臺灣博碩士論文加值系統

利用氣相層析火燄離子偵測法分析除草劑Butachlor，發現Butachlor原體除主要成分之外，另外含有六個含量大於0.1% 的主要不純物質(雜質I~VI)，本論文利用氣相層析質譜儀進行這六個雜質鑑定分析，所得質譜分析結果與質譜儀資料庫比對，其中包含雜質I、雜質II以及主要成分可以正確辨認化學結構，其餘四個雜質則無法從質譜資料庫中比對出相同的成分。

經由質譜分析之離子斷片圖譜以及相關原體製程資料，可推論得到部分雜質可能之化學結構，其中雜質II標準樣品可購自試藥供應商，雜質III標準樣品則由興農公司提供，雜質I可經由有機合成方式製備取得，並經由氣相層析質譜儀(GC / MS)、核磁共振光譜儀(NMR)分析證明推論之化學結構正確。

雜質IV、雜質V以及雜質VI因無法推論可能之架構，因此鑑定工作採用製備級液相層析儀，進行雜質分離收集，並經純化成樣品，再利用氣相層析質譜儀、核磁共振光譜儀分析比對，鑑定出可能之化學結構。

經實驗後發現除草劑Butachlor中主要六個不純物之成分，雜質I為Butyl chloroacetate，雜質II為Dibutoxymethane，雜質III為2-Chloro-
N-(2,6-diethyl-phenyl)-acetamide，雜質IV可能為2,2-Dichloro-N-butoxy
methyl-N-(2,6-diethyl-phenyl)-acetamide，雜質V可能為2-Chloro-N-but
oxymethyl-N-(2-sec-butyl-6-ethyl-phenyl)-acetamide，雜質VI可能為2-
Chloro-N-butoxymethyl-N-(2,4,6-triethyl-phenyl)-acetamide.

Beside of the active ingredient, there are six major impurities which exceed the amount of 0.1% and have been found when the analytical technique of gas chromatography with flame ionization detector was used to analyze Butachlor herbicide. These impurities were named with impurity I to impurity VI for easy identification. Gas chromatography with mass detector was used to identify these impurities in this study. The mass spectra of these impurities were compared with the NIST mass library to find out possible matching chemicals for these impurities. The exact matches include impurity I , impurity II and the active ingredient while the other four impurities can not be identified successfully with the NIST mass library.
The possible structures of these impurities can be proposed from the fragments of mass spectra and the manufacturing process of Butachlor. Standard reference substance of impurity II was purchased from the vendor. Standard reference substance of impurity III was obtained from Sinon corporation and further confirmed the gas chromatography/mass spectrometry. Impurity I was prepared by organic synthesis route and the results were confirmed by gas chromatography with mass detector and NMR assay.
The chemical structures of impurity IV, impurity V and impurity VI can not be proposed as lack of sufficient evidence and information. Thus the preparative HPLC purification technique was applied to get enough amounts of impurity IV, impurity V and impurity VI. The accuracy of these collected impurities were confirmed by gas chromatography with mass detector. NMR assay were applied subsequently to deduce the possible structures of impurity IV, impurity V and impurity VI.
During the study works of this these, the six major impurities of Butachlor were identified successfully. Impurity I was Butyl chloroacetate. Impurity II was Dibutoxymethane. Impurity III was 2-Chloro-N-(2,6-diethyl-phen
yl)-acetamide. Impurity IV probably was 2,2-Dichloro-N-butoxymethyl-N-
(2,6-diethyl-phenyl)-acetamide. Impurity V probably was 2-Chloro-N-buto
xymethyl-N-(2-sec-butyl-6-ethyl-phenyl)-acetamide. Impurity VI probably
was 2-Chloro-N-butoxymethyl-N-(2,4,6-triethyl-phenyl)-acetamide.

目錄
誌謝------------------------------------------------------------------------------I
摘要-----------------------------------------------------------------------------II
Abstract------------------------------------------------------------------------IV
一、緒論 ----------------------------------------------------------------------------1
二、實驗方法與步驟 -------------------------------------------------------------5
2.1實驗儀器與設備 ---------------------------------------------------------5
2.2實驗藥品 ------------------------------------------------------------------6
2.3實驗方法 ------------------------------------------------------------------7
2.4實驗步驟 ---------------------------------------------------------------- 19
三、結果與討論 ------------------------------------------------------------------20
3.1氣相層析分析 ----------------------------------------------------------20
3.2氣相層析質譜分析 ----------------------------------------------------20
3.3雜質I合成實驗 --------------------------------------------------------30
3.4雜質IV、雜質V及雜質VI分離實驗 ----------------------------40
3.5 Butachlor各雜質鑑定結果 -------------------------------------------50
四、結論 ---------------------------------------------------------------------------57
五、參考文獻 ---------------------------------------------------------------------58
六、附錄---------------------------------------------------------------------------- 60

圖目錄
圖1： Butachlor氣相層析圖---------------------------------------------------21
圖2： Butachlor氣相層析質譜圖---------------------------------------------21
圖3： Butachlor雜質I氣相層析質譜圖( RT 6.97分)--------------------22
圖4： Butachlor雜質II氣相層析質譜圖( RT 7.26分)-------------------22
圖5： Butachlor雜質III氣相層析質譜圖( RT 12.01分)-----------------23
圖6： Butachlor主成分氣相層析質譜圖( RT 14.81分)------------------23
圖7： Butachlor雜質IV氣相層析質譜圖( RT 15.03分)----------------24
圖8： Butachlor雜質V氣相層析質譜圖( RT 15.17分)----------------- 24
圖9： Butachlor雜質VI氣相層析質譜圖( RT 15.37分)----------------25
圖10：Butachlor雜質II氣相層析圖-----------------------------------------26
圖11：Butachlor雜質II 質譜圖資料庫比對結果-------------------------27
圖12：Butachlor雜質II 1H光譜圖-------------------------------------------61
圖13：Butachlor雜質II 13C光譜圖------------------------------------------62
圖14：Butachlor主成分資料庫比對結果------------------------------------29
圖15：Butachlor雜質I氣相層析圖------------------------------------------30
圖16：Butachlor雜質I質譜圖資料庫比對結果---------------------------31
圖17：Butachlor雜質I 1H 光譜圖-------------------------------------------63
圖18：Butachlor雜質I 13C 光譜圖-------------------------------------------64
圖19：Butachlor雜質III氣相層析圖----------------------------------------35
圖20：Butachlor雜質III氣相層析質譜圖----------------------------------36
圖21：Butachlor雜質III 1H光譜圖------------------------------------------65
圖22：Butachlor雜質III 13C光譜圖-----------------------------------------66
圖23：Butachlor雜質製備級HPLC流析分離圖---------------------------41
圖24：Butachlor雜質IV氣相層析圖----------------------------------------41
圖25：Butachlor雜質IV氣相層析質譜圖----------------------------------42
圖26：Butachlor雜質IV 1H光譜圖------------------------------------------67
圖27：Butachlor雜質IV 13C光譜圖-----------------------------------------68
圖28：Butachlor雜質V氣相層析圖-----------------------------------------44
圖29：Butachlor雜質V氣相層析質譜圖-----------------------------------45
圖30：Butachlor雜質V 1H光譜圖-------------------------------------------69
圖31：Butachlor雜質V 13C光譜圖------------------------------------------70
圖32：Butachlor雜質VI 氣相層析圖---------------------------------------47
圖33：Butachlor雜質VI氣相層析質譜圖----------------------------------48
圖34：Butachlor雜質VI 1H光譜圖------------------------------------------71
圖35：Butachlor雜質VI 13C 光譜-------------------------------------------72

表目錄
表1：除草劑Butachlor原體主要不純物波峰面積及滯留時間---------20
表2：除草劑Butachlor原體氣相層析質譜分析結果---------------------25
表3：除草劑Butachlor雜質推測之可能化學結構------------------------39
表4：除草劑Butachlor主要雜質的鑑定結果------------------------------50

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