指導教授 : 于淑君 博士 2013 / 07
DESCRIPTION
Synthesis and Characterization of Aminodipyridylphosphine Oxide Iron(II) Complexes. Catalytic Application on Microwave-Assisted Amidation of Aldehydes. 指導教授 : 于淑君 博士 2013 / 07 . 學 生 : 蔡俊偉. Green Chemistry. 能源的綠色化 提升能源的效率如微波. 化學反應的綠色化 原子 經濟反應. 原料的綠色化 無毒無害的原料 可再生資源. - PowerPoint PPT PresentationTRANSCRIPT
1
Synthesis and Characterization of Aminodipyridylphosphine Oxide Iron(II)
Complexes. Catalytic Application on Microwave-Assisted Amidation of Aldehydes
指導教授 : 于淑君 博士2013 / 07
學 生 : 蔡俊偉
2
Green Chemistry
化學反應的綠色化 原子經濟反應 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
原料的綠色化 無毒無害的原料 可再生資源
觸媒的綠色化 無毒無害的觸媒
能源的綠色化 提升能源的效率如微波
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.
3
Green Catalysts
• Solid acid catalysts– Ex, Nafion-H, SO4
2-/ZrO2 、 SO42-/TiO2, …
• HPA catalysts– H3PMo12O40, H4PW11VO40
• Zeolite catalysts– ZSM-5, X-type, Y-type
• Metal catalysts– heterogeneous catalysis, homogeneous catalysis
• EnzymeSheldon, R., A.; Arends, I., W.,C., E.; and Hanefeld, U. (2007) Green Chemistry and Catalysis, Wiley-VCH Verlag GmbH, Weinheim
4
Application of Green Chemistry
Sonogashira coupling
N
Cl+
Si(CH3)3
N
Si(CH3)3
time yield (%)Conventional 18 h 80
Microwave assisted 25 min 97
+ H2O2
NOHOH
OO
FeCl3. 6 H2O (5 mol%)
pyrrodlidine (10 mol%)
(10 mol%)
t-amyl alcohol/water (90/10)rt. 1 h
O
H2O
30% / 2 equiv
+
conv. 99%sel. 95%
+ H2O2
30% 3 equiv
0.5 mol %
Ru
NO
O
O
ON
N
N
t-AmOH / water (90/10)rt. 12 h
O
+ H2O
yield = 71 %
epoxidation
物質 動物 , 途徑
Lethal Dose, 50%
(LD50)
FeCl3.6H2O 大鼠 , 口服 1872 mg/ kg
RuCl 3大鼠 , 口服 210 mg/kg
Anilkumar, G.; Bhor, S.; et. al. Tetrahedron Asymm., 2005 , 16, 3536–3561
Hasan, K.; Browne, N. and Kozak,C.,M. Green Chem., 2011, 13, 1230.
55
Phosphine Ligand Phosphines are electronically and sterically tunable.
Chemical waste - water bloom
Air/water sensitive and thermally unstable.
Metal leaching.
. Expensive.
P P PPO
OO
P(Bu)3 P(OiPr)3 P(Me)3 P(o-tolyl)3
R NH
PO
NN
R = CH3 = (CH3)8OH
Kinzel, E. J. Chem. Soc. Chem. Commun. 1986 1098.
6
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
The Catalytic Applications of Fe(II)
Ring Opening Reactions
Kharasch Reaction
Cross-Coupling Reactions
Mukaiyama-aldol reaction
Cycloadditions[2+1]-Cycloadditions[2+2]-Cycloadditions
Acetalization
Diels-Alder Reaction
Sulfide Oxidations
Aminochlorination
Allylic Aminations
Baeyer-Villiger Reactions
Amidation Reaction
7
8
Amide Bond
R1 NR3
O
R2
Amide
R1P
NR3
O
R2
R
Phosphoramide
R1S
NR3
O
R2
O
Sulfonamide
C. A. G. N. Montalbetti, V. Falque Tetrahedron , 2005, 61, 10827–10852
+R H
OSO
ONI R N
OS
H
O
O
9
Application of Acyl Sulfonamides
HCV NS5B polymerase allosteric inhibitors
antitumor activity Navitoclax
S. Jana, F. Hof. J. Org. Chem. 2011, 76, 3733–3741
Hepatitis C Virus Non-structural protein 5B, NS5B
Acyl Sulfonamides
10
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
SO O
R1 NH2+ H R2
O 2 mol% Rh2(esp)2
PHI(OC(O)tBu)0 to 50 oC, IPA, 24 h
SO O
R1 NH
R2
O
Me H
Me O+ PhI=NTs
5 mol% Ru(TTP)CO
CH2Cl2, RT, 1h Me NHTs
Me O
11
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
HO NH
PO
NN
12
+Degas DMF
95 oC, 6 hourN3
[P(2-py)3]
NN
N
P1ml DI water
NH
PO
NN
Mix solvent MeOH:CH3CN= 1: 5, RT, 12 hour
Cat.
NH
PO
NN Fe
NH
PO
NN FeCl2.4H2O
HNP
O
NN
Cl
Cl
2
80 %
Br 1.NaN3 , DMF/H2O
2. 50 oC / 8 hour
N3
80 %
Synthesis of 4C-Ppy2 and (4C-Ppy2)2FeCl2
IR (KBr) : py CC NC,
Ring stretching = 1590(s), 1426(s) cm-1
80 %
IR Spectra of 4C-Ppy2 and (4C-Ppy2)2FeCl2
νC - C (Py ring)
νC - N (Py ring)
Wavenumber (cm-1)pyridine ring
vibration
ν(C = N) 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
11C-Ppy2-MnCl2 1574 → 1586 12b.
b. a.
NH
PO
NN Fe
HNP
O
NN
Cl
Cl
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
14
Iron Complexes –Catalyzed Amidation Reactions of Aldehyde with PhINTs
entry catalytic Yield(%)a
1 FeCl2 20 2 FeCl3 15 3 FeCl2 + 4C-Ppy2 90 4 FeCl3 + 4C-Ppy2 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
H
O
CHCl3, PhINTs, 40 oC, 3 h
O
NH
TsFe cat.5 mol %
15
AA Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
NH
PO
NN Fe
HNP
O
NN
Cl
Cl 1.46710-6 mol/mg Fe
2 4 6 8 10 12 14 160
0.1
0.2
0.3
0.4
0.5
0.6
f(x) = 0.0344666666666667 x + 0.0557999999999995R² = 0.996640441478057
Series1Linear (Series1)
ppm 吸收度3 0.153
6 0.267
9 0.365
12 0.483
15 0.562
mol/mg Fe
1 1.679 10-6
2 1.653 10-6
3 1.589 10-6
NH
PO
NN Fe
Cl
Cl2.48710-6 mol/mg Fe
Calculated base on chemical formula AA data
experimental AA data
16
Colorimetry of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
N N
1,10-Phenanthroline
Fe2+ + 3phen (phen)3Fe(II)
Visible spectrum of (phen)3Fe(II)
max = 510nm
4C-Ppy2-FeCl2 (3)
mol/mg
FeCl2·4H2O
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
二價鐵純度 b 80 % 81 %
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.
17
1010510_120306141741 #542 RT: 1.27 AV: 1 SB: 22 1.80-1.84 NL: 2.77E6T: ITMS + c ESI Full ms [ 150.00-1000.00]
350 400 450 500 550 600 650 700m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
1010510_120306141741 #542 RT: 1.27 AV: 1 SB: 22 1.80-1.84 NL: 2.77E6T: ITMS + c ESI Full ms [ 150.00-1000.00]
350 400 450 500 550 600 650 700m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
676.14
401.27
384.51 579.08 668.26433.30366.27 521.89 694.14550.51459.12 494.26 650.32603.57
678.09
1010510_120306141741 #543 RT: 1.27 AV: 1 SB: 29 1.79-1.85 NL: 1.04E6T: ITMS + c ESI Full ms [ 150.00-1000.00]
675 676 677 678 679 680 681 682 683m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
676.02
678.09
677.11
679.06
680.04
681.14
ESI-MS Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2+
= 676 (m/z)
Simulated MS DataSimulated MS Data
[CH3(CH2)3N(H)P(O)(2-py)2]FeCl2+
= 401
(m/z)
Experimental MS Data
NH
PO
NN H
NPO
NNFe
Cl
Cl
Experimental MS Data
NH
PO
NN FeCl2
1010510_120306141741 #543 RT: 1.27 AV: 1 SB: 29 1.79-1.85 NL: 1.38E5T: ITMS + c ESI Full ms [ 150.00-1000.00]
398 399 400 401 402 403 404 405 406 407 408m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
401.14
403.14
402.25
404.18
399.21
18
EPR Spectrum of [CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
g = 2.199N
N N
NM
M = FeCl2
g = 2.04 (radical)
77 k, MeOH 300 k, MeOH
Li Zhong-Fang, et al. Chinese Journal of Inoranic chemistry 2003, 19.7, 691-698.
NH
PO
NN Fe
HNP
O
NN
Cl
Cl
19
+
Degas DMF
95 oC, 6 houtrHO N3
[P(2-py)3]
NN
N
P 1ml DI water
Aminodipyridylphosphine Oxide Ligand
HO NH
PO
NN
80 %
HO Br1.NaN3 / DMF
2. RT / 6 hourHO N3
93 %
Synthesis of 11C-Ppy2
Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem. 2008, 73, 4920-4928.
20
Synthesis of (11C-Ppy2)2-FeCl2
MeOH:CH3CN= 1: 5, RT, 12 hourr
Cat.
HO NH
PO
NN Fe
HO NH
PO
NN FeCl2.4H2O
OHHNP
O
NN
Cl
Cl
IR (KBr) : py CC NC, Ring stretching = 1588(s), 1425 (s) cm-1
21
3000 2500 2000 1500 10000
20
40
60
80
100
120
140
160
180
B
A
L1 L1-FeCl2
IR Spectra of 11C-Ppy2 and (11C-Ppy2)2-FeCl2
1575cm-1
1424cm-1
1588cm-1
1426cm-1
Wavenumber
T( %
)
νC - C (Py ring)
νC - N (Py ring)
22
AA Spectrum of [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
HO NH
PO
NN Fe
Cl
Cl
HO NH
PO
NN Fe OH
HNP
O
NN
Cl
Cl
1.106 10-6 mol/mg Fe
1.937 10-6 mol/mg Fe
2 4 6 8 10 12 14 160
0.1
0.2
0.3
0.4
0.5
0.6f(x) = 0.0344666666666667 x + 0.0601999999999997R² = 0.993462133150962
mol/mg Fe
1 1.324 10-6
2 1.413 10-6
experimental AA data
Calculated base on chemical formula AA data
23
Colorimetry of [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
N N
1,10-Phenanthroline
Fe2+ + 3phen (phen)3Fe(II)
Visible spectrum of (phen)3Fe(II)
max = 510nm
(11C-Ppy2)2-FeCl2 (6)
mol/mg
FeCl2·4H2O
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
二價鐵純度 b 78 % 81 %
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.
1020704_130705183651 #494-617 RT: 0.84-1.11 AV:93 NL: 6.98E6T: ITMS + c ESI Full ms [350.00-2000.00]
350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
390.36417.31
869.34
778.51 914.03444.27 965.38577.20480.28 833.38515.20372.41 630.10 664.33 700.38 942.37728.42547.56
ESI-MS Spectrum of [HO(CH2)11N(H)P(O)(2-py)2]2FeCl2
[HO3(CH2)11N(H)P(O)(2-py)2]2FeCl+ = 869 (m/z)
24
1011107-3 #6608 RT: 11.59 AV: 1 NL: 4.94E5F: ITMS - c ESI Full ms [300.00-800.00]
711 712 713 714 715 716 717 718 719 720 721 722m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
713.65
714.68 715.67
716.67
717.66718.69711.69 719.73710.98 721.74720.80
Experimental MS Data
Simulated MS Data
HO NH
PO
NN Fe OH
HNP
O
NN
Cl
25
Optimization of Reaction Conditions
entry Equiv PhINts Temp. hour Solvent Conv.%1 2 rt 18 CH2Cl2 87%2 2 40 18 CH2Cl2 95%3 2 40 6 CH2Cl2 85%4 0.5 40 6 CH2Cl2 56%5 1.5 40 6 CH2Cl2 88%6 1.5 40 3 CH2Cl2 56%7 1.5 40 3 CHCl3 89%8 1.5 40 3 CH3CN 65%9b 1.5 40 18 CHCl3 30%10 1.5 rt 3 CHCl3 50%
[CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
+5 mol %H
O
SO
ONI N
OS
H
O
O
5 mol %
b. no cat.
26
Entry Solvent Time (hr)
Polarity (P * ) Yielda (%)
1 CHCl3 3 4.1 892 CH2Cl2 3 3.1 563 CH2Cl2 6 854 CH3CN 3 5.8 655 CH2Cl2 : Toluene = 1 : 1 3 0.5 × 3.1 + 0.5 × 2.4 246 CHCl3 : Toluene = 2 : 1 3 0.67 × 4.1 + 0.33 × 2.4 187 DMSO 3 7.2 NA8 MeOH 3 5.1 209 [Bmim]Br 3 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
Reaction Conditions ScreeningCH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
+5 mol %H
O
SO
ONI N
OS
H
O
O
P *AB=QAP *
A+QBP *B
27
CH3(CH2)3N(H)P(O)(2-py)2]2FeCl2
+5 mol %
CHCl3, 40oC, 3hR H
OSO
ONI R N
OS
H
O
O
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
28
CH3(CH2)11N(H)P(O)(2-py)2]2FeCl2
+5 mol %
CHCl3, 40oC, 3hR H
OSO
ONI R N
OS
H
O
O
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.
Summary of Fe(II) catalytic ActivityEntry Product 4C-Ppy2-
FeCl2
Yield(%)a
11C-Ppy2-FeCl2
Yield(%)a
Entry Product 4C-Ppy2-FeCl2
Yield(%)a
11C-Ppy2-FeCl2
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 5964b
57 11 6784b
65
6 92 83 12 87 80
NH
O
Ts NH
O
Ts
NH
O
TsNH
O
F
Ts
NH
O
nn = 6
Ts NH
O
Br
Ts
NH
O
TsNH
O
Ts
NH
O
Ts NH
O
MeO
Ts
NH
O
Ts NH
O
Ts
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.
30
Proposed Mechanism of Amidation Reactions of Aldehyde with PhINTs
RNH
PO
NN
Fe N SO
O
Cl
Cl
4+
SN
IO O Ph
RNH
PO
NN
FeCl
Cl
2
NN Fe N Ts
R
OH
R H
O
Product
R NH
OTs
RNH
PO
NN
FeCl
Cl
I
SN
IO O Ph
I
2+
H2O
SNH2
O O
J. W. W. Chang and P. W. H. Chan* J. Org. Chem. 2011, 76, 4894-4904
31
Microwave Assisted Amidation Reactions of Aldehyde with PhINTs
entry M.W. power time. ( s ) solvent Yield Dielectric loss
1 300W 5min CHCl3 29% 0.432 300W 5min CHCl3 + 3drop [Bmim]
[PF6]20%
3 300W 2min DMSO No product 37.124b 300W 5min CHCl3 5%5 300W 5min CHCl3 + 1 drop DMSO 11% 0.43+37.126 600w 7min CHCl3 53%,7 600w 7min CHCl3 + 1 drop MeOH 28% 0.43+21.48 600w 7min CHCl3 + 1 drop DI water 22%, 0.43+9.899c 600w 7min CHCl3 67%
10d 600w 7min CHCl3 87%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
H
O
M.W.PhINTs
O
NH
Ts4C-Fe cat.
32
Optimization of Reaction Conditions under Focused Microwave
entry M.W. power time. ( min ) aldehyde ( M) temp. (oC) yield(%)
1 50 W 1 0.5 M 35 30%2 100w 1 0.5 M 43 40%3 150W 1 0.5 M 64 47%4 150W 2 0.5 M 63 52%5 150W 5 0.5 M 66 68%
150W 8 0.5 M 65 77%6 150W 10 0.5 M 70 75%7 150W 1 0.5M+1 drop BmimBr 69 76%8 150W 3 0.5M+1 drop BmimBr 83 88%9 150W 3 0.5M+2 drop BmimBr 124 67%
10 150W 5 0.5M+1 drop BmimBr 95 91%11 200W 1 0.5M 66 57%
12 200W 1 0.5M+1 drop BmimBr 110 54% 13 250W 1 0.5M 62 63%
14 250W 2 0.5M 68 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 .
H
O
Focus M.W.
O
NH
Ts4C-Fe cat.+ S
O
ONI
33
(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)
34
Summary of Fe(II) catalytic Activity under Focused Microwave
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)
Entry Product (4C-Ppy2)2-FeCl2
Yield(%)a
(11C-Ppy2)2-FeCl2
Yield(%)a
Entry Product (4C-Ppy2)2-FeCl2
Yield(%)a
(11C-Ppy2)2-FeCl2
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
NH
O
TsNH
O
Ts
NH
O
Ts NH
O
F
Ts
NH
O
nn = 6
Ts NH
O
Br
Ts
NH
O
Ts NH
O
Ts
NH
O
Ts NH
O
MeO
Ts
NH
O
Ts NH
O
Ts
SSS S S
SSS
HS(CH2)11NH
P(2-py)2
O
HAuCl4. 4H2O
2. CH3(CH2)7SH/CHCl33. NaBH4/H2O/12h
1. [CH3(CH2)7]4N+Br-/CHCl3/rt/1h
CHCl3, 65oC,16 h
N P(2-py)2
OH
S
S S S
S
N P(2-py)2O
H
NH
O(2-py)2P
SS S
N
S
S S S
SNPH
SS S
Au
Au Au
NH
O(2-py)2P
O
NPH
OCl2Fe(2-py)2
HPO
NH
PO
(2-py)2FeCl2
FeCl2/ dry CHCl3:MeOH = 6 :1
rt / 16 hr
(2-py)2FeCl2
Cl2Fe(2-py)2
35
Synthesis of the RS-Au-L1-FeCl2
RS-Au-L1-FeCl2RS-Au-L1
Au-RSRS = CH3(CH2)7SH
36
3500 3000 2500 2000 1500 1000-20
0
20
40
60
80
100
120
140
160
B
A
Au-L1-FeCl2 Au-L1 L1
IR Spectra of L1 ,Au-L1 and Au-L1-FeCl2
1575cm-1
1585cm-1
1426cm-1
1428cm-1
1575cm-1
1422cm-1
Wavenumber
T (%
)
37
9
N P(2-py)2
OH
S
S S S
S
N P(2-py)2
O
HNH
O(2-py)2P
SS SAu
NH
O(2-py)2P
TEM Image of RS-Au-L1-FeCl2
Particle size distribution 7.32 ± 1.2 nm
N
S
S S S
SNPH
SS SAu
O
NPH
OCl2Fe(2-py)2
HPO
NH
PO
(2-py)2FeCl2
(2-py)2FeCl2
Cl2Fe(2-py)2
Particle size distribution 2.68 ± 0.3 nm
FeRS-Au-L1
Element Weight%
Atomic%
Fe 6.23 7.05Cu 70.60 70.21Au 19.67 6.31
38
H
O
CHCl3, PhINTs, 40 oC, 3 h
O
NH
TsRS-Au-L1-FeCl2
5 mol %
RS-Au-L1-FeCl2 Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs
30 %
39
Summary
1.We have success fully synthesized green catalysts [4C-Ppy2]2-FeCl2 、 [ 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.
40
41
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
二價鐵純度 a 80 % 78 % 81 %
a. ( 傳統比色分析 / AA 實驗值 ) × 100%
42
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
43
(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)
44
45
Reported Fe(II) Complex –Catalyzed Amidation Reactions of Aldehyde with PhINTs
N
pyridine
+FeCl2Catalyst =(10 mol%)
4
J. W. W. Chang and P. W. H. Chan* J. Org. Chem. 2011, 76, 4894-4904
46
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
47
non classed Staudinger reaction mechanism
R N N N + Ppy
yp
ypR N N N
P pyyp
py
N
N N
P pypy
pyR
N N NP pypypy
R
N P pypypy
R
H2OOH
H+ N Ppypy
ROH
N
H O
Ppy
pyR N
H O
Ppy
pyR
py H+
48
Staudinger reaction mechanism
49
P P PPOO
O
P(Bu)3 P(OiPr)3 P(Me)3 P(o-tolyl)3
25 mL 211.5 USD
25 G 396 USD
100 mL 31.9 USD
10G 135.5USD
50
理論值 =0.0002 mol*0.05 = 0.00001mol
0.00001*55.845/15.584´10-4g (in 1ml )
CHCl3 (ml)Aldehyde (mol)
Temp./Time AA (mg/L)取 0.1 ml total Fe g
4C-0.2M 1 0.2 40oC/3h 4.614 4.614´10-4g
4C-0.3M 1 0.3 40oC/3h 6.786 6.786´10-4g
4C-0.3M 0.67 0.2 40oC/3h 7.697 5.156´10-4g
4C-0.2M 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
51
2 N (gas) + 2 H (gas)
N2 (gas) + H2 (gas)
iron
iron 1/2 N2
iron N
NH iron
NH H
ironN
H H H NH3 (gas)
Activation energy for the gas Phase disociation of the nitrogenmolecule (by for example, a spark)
Activation energy for the disociation of nitrogen in the presence of an iron catalyst
Ener
gy
52
NaN3 / DMF
rt / 6hrBr OH N3 OH
PBr3 / ether
rt / 6hr
N3 Br
97 %
50 %
1. CS(NH2)2 / ethanol
2. reflux , 16 hr
3. NaOH / 5 min
4. HCl /20 min
HS N3
90 %
P(2-py)3
H2O / CH3CN
110 oC / 16 h
NHSH
PO
NN
47%
Synthesis of Spacer-Linker
Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem. 2008, 73, 4920-4928.
L1
1H NMR Spectra of Au NPs L1 and L1-Metal
53
RS-Au-L1-FeCl2
RS-Au-L1
d4-MeOH *
9
N P(2-py)2
OH
S
S S S
S
N P(2-py)2
O
HNH
O(2-py)2P
SS SAu
NH
O(2-py)2P
Py
N-H
NHSH
PO
NN
N-H
54
Characteristics of catalysts Homogenous Heterogeneous Hybrid
Cat. structure Known Unknown Known
Catalyst modification Easy Difficult Easy
Activity High Low High
Selectivity High Low High
Conditions of catalysis Mild Harsh Mild
Poisoning of cat. 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
Types of Metal Catalysts
55
物質 動物 , 途徑 Lethal Dose, 50%
(LD50)
水 大鼠 , 口服 >90,000mg/kg
甲醇 大鼠 , 口服 5,628 mg/kg
氯化鈉 大鼠 , 口服 3,000 mg/kg
維他命A 大鼠 , 口服 2,000 mg/kg
二氯化亞鐵 大鼠 , 口服 1678mg /kg
三氯化鐵 大鼠 , 口服 1872mg/ kg
釕鹽
56
• http://macro.lsu.edu/howto/solvents/Polarity%20index.htm 和 Skoog 的 Principle of Instrumental Analysis 第六版的第 832 頁
Cl Cl
O2 HCl2 CH3OH H3C
O OCH3
O+ +
光氣CH3OH CO O21/2 H3C
O OCH3
OH2O+ + +
Zeolite catalysts
傳統
碳酸二甲酯