臺灣博碩士論文加值系統

本論文為利用循環伏安法和光譜電化學法研究鄰苯二胺化合物的電化學性質。研究結果顯示，當胺基的對位有取代基保護時，在循環伏安圖中可以觀察到可逆的氧化反應，顯示取代基具有保護的作用。推電子取代基使鄰苯二胺較容易氧化，拉電子取代基則使鄰苯二胺較難氧化。利用光譜電化學可測定化合物氧化後的穩定性，鄰苯二胺氧化後，其吸收光譜在近紅外光區有吸收峰產生，推測為鄰苯二胺之其中一個氮原子氧化後，產生了價間電荷轉移現象所致。

Electrochemical properties of a series of ortho-phenylenediamines have been studied by using cyclic voltammetry and spectroelectrochemical method. The para-substituents, methyl and methoxy groups could provide the steric protection to the oxidized ortho-phenylenediamine, prevent it from undergoing dimerization and polymerization. Furthermore, strong electron donating methoxy group could stabilized the oxidized ortho-phenylenediamine, exhibits a more negative oxidation potential. UV/Vis/NIR spectroelectrochemical method was used to monitor ortho-phenylenediamine oxidation. Broad band absorptions at near-infrared region in the absorption spectra of compound 4、5 and 6 indicate intervalence charge transfer occurred between nitrogens.

目錄
目錄 ..............................................................................................................................I
圖目錄 ........................................................................................................................IV
表目錄 ........................................................................................................................XI
第一章　序論 ..............................................................................................................1
　　第一節 苯胺及其衍生物之相關研究 ................................................................1
第二節 苯二胺化合物之相關研究 ....................................................................3
　 第三節 常用於合成苯胺化合物之方法—C-N耦合反應(C-N coupling)..........4
　　第四節 價間電荷轉移現象(Intervalence charge transfer,IVCT) ........................7
　　第五節 研究目的 ................................................................................................9
第二章 實驗 ..............................................................................................................10
　　第一節 藥品 ......................................................................................................10
　　第二節 鄰苯二胺化合物合成製備方法 ..........................................................12
(1) 化合物1 ................................................................................................14
　　　　(2) 化合物2 ................................................................................................14
　　　　(3) 化合物3 ................................................................................................14
　　　　(4) 化合物4 ................................................................................................15
(5) IPrHCl .................................................................................................16
(6) 化合物5 ................................................................................................17
(7) 化合物6 ................................................................................................18
(8) 化合物7 ................................................................................................19
(9) 化合物8 ................................................................................................19
(10) 化合物9 ..............................................................................................20
(11) 化合物10 ............................................................................................21
(12) p-dimethoxy-NH2-TPA .......................................................................21
(13) 化合物11 ............................................................................................22
第三節 儀器設備 ..............................................................................................24
Ⅰ、電化學儀器 ..........................................................................................24
Ⅱ、光譜電化學儀器 ..................................................................................24
第三章 鄰苯二胺化合物電化學及光譜電化學研究 ..............................................25
第一節 鄰苯二胺電化學研究 ..........................................................................25
(1) 化合物1電化學 .......................................................................................25
a. 循環伏安法 ...........................................................................................25
b. 光譜電化學 ...........................................................................................28
(2) 化合物2電化學 .......................................................................................31
a. 循環伏安法 ...........................................................................................31
b. 光譜電化學 ...........................................................................................33
(3) 化合物3電化學 .......................................................................................37
a. 循環伏安法 ...........................................................................................37
b. 光譜電化學 ...........................................................................................39
(4) 化合物4電化學 .......................................................................................43
a. 循環伏安法 ...........................................................................................43
b. 光譜電化學 ...........................................................................................45
(5) 化合物5電化學 .......................................................................................49
a. 循環伏安法 ...........................................................................................49
b. 光譜電化學 ...........................................................................................51
(6) 化合物6電化學 .......................................................................................55
a. 循環伏安法 ...........................................................................................55
b. 光譜電化學 ...........................................................................................57
(7) 化合物7電化學 .......................................................................................61
a. 循環伏安法 ...........................................................................................61
b. 光譜電化學 ...........................................................................................63
(8) 化合物8電化學 .......................................................................................65
a. 循環伏安法 ...........................................................................................65
b. 光譜電化學 ...........................................................................................68
第四章 結論 ..............................................................................................................72
第五章 參考文獻 ......................................................................................................73
第六章 附錄 ..............................................................................................................75
(1) 化合物5、6與水的作用研究 ...................................................................75
(2) 化合物6循環伏安法(電解質為TBAPF6) ................................................79
(3) NMR光譜 ...................................................................................................80 
圖目錄
Fig. 1-1 Cyclic polarograms of TPA and TPB：(A) 2.00×10-3 M TPA , (B) saturated
solution (ca .5×10-4 M) of TPB (medium：0.1 M TEAP/CH3CN, platinum
button electrode, scan rate 130mV/s for both curves) ...................................2
Fig. 1-2 Palladium-Catalyzed Coupling of Functionalized Primary and Secondary
Amines with Aryl and Heteroaryl Halides: Two Ligands Suffice in Most
Cases. .............................................................................................................6
Fig. 1-3 Potential energy curves for electron transfer in ligand-bridged dinuclear
complexes with (a) negligible, (b) weak (Hab = λ/4) and (c) strong　(Hab =
3λ/4) electronic coupling. The dotted and solid curves represent the
diabatic and adiabatic surfaces, respectively. ................................................8
Fig. 2-1 The structure of ortho-phenylenediamines. ................................................12
Fig. 3-1 Cyclic voltammograms of 1.0×10-3 M compound 1 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC ( Fc+/Fc0= +0.54 V)
......................................................................................................................25
Fig. 3-2 Cyclic voltammograms of 1.0×10-3 M compound 1 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................26
Fig. 3-3 Spectral change of 5.0×10-5 M compound 1 at Eappl.=+0.65 V in CH2Cl2
containing 0.1 M TBAP. ............................................................................28
Fig. 3-4 Absorption spectra of 5.0×10-5 M compound 1 in CH2Cl2 containing 0.1 M
TBAP at -0.20 V. .........................................................................................29
Fig. 3-5 Spectral change of 5.0×10-5 M compound 1 at Eappl.=+0.30 V in CH2Cl2
containing 0.1 M TBAP. ............................................................................30

Fig. 3-6 Absorption spectra of 5.0×10-5 M compound 1 in CH2Cl2 containing 0.1 M
TBAP at -0.20 V. …….................................................................................30
Fig. 3-7 Cyclic voltammograms of 1.0×10-3 M compound 2 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................31
Fig. 3-8 Cyclic voltammograms of 1.0×10-3 M compound 2 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................32
Fig. 3-9 Spectral change of 5.0×10-5 M compound 2 at Eappl.=+0.66 V in CH2Cl2
containing 0.1 M TBAP. ............................................................................33
Fig. 3-10 Absorption spectra of 5.0×10-5 M compound 2 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................34
Fig. 3-11 Spectral change of 5.0×10-5 M compound 2 at Eappl.=+0.66 V in CH2Cl2
containing 0.1 M TBAP. ............................................................................35
Fig. 3-12 Spectral change of 5.0×10-5 M compound 2 at Eappl.=+1.30 V in CH2Cl2
containing 0.1 M TBAP. ............................................................................35
Fig. 3-13 Absorption spectra of 5.0×10-5 M compound 2 in CH2Cl2 containing 0.1 M
TBAP at +0.66 V. …………........................................................................36
Fig. 3-14 Absorption spectra of 5.0×10-5 M compound 2 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................36
Fig. 3-15 Cyclic voltammograms of 1.0×10-3 M compound 3 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC ( Fc+/Fc0= +0.54 V)
......................................................................................................................37
Fig. 3-16 Cyclic voltammograms of 1.0×10-3 M compound 3 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................38
Fig. 3-17 Spectral change of 5.0×10-5 M compound 3 at Eappl.=+0.51 V in CH3CN
containing 0.1 M TBAP. ..............................................................................39
Fig. 3-18 Absorption spectra of 5.0×10-5 M compound 3 in CH3CN containing 0.1 M
TBAP at +0.11 V. .........................................................................................40
Fig. 3-19 Spectral change of 5.0×10-5 M compound 3 at Eappl.=+0.51 V in CH3CN
containing 0.1 M TBAP. ..............................................................................41
Fig. 3-20 Spectral change of 5.0×10-5 M compound 3 at Eappl.=+0.91 V in CH3CN
containing 0.1 M TBAP. ..............................................................................41
Fig. 3-21 Absorption spectra of 5.0×10-5 M compound 3 in CH3CN containing 0.1 M
TBAP at +0.51 V. ........................................................................................42
Fig. 3-22 Absorption spectra of 5.0×10-5 M compound 3 in CH3CN containing 0.1 M
TBAP at +0.11 V. .........................................................................................42
Fig. 3-23 Cyclic voltammograms of 1.0×10-3 M compound 4 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................43
Fig. 3-24 Cyclic voltammograms of 1.0×10-3 M compound 4 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................44
Fig. 3-25 Spectral change of 5.0×10-5 M compound 4 at Eappl.=+0.78 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................45
Fig. 3-26 Absorption spectra of 5.0×10-5 M compound 4 in CH2Cl2 containing 0.1 M
TBAP at -0.20 V. .........................................................................................46
Fig. 3-27 Spectral change of 5.0×10-5 M compound 4 at Eappl.=+0.78 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................47
Fig. 3-28 Spectral change of 5.0×10-5 M compound 4 at Eappl.=+1.12 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................47
Fig. 3-29 Absorption spectra of 5.0×10-5 M compound 4 in CH2Cl2 containing 0.1 M
TBAP at +0.78 V. ........................................................................................48
Fig. 3-30 Absorption spectra of 5.0×10-5 M compound 4 in CH2Cl2 containing 0.1 M
TBAP at -0.20 V. .........................................................................................48
Fig. 3-31 Cyclic voltammograms of 1.0×10-3 M compound 5 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................49
Fig. 3-32 Cyclic voltammograms of 1.0×10-3 M compound 5 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................50
Fig. 3-33 Spectral change of 5.0×10-5 M compound 5 at Eappl.=+0.63 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................51
Fig. 3-34 Absorption spectra of 5.0×10-5 M compound 5 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................52
Fig. 3-35 Spectral change of 5.0×10-5 M compound 5 at Eappl.= + 0.63 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................53
Fig. 3-36 Spectral change of 5.0×10-5 M compound 5 at Eappl.= + 0.99 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................53
Fig. 3-37 Absorption spectra of 5.0×10-5 M compound 5 in CH2Cl2 containing 0.1 M
TBAP at +0.63 V. ........................................................................................54
Fig. 3-38 Absorption spectra of 5.0×10-5 M compound 5 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................54
.Fig. 3-39 Cyclic voltammograms of 1.0×10-3 M compound 6 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................55

Fig. 3-40 Cyclic voltammograms of 1.0×10-3 M compound 6 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
......................................................................................................................56
Fig. 3-41 Spectral change of 5.0×10-5 M compound 6 at Eappl.=+0.52 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................57
Fig. 3-42 Absorption spectra of 5.0×10-5 M compound 6 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................58
Fig. 3-43 Spectral change of 5.0×10-5 M compound 6 at Eappl.=+0.52 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................59
Fig. 3-44 Spectral change of 5.0×10-5 M compound 6 at Eappl.=+0.92 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................59
Fig. 3-45 Absorption spectra of 5.0×10-5 M compound 6 in CH2Cl2 containing 0.1 M
TBAP at +0.52 V. ........................................................................................60
Fig. 3-46 Absorption spectra of 5.0×10-5 M compound 6 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................60
Fig. 3-47 Cyclic voltammograms of 1.0×10-3 M compound 7 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................61
Fig. 3-48 Cyclic voltammograms of 1.0×10-3 M compound 7 in DMF containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.51 V）
......................................................................................................................62
Fig. 3-49 Spectral change of 5.0×10-5 M compound 7 at Eappl.=+0.98 V in CH2Cl2
containing 0.1 M TBAP. ...........................................................................63
Fig. 3-50 Absorption spectra of 5.0×10-5 M compound 7 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................64

Fig. 3-51 Cyclic voltammograms of 1.0×10-3 M compound 8 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................65
Fig. 3-52 Cyclic voltammograms of 1.0×10-3 M compound 8 in CH3CN containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.50 V）
.....................................................................................................................66
Fig. 3-53 Spectral change of 5.0×10-5 M compound 8 at Eappl.=+0.41 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................68
Fig. 3-54 Absorption spectra of 5.0×10-5 M compound 8 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................69
Fig. 3-55 Spectral change of 5.0×10-5 M compound 8 at Eappl.=+0.05 V in CH2Cl2
containing 0.1 M TBAP. ..............................................................................70
Fig. 3-56 Absorption spectra of 5.0×10-5 M compound 8 in CH2Cl2 containing 0.1 M
TBAP at 0.00 V. ...........................................................................................70
Fig. S1 Cyclic voltammograms of 1.0×10-3 M compound 5 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................75
Fig. S2 Spectral change of 5.0×10-5 M compound 5 in CH2Cl2 containing 0.1 M TBAP. ..........................................................................................................76
Fig. S3 Cyclic voltammograms of 1.0×10-3 M compound 6 in CH2Cl2 containing
0.1M TBAP. Scan rate=0.1V/s . Working electrode：GC（Fc+/Fc0= +0.54 V）
......................................................................................................................77
Fig. S4 Spectral change of 5.0×10-5 M compound 6 in CH2Cl2 containing 0.1 M TBAP. ..........................................................................................................78
Fig. S5 Cyclic voltammograms of 1.0×10-3 M compound 6 in CH2Cl2 containing 0.1M TBAPF6. Scan rate=0.1V/s . Working electrode：GC . ……………....79
Scheme1-1 The electrochemical oxidation of aniline. ..................................................1
Scheme1-2 The electrochemical dimerizrtion of TPA. .................................................2
Scheme1-3 Electrochemically oxidative polymerization mechanism of
o-phenylenediamine. ...............................................................................4
Scheme1-4 Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides. .......................................................................4
Scheme1-5 Palladium-catalyzed aromatic aminations with in situ generated
aminos tannanes. .....................................................................................5
Scheme1-6 Pd catalyzed coupling of 1,2-dibromoarenes and anilines: formation of
N,N-diaryl-o-phenylenediamines. ...........................................................5
Scheme1-7 The mechanism of C-N coupling. ..............................................................6
Scheme2-1 The synthesis routes of ortho-Phenylenediamines. ..................................13
Scheme3-1 Electrochemically oxidative polymerization or dimerization mechanism of
compound 1. …..........................................................................................27
Scheme3-2 Electrochemically oxidative polymerization or dimerization mechanism of
compound 8. ..............................................................................................67






表目錄
Table. 1-1 Electrochemical characteristics of tri-para-substituted triphenylamines.
........................................................................................................................3
Table. 3-1. Oxidation Potentials of o-phenylenediamine derivatives with CH2Cl2 and
with CH3CN,respectively,containing 0.1 M TBAP. ..................................71

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