Supporting Information
Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: A
selective and sustainable oxidation protocol with high turn over number
Vivek Polshettiwar and Rajender S. Varma*
Sustainable Technology Division, National Risk Management Research Laboratory,
U. S. Environmental Protection Agency, MS 443, Cincinnati, Ohio 45268, USA
Contents:
S3:
Experimental Details (Material synthesis, oxidation reactions and Pd-leaching study)
S7:
TEM and XRD of pine structured α-Fe2O3
S8:
MS spectrum of benzaldehyde
S9:
1
S9:
13
S10:
MS spectrum of 4-chloro-benzaldehyde
S11:
1
S11:
13
S12:
MS spectrum of 2-chloro-benzaldehyde
S13:
1
S13:
13
S14:
MS spectrum of 4-fluoro-benzaldehyde
S15:
1
S15:
13
S16:
MS spectrum of 2-fluoro-benzaldehyde
S17:
1
S17:
13
S18:
MS spectrum of 4-bromo-benzaldehyde
H-NMR spectrum of benzaldehyde
C-NMR spectrum of benzaldehyde
H-NMR spectrum of 4-chloro-benzaldehyde
C-NMR spectrum of 4-chloro-benzaldehyde
H-NMR spectrum of 2-chloro-benzaldehyde
C-NMR spectrum of 2-chloro-benzaldehyde
H-NMR spectrum of 4-fluoro-benzaldehyde
C-NMR spectrum of 4-fluoro-benzaldehyde
H-NMR spectrum of 2-fluoro-benzaldehyde
C-NMR spectrum of 2-fluoro-benzaldehyde
S 1
S19:
1
S19:
13
S20:
MS spectrum of 2-methoxy-benzaldehyde
S21:
1
S21:
13
S22:
MS spectrum of phenyl butryaldehyde
S23:
1
S23:
13
S24:
MS spectrum of hexanal
S25:
1
S25:
13
S26:
MS spectrum of piperonyl aldehyde
S27:
1
S27:
13
S28:
MS spectrum of 2-furyl aldehyde
S29:
1
S29:
13
H-NMR spectrum of 4-bromo-benzaldehyde
C-NMR spectrum of 4-bromo-benzaldehyde
H -NMR spectrum of 2-methoxy-benzaldehyde
C-NMR spectrum of 2-methoxy-benzaldehyde
H -NMR spectrum of phenyl butryaldehyde
C-NMR spectrum of phenyl butryaldehyde
H -NMR spectrum of hexanal
C-NMR spectrum of hexanal
H -NMR spectrum of piperonyl aldehyde
C-NMR spectrum of piperonyl aldehyde
H -NMR spectrum of 2-furyl aldehyde
C-NMR spectrum of 2-furyl aldehyde
S 2
General Experimental:
The phase of the as-synthesized nanoparticles was determined by XRD in a MMS X-ray diffractometer with a
Cu Kα source in the 2θ range 10 to 70. The data were collected with a step of 0.5 deg/min. TEM micrographs
were recorded on a JEOL JSM-1200 II microscope at an operating voltage of 120 kV. The particles were
dispersed in ethanol by ultrasonication, loaded on a carbon coated copper grid, and then allowed to dry at
room temperature before recording the micrographs. Elemental analyses of the catalyst before as well as after
the reactions were performed on a Perkin Elmer Optima 3300 DV ICP-AES. Five mg of each sample was
dissolved in 2.5 mL of concentrated aqua regia and the volume was adjusted to 50 mL in a volumetric flask.
This solution was then used for the elemental analysis. Gas chromatographic mass spectroscopy (GCMS)
spectra were collected on a HP 6890 series GC system coupled with a 5973 Mass Selective Detector. Thin
layer chromatography (TLC) (silica gel; 10 % ethyl acetate: hexane) and gas chromatography (GC) were used
to monitor the reactions. The substrate conversions and product selectivities were determined by GC-MS. The
crude products were identified by GC-MS qualitative analysis using a GC system with a Mass selective
detector. The identities were further confirmed for representative compounds by 1H and 13C NMR spectra that
were recorded in deuterated chloroform-d (CDCl3) with tetramethylsilane (TMS) as internal reference using a
300 MHz NMR spectrometer.
Synthesis of magnetic nano-ferrites:
FeSO4·7H2O (13.9 g) and Fe2(SO4)3 (20 g) were dissolved in 500 mL water in a 1000 mL beaker. Ammonium
hydroxide (25 %) was added slowly to adjust the pH of the solution to 10. The reaction mixture was then
continually stirred for 1 h at 60 0C. The precipitated nanoparticles were separated magnetically, washed with
water until the pH reached 7, and then dried under a vacuum at 60 °C for 2 h. Ferrite was characterized by Xray diffraction (XRD) (Fig 1b) and transmission electron microscopy (TEM) (Fig 1a) This magnetic nanoferrite (Fe3O4) was then used for further chemical modification.
S 3
Surface modification of nano-ferrites:
Nano-Fe3O4 (2 gm) was dispersed in 25 mL water by sonication for 30 min. Dopamine hydrochloride (2 gm)
dissolved in 5 mL of water was added to this solution and again sonicated for 2 h. The amine-functionalized
nanomaterial was then precipitated using acetone, isolated by centrifugation, and dried under vacuum at 60 0C
for 2 h.
FT-IR evidently confirms the anchoring of dopamine on ferrite surfaces.
21.1
20
19
18
17
16
15
%T 14
3836.36
13
3672.72
3747.22
12
2315.26
11
1407.55
10
9
2070.66
8
7.5
4000.0
529.37
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
600
454.70
370.0
cm-1
Fig. FT-IR of dopa-amine functionalized catalyst
Synthesis of nano-ferrite-Pd catalyst:
Amine-functionalized Nano-Fe3O4 (1 gm) was dispersed in water and sodium palladium chloride solution in
water was added to the mixture to get 10 wt % of Pd. Hydrazine monohydrate solution in water was added
dropwise to bring the pH of this mixture to 9, followed by addition of 0.1 gm of NaBH4. The reaction mixture
was then stirred for 24 h at room temperature. The product was allowed to settle, washed several times with
water and acetone, and dried under vacuum at 60 0C for 2 h. Catalyst characterization by X-ray diffraction
(XRD) (Fig 1d) and transmission electron microscopy (TEM) (Fig 1c) confirm the anchoring of Pd
nanoparticles ferrite surfaces. The weight percentage of Pd in the catalyst was found to be 7.91 % by ICP-AES
analysis.
S 4
Oxidation of alcohols using nano-ferrite-Pd catalyst:
10 mmol of alcohol and 0.025 mole % of nano-ferrite-Pd catalyst were placed in a 10 mL glass tube with a
magnetic stirrer bar. H2O2 (1 equiv) was then added dropwise to the reaction mixture under stirring at room
temperature. The reaction was continuously stirred at 75-80 0C for 6 h. After completion of the reaction,
stirring was stopped. Within 30-45 s, the reaction mixture turned clear and catalyst was deposited on the
magnetic bar, which was easily removed from reaction mixture using an external magnet. Conversion and
selectivity were periodically determined by GC analysis. All products are known in the literature and were
identified by comparison of their 1H and
13
CNMR with literature data and comparing their GC-MS spectra
with standard Wiley mass spectral library.
Oxidation of olefins using nano-ferrite-Pd catalyst:
10 mmol of olefins and 0.025 mole % of nano-ferrite-Pd catalyst were placed in a 10 mL glass tube with a
magnetic stirrer bar. H2O2 (2 equiv) was then added to the reaction mixture dropwise under stirring at room
temperature and the same procedure described above was followed
Recyclability and Pd-leaching study:
For practical applications of heterogeneous systems, the lifetime of the catalyst and its level of reusability are
very important factors. To clarify this issue, we established a set of experiments for the oxidation of benzyl
alcohol using the recycled nano-Fe3O4-Pd catalyst. After the completion of the first reaction to afford the
corresponding aldehyde, the catalyst was recovered magnetically, washed with methanol, and finally dried at
60 0C for 10 min. A new reaction was then performed with fresh reactants and H2O2, under the same
conditions. The nanoferrite-supported Pd catalyst could be used at least 5 times without any change in activity.
S 5
Recyclability of Pd-Catalyst
800
TON
700
600
500
400
1
2
3
4
5
Run
Metal leaching was studied by ICP-AES analysis of the catalyst before and after the five reaction cycles.
The Pd concentration was found to be 7.91 % before reaction and 7.86 % after the reaction, which confirmed
negligible Pd leaching; this is due to dopamine anchor on nano-ferrite surface (Scheme 1), which is acting as a
chelating agent and preventing Pd-leaching. Also, no Pd metal was detected in the final oxidation product.
In fact, to date there is no 100% leach proof Pd catalyst; hence, the most important criteria in choosing
the catalyst is Pd metal recovery. It would be preferable to use a more accessible, lower cost Pd catalyst
provided that the process works at high TONs, and that the catalyst leaves no remnants of metal within the end
product, since metal contamination is highly regulated by the pharmaceutical industry. All above conditions
were well satisfied by our recyclable nano-ferrite-supported Pd catalyst, which works at high TON with
excellent selectivity and yields negligible Pd concentration in the end product after completion of the reaction.
S 6
TEM and XRD images of pine structured α-Fe2O3
Figure 1 TEM of single-crystal α-Fe2O3
Intensity (A.U.)
2000
1600
1200
800
400
0
20
30
40
50
60
70
2θ (Deg)
Figure 2 XRD of single-crystal α-Fe2O3
S 7
MS Spectrum of Benzaldehyde
S 8
1
H-NMR spectrum of benzaldehyde
Current Data Parameters
NAME
Benzaldehyde-1H
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20080912
Time
11.15
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zg30
TD
65536
SOLVENT
CDCl3
NS
16
DS
2
SWH
6172.839 Hz
FIDRES
0.094190 Hz
AQ
5.3084660 sec
RG
90.5
DW
81.000 usec
DE
6.00 usec
TE
298.0 K
D1
1.00000000 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
1H
P1
10.37 usec
PL1
-3.00 dB
SFO1
300.1318534 MHz
F2 - Processing parameters
SI
32768
SF
300.1300000 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
6
5
4
3
2
1
0
ppm
Current Data Parameters
NAME
Benzaldehyde-13C
EXPNO
1
PROCNO
1
77 .5 2
7 7. 29
77 . 09
7 6. 6 7
13 6. 41
1 34 . 47
13 4 .1 1
1 33 . 65
13 0 .1 6
1 2 9. 75
1 29 .5 6
12 9. 46
1 29 .3 2
12 9. 2 0
1 29 . 00
12 8 .5 8
1 28 . 46
12 0 .2 9
1 1 5. 40
1 71 . 31
C-NMR spectrum of benzaldehyde
1 92 .4 6
13
7
3.65
8
2.04
9
1.00
10
F2 - Acquisition Parameters
Date_
20080912
Time
12.23
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zgpg30
TD
65536
SOLVENT
CDCl3
NS
1024
DS
4
SWH
17985.611 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
16384
DW
27.800 usec
DE
6.00 usec
TE
299.3 K
D1
2.00000000 sec
d11
0.03000000 sec
DELTA
1.89999998 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.4752953 MHz
======== CHANNEL f2 ========
CPDPRG2
waltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.1312005 MHz
F2 - Processing parameters
SI
32768
SF
75.4677490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
ppm
S 9
MS spectrum of 4-chloro-benzaldehyde
S 10
1
H-NMR spectrum of 4-chloro-benzaldehyde
Current Data Parameters
NAME
4-Chlorobenzaldehyde-1H
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20080912
Time
13.41
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zg30
TD
65536
SOLVENT
CDCl3
NS
16
DS
2
SWH
6172.839 Hz
FIDRES
0.094190 Hz
AQ
5.3084660 sec
RG
512
DW
81.000 usec
DE
6.00 usec
TE
298.4 K
D1
1.00000000 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
1H
P1
10.37 usec
PL1
-3.00 dB
SFO1
300.1318534 MHz
F2 - Processing parameters
SI
32768
SF
300.1300000 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
9.0
8.5
8.0
7.0
6.5
6.0
5.5
5.0
ppm
Curr ent Data Pa rameters
NAME
4-Chlo robenzaldeh yde-13C
EXPN O
1
PROC NO
1
-0.02
14 .1 9
60.38
77.43
77 .2 0
77.00
76 .5 8
140.97
134.7 5
13 0. 89
129.4 6
C-NMR spectrum of 4-chloro-benzaldehyde
190. 80
13
7.5
1.99
9.5
2.02
10.0
1.00
10.5
F2 - Acquisitio n Parameter s
Date _
20080912
Time
14.49
INST RUM
spect
PROB HD
5 mm B BO BB-1H
PULP ROG
zgpg30
TD
65536
SOLV ENT
CDCl3
NS
1024
DS
4
SWH
1 7985.611 Hz
FIDR ES
0.274439 Hz
AQ
1 .8219508 se c
RG
23170.5
DW
27.800 us ec
DE
6.00 us ec
TE
299.3 K
D1
2. 00000000 se c
d11
0. 03000000 se c
DELT A
1. 89999998 se c
MCRE ST
0. 00000000 se c
MCWR K
0. 01500000 se c
==== ==== CHANNE L f1 ====== ==
NUC1
13C
P1
8.60 us ec
PL1
-3.00 dB
SFO1
75 .4752953 MH z
==== ==== CHANNE L f2 ====== ==
CPDP RG2
waltz16
NUC2
1H
PCPD 2
70.00 us ec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300 .1312005 MH z
F2 - Processing parameters
SI
32768
SF
75 .4677490 MH z
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 11
MS spectrum of 2-chloro-benzaldehyde
S 12
1
H-NMR spectrum of 2-chloro-benzaldehyde
Current Data Parameters
NAME
2-Chlorobenzaldehyde-1H
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20080912
Time
12.28
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zg30
TD
65536
SOLVENT
CDCl3
NS
16
DS
2
SWH
6172.839 Hz
FIDRES
0.094190 Hz
AQ
5.3084660 sec
RG
90.5
DW
81.000 usec
DE
6.00 usec
TE
298.4 K
D1
1.00000000 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
1H
P1
10.37 usec
PL1
-3.00 dB
SFO1
300.1318534 MHz
F2 - Processing parameters
SI
32768
SF
300.1300000 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
9.0
8.5
8.0
7.0
6.5
6.0
5.5
5.0
ppm
Curr ent Data Pa rameters
NAME
2-Chlo robenzaldeh yde-13C
EXPN O
1
PROC NO
1
-0.04
14 .1 6
20.98
35 .2 9
77.50
77.28
77.08
76.6 6
137.8 8
13 5. 44
135.0 8
134.71
134.3 8
133.12
132. 47
132.1 9
131. 29
130.9 7
13 0. 90
130.5 8
130.10
129.6 7
129.3 5
129.0 1
127.5 9
127. 26
126.8 7
12 6. 80
126.6 1
C-NMR spectrum of 2-chloro-benzaldehyde
189.6 8
13
7.5
3.02
9.5
0.99
10.0
1.00
10.5
F2 - Acquisitio n Parameter s
Date _
20080912
Time
13.36
INST RUM
spect
PROB HD
5 mm B BO BB-1H
PULP ROG
zgpg30
TD
65536
SOLV ENT
CDCl3
NS
1024
DS
4
SWH
1 7985.611 Hz
FIDR ES
0.274439 Hz
AQ
1 .8219508 se c
RG
18390.4
DW
27.800 us ec
DE
6.00 us ec
TE
299.3 K
D1
2. 00000000 se c
d11
0. 03000000 se c
DELT A
1. 89999998 se c
MCRE ST
0. 00000000 se c
MCWR K
0. 01500000 se c
==== ==== CHANNE L f1 ====== ==
NUC1
13C
P1
8.60 us ec
PL1
-3.00 dB
SFO1
75 .4752953 MH z
==== ==== CHANNE L f2 ====== ==
CPDP RG2
waltz16
NUC2
1H
PCPD 2
70.00 us ec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300 .1312005 MH z
F2 - Processing parameters
SI
32768
SF
75 .4677490 MH z
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 13
MS spectrum of 4-fluoro-benzaldehyde
S 14
1
H-NMR spectrum of 4-fluoro-benzaldehyde
Current Data Parameters
NAME
4-Fluorobenzaldehyde-1H
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20080912
Time
16.07
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zg30
TD
65536
SOLVENT
CDCl3
NS
16
DS
2
SWH
6172.839 Hz
FIDRES
0.094190 Hz
AQ
5.3084660 sec
RG
50.8
DW
81.000 usec
DE
6.00 usec
TE
298.4 K
D1
1.00000000 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
1H
P1
10.37 usec
PL1
-3.00 dB
SFO1
300.1318534 MHz
F2 - Processing parameters
SI
32768
SF
300.1300000 MHz
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
9.0
8.5
8.0
7.0
6.5
6.0
5.5
5.0
ppm
Curr ent Data Pa rameters
NAME
4-Fluo robenzaldeh yde-13C
EXPN O
1
PROC NO
1
-0.15
77.55
77. 34
77.13
76. 70
133 .54
133.01
132 .97
132.76
132 .71
132.62
132 .49
132 .41
132.19
132 .06
131.79
131 .67
116.72
116 .37
116.07
115 .58
115.29
168 .12
164.72
C-NMR spectrum of 4-fluro-benzaldehyde
190 .73
190 .37
13
7.5
2.01
9.5
2.13
10.0
1.00
10.5
F2 - Acquisitio n Parameter s
Date _
20080912
Time
17.15
INST RUM
spect
PROB HD
5 mm B BO BB-1H
PULP ROG
zgpg30
TD
65536
SOLV ENT
CDCl3
NS
1024
DS
4
SWH
1 7985.611 Hz
FIDR ES
0.274439 Hz
AQ
1 .8219508 se c
RG
20642.5
DW
27.800 us ec
DE
6.00 us ec
TE
299.5 K
D1
2. 00000000 se c
d11
0. 03000000 se c
DELT A
1. 89999998 se c
MCRE ST
0. 00000000 se c
MCWR K
0. 01500000 se c
==== ==== CHANNE L f1 ====== ==
NUC1
13C
P1
8.60 us ec
PL1
-3.00 dB
SFO1
75 .4752953 MH z
==== ==== CHANNE L f2 ====== ==
CPDP RG2
waltz16
NUC2
1H
PCPD 2
70.00 us ec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300 .1312005 MH z
F2 - Processing parameters
SI
32768
SF
75 .4677490 MH z
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 15
MS spectrum of 2-fluoro-benzaldehyde
S 16
1
H-NMR spectrum of 2-fluoro-benzaldehyde
C ur r en t Da t a Pa r am et er s
N AM E
2 - Fl ur o be nz al d eh yd e -1 H
E XP N O
1
P RO C NO
1
F 2 - A cq ui s it io n P ar am e te rs
D at e _
2 00 80 91 2
T im e
14 .5 4
I NS T RU M
sp ec t
P RO B HD
5 mm B B O BB -1 H
P UL P RO G
z g3 0
TD
65 53 6
S OL V EN T
CD Cl 3
NS
16
DS
2
S WH
6 17 2. 83 9 H z
F ID R ES
0 .0 94 19 0 H z
AQ
5 . 30 84 66 0 s ec
RG
10 1. 6
DW
8 1. 00 0 u se c
DE
6 .0 0 u se c
TE
29 8. 3 K
D1
1. 0 00 00 00 0 s ec
M CR E ST
0. 0 00 00 00 0 s ec
M CW R K
0. 0 15 00 00 0 s ec
= == = == == C H AN NE L f 1 == = == == =
N UC 1
1H
P1
10 .3 7 u se c
P L1
-3 .0 0 d B
S FO 1
3 00 . 13 18 53 4 M Hz
F 2 - P ro ce s si ng pa ra me t er s
SI
32 76 8
SF
3 00 . 13 00 00 0 M Hz
W DW
EM
S SB
0
LB
0 .3 0 H z
GB
0
PC
1 .0 0
8.5
8.0
7.0
6.5
6.0
5.5
5.0
ppm
Cu rren t Da ta P ara mete rs
NA ME
2 -Flu rob enza ldeh yde- 13C
EX PNO
1
PR OCNO
1
-0.08
77 .49
77.27
77 .07
76.64
166.37
162.94
13 6.36
136.24
13 2.66
130.82
13 0.71
128.69
12 8.66
128.32
126.03
125.99
124.63
12 4.58
124.24
12 4.13
124.04
121.64
121.35
117.12
116.61
116.33
11 5.38
115.09
C-NMR spectrum of 2-fluoro-benzaldehyde
19 0.81
187.12
18 7.03
13
7.5
2.13
9 .0
1.13
9.5
1.01
10.0
1.00
10.5
F2 - A cqui siti on Para mete rs
Da te_
20 0809 12
Ti me
16. 02
IN STRU M
spe ct
PR OBHD
5 mm BBO BB- 1H
PU LPRO G
zgpg 30
TD
655 36
SO LVEN T
CDC l3
NS
10 24
DS
4
SW H
179 85.6 11 H z
FI DRES
0. 2744 39 H z
AQ
1.8 2195 08 s ec
RG
1 8390 .4
DW
27.8 00 u sec
DE
6. 00 u sec
TE
299 .4 K
D1
2 .00 0000 00 s ec
d1 1
0 .03 0000 00 s ec
DE LTA
1 .89 9999 98 s ec
MC REST
0 .00 0000 00 s ec
MC WRK
0 .01 5000 00 s ec
== ==== == C HANN EL f1 = ==== ===
NU C1
1 3C
P1
8. 60 u sec
PL 1
-3. 00 d B
SF O1
7 5.4 7529 53 M Hz
== ==== == C HANN EL f2 = ==== ===
CP DPRG 2
w altz 16
NU C2
1H
PC PD2
70. 00 u sec
PL 2
-3. 00 d B
PL 12
12. 69 d B
PL 13
13. 50 d B
SF O2
30 0.1 3120 05 M Hz
F2 - P roce ssin g p aram eter s
SI
327 68
SF
7 5.4 6774 90 M Hz
WD W
EM
SS B
0
LB
1. 00 H z
GB
0
PC
1. 40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 17
MS spectrum of 4-bromo-benzaldehyde
S 18
1
H-NMR spectrum of 4-bromo-benzaldehyde
C ur r en t Da t a Pa r am et er s
N AM E
4 - Br om o be nz al d eh yd e -1 H
E XP N O
1
P RO C NO
1
F 2 - A cq ui s it io n P ar am e te rs
D at e _
2 00 80 91 2
T im e
17 .2 1
I NS T RU M
sp ec t
P RO B HD
5 mm B B O BB -1 H
P UL P RO G
z g3 0
TD
65 53 6
S OL V EN T
CD Cl 3
NS
16
DS
2
S WH
6 17 2. 83 9 H z
F ID R ES
0 .0 94 19 0 H z
AQ
5 . 30 84 66 0 s ec
RG
40 6. 4
DW
8 1. 00 0 u se c
DE
6 .0 0 u se c
TE
29 8. 5 K
D1
1. 0 00 00 00 0 s ec
M CR E ST
0. 0 00 00 00 0 s ec
M CW R K
0. 0 15 00 00 0 s ec
= == = == == C H AN NE L f 1 == = == == =
N UC 1
1H
P1
10 .3 7 u se c
P L1
-3 .0 0 d B
S FO 1
3 00 . 13 18 53 4 M Hz
F 2 - P ro ce s si ng pa ra me t er s
SI
32 76 8
SF
3 00 . 13 00 00 0 M Hz
W DW
EM
S SB
0
LB
0 .3 0 H z
GB
0
PC
1 .0 0
9.5
9 .0
8.5
8.0
7.0
6.5
6.0
5.5
5.0
pp m
Current Data Parameters
NAME
4-Bromobenzaldehyde-13C
EXPNO
1
PROCNO
1
-0. 02
14. 19
77.44
77. 22
77. 02
76.59
135 .11
132.45
130 .95
129.77
C-NMR spectrum of 4-bromo-benzaldehyde
191.00
13
7.5
4.02
10.0
1.00
10.5
F2 - Acquisition Parameters
Date_
20080912
Time
18.28
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zgpg30
TD
65536
SOLVENT
CDCl3
NS
1024
DS
4
SWH
17985.611 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
23170.5
DW
27.800 usec
DE
6.00 usec
TE
299.6 K
D1
2.00000000 sec
d11
0.03000000 sec
DELTA
1.89999998 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.4752953 MHz
======== CHANNEL f2 ========
CPDPRG2
waltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.1312005 MHz
F2 - Processing parameters
SI
32768
SF
75.4677490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 19
MS spectrum of 2-methoxy-benzaldehyde
S 20
1
H -NMR spectrum of 2-methoxy-benzaldehyde
Cu rren t Da ta P aram eter s
NA ME
m -Ani sald ehyd e-1H
EX PNO
1
PR OCNO
1
F2 - A cqui siti on P aram eters
Da te_
200 8091 2
Ti me
22.1 3
IN STRU M
spec t
PR OBHD
5 mm BBO BB-1 H
PU LPRO G
zg3 0
TD
6553 6
SO LVEN T
CDCl 3
NS
16
DS
2
SW H
617 2.83 9 Hz
FI DRES
0.0 9419 0 Hz
AQ
5.30 8466 0 sec
RG
50. 8
DW
8 1.00 0 use c
DE
6.0 0 use c
TE
297. 9 K
D1
1 .000 0000 0 sec
MC REST
0 .000 0000 0 sec
MC WRK
0 .015 0000 0 sec
== ==== == C HANN EL f 1 == ===== =
NU C1
1H
P1
10.3 7 use c
PL 1
-3.0 0 dB
SF O1
30 0.13 1853 4 MHz
F2 - P roce ssin g pa rame ters
SI
3276 8
SF
30 0.13 0000 0 MHz
WD W
EM
SS B
0
LB
0.3 0 Hz
GB
0
PC
1.0 0
5
4
3
2
1
0
ppm
3.02
6
C-NMR spectrum of 2-methoxy-benzaldehyde
Curre nt Data Param eters
NAME
m-Anisald ehyde-13C
EXPNO
1
PROCN O
1
-0.0 5
192. 42
192.07
189. 71
168.98
160. 14
159.56
139.81
137. 81
137.40
135. 91
131.07
130. 38
130.00
129.62
129.39
129.34
128.99
128.45
124. 59
123.73
123. 39
122.97
122. 45
121.92
121.81
121.73
121.38
120.96
120.62
119. 87
119.81
119. 38
114.36
114. 02
113.30
112.87
112. 60
112.55
112. 17
111.69
111. 65
105.34
77.5 7
77.34
77.14
76.72
74.49
60.3 3
58.01
55.5 6
55.39
55.1 1
52.08
51.68
23.63
14.14
13
7
2.98
8
0.88
9
0.97
10
F2 - Acquisition P arameters
Date_
200 80912
Time
23.21
INSTR UM
spect
PROBH D
5 mm BBO BB-1H
PULPR OG
z gpg30
TD
65536
SOLVE NT
CDCl3
NS
1024
DS
4
SWH
1798 5.611 Hz
FIDRE S
0.2 74439 Hz
AQ
1.82 19508 sec
RG
16384
DW
2 7.800 usec
DE
6.00 usec
TE
298.8 K
D1
2.000 00000 sec
d11
0.030 00000 sec
DELTA
1.899 99998 sec
MCRES T
0.000 00000 sec
MCWRK
0.015 00000 sec
===== === CHANNEL f 1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.47 52953 MHz
===== === CHANNEL f 2 ========
CPDPR G2
wa ltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.13 12005 MHz
F2 - Processing pa rameters
SI
32768
SF
75.46 77490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 21
MS spectrum of phenyl butryaldehyde
S 22
1
H -NMR spectrum of phenyl butryaldehyde
Curr ent Data Pa rameters
NAME
3-Phen ylbuteralde hyde-1H
EXPN O
1
PROC NO
1
F2 - Acquisitio n Parameter s
Date _
20080912
Time
21.00
INST RUM
spect
PROB HD
5 mm B BO BB-1H
PULP ROG
zg30
TD
65536
SOLV ENT
CDCl3
NS
16
DS
2
SWH
6172.839 Hz
FIDR ES
0.094190 Hz
AQ
5 .3084660 se c
RG
50.8
DW
81.000 us ec
DE
6.00 us ec
TE
298.2 K
D1
1. 00000000 se c
MCRE ST
0. 00000000 se c
MCWR K
0. 01500000 se c
==== ==== CHANNE L f1 ====== ==
NUC1
1H
P1
10.37 us ec
PL1
-3.00 dB
SFO1
300 .1318534 MH z
F2 - Processing parameters
SI
32768
SF
300 .1300000 MH z
WDW
EM
SSB
0
LB
0.30 Hz
GB
0
PC
1.00
4
3
2
1
0
ppm
3.90
5
6.30
6
C-NMR spectrum of phenyl butryaldehyde
205.72
20 5.65
201.82
175.56
16 5.86
146.67
14 6.41
145.66
14 5.51
143.81
12 9.91
129.12
128.85
128.70
128.57
12 8.45
128.38
12 7.71
127.48
127.27
127.05
126.93
126.79
126.56
12 6.48
126.39
12 6.30
126.11
12 6.06
92.78
92.30
91 .49
84.66
82 .36
77.56
77 .13
76.71
69 .73
69.41
68 .98
63.56
62.66
60 .40
51.98
51 .74
45.69
42 .91
42.30
42 .01
40.85
37 .41
37.16
37.08
36 .54
36.27
35 .40
34.33
34 .09
28.03
23.50
23.23
22.18
21.89
20.59
13
7
2.28
8
1.29
9
1.00
10
Current Data Parameters
NAME
3-Phenylbuteraldehyde-13C
EXPNO
1
PROCNO
1
F2 - Acquisition Parameters
Date_
20080912
Time
22.08
INSTRUM
spect
PROBHD
5 mm BBO BB-1H
PULPROG
zgpg30
TD
65536
SOLVENT
CDCl3
NS
1024
DS
4
SWH
17985.611 Hz
FIDRES
0.274439 Hz
AQ
1.8219508 sec
RG
14596.5
DW
27.800 usec
DE
6.00 usec
TE
298.9 K
D1
2.00000000 sec
d11
0.03000000 sec
DELTA
1.89999998 sec
MCREST
0.00000000 sec
MCWRK
0.01500000 sec
======== CHANNEL f1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.4752953 MHz
======== CHANNEL f2 ========
CPDPRG2
waltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.1312005 MHz
F2 - Processing parameters
SI
32768
SF
75.4677490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 23
MS spectrum of hexanal
S 24
1
H -NMR spectrum of hexanal
Curren t Data P arameter s
NAME
H exanal-1 H
EXPNO
1
PROCNO
1
F2 - A cquisiti on Param eters
Date_
2008091 2
Time
18.3 4
INSTRU M
spec t
PROBHD
5 mm BBO BB-1 H
PULPRO G
zg3 0
TD
6553 6
SOLVEN T
CDCl 3
NS
16
DS
2
SWH
6172.83 9 Hz
FIDRES
0.09419 0 Hz
AQ
5.308466 0 sec
RG
287. 4
DW
81.00 0 use c
DE
6.0 0 use c
TE
298. 7 K
D1
1 .0000000 0 sec
MCREST
0 .0000000 0 sec
MCWRK
0 .0150000 0 sec
====== == CHANN EL f1 == ===== =
NUC1
1H
P1
10.3 7 use c
PL1
-3.0 0 dB
SFO1
30 0.131853 4 MHz
F2 - P rocessin g parame ters
SI
3276 8
SF
30 0.130000 0 MHz
WDW
EM
SSB
0
LB
0.3 0 Hz
GB
0
PC
1.0 0
1.0
0.5
0.0
-0.5
ppm
C ur re n t D at a Pa ra m e te rs
N AM E
H ex an a l -1 3C
E XP NO
1
P RO CN O
1
- 0. 03
1 4. 17
13 .8 3
2 4. 35
22 .6 5
2 2. 56
22 .2 7
3 4. 08
33 .9 8
3 1. 65
31 .2 0
7 2. 08
C-NMR spectrum of hexanal
7 7. 42
77 .2 0
7 7. 00
76 .5 7
13
1.5
1.76
2.0
2.51
2.5
1.14
3.0
1.00
3.5
F 2 - A cq u is it io n P a ra me te rs
D at e_
20 0 8 09 12
T im e
1 9. 41
I NS TR U M
s pe ct
P RO BH D
5 mm B BO B B- 1H
P UL PR O G
z g pg 30
TD
6 55 36
S OL VE N T
C DC l3
NS
10 24
DS
4
S WH
1 79 8 5 .6 11 H z
F ID RE S
0. 2 7 44 39 H z
AQ
1 .8 2 1 95 08 s ec
RG
1 8 3 90 .4
DW
2 7 .8 00 u se c
DE
6. 00 u se c
TE
2 99 .6 K
D1
2. 00 0 0 00 00 s ec
d 11
0. 03 0 0 00 00 s ec
D EL TA
1. 89 9 9 99 98 s ec
M CR ES T
0. 00 0 0 00 00 s ec
M CW RK
0. 01 5 0 00 00 s ec
= == == = == CH AN NE L f 1 = == == == =
N UC 1
1 3C
P1
8. 60 u se c
P L1
- 3. 00 d B
S FO 1
75 .4 7 5 29 53 M Hz
= == == = == CH AN NE L f 2 = == == == =
C PD PR G 2
w a l tz 16
N UC 2
1H
P CP D2
7 0. 00 u se c
P L2
- 3. 00 d B
P L1 2
1 2. 69 d B
P L1 3
1 3. 50 d B
S FO 2
3 00 .1 3 1 20 05 M Hz
F 2 - P ro c es si ng p a r am et er s
SI
3 27 68
SF
75 .4 6 7 74 90 M Hz
W DW
EM
S SB
0
LB
1. 00 H z
GB
0
PC
1. 40
90
80
70
60
50
40
30
20
10
0
-1 0
ppm
S 25
MS spectrum of piperonyl aldehyde
S 26
1
H -NMR spectrum of piperonyl aldehyde
Cu rren t Da ta P aram eter s
NA ME
P iern al-1 H
EX PNO
1
PR OCNO
1
F2 - A cqui siti on P aram eters
Da te_
200 8091 2
Ti me
19.4 7
IN STRU M
spec t
PR OBHD
5 mm BBO BB-1 H
PU LPRO G
zg3 0
TD
6553 6
SO LVEN T
CDCl 3
NS
16
DS
2
SW H
617 2.83 9 Hz
FI DRES
0.0 9419 0 Hz
AQ
5.30 8466 0 sec
RG
161. 3
DW
8 1.00 0 use c
DE
6.0 0 use c
TE
298. 6 K
D1
1 .000 0000 0 sec
MC REST
0 .000 0000 0 sec
MC WRK
0 .015 0000 0 sec
== ==== == C HANN EL f 1 == ===== =
NU C1
1H
P1
10.3 7 use c
PL 1
-3.0 0 dB
SF O1
30 0.13 1853 4 MHz
F2 - P roce ssin g pa rame ters
SI
3276 8
SF
30 0.13 0000 0 MHz
WD W
EM
SS B
0
LB
0.3 0 Hz
GB
0
PC
1.0 0
9 .0
8.5
8.0
7.5
2.05
6.5
6.0
5.5
5.0
ppm
Curre nt Data Param eters
NAME
Pierna l-13C
EXPNO
1
PROCN O
1
1 4 .1 7
77 .4 6
7 7. 2 4
77 . 04
7 6 .6 2
1 08 .3 4
10 6. 9 2
10 2. 1 0
1 31 . 91
12 8. 5 9
15 3. 09
14 8. 7 1
C-NMR spectrum of piperonyl aldehyde
1 90 .2 2
13
7.0
2.02
9.5
0.98
10.0
1.00
10.5
F2 - Acquisition P arameters
Date_
200 80912
Time
20.54
INSTR UM
spect
PROBH D
5 mm BBO BB-1H
PULPR OG
z gpg30
TD
65536
SOLVE NT
CDCl3
NS
1024
DS
4
SWH
1798 5.611 Hz
FIDRE S
0.2 74439 Hz
AQ
1.82 19508 sec
RG
26008
DW
2 7.800 usec
DE
6.00 usec
TE
299.2 K
D1
2.000 00000 sec
d11
0.030 00000 sec
DELTA
1.899 99998 sec
MCRES T
0.000 00000 sec
MCWRK
0.015 00000 sec
===== === CHANNEL f 1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.47 52953 MHz
===== === CHANNEL f 2 ========
CPDPR G2
wa ltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.13 12005 MHz
F2 - Processing pa rameters
SI
32768
SF
75.46 77490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
ppm
S 27
MS spectrum of 2-furyl aldehyde
S 28
1
H -NMR spectrum of 2-furyl aldehyde
Cu rren t Da ta P aram eter s
NA ME
2 -Fur alde hyde -1H
EX PNO
1
PR OCNO
1
F2 - A cqui siti on P aram eters
Da te_
200 8091 2
Ti me
23.2 6
IN STRU M
spec t
PR OBHD
5 mm BBO BB-1 H
PU LPRO G
zg3 0
TD
6553 6
SO LVEN T
CDCl 3
NS
16
DS
2
SW H
617 2.83 9 Hz
FI DRES
0.0 9419 0 Hz
AQ
5.30 8466 0 sec
RG
101. 6
DW
8 1.00 0 use c
DE
6.0 0 use c
TE
297. 8 K
D1
1 .000 0000 0 sec
MC REST
0 .000 0000 0 sec
MC WRK
0 .015 0000 0 sec
== ==== == C HANN EL f 1 == ===== =
NU C1
1H
P1
10.3 7 use c
PL 1
-3.0 0 dB
SF O1
30 0.13 1853 4 MHz
F2 - P roce ssin g pa rame ters
SI
3276 8
SF
30 0.13 0000 0 MHz
WD W
EM
SS B
0
LB
0.3 0 Hz
GB
0
PC
1.0 0
8 .5
8.0
7 .0
6 .5
6 .0
5 .5
5 .0
ppm
Curre nt Data Param eters
NAME
2-Furalde hyde-13C
EXPNO
1
PROCN O
1
- 0.0 8
4 6.2 3
62 .52
6 0.2 9
7 7.5 5
77 .32
77 .12
7 6.70
1 12.5 7
12 1.0 5
13 9.7 8
1 38. 46
1 52. 95
1 48.4 9
14 8.0 7
1 71.0 1
C-NMR spectrum of 2-furyl aldehyde
1 77.8 2
13
7 .5
1.00
9 .0
1.03
9 .5
1.00
1 0 .0
1.00
1 0 .5
F2 - Acquisition P arameters
Date_
200 80913
Time
0.33
INSTR UM
spect
PROBH D
5 mm BBO BB-1H
PULPR OG
z gpg30
TD
65536
SOLVE NT
CDCl3
NS
1024
DS
4
SWH
1798 5.611 Hz
FIDRE S
0.2 74439 Hz
AQ
1.82 19508 sec
RG
16384
DW
2 7.800 usec
DE
6.00 usec
TE
298.7 K
D1
2.000 00000 sec
d11
0.030 00000 sec
DELTA
1.899 99998 sec
MCRES T
0.000 00000 sec
MCWRK
0.015 00000 sec
===== === CHANNEL f 1 ========
NUC1
13C
P1
8.60 usec
PL1
-3.00 dB
SFO1
75.47 52953 MHz
===== === CHANNEL f 2 ========
CPDPR G2
wa ltz16
NUC2
1H
PCPD2
70.00 usec
PL2
-3.00 dB
PL12
12.69 dB
PL13
13.50 dB
SFO2
300.13 12005 MHz
F2 - Processing pa rameters
SI
32768
SF
75.46 77490 MHz
WDW
EM
SSB
0
LB
1.00 Hz
GB
0
PC
1.40
200
180
160
140
120
100
80
60
40
20
0
p pm
S 29