本研究以合成新的有機螫合劑及其分析應用之探討為重點，所研究的範圍包括
有兩部份；第一部份所合成之螯合劑是屬於可同時與多種重金屬形成錯化合
物的亞烷基－雙二硫氨基甲酸鈉螫合劑，在本論文中，合成了五種具有不同鏈
長的亞甲基螫合劑並探討它們應用於同時萃取及濃縮各種水樣中多種微量重
金屬的能力。實驗結果証明這五種螫合劑對二價的銅、鋅、鎳、鉛、鎘、鈷
及三價的鐵離子這七種離子在酸鹼值 4-8 之間時皆有非常好的效果；但對於
六價鉻，則只有其中之六亞甲基-雙二硫氨基甲酸鈉(HMBDTC)在酸鹼值5.0-5.5
的條件下有良好的螫合效果(95%)。進一步比較 HMBDTC 與應用最廣的二乙基
二硫氨基甲酸鈉(NaDDC)及 比咯啶二硫氨基甲酸銨(APDC) 在同時萃取、濃縮
多種重金離子的能力，發現這三種試劑對二價的銅、鋅、鎳、鉛、鎘、鈷及
三價的鐵離子的效果同樣好，但對於六價鉻，則 HMBDTC 的效果最佳。另為
瞭解這些螫合劑與各種金屬離子形成錯化合物的效率，選用 HMBDTC 分別與
各種重金屬離子形成錯化合物並求出這些錯化合物的溶解度積常數，由其溶
解度積常數皆小於 10 -7 的結果可知這類螫合劑與重金屬離子在形成錯化
合物的程度是非常完全的。另方面，由HMBDTC 與六價鉻所形成錯化合物的
組成比及利用紫外/可見光及紅外線光譜儀及元素分析儀分別測定殘存液或
錯化合物的結果皆顯示，HMBDTC與六價鉻在形成錯化合物的過程中並未涉及
氧化-還原的步驟，而認為應由 HMBDTC 中的兩個硫原子直接與六價鉻作用
而形成錯化合物。
第二部份是屬於對特定金屬離子具有特殊選擇性的大環冠狀二醯胺化合
物的研究，在此研究中，成功地開發出一種合成這系列化合物非常簡便的方
法，此方法可由最穩定的起始物、在正常反應條件下，只經兩步的合成步驟
即可合成出一系列具有 2-4 個氧原子或具有 2 個硫原子的大環冠狀二醯胺
化合物。初步探討結果發現，含有三個氧原子的大環冠狀化合物對釔離子具
有特殊選擇效果；但對IA 及 IIA 族元素的銫及鍶離子則完全沒有抓取效果;
而對某些重金屬離子的研究亦發現對銅離子的選擇性優於鋅、鎳、鈷及鎘離
子。另外研究含有 2 個硫原子的大環冠狀二醯胺化合物與四價鉑及兩價鈀作
用後所形成錯化合物的各種光譜得知此類錯化合物在形成過程中涉及脫去醯胺
基上的質子，再利用共振的醯胺基結構將四價鉑或兩價鈀抓於大環之環洞內
而形成穩定的錯化合物；這項推論結構業經 Pd-6b 錯化合物的 X-射線單晶
結構證明完全正確。綜合這些初步的研究，深信所合成的這些大環冠狀二
醯胺化合物應具有對某些金屬離子之抓取具有特殊選擇性存在。

This study is aimed at the synthesis and applications of new novel
organic chelating reagents. There are two parts in this study. In
the first part, a series of alkylene bisdithiocarbamates have been
synthesized and their chelating ability for simultaneous preconcen-
traction of trace element in aquatic samples have been studied. The
results show that they are excellent chelating reagents for heavy
metal ions such as Cu(II), Fe(III), Zn(II), Ni(II), Co(II), Pb(II)
and Cd(II) at pH= 4-8. Cr(VI) can be successfully extracted with
HMBDTC up to 95% if the pH of the solution is fixed at 5.0-5.5.
In addition, the efficiency of HMBDTC for the extraction of Cu(II),
Fe(III), Zn(II), Ni(II), Co(II), Pb(II) and Cd(II) is comparable
with those of ammonium pyrrolidine dithiocarbamate(APDC) and sodium
diethyl dithiocarbamate(NaDDC), and is better for extracting Cr(VI).
In order to understand the complexing ability, the solubility product
constants (Ksp) of metal complexes formed by HMBDTC with various
metal ions were measured; and the small Ksp(≦10-7) indicated near
complete complex formation. Moreover, no oxidation-reduction process
occurred during complex formation of Cr(VI) with HMBDTC , as was
confirmed by the stoichiometric study, together with UV and IR
measurements and elemental analysis. Therefore, it is believed that
the two sulfur atoms in HMBDTC chelate directly with chromate and
form a polymeric or a ring structure in the complexation of Cr(VI)
with HMBDTC. In the second part, a simple and convenient method for
preparing macrocyclic diamides containing two sulfur atomsor two
to four oxygen atoms of various ring size is developed. This method
is not only simpler and more convenient than the previous methods,
but also has many advantages. First, it is composed of two isolation
steps using easily handled starting materials. Secondly, macrocyclic
diamides, even those containing one hydrogen on the amide nitrogen
can be obtained. Thirdly, no high dilution technique or prolonged
reaction time is needed. Fourthly, no two-to-two condensation products
were found. Primary studyshows these macrocyclic diamides containing
three oxygen atoms are highly selective and efficient for chelating
Y(III); but not for IA and IIA elements such as Cs(I) and Sr(II).
And the selectivity and efficiency for Cu(II) is better than those
of Zn(II), Ni(II), Co(II), and Cd(II). Moreover, macrocyclic diamides
containing two sulfur atoms are highly selective for Pt(IV) and Pd(II).
The complex formation process involves the deprotonation of the amide
hydrogen and Pt(IV) or Pd(II) is captured within the ring . This
has been proven by the X-ray diffraction study of the single crystal
of Pd-6b. Therefore, depending on the size of the ring , difference
in metal ions or heteroatom on the ring, special selectivity have
been observed. Thus, these new macrocyclic diamides have demonestrated
their abilities as new ligands.
This study is aimed at the synthesis and applications of new novel