Catalytic Epoxidation of Fatty Acid Methyl Esters by Modified
Metalloporphyrins with Variable Metals and Electron-donating
Substituents
Weijie Zhanga, Pingping Jianga, Jianghao Wua, Pingbo Zhanga, Kelei Jiangb
a
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical
and Material Engineering, Jiangnan University, Wuxi 214122, P.R. China.
b
Technology, Policy and Management, Technische Universiteit Delft, Tilburg Area, Netherlands
Table S1 UV-Vis spectra and FT-IR spectra of different porphyrins
Porphyrin
FTIR(cm-1)
UV–vis (λmax/nm)
Porphyrin
FTIR(cm-1)
UV–vis (λmax/nm)
H2TPP
985
420
Zn TPP
997(Mn-N)
422
Mn(TPP)Cl
1008
477
Mn(TMOPP)Cl
1237(C-O), 1005 (Mn-N)
477
Fe(TPP)Cl
997
425
Mn(THPP)Cl
1284 (C-O), 1008 (Mn-N)
480
Co TPP
1004
420
Mn(TDMPP)Cl
1340 (C-N), 1002 (Mn-N)
490
Ni TPP
1004
418
Mn(TPPS4)Cl
1200 (O=S=O), 1000 (Mn-N)
412
A
B
C
D
E
2400
2000
1600
1200
-1
Wavenumber(cm )
800
Fig. S1 FT-IR spectra of: A, Mn(TPP)Cl; B, Fe(TPP)Cl; C, Co TPP; D, Ni TPP; E, Zn TPP
A
B
C
D
E
2400
2000
1600
1200
-1
Wavenumber(cm )
800
Fig. S2 FT-IR spectra of: A, Mn(THPP)Cl; B, Mn(TPPS4)Cl; C, Mn(TDMPP)Cl; D,
Mn(TMOPP)Cl; E, Mn(TPP)Cl
E
D
C
B
A
300
350
400
450
500
550
600
650
700
λ(nm)
Fig. S3 UV-vis spectra of A, Mn(TPP)Cl; B, Fe(TPP)Cl; C, CoTPP; D, NiTPP; E, ZnTPP
D
C
B
A
300 350 400 450 500 550 600 650 700 750
λ（ nm）
Fig. S4 UV-vis spectra of A, Mn(TMOPP)Cl; B, Mn(THPP)Cl; C, Mn(TDMPP)Cl; D,
Mn(TPPS4)Cl
In these papers (J Am Oil Chem Soc 70(1993):1139, J Am Oil Chem Soc
75(1998):15, Catal Lett 137(2010):88-93 and J Am Oil Chem Soc 87(2010):83),
the main products were monitored by
1H
and
13C
NMR analysis. The
conversion can be monitored by the area decrease of the double-bond
hydrogen signals which is at 5.4 ppm in the 1H NMR spectra of epoxidized
FAMEs. The presence of signals between 50 and 60 ppm in the
13C
NMR
spectra was attributed to the epoxy carbons. So, the selectivity could also be
monitored by the area increase of the epoxy carbons signals between 50 and
60 ppm of the 13C NMR spectra of epoxidized FAMEs. An example was also
listed below. In fact, the conversion, yield and selectivity in this article were
derived from the iodine value and epoxy value.
Fig. S5 Structural formula of FAMEs and epoxidized FAMEs and serial numbers of H
2
2
8
8'
8
7
4
ppm 6.0
5
3
5.0
4.0
3.0
7'
10
4
1
6
9
2.0
1.0
5'
1' 3'
0.0
ppm6.0
5.0
4.0
10
6
9
3.0
2.0
1.0
0.0
Fig. S6 1HNMR spectrum of FAMEs and epoxidized FAMEs
30.0
29.0
28.0
27.0
26.0
25.0
ppm
30.0
ppm
ppm
29.0
200
28.0
150
27.0
26.0
100
25.0
50
0
ppm
200
150
100
Fig. S7 13C NMR spectrum of FAMEs and epoxidized FAMEs
50
0
0.5
Mn (TPP) Cl
Mn (TMOPP) Cl
Mn (THPP) Cl
Mn (TDMPP) Cl
Mn TPPS4
Conversion
0.4
-H
-OCH3
0.3
-OH
0.2
-N(CH3)2
0.1
-SO3Na
0.0
0
100
200
300
Time(min)
400
500
Fig. S8 Substituents electronic effects observed with FAMEs as the substrate.