one(7或8)與POCl3進行氯化反應或經HMDS矽化反應形成之中間體，分別與胺類化合物進行反應得到8位取代之產物49~56及63。而經矽化中間體進行取代反應則有副產物為6位取代之單環化合物57~60。

This study including synthesis and reaction mechanisms were divided into six parts. I. The base of mono and heterobicycles containing 1,2,4-triazine ring has synthesized. II. An intramolecular rearrangement- romatized ring cyclization mechanism for the compound 3-amino-2- benzyl-6-hydrazino-1,2,4-triazin-5(2H)-one(12) reacted with carbon disulfide in a water/pyridine mixture to afford bicyclic adduct 6-amino- 3-benzylmercaptor-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)-one(18) is explored. III. 3-amino-1,2,4-triazin-5(2H)-one(2) and its 6-bromo derivative 3 can be oxidize via diazotization to afford 1,2,4-triazin- 3,5(2H,4H)-dione(5) and its 6-bromo derivative 6, respectively. The resonance and inductive effects of 6-bromo increase the oxidation rate and yield. IV. The N-2 substituted compounds 29、30、31 and 32 were got when using the sililated intermediate of compound 5 (or 6) reacted with bromide compounds, respectively. The N-4 substituted compounds 37、38、39、40 and 2, 4-N,N symmetry disubstituted compounds 33、34、35、36 were getatable, respectively, when compound 5 (or 6) reacted with bromide compounds in K2CO3. Additionally an unsymmetry of 2,4-N,N disubstituted compounds 41、42、43、44 can be synthesize from these N-2 or N-4 mono substituted compounds. V. The experiments evident the bromination of 3-amino-2-benzyl-1,2,4-triazin-5(2H)-one(10) no aromatization in 1,2,4-triazine ring. The brominated compounds 11、45 or 46 was got in different reaction time. VI. The chlorinated or sililated intermediate of compounds 3-alkyl-6-amino-1,2,4-triazolo[3,4-f] [1,2,4]triazin-8(7H)-one(7 or 8) reacted with amine compounds to afford 8-substituted adducts 49~56 and 63, respectively. But, the 6-substituted monocyclic by-products 57~60, respectively, was got from substitution via sililated intermediate.

誌 謝--------------------------------------------------------------------------------- I
縮 寫-------------------------------------------------------------------------------- II
表目錄------------------------------------------------------------------------------- III
圖目錄------------------------------------------------------------------------------- IV
壹. 中文摘要------------------------------------------------------------------------ 1
英文摘要----------------------------------------------------------------------- 2
貳. 緒 論
2.1 導論-------------------------------------------------------------------------- 3
2.2 研究動機------------------------------------------------------------------- 16
參. 研究內容、合成方法、結構鑑定、反應機制探討、結果與討論
3.1 研究內容大綱--------------------------------------------------------------17
3.1.1 含1,2,4-triazine單環及雙環雜環之起始原料合成
3.1.2 3-Amino-2-benzyl-6-hydrazino-1,2,4-triazin-5(2H)-one與二硫化碳在水/吡啶中之重排環合反應機制探討
3.1.3 3-Amino-1,2,4-triazin-5(2H)-one經偶氮化之氧化反應與機制探討
3.1.4 1,2,4-Triazin-3,5(2H,4H)-dione不對稱取代合成
3.1.5 3-Amino-2-benzyl-1,2,4-triazin-5(2H)-one之溴化反應
3.1.6 6-Amino-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)-one雙環雜環之8-取代合成
3.2 各論
3.2.1 含1,2,4-triazine單環及雙環雜環之起始原料合成------------20
3.2.2 3-Amino-2-benzyl-6-hydrazino-1,2,4-triazin-5(2H)-one與二硫化碳在水/吡啶中之重排環合反應機制探討--------------------22
3.2.2.1 2-Benzyl-3-methylamino-6-hydrazino-1,2,4-triazin-5(2H)- one的合成--------------------------------------------------------23
3.2.2.2 2-(4-Mthylbenzyl)-3-amino-6-hydrazino-1,2,4-triazin- 5(2H)-one的合成------------------------------------------------36
3.2.2.3 重排環合之反應機制探討-------------------------------------37
3.2.3 3-Amino-1,2,4-triazin-5(2H)-one經偶氮化之氧化反應與機制探討---------------------------------------------------------------------40
3.2.3.1 3-Amino-2-benzyl-6-(H or Bromo)-1,2,4-triazin-5(2H)- one的合成及氧化----------------------------------------------------41
3.2.3.2 3-Amino-6(H or Bromo)-2-(2-hydroxyethoxymethyl)- 1,2,4-triazin-5(2H)-one之氧化--------------------------------43
3.2.3.3 討論----------------------------------------------------------------44
3.2.4 1,2,4-Triazin-3,5(2H,4H)-dione不對稱取代合成---------------48
3.2.4.1 4-Allyl-2-benzyl-6-(H or Bromo)-1,2,4-triazin-3,5(2H,4H)- dione不對稱取代衍生物的合成-----------------------------50
3.2.4.2 2-Allyl-4-benzyl-6-(H or Bromo)-1,2,4-triazin-3,5(2H,4H)- dione不對稱取代衍生物的合成-----------------------------51
3.2.4.3 結構鑑定與討論-------------------------------------------------52
3.2.5 3-Amino-2-benzyl-1,2,4-triazin-5(2H)-one之溴化反應--------58
3.2.5.1 3-Amino-2-benzyl-1,2,4-triazin-5(2H)-one(10)之溴化反應----------------------------------------------------------------------58
3.2.5.2 3-Amino-6-bromo-4-(4-bromobenzyl)-3,4-dihydro-1,2,4- triazin-5(2H)-one(48)之合成----------------------------------67
3.2.6 6-Amino-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)-one雙環雜環之8-取代合成---------------------------------------------------------75
3.2.6.1 3-Alkyl-6-amino-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)- one之8-amino取代衍生物的合成---------------------------75
3.2.6.2 3-Alkyl-6-amino-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)- one之8-phenylhydrazine取代衍生物的合成-------------84
3.2.6.3 3-Ethyl-6-amino-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H)- one之8-hydrazone取代衍生物的合成---------------------86
3.2.7 總結---------------------------------------------------------------------89

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