Synthesis and Characterization of
Aminodipyridylphosphine Oxide Iron(II)
Complexes. Catalytic Application on
Microwave-Assisted Amidation of Aldehydes
學
生: 蔡俊偉
指導教授: 于淑君 博士
2013 / 07
1
Green Chemistry
能源的綠色化
提升能源的效率
如微波
原料的綠色化
無毒無害的原料
可再生資源
化學反應的綠色化
原子經濟反應
觸媒的綠色化
無毒無害的觸媒
產品的綠色化
環境友好產品
溶劑的綠色化
無毒無害的溶劑
Chahbane, N.; Popescue, D., L.; Mitchell, D., A.; Chanda, A.; Lenoir, D.; Ryabov, A.D.; Schramm,
K., W. and Collins, T., J. Green Chem. 2007, 9, 49–57.
2
Green Catalysts
• Solid acid catalysts
– Ex, Nafion-H, SO42-/ZrO2、SO42-/TiO2, …
• HPA catalysts
– H3PMo12O40, H4PW11VO40
• Zeolite catalysts
– ZSM-5, X-type, Y-type
• Metal catalysts
– heterogeneous catalysis, homogeneous catalysis
• Enzyme
Sheldon, R., A.; Arends, I., W.,C., E.; and Hanefeld, U. (2007) Green Chemistry and Catalysis,
3
Wiley-VCH Verlag GmbH, Weinheim
Application of Green Chemistry
epoxidation
FeCl3.6H2O
Lethal Dose,
動物, 途徑
50%
(LD50)
大鼠, 口服 1872 mg/ kg
RuCl 3
大鼠, 口服 210 mg/kg
物質
Anilkumar, G.; Bhor, S.; et. al. Tetrahedron
Asymm., 2005 , 16, 3536–3561
Sonogashira coupling
Conventional
Microwave assisted
time
yield (%)
18 h
80
25 min
97
Hasan, K.; Browne, N. and Kozak,
C.,M. Green Chem., 2011, 13, 1230.
4
Phosphine Ligand
 Phosphines are electronically and sterically tunable.
P
P(Bu)3
O
P O
O
P(OiPr)3
P
P(Me)3
P
P(o-tolyl)3
Chemical waste - water bloom
 Air/water sensitive and thermally unstable.
 Metal leaching.
. Expensive.
Kinzel, E. J. Chem. Soc. Chem. Commun. 1986 1098.
5
5
The importance of Fe(II)
 Iron is one of the most abundant metals on earth. (5.6% of
earth’s crust. 4th most abundant element after oxygen, silicon,
and aluminum.
• Iron is environmentally friendly metal
• low toxic
• In body play a important role to transport oxygen (woman
2.5g ， man 4g) 60 mg/kg to iron poisoning
6
The Catalytic Applications of Fe(II)
 Ring Opening Reactions
Diels-Alder Reaction
 Kharasch Reaction
 Sulfide Oxidations
 Cross-Coupling Reactions
Aminochlorination
Mukaiyama-aldol reaction
Allylic Aminations
Cycloadditions
[2+1]-Cycloadditions
[2+2]-Cycloadditions
Baeyer-Villiger Reactions
Amidation Reaction
Acetalization
7
Amide Bond
C. A. G. N. Montalbetti, V. Falque Tetrahedron , 2005, 61, 10827–10852
8
Application of Acyl Sulfonamides
HCV NS5B polymerase
allosteric inhibitors
antitumor activity
Navitoclax
Hepatitis C Virus Non-structural protein 5B, NS5B
9
S. Jana, F. Hof. J. Org. Chem. 2011, 76, 3733–3741
Acyl Sulfonamides
J. Chan,* K. D. Baucom, and J. A. Murry J. Am. Chem. Soc. 2007, , 129, 14106-14107
J. W. W. Chang and P. W. H. Chan* Angew. Chem. Int. Ed. 2008, 47, 1138-1140
J. W. W. Chang and P. W. H. Chan* J. Org. Chem. 2011, 76, 4894-4904
10
Motivation
 Well-defined structure
 Iron is environmentally friendly metal
 Iron is less expensive than other transition metals.
- Rh2(esp)2
$ 30172 USD/mol ReagentPlus® (Aldrich)
- Ru(TTP)CO $ 20740 USD/mol reagent grade (Sigma-Aldrich)
- FeCl2.4H2O $ 148 USD/mol reagent grade (Sigma-Aldrich)
 Using bipyridine ligand to replace phosphine ligand in
organomatallic catalysis.
 Microwave to replace thermal energy
11
Synthesis of 4C-Ppy2 and (4C-Ppy2)2FeCl2
80 %
80 %
80 %
IR (KBr) :  py
C
C, C
N
Ring stretching = 1590(s), 1426(s) cm-1
12
IR Spectra of 4C-Ppy2 and (4C-Ppy2)2FeCl2
Wavenumber (cm-1)
pyridine ring
vibration
ν(C = N)
νC－C (Py ring)
νC－N (Py ring)
a.
b.
Δν
Ln- FeCl2a
1650 → 1668
18
PdCl2(2-pmOpe)2b
1594 → 1609
15
11C-Ppy2-Cu(OTf)
1570 → 1592
22
11C-Ppy2-NiBr2
1577 → 1592
15
11C-Ppy2-Pd(OAc)2 1574 → 1586
12
1574 → 1586
12
11C-Ppy2-MnCl2
b.
Hahn, F. E.; Langehahn, V.; Lügger, T.; Pape, T.; Le Van, D.
Angew. Chem. Int. Ed. 2005, 44, 3759-3763.
Zerong, L.; Zhongquan, L.; Ning, M. and Biao, W. Bull. Korean
Chem. Soc. 2011, 32, 2537-3543
Iron Complexes –Catalyzed Amidation Reactions
of Aldehyde with PhINTs
entry
1
2
3
4
catalytic
FeCl2
FeCl3
FeCl2 + 4C-Ppy2
FeCl3 + 4C-Ppy2
Yield(%)a
20
15
90
76
a Yields
were determined by H-NMR. Reaction conditions: aldehyde (1 equiv.), PhINTs
(1.5 equiv.), catalyst (0.05 equiv.), solvent = 0.67 mL, 50 oC, 3 hr
14
AA Spectrum of
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
Calculated base on chemical
formula AA data
2.48710-6 mol/mg Fe
1.46710-6 mol/mg Fe
0.7
0.6
y = 0.0345x + 0.0558
R² = 0.9966
0.5
0.4
ppm
吸收度
3
0.153
6
0.267
Series1
9
0.3
0.365
Linear (Series1)
0.2
12
0.483
15
0.562
experimental AA data
mol/mg Fe
1
1.679  10-6
2
1.653  10-6
3
1.589 10-6
0.1
0
0
5
10
15
20
15
Colorimetry of
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
Fe2+ + 3phen  (phen)3Fe(II)
N
N
1,10-Phenanthroline
4C-Ppy2-FeCl2 (3)
FeCl2·4H2O
mol/mg
mol/mg
理論值a
1.48 × 10-6
5.031 × 10-6
AA 實驗值
1.58 × 10-6
4.671 × 10-6
傳統比色分析
1.42× 10-6
3.783 × 10-6
80 %
81 %
二價鐵純度b
max = 510nm
a. Calculated base on chemical formula AA data
b. (傳統比色分析/ AA 實驗值) × 100%
Harvey, J.; Aubrey, E.; John, A. Smart, Analytical
Chemistry 1955, 27, 26-29.
Visible spectrum of (phen)3Fe(II)
16
ESI-MS Spectrum of
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
1010510_120306141741 #542 RT: 1.27 AV: 1 SB: 22 1.80-1.84
T: ITMS + c ESI Full ms [ 150.00-1000.00]
NL: 2.77E6
676.14
100
[CH3(CH2)3N(H)P(O)(2-py)2]FeCl2+
95
= 401
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2+ = 676 (m/z)
(m/z)
90
85
80
Simulated MS Data
Simulated MS Data
75
70
678.09
60
55
1010510_120306141741 #543 RT: 1.27
T: ITMS + c ESI Full m s [ 150.00-1000.00]
AV: 1
SB: 29 1.79-1.85
Experimental MS Data
95
50
1010510_120306141741 #543 RT: 1.27
T: ITMS + c ESI Full m s [ 150.00-1000.00]
676.02
100
NL: 1.38E5
401.14
100
90
403.14
75
70
65
65
678.09
Relative Abundance
60
55
50
45
40
60
55
50
45
40
30
30
402.25
679.06
25
25
20
20
404.18
15
680.04
15
10
10
399.21
5
5
681.14
0
0
25
677.11
35
35
30
Experimental MS Data
85
70
35
NL: 1.04E6
80
75
40
SB: 29 1.79-1.85
90
80
45
AV: 1
95
85
Relative Abundance
Relative Abundance
65
398
399
400
401
402
403
m /z
404
405
406
407
675
408
676
677
678
679
m /z
680
681
682
683
20
401.27
15
10
384.51
366.27
5
433.30
459.12
494.26
521.89
579.08
550.51
603.57
668.26
650.32
0
350
400
450
500
550
m/z
600
650
694.14
17
700
EPR Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
g = 2.199
g = 2.04 (radical)
77 k, MeOH
300 k, MeOH
18
Li Zhong-Fang, et al. Chinese Journal of Inoranic chemistry 2003, 19.7, 691-698.
Synthesis of 11C-Ppy2
93 %
80 %
Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem. 2008, 73, 4920-4928.
19
Synthesis of (11C-Ppy2)2-FeCl2
IR (KBr) :  py
C
C, C
N
Ring stretching = 1588(s), 1425 (s) cm-1
20
IR Spectra of 11C-Ppy2 and (11C-Ppy2)2-FeCl2
L1
L1-FeCl2
180
160
140
T( B%)
120
1575cm-1
100
1424cm-1
80
60
νC－C (Py ring)
40
1588cm-1
20
0
3000
νC－N (Py ring)
1426cm-1
2500
2000
1500
1000
A
Wavenumber
21
AA Spectrum of
[HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
Calculated base on chemical
formula AA data
1.106  10-6 mol/mg Fe
1.937  10-6 mol/mg Fe
0.7
0.6
y = 0.0345x + 0.0602
R² = 0.9935
experimental AA data
0.5
mol/mg Fe
0.4
0.3
1
1.324  10-6
2
1.413  10-6
0.2
0.1
0
0
2
4
6
8
10
12
14
16
22
Colorimetry of
[HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
Fe2+ + 3phen  (phen)3Fe(II)
N
N
1,10-Phenanthroline
(11C-Ppy2)2-FeCl2 (6)
FeCl2·4H2O
mol/mg
mol/mg
理論值a
1.11 × 10-6
5.031 × 10-6
AA 實驗值
1.32 × 10-6
4.671 × 10-6
傳統比色分析
1.03× 10-6
3.783 × 10-6
78 %
81 %
二價鐵純度b
max = 510nm
a. Calculated base on chemical formula AA data
b. (傳統比色分析/ AA 實驗值) × 100%
Harvey, J.; Aubrey, E.; John, A. Smart, Analytical Chemistry 1955, 27, 26-29.
23 Fe(II)
Visible spectrum of (phen)
3
ESI-MS Spectrum of
[HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
1020704_130705183651 #494-617 RT: 0.84-1.11 AV:93 NL: 6.98E6
T: ITMS + c ESI Full ms [350.00-2000.00]
869.34
100
95
90
85
80
[HO3(CH2)11N(H)P(O)(2-py)2]2FeCl+ = 869 (m/z)
75
70
Simulated MS Data
60
55
50
45
1011107-3 #6608 RT: 11.59 AV: 1 NL: 4.94E5
F: ITMS - c ESI Full ms [300.00-800.00]
713.65
100
40
95
Experimental MS Data
90
35
85
80
75
70
30
65
Relative Abundance
Relative Abundance
65
25
60
55
50
45
714.68
715.67
40
35
20
30
25
20
15
10
716.67
15
390.36
417.31
10
717.66
5
0
718.69
710.98 711.69
711
712
713
714
715
716
717
718
719
719.73
720.80
720
721
721.74
722
m/z
444.27
5
372.41
0
350
400
450
577.20
480.28 515.20
547.56
500
550
600
778.51
630.10 664.33 700.38 728.42
650
700
m/z
750
800
833.38
850
914.03
965.38
942.37
900
950
1000
24
Optimization of Reaction Conditions
entry
5 mol % 1
2
3
4
5
6
7
8
9b
10
Equiv PhINts
2
2
2
0.5
1.5
1.5
1.5
1.5
1.5
1.5
b. no cat.
Temp.
rt
40
40
40
40
40
40
40
40
rt
hour
18
18
6
6
6
3
3
3
18
3
Solvent
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CHCl3
CH3CN
CHCl3
CHCl3
Conv.%
87%
95%
85%
56%
88%
56%
89%
65%
30%
50%
25
Reaction Conditions Screening
Entry
1
2
3
4
5
6
7
8
9
Solvent
Time
(hr)
CHCl3
3
CH2Cl2
3
CH2Cl2
6
CH3CN
3
CH2Cl2 : Toluene = 1 : 1
3
CHCl3 : Toluene = 2 : 1
3
DMSO
3
MeOH
3
[Bmim]Br
3
Polarity (P＊)
Yielda (%)
4.1
3.1
89
56
85
5.8
65
0.5 × 3.1 + 0.5 × 2.4
24
0.67 × 4.1 + 0.33 × 2.4 18
7.2
NA
5.1
20
13
a Yields
were determined by H-NMR. Reaction conditions: aldehyde (1 equiv.), PhINTs (1.5 equiv.), catalyst
(0.05 equiv.), solvent = 0.67 mL, 50 oC, 3 hr NA = not available
P＊AB=QAP＊A+QBP＊B
26
4C-Ppy2-Fe(II)Complex –Catalyzed Amidation
Reactions of Aldehyde with PhINTs
General reaction conditions: Aldehyde (1 equiv.), PhINTs (1.5 equiv.), Catalyst (0.05 equiv.)
Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2 equiv. c 18 h
27
11C-Ppy2-FeCl2 Complex –Catalyzed Amidation
Reactions of Aldehyde with PhINTs
General reaction conditions: Aldehyde (1 equiv.), PhINTs (1.5 equiv.), Catalyst (0.05 equiv.)
Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2.0 equiv.
28
Summary of Fe(II) catalytic Activity
4C-Ppy2FeCl2
Yield(%)a
11C-Ppy2FeCl2
Yield(%)a
Entry
4C-Ppy2FeCl2
Yield(%)a
11C-Ppy2FeCl2
Yield(%)a
1
90
86
7
90
85
2
92
87
8
85
77
3
82
80
9
85
86
4
90
85
10
78
75
5
59
64b
57
11
67
84b
65
6
92
83
12
87
80
Entry
Product
Product
General reaction conditions: Aldehyde (1 equiv.), PhINTs (1.5 equiv.), Catalyst (0.05 equiv.)
Solvent = 0.67 mL, 40 oC, 3 h. a Yields were determined by 1H-NMR. b. PhINTs = 2.0 equiv.
Proposed Mechanism of Amidation Reactions of
Aldehyde with PhINTs
J. W. W. Chang and P. W. H. Chan* J. Org. Chem.
2011, 76, 4894-4904
30
Microwave Assisted Amidation Reactions of
Aldehyde with PhINTs
entry
M.W. power
time. ( s )
1
2
300W
300W
5min
5min
3
4b
5
6
7
8
9c
10d
300W
300W
300W
600w
600w
600w
600w
600w
2min
5min
5min
7min
7min
7min
7min
7min
solvent
CHCl3
CHCl3 + 3drop
[Bmim][PF6]
DMSO
CHCl3
CHCl3 + 1 drop DMSO
CHCl3
CHCl3 + 1 drop MeOH
CHCl3 + 1 drop DI water
CHCl3
CHCl3
Yield
Dielectric loss
29%
20%
0.43
No product
5%
11%
53%,
28%
22%,
67%
87%
37.12
0.43+37.12
0.43+21.4
0.43+9.89
a Yields
were determined by H-NMR. Reaction conditions: aldehyde (1 equiv.), PhINTs (1.5 equiv.), catalyst (0.05 equiv.), solvent =
0.67 mL. b no cat. . c aldehyde = 0.4 mol PhINTs = 0.6 mol Fe cat. = 10 mol% solvent = 1 ml. d solvent = 0.4 mL
31
Optimization of Reaction Conditions under
Focused Microwave
entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
M.W. power
time. ( min )
aldehyde ( M)
temp. (oC)
yield(%)
50 W
100w
150W
150W
150W
150W
150W
150W
150W
150W
150W
200W
200W
250W
250W
1
1
1
2
5
8
10
1
3
3
5
1
1
1
2
0.5 M
0.5 M
0.5 M
0.5 M
0.5 M
0.5 M
0.5 M
0.5M+1 drop BmimBr
0.5M+1 drop BmimBr
0.5M+2 drop BmimBr
0.5M+1 drop BmimBr
0.5M
0.5M+1 drop BmimBr
0.5M
0.5M
35
43
64
63
66
65
70
69
83
124
95
66
110
62
68
30%
40%
47%
52%
68%
77%
75%
76%
88%
67%
91%
57%
54%
63%
51%
a Yields were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.), catalyst
(0.05 equiv.), solvent CHCl3 = 0.4 mL .
32
(4C-Ppy2)2-Fe(II) Complex Catalyzed Amidation
Reactions of Aldehyde with PhINTs
a Yields
were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.), catalyst (0.05
equiv.), solvent CHCl3 = 0.4 mL. b PhINTs (2.0 equiv)
33
Summary of Fe(II) catalytic Activity under
Focused Microwave
(4C-Ppy2)2FeCl2
Yield(%)a
(11C-Ppy2)2FeCl2
Yield(%)a
Entry
(4C-Ppy2)2FeCl2
Yield(%)a
(11C-Ppy2)2FeCl2
Yield(%)a
1
90
80
7
82
73
2
93
83
8
86
72
3
76
64
9
71
63
4
86
78
10
75
75
5
54
50
11
80b
65b
6
90
80
12
84
68
Entry
a Yields
Product
Product
were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.),
catalyst (0.05 equiv.), solvent CHCl3 = 0.4 mL. b PhINTs (2.0 equiv)
34
Synthesis of the RS-Au-L1-FeCl2
RS = CH3(CH2)7SH
Au-RS
RS-Au-L1
RS-Au-L1-FeCl2
35
IR Spectra of L1 ,
Au-L1 and Au-L1-FeCl2
Au-L1-FeCl2
Au-L1
L1
160
140
1585cm-1
120
B
T (%)
100
1428cm-1
1575cm-1
1422cm-1
80
60
40
1575cm-1
20
0
1426cm-1
-20
3500
3000
2500
2000
A
Wavenumber
1500
1000
36
TEM Image of RS-Au-L1-FeCl2
O
(2-py)2P N
H
O
(2-py)2P N
H
HO
N P(2-py)2
SS S
S Au S
SSS
O
N P(2-py)2
H
9
RS-Au-L1
Fe
Particle size distribution 2.68 ± 0.3 nm
Particle size distribution 7.32 ± 1.2 nm
Element
Weight
%
Atomic
%
Fe
6.23
7.05
Cu
70.60
70.21
Au
19.67
6.31
37
RS-Au-L1-FeCl2 Complex –Catalyzed Amidation
Reactions of Aldehyde with PhINTs
30 %
38
Summary
1.We have success fully synthesized green catalysts [4C-Ppy2]2FeCl2、 [ 11C-Ppy2]2-FeCl2 .Their Structure were studied by
IR, ESI-MS, AA, EPR spectroscopies
2.We have successfully demonstrated the catalytic activity of
the Fe(II) complexes for amidation reactions of aldehyde with
PhINTs.
3. The Fe(II)-catalyzed amidation reactions of aldehyde with
PhINTs can be further accelerated under microwave irradiation
conditions.
39
40
4C-Ppy2-FeCl2 (3)
11C-Ppy2-FeCl2 (6)
FeCl2.6H2O
AA 理論值
1.48 × 10-6 mol/mg
1.11 × 10-6 mol/mg
5.031 × 10-6 mol/mg
AA 實驗值
1.58 × 10-6 mol/mg
1.32 × 10-6 mol/mg
4.671 × 10-6 mol/mg
傳統比色分析
1.42× 10-6 mol/mg
1.03× 10-6 mol/mg
3.783 × 10-6 mol/mg
80 %
78 %
81 %
二價鐵純度a
a. (傳統比色分析/ AA 實驗值) × 100%
41
瓦數
時間
焦耳
600 W
7 min
252000
5.5 倍
150 W
5 min
45000
31倍
130 W
180*60
1404000
傳統加熱
620 W 300 oC 6格
1.3格 130W
42
(11C-Ppy2)2-Fe(II) ComplexCatalyzed Amidation
Reactions of Aldehyde with PhINTs
a Yields
were determined by H-NMR. Reaction conditions: aldehyde = 0.2 mol (1 equiv.), PhINTs (1.5 equiv.),
catalyst (0.05 equiv.), solvent CHCl3 = 0.4 mL. b PhINTs (2.0 equiv)
43
44
Reported Fe(II) Complex –Catalyzed Amidation
Reactions of Aldehyde with PhINTs
J. W. W. Chang and P. W. H. Chan* J. Org. Chem. 2011, 76, 4894-4904
45
Reproposed Mechanism of Amidation Reactions
of Aldehyde with PhINTs
J. W. W. Chang and P. W. H. Chan* J. Org. Chem. 2011, 76, 4894-4904
46
non classed Staudinger reaction mechanism
47
Staudinger reaction mechanism
48
P
P(Bu)3
25 mL
211.5 USD
O
P O
O
P(OiPr)3
100 mL
31.9 USD
P
P
P(Me)3
P(o-tolyl)3
25 G
396 USD
10G
135.5USD
49
理論值 =
0.0002 mol*0.05 = 0.00001mol
0.00001*55.845/1
5.584´10-4g (in 1ml )
CHCl3 (ml)
4C-0.2M
Aldehyde
(mol)
1
Temp./Time AA (mg/L)
取0.1 ml
0.2
40oC/3h
4C-0.3M
1
0.3
4C-0.3M
0.67
4C-0.2M
total Fe g
4.614
4.614´10-4g
40oC/3h
6.786
6.786´10-4g
0.2
40oC/3h
7.697
5.156´10-4g
1
0.2
Rt. / 10 min
4.005
4.005´10-4g
4C-0.3M
1
0.3
Rt. / 10 min
3.779
3.779´10-4g
11C-0.2M
1
0.2
40oC/3h
3.560
3.560´10-4g
11C-0.3M
1
0.3
40oC/3h
3.615
3.615´10-4g
50
Energy
Activation energy for the gas
Phase disociation of the nitrogen
molecule (by for example, a spark)
Activation energy for the
disociation of nitrogen in the
presence of an iron catalyst
iron
iron
iron
iron
iron
51
Synthesis of Spacer-Linker
L1
Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem. 2008, 73, 4920-4928.
52
1
H NMR Spectra of Au NPs L1 and L1-Metal
N-H
O
(2-py)2P N
H
O
(2-py)2P N
H
HO
N P(2-py)2
SS S
S Au S
SSS
O
N P(2-py)2
H
9
RS-Au-L1
Py
N-H
RS-Au-L1-FeCl2
d4-MeOH
＊
53
Types of Metal Catalysts
Characteristics of
catalysts
Homogenous
Heterogeneous
Hybrid
Known
Unknown
Known
Catalyst modification
Easy
Difficult
Easy
Activity
High
Low
High
Selectivity
High
Low
High
Conditions of catalysis
Mild
Harsh
Mild
High risk
Low risk
Low risk
Mechanical strength
Low
High
High
Cat. stabilities
Low
High
High
Separation ＆ recycle of cat.
Difficult
Easy
Easy
Industrialization
Difficult
Applicable
Applicable
Cat. structure
Poisoning of cat.
54
水
甲醇
大鼠, 口服
大鼠, 口服
Lethal Dose,
50%
(LD50)
>90,000mg/kg
5,628 mg/kg
氯化鈉
大鼠, 口服
3,000 mg/kg
維他命A
二氯化亞鐵
三氯化鐵
大鼠, 口服
大鼠, 口服
大鼠, 口服
2,000 mg/kg
1678mg /kg
1872mg/ kg
物質
動物, 途徑
釕鹽
55
• http://macro.lsu.edu/howto/solvents/Polarity
%20index.htm 和 Skoog 的 Principle of
Instrumental Analysis第六版的第832頁
傳統
光氣
Zeolite catalysts
碳酸二甲酯
56