1 Supporting Information for Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate Michael North* 1 and Marta Omedes-Pujol 1 School of Chemistry and University Research Centre in Catalysis and Intensified Processing, Bedson Building, University of Newcastle, Newcastle upon Tyne, UK, NE1 7RU. Contents Chiral GC traces Chiral GC conditions 3 Cyanohydrin acetate derived from benzaldehyde 4 Cyanohydrin acetate derived from 4-fluorobenzaldehyde 8 Cyanohydrin acetate derived from 4-chlorobenzaldehyde 11 Cyanohydrin acetate derived from 3-chlorobenzaldehyde 14 Cyanohydrin acetate derived from 2-methylbenzaldehyde 17 Cyanohydrin acetate derived from 3-methylbenzaldehyde 20 Cyanohydrin acetate derived from 4-methylbenzaldehyde 23 Cyanohydrin acetate derived from nonanal 26 Cyanohydrin acetate derived from pivaldehyde 29 Cyanohydrin acetate derived from cyclohexane carboxaldehyde 32 Cyanohydrin acetate derived from 3-fluorobenzaldehyde 35 Cyanohydrin acetate derived from 4-trifluoromethylbenzaldehyde 36 Cyanohydrin acetate derived from 4-bromobenzaldehyde 37 Cyanohydrin acetate derived from 3,5-difluorobenzaldehyde 38 Chiral HPLC traces HPLC of methyl mandelate 39 NMR spectra of (R)-mandelic acid complexes used to determine enantiomeric excesses (3,4-Dichlorophenyl)hydroxyacetonitrile 40 (3,4-Dimethylphenyl)hydroxyacetonitrile 41 Kinetic plots used to determine the order with respect to catalyst concentration 0.2 mol % catalyst 42 0.3 mol % catalyst 43 0.4 mol % catalyst 44 0.6 mol % catalyst 45 0.8 mol % catalyst 46 plot of log([2]) against log(k 2obs avg ) 47 Kinetic plots used to determine the activation parameters in propylene carbonate Kinetics at 253 K 48 Kinetics at 263 K 49 Kinetics at 273 K 50
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1
Supporting Information
for
Kinetics and mechanism of vanadium catalysed asymmetric
cyanohydrin synthesis in propylene carbonate
Michael North*1 and Marta Omedes-Pujol
1
School of Chemistry and University Research Centre in Catalysis and Intensified Processing,
Bedson Building, University of Newcastle, Newcastle upon Tyne, UK, NE1 7RU.
Contents
Chiral GC traces
Chiral GC conditions 3
Cyanohydrin acetate derived from benzaldehyde 4
Cyanohydrin acetate derived from 4-fluorobenzaldehyde 8
Cyanohydrin acetate derived from 4-chlorobenzaldehyde 11
Cyanohydrin acetate derived from 3-chlorobenzaldehyde 14
Cyanohydrin acetate derived from 2-methylbenzaldehyde 17
Cyanohydrin acetate derived from 3-methylbenzaldehyde 20
Cyanohydrin acetate derived from 4-methylbenzaldehyde 23
Cyanohydrin acetate derived from nonanal 26
Cyanohydrin acetate derived from pivaldehyde 29
Cyanohydrin acetate derived from cyclohexane carboxaldehyde 32
Cyanohydrin acetate derived from 3-fluorobenzaldehyde 35
Cyanohydrin acetate derived from 4-trifluoromethylbenzaldehyde 36
Cyanohydrin acetate derived from 4-bromobenzaldehyde 37
Cyanohydrin acetate derived from 3,5-difluorobenzaldehyde 38
Chiral HPLC traces
HPLC of methyl mandelate 39
NMR spectra of (R)-mandelic acid complexes used to determine enantiomeric excesses
(3,4-Dichlorophenyl)hydroxyacetonitrile 40
(3,4-Dimethylphenyl)hydroxyacetonitrile 41
Kinetic plots used to determine the order with respect to catalyst concentration
0.2 mol % catalyst 42
0.3 mol % catalyst 43
0.4 mol % catalyst 44
0.6 mol % catalyst 45
0.8 mol % catalyst 46
plot of log([2]) against log(k2obs avg) 47
Kinetic plots used to determine the activation parameters in propylene carbonate
Kinetics at 253 K 48
Kinetics at 263 K 49
Kinetics at 273 K 50
2
Kinetics at 283 K 51
Kinetics at 293 K 52
Kinetic plots used to construct the Hammett plot
Benzaldehyde 53
3,4-Dichlorobenzaldehyde 54
4-Chlorobenzaldehyde 55
4-Methylbenzaldehyde 56
4-Fluorobenzaldehyde 57
3-Fluorobenzaldehyde 58
3-Methylbenzaldehyde 59
4-Trifluoromethylbenzaldehyde 60
4-Bromobenzaldehyde 61
3,5-Difluorobenzaldehyde 62
3,4-Dimethylbenzaldehyde 63
3-Chlorobenzaldehyde 64
3
Chiral GC conditions
Chiral gas chromatography was performed on a Varian450-GC instrument with a TCD detector
using Supelco Gamma DEX 120 fused silica capillary columns (26–30 m 0.25 mm 0.25 m
film thickness) with hydrogen as a carrier gas. Analyses were performed using one of the following
methods:
Method 1: initial temperature 95 °C, hold for 2 minutes then ramp rate of 3 °C/minute to 180 °C,
then hold for another 5 minutes. Flow rate: 2 mL/min.
Method 2: initial temperature 95 °C, hold for 2 minutes then ramp rate of 5 °C/minute to 180 °C,
then hold for another 5 minutes. Flow rate: 1 mL/min.
Method 3: initial temperature 95 °C, hold for 2 minutes then ramp rate of 2 °C/minute to 180 °C,
then hold for another 5 minutes. Flow rate: 2 mL/min.
Method 4: initial temperature 95 °C, hold for 5 minutes then ramp rate of 0.5 °C/minute to 180 °C,
then hold for another 5 minutes. Flow rate: 2 mL/min.
Method 5: initial temperature 95 °C, hold for 2 minutes then ramp rate of 5 °C/minute to 180 °C,
then hold for another 5 minutes. Flow rate: 2 mL/min.
Retention times were found to vary as the chiral GC column aged and were also different from
column to column. In many cases it was necessary to change the method used to analyse a particular
cyanohydrin acetate when the chiral GC column was replaced. The GC traces presented in the
following pages were recorded over a period of three years on three different chiral columns, which
accounts for the variation in retention times.
4
Cyanohydrin acetate derived from benzaldehyde (Analysed using GC methods 1 or 5).
Racemate (method 1)
Racemate (method 5)
Sample prepared using catalyst 1 in dichloromethane (Table 1)
24.1524.124.052423.9523.923.8523.823.7523.723.6523.623.5523.523.4523.423.3523.323.2523.223.1523.123.052322.9522.922.8522.822.7522.7
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0 RT [min]
benz_rac_3.DATAµV
15.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.414.3514.314.2514.214.1514.114.051413.9513.913.85
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000 RT [min]
benz_rac_1.DATAµV
15.915.8515.815.7515.715.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.4
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500RT [min]
mop_325_01.DATAµV
5
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
15.715.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.6
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500 RT [min]
mop_326_01.DATAµV
15.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.55
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
RT [min]
mop_467_1.DATAµV
15.915.8515.815.7515.715.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.8
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
RT [min]
mop_250_02.DATAµV
6
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 2)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 3)
15.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.75
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500 RT [min]
mop_334_01.DATAµV
16.11615.915.815.715.615.515.415.315.215.11514.914.814.714.614.514.4
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000 RT [min]
mop_336_01.DATAµV
15.815.7515.715.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.75
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
RT [min]
mop_335_01.DATAµV
7
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 4)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 1)
15.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.85
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000 RT [min]
mop_320_01.DATAµV
25.425.325.225.12524.924.824.724.624.524.424.324.224.12423.923.823.723.623.523.423.323.223.12322.922.822.722.622.522.4
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000 RT [min]
benz1_VNCS_PC_2.DATAµV
8
Cyanohydrin acetate derived from 4-fluorobenzaldehyde
Analysed using GC method 2.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
1817.917.817.717.617.517.417.317.217.11716.916.816.716.616.516.416.316.216.116
4,600
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200RT [min]
rac_pF_1.DATAµV
15.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.4
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400 RT [min]
mop_299_01.DATAµV
9
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
15.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.5
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400RT [min]
mop_300_01.DATAµV
15.6515.615.5515.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.414.3514.314.25
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500 RT [min]
mop_301_01.DATAµV
1918.918.818.718.618.518.418.318.218.11817.917.817.717.617.517.417.317.217.11716.9
10,000
9,500
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500 RT [min]
mop_251_01.DATAµV
10
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 5)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 5)
15.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.5
-6,000
-6,500
-7,000
-7,500
-8,000
-8,500
-9,000
-9,500
-10,000
-10,500
-11,000
-11,500
-12,000
-12,500
-13,000
-13,500
-14,000
-14,500
-15,000 RT [min]
mop_348_01.DATAµV
1817.917.817.717.617.517.417.317.217.11716.916.816.716.616.516.416.3
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500RT [min]
p-F2_VONCS_PC_1.DATAµV
11
Cyanohydrin acetate derived from 4-chlorobenzaldehyde
Analysed using GC method 3.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
36.636.436.23635.835.635.435.23534.834.634.434.23433.833.633.433.23332.832.632.432.23231.831.6
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500 RT [min]
pCl_racemic_11.DATAµV
36.336.236.13635.935.835.735.635.535.435.335.235.13534.934.834.734.634.534.434.334.234.134
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500 RT [min]
mop_311_01.DATAµV
12
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
36.236.13635.935.835.735.635.535.435.335.235.13534.934.834.734.634.534.434.334.234.13433.9
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400RT [min]
mop_312_01.DATAµV
36.536.436.336.236.13635.935.835.735.635.535.435.335.235.13534.934.834.734.634.534.434.334.234.13433.933.833.7
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0RT [min]
mop_313_01.DATAµV
36.636.436.23635.835.635.435.23534.834.634.434.23433.833.6
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500
-4,000 RT [min]
mop_333_01.DATAµV
13
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 7)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 3)
36.436.23635.835.635.435.23534.834.634.434.23433.833.633.4
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500RT [min]
mop_351_01.DATAµV
3534.934.834.734.634.534.434.334.234.13433.933.833.733.633.533.433.333.233.13332.932.832.7
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500RT [min]
p-Cl1_VONCS_PC_1.DATAµV
14
Cyanohydrin acetate derived from 3-chlorobenzaldehyde (Analysed using GC methods 3 or 4).
Racemate (method 3)
Racemate (method 4)
Sample prepared using catalyst 1 in dichloromethane (Table 1)
32.9532.932.8532.832.7532.732.6532.632.5532.532.4532.432.3532.332.2532.232.1532.132.053231.9531.931.8531.831.7531.731.6531.6
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
RT [min]
m-Cl_rac_3.DATAµV
79.879.679.479.27978.878.678.478.27877.877.677.477.27776.876.676.476.27675.875.675.475.27574.874.674.474.2
200
100
0
-100
-200
-300
-400
-500
-600
-700
-800
-900
-1,000
-1,100
-1,200
-1,300
-1,400
-1,500
-1,600
-1,700
-1,800
-1,900 RT [min]
mCl_racemic_12.DATAµV
35.435.23534.834.634.434.23433.833.633.433.23332.832.632.4
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000 RT [min]
mop_328_01.DATAµV
15
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
34.3534.334.2534.234.1534.134.053433.9533.933.8533.833.7533.733.6533.633.5533.533.4533.433.3533.333.2533.2
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0 RT [min]
mop_329_01.DATAµV
34.834.734.634.534.434.334.234.13433.933.833.733.633.533.433.333.233.133
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
RT [min]
mop_327_01.DATAµV
36.23635.835.635.435.23534.834.634.434.23433.833.633.433.23332.8
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
RT [min]
mop_252_02.DATAµV
16
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 6)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 12)
35.535.435.335.235.13534.934.834.734.634.534.434.334.234.13433.933.833.733.633.533.433.333.233.13332.932.8
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
RT [min]
mop_349_01.DATAµV
82.58281.58180.58079.57978.57877.57776.57675.57574.57473.57372.57271.5
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000RT [min]
m-Cl2_VONCS_PC_2.DATAµV
17
Cyanohydrin acetate derived from 2-methylbenzaldehyde
Analysed using GC method 3.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
27.9527.927.8527.827.7527.727.6527.627.5527.527.4527.427.3527.327.2527.227.1527.127.052726.9526.926.8526.826.7526.726.6526.626.5526.526.4526.4
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200
-1,400
-1,600
-1,800
-2,000 RT [min]
o-CH3_rac_3.DATAµV
30.630.430.23029.829.629.429.22928.828.628.428.22827.827.627.427.2
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500
-4,000
-4,500
-5,000
-5,500
-6,000 RT [min]
mop_317_01.DATAµV
18
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
29.529.429.329.229.12928.928.828.728.628.528.428.328.228.12827.9
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600 RT [min]
mop_318_01.DATAµV
29.929.829.729.629.529.429.329.229.12928.928.828.728.628.528.428.328.228.12827.927.827.727.627.527.427.327.2
5,000
4,800
4,600
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400 RT [min]
mop_319_01.DATAµV
19
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 9)
29.729.629.529.429.329.229.12928.928.828.728.628.528.428.328.228.12827.9
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400 RT [min]
mop_253_02.DATAµV
2827.9527.927.8527.827.7527.727.6527.627.5527.527.4527.427.3527.327.2527.227.1527.127.052726.9526.926.8526.826.7526.726.65
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200RT [min]
o-CH3_rt_24h_PC_1.DATAµV
20
Cyanohydrin acetate derived from 3-methylbenzaldehyde
Analysed using GC method 5.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
17.6517.617.5517.517.4517.417.3517.317.2517.217.1517.117.0517
1,600
1,550
1,500
1,450
1,400
1,350
1,300
1,250
1,200
1,150
1,100
1,050
1,000
950
900
850
800
750
700
650
600
550
500
450
400RT [min]
m-CH3_rac_7.DATAµV
17.8517.817.7517.717.6517.617.5517.517.4517.417.3517.317.2517.217.1517.117.051716.9516.916.8516.816.7516.716.6516.6
10,000
9,000
8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
0
-1,000
-2,000 RT [min]
mop_302_01.DATAµV
21
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
17.517.4517.417.3517.317.2517.217.1517.117.051716.9516.916.8516.816.75
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600RT [min]
mop_303_01.DATAµV
17.917.8517.817.7517.717.6517.617.5517.517.4517.417.3517.317.2517.217.1517.117.051716.9516.916.8516.816.7516.716.6516.616.5516.516.4516.4
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000 RT [min]
mop_304_01.DATAµV
18.318.218.11817.917.817.717.617.517.417.317.217.11716.916.816.716.616.516.416.316.2
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000 RT [min]
mop_254_02.DATAµV
22
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 10)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 7)
16.716.6516.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.915.85
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200
-1,400
-1,600
-1,800 RT [min]
m-CH3_10degrees_24h_PC_2.DATAµV
16.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.9
700
600
500
400
300
200
100
0
-100
-200
-300
-400
-500
-600
-700
-800
-900
-1,000
-1,100
-1,200
-1,300
-1,400
-1,500
-1,600 RT [min]
m-CH3_in PC_3.DATAµV
23
Cyanohydrin acetate derived from 4-methylbenzaldehyde
Analysed using GC method 3.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
30.530.430.330.230.13029.929.829.729.629.529.429.329.229.12928.928.828.728.628.528.428.328.228.12827.927.827.727.6
4,800
4,600
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000 RT [min]
pCH3_racemic_11.DATAµV
3130.930.830.730.630.530.430.330.230.13029.929.829.729.629.529.429.329.229.1
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500
-4,000
-4,500
-5,000
-5,500
-6,000
-6,500RT [min]
mop_308_01.DATAµV
24
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
31.631.531.431.331.231.13130.930.830.730.630.530.430.330.230.13029.929.829.729.629.529.429.329.229.12928.928.828.7
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
RT [min]
mop_309_01.DATAµV
31.331.231.13130.930.830.730.630.530.430.330.230.13029.929.829.729.629.529.429.329.229.129
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200
-1,400
-1,600
-1,800
-2,000
-2,200
-2,400
-2,600
-2,800
-3,000
-3,200RT [min]
mop_310_01.DATAµV
3130.930.830.730.630.530.430.330.230.13029.929.829.729.629.529.429.329.229.1
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500
-4,000
-4,500
-5,000
-5,500 RT [min]
mop_324_01.DATAµV
25
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 8)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 11)
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 4)
31.631.431.23130.830.630.430.23029.829.629.429.22928.828.6
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400 RT [min]
mop_321_01.DATAµV
31.13130.930.830.730.630.530.430.330.230.13029.929.829.729.629.529.429.329.229.129
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
RT [min]
mop_356_01.DATAµV
30.330.230.13029.929.829.729.629.529.429.329.229.12928.928.828.728.628.528.428.328.228.12827.927.827.727.6
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200 RT [min]
p-CH3_VONCS_PC_1.DATAµV
26
Cyanohydrin acetate derived from nonanal
Analysed using GC method 5.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
15.7815.7615.7415.7215.715.6815.6615.6415.6215.615.5815.5615.5415.5215.515.4815.4615.4415.4215.415.3815.3615.3415.3215.315.2815.2615.2415.22
2,200
2,100
2,000
1,900
1,800
1,700
1,600
1,500
1,400
1,300
1,200
1,100
1,000
900
800
700 RT [min]
nonaldehyde_rac_1.DATAµV
16.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.915.8515.8
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0 RT [min]
mop_322_01.DATAµV
27
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
17.11716.916.816.716.616.516.416.316.216.11615.915.815.715.615.5
10,000
9,000
8,000
7,000
6,000
5,000
4,000
3,000
2,000
1,000
0
-1,000
-2,000
-3,000
RT [min]
mop_323_01.DATAµV
15.815.7515.715.6515.615.5515.515.4515.415.3515.315.2515.2
1,100
1,000
900
800
700
600
500
400
300
200
100
0
-100
-200
-300
-400RT [min]
nonanal_inPC_1.DATAµV
16.6216.616.5816.5616.5416.5216.516.4816.4616.4416.4216.416.3816.3616.3416.3216.316.2816.2616.2416.2216.216.1816.1616.14
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500 RT [min]
mop_255_01.DATAµV
28
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 12)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 15)
1615.9515.915.8515.815.7515.715.6515.615.5515.515.4515.415.3515.315.2515.2
1,500
1,400
1,300
1,200
1,100
1,000
900
800
700
600
500
400
300
200
100
0
-100
-200
-300 RT [min]
nonanal_0C_18h_PC_1.DATAµV
16.716.6516.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.9
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500 RT [min]
mop_342_01.DATAµV
29
Cyanohydrin acetate derived from pivaldehyde
Analysed using GC method 5.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
4.924.94.884.864.844.824.84.784.764.744.724.74.684.664.644.624.64.584.564.544.524.54.484.464.444.424.44.384.36
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500RT [min]
pivaldehyde_rac_2.DATAµV
5.555.55.455.45.355.35.255.25.155.15.0554.954.94.854.84.754.74.654.6
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500RT [min]
mop_305_01_17_10_2008 11_36_58.DATAµV
30
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
5.85.755.75.655.65.555.55.455.45.355.35.255.25.155.15.0554.954.94.854.84.754.74.654.64.55
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200 RT [min]
mop_306_01.DATAµV
5.465.445.425.45.385.365.345.325.35.285.265.245.225.25.185.165.145.125.15.085.065.045.0254.984.964.944.924.94.884.864.844.824.84.784.76
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000 RT [min]
mop_307_01.DATAµV
5.85.755.75.655.65.555.55.455.45.355.35.255.25.155.15.0554.954.94.854.84.754.74.654.64.55
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500
-2,000
-2,500
-3,000
-3,500 RT [min]
mop_257_01.DATAµV
31
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 14)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 17)
5.365.345.325.35.285.265.245.225.25.185.165.145.125.15.085.065.045.0254.984.964.944.924.94.884.864.844.824.84.784.764.744.724.7
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0RT [min]
mop_344_01.DATAµV
5.365.345.325.35.285.265.245.225.25.185.165.145.125.15.085.065.045.0254.984.964.944.924.94.884.864.844.824.84.784.764.744.724.7
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500 RT [min]
mop_332_01.DATAµV
32
Cyanohydrin acetate derived from cyclohexane carboxaldehyde
Analysed using GC method 5.
Racemate
Sample prepared using catalyst 1 in dichloromethane (Table 1)
13.7513.713.6513.613.5513.513.4513.413.3513.313.2513.213.1513.113.05
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600 RT [min]
CyCHO_rac_3.DATAµV
14.314.2814.2614.2414.2214.214.1814.1614.1414.1214.114.0814.0614.0414.021413.9813.9613.9413.9213.913.8813.8613.8413.8213.8
1,400
1,200
1,000
800
600
400
200
0
-200
-400
-600
-800
-1,000
-1,200
-1,400
-1,600
-1,800
-2,000
-2,200
-2,400
-2,600
-2,800
-3,000
-3,200 RT [min]
mop_314_01.DATAµV
33
Sample prepared using catalyst 1 in propylene carbonate (Table 1)
Sample prepared using catalyst 2 in dichloromethane (Table 1)
Sample prepared using catalyst 2 in propylene carbonate (Table 1)
14.614.5514.514.4514.414.3514.314.2514.214.1514.114.051413.9513.913.8513.813.7513.713.6513.6
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200
0
-200 RT [min]
mop_315_01.DATAµV
14.514.4514.414.3514.314.2514.214.1514.114.051413.9513.913.8513.813.7513.713.6513.6
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600 RT [min]
mop_316_01.DATAµV
14.9514.914.8514.814.7514.714.6514.614.5514.514.4514.414.3514.314.2514.214.1514.114.051413.9513.913.8513.813.7513.713.6513.613.55
4,400
4,200
4,000
3,800
3,600
3,400
3,200
3,000
2,800
2,600
2,400
2,200
2,000
1,800
1,600
1,400
1,200
1,000
800
600
400
200RT [min]
mop_256_01.DATAµV
34
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 13)
Sample prepared using catalyst 2 in propylene carbonate (Table 2, entry 16)
14.414.3514.314.2514.214.1514.114.051413.9513.913.8513.813.75
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500 RT [min]
mop_343_01.DATAµV
14.7514.714.6514.614.5514.514.4514.414.3514.314.2514.214.1514.114.051413.9513.913.8513.813.7513.713.6513.6
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
RT [min]
mop_331_01.DATAµV
35
Cyanohydrin acetate derived from 3-fluorobenzaldehyde
Analysed using GC method 3.
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 6)
2524.824.624.424.22423.823.623.423.22322.822.622.422.22221.821.621.421.22120.820.6
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0 RT [min]
mF_racemic_11.DATAµV
2423.923.823.723.623.523.423.323.223.12322.922.822.722.622.522.422.322.222.12221.921.821.721.621.521.421.321.2
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
RT [min]
m-F2_VONCS_PC_1.DATAµV
36
Cyanohydrin acetate derived from 4-trifluoromethylbenzaldehyde
Analysed using GC method 2.
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 8)
16.716.6516.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.915.85
10,500
10,000
9,500
9,000
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000 RT [min]
rac_pCF3_1.DATAµV
16.916.8516.816.7516.716.6516.616.5516.516.4516.416.3516.316.2516.216.1516.116.051615.9515.915.8515.815.7515.715.6515.615.5515.515.45
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0RT [min]
p-CF3_VONCS_inPC_1.DATAµV
37
Cyanohydrin acetate derived from 4-bromobenzaldehyde
Analysed using GC method 3.
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 9)
40.340.240.14039.939.839.739.639.539.439.339.239.13938.938.838.738.638.5
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0 RT [min]
pBr_racemic_12.DATAµV
39.739.639.539.439.339.239.13938.938.838.738.638.538.438.338.2
2,000
1,900
1,800
1,700
1,600
1,500
1,400
1,300
1,200
1,100
1,000
900
800
700
600
500
400
300
200
100
0
-100
-200
-300 RT [min]
p-Br_inPC_1.DATAµV
38
Cyanohydrin acetate derived from 3,5-difluorobenzaldehyde
Analysed using GC method 2.
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 10)
15.515.4515.415.3515.315.2515.215.1515.115.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.414.3514.314.2514.214.1514.114.05
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
RT [min]
rac_35F_1.DATAµV
15.115.051514.9514.914.8514.814.7514.714.6514.614.5514.514.4514.4
700
600
500
400
300
200
100
0
-100
-200
-300
-400
-500
-600
-700
-800
-900
-1,000
-1,100
-1,200
-1,300
-1,400 RT [min]
3,5-F_VONCS_inPC_0degrees_1.DATAµV
39
HPLC of methyl mandelate
The analysis was performed on a Chirasil OD column using 80% hexane, 20% propan-2-ol as
eluent with a flow rate of 1 mL per minute.
Racemate
Sample with 81% ee
40
NMR spectra of (R)-mandelic acid complexes used to determine enantiomeric excesses
(3,4-Dichlorophenyl)hydroxyacetonitrile
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 2)
ppm (t1)5.3005.3505.400
1.0
0
0.9
4
ppm (t1)5.3005.3505.400
1.0
0
2.3
5
41
(3,4-Dimethylphenyl)hydroxyacetonitrile
Racemate
Sample prepared using catalyst 2 in propylene carbonate (Table 5, entry 11)
ppm (t1)5.2505.3005.3505.400
1.0
0
0.9
8
ppm (t1)5.2505.3005.3505.400
1.0
0
12.5
0
42
Kinetic plots used to determine the order with respect to catalyst concentration
The units for the vertical scales are ln[(B0At)/(BtA0)]/(A0B0), where A = [PhCHO], B =
[Me3SiCN], and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively.
0.2 mol % catalyst run 1
0.2 mol % catalyst run 2
0.2 mol % catalyst run 3
y = 0,00057x + 0,03906R² = 0,99406
0
0,5
1
1,5
2
2,5
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0,00099x - 0,10040R² = 0,99936
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
y = 0,00090x + 0,13174R² = 0,99423
0
0,5
1
1,5
2
2,5
3
3,5
4
4,5
0 1000 2000 3000 4000 5000
un
its
Time (s)
43
0.3 mol % catalyst run 1
0.3 mol % catalyst run 2
0.3 mol % catalyst run 3
y = 0,00087x + 0,11006R² = 0,99362
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0,00116x - 0,12924R² = 0,99651
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
y = 0,00127x + 0,07207R² = 0,99932
0
1
2
3
4
5
6
7
0 1000 2000 3000 4000 5000
un
its
Time (s)
44
0.4 mol % catalyst run 1
0.4 mol % catalyst run 2
0.4 mol % catalyst run 3
y = 0,00100x + 0,17318R² = 0,97298
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0,00170x - 0,19119R² = 0,99457
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000
un
its
Time (s)
y = 0,00155x + 0,04224R² = 0,99948
0
1
2
3
4
5
6
7
0 500 1000 1500 2000 2500 3000 3500 4000 4500
un
its
Time (s)
45
0.6 mol % catalyst run 1
0.6 mol % catalyst run 2
0.6 mol % catalyst run 3
y = 0,00220x + 0,00433R² = 0,99320
0
0,5
1
1,5
2
2,5
0 200 400 600 800 1000 1200
un
its
Time (s)
y = 0,00205x + 0,00922R² = 0,99313
0
0,5
1
1,5
2
2,5
3
3,5
4
4,5
0 500 1000 1500 2000
un
its
Time (s)
y = 0,00229x - 0,01545R² = 0,99730
0
1
2
3
4
5
6
0 500 1000 1500 2000 2500
un
its
Time (s)
46
0.8 mol % catalyst run 1
0.8 mol % catalyst run 2
0.8 mol % catalyst run 3
y = 0,00296x + 0,12829R² = 0,99373
0
1
2
3
4
5
6
0 200 400 600 800 1000 1200 1400 1600 1800
un
its
Time (s)
y = 0,00370x + 0,12139R² = 0,99756
0
0,5
1
1,5
2
2,5
3
3,5
4
0 200 400 600 800 1000
un
its
Time (s)
y = 0,00296x - 0,11154R² = 0,99853
0
1
2
3
4
5
6
7
8
9
10
0 500 1000 1500 2000 2500 3000 3500
un
its
Time (s)
47
Plot of log([2]) against log(k2obs avg)
Since k2obs = k2[2]x, log(k2obs) = log(k2) + xlog([2]), therefore a plot of log([2]) against log(k2obs)
provides an alternative way of determining the order with respect to catalyst 2. The plot is shown
below and its slope is consistent with an order of 1.0 with respect to catalyst.
y = 0.9973x - 0.1858R² = 0.9864
-3.30
-3.10
-2.90
-2.70
-2.50
-2.30
-3.0 -2.8 -2.6 -2.4 -2.2 -2.0
log(k
2o
bs a
vg)
log([2])
48
Kinetic plots used to determine the activation parameters in propylene carbonate
The units for the vertical scales are ln[(B0At)/(BtA0)]/(A0B0), where A = [PhCHO], B =
[Me3SiCN], and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively.
Kinetics at 253 K (run 1)
Kinetics at 253 K (run 2)
y = 0,00011x - 0,04367R² = 0,97681
0
0,5
1
1,5
2
2,5
0 5000 10000 15000 20000
un
its
Time (s)
y = 0,00006x + 0,00497R² = 0,99551
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
0 5000 10000 15000 20000 25000 30000
un
its
Time (s)
49
Kinetics at 263 K (run 1)
Kinetics at 263 K (run 2)
y = 0,00029x - 0,06459R² = 0,99861
0
0,5
1
1,5
2
2,5
3
0 2000 4000 6000 8000 10000
un
its
Time (s)
y = 0,00020x + 0,00223R² = 0,99873
0
1
2
3
4
5
6
0 5000 10000 15000 20000 25000 30000
un
its
Time (s)
50
Kinetics at 273 K (run 1)
Kinetics at 273 K (run 2)
y = 0,00057x + 0,03906R² = 0,99406
0
0,5
1
1,5
2
2,5
0 500 1000 1500 2000 2500 3000 3500 4000
un
its
Time (s)
y = 0,00047x + 0,04330R² = 0,99673
0
0,5
1
1,5
2
2,5
3
3,5
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
51
Kinetics at 283 K (run 1)
Kinetics at 283 K (run 2)
y = 0,00150x - 0,01360R² = 0,99472
0
0,5
1
1,5
2
2,5
3
0 500 1000 1500 2000
un
its
Time (s)
y = 0,00172x - 0,09214R² = 0,99809
0
1
2
3
4
5
6
7
8
0 500 1000 1500 2000 2500 3000 3500 4000 4500
un
its
Time (s)
52
Kinetics at 293 K (run 1)
Kinetics at 293 K (run 1)
y = 0,00255x + 0,00790R² = 0,99259
0
0,5
1
1,5
2
2,5
3
0 200 400 600 800 1000 1200
un
its
Time (s)
y = 0,00325x - 0,03712R² = 0,99605
0
1
2
3
4
5
6
7
8
0 500 1000 1500 2000 2500
un
its
Time (s)
53
Kinetic plots used to construct the Hammett plot
The units for the vertical scales are ln[(B0At)/(BtA0)]/(A0B0), where A = [PhCHO], B =
[Me3SiCN], and the subscripts 0 and t refer to initial concentrations and concentrations at time t,
respectively.
Benzaldehyde run 1
y = 0.00090x - 0.03774R² = 0.99769
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
un
its
Time (s)
Benzaldehyde run 2
y = 0.00090x + 0.13174R² = 0.99423
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 500 1000 1500 2000 2500 3000 3500 4000 4500
un
its
Time (s)
54
3,4-Dichlorobenzaldehyde run 1
y = 0.00117x - 0.07564R² = 0.99841
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
3,4-Dichlorobenzaldehyde run 2
y = 0.00124x - 0.07314R² = 0.99924
0
1
2
3
4
5
6
7
8
9
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
55
4-Chlorobenzaldehyde run 1
y = 0.00093x - 0.01580R² = 0.99883
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
4-Chlorobenzaldehyde run 2
y = 0.00099x - 0.10772R² = 0.99778
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
56
4-Methylbenzaldehyde run 1
y = 0.00058x + 0.05771R² = 0.99864
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
4-Methylbenzaldehyde run 2
y = 0.00058x + 0.15474R² = 0.99180
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 1000 2000 3000 4000 5000 6000 7000 8000
un
its
Time (s)
57
4-Fluorobenzaldehyde run 1
y = 0.00056x - 0.06626R² = 0.99071
0
0.5
1
1.5
2
2.5
3
3.5
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
4-Fluorobenzaldehyde run 2
y = 0.00047x - 0.14530R² = 0.99042
0
0.5
1
1.5
2
2.5
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
58
3-Fluorobenzaldehyde run 1
y = 0.00104x - 0.07604R² = 0.99890
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
3-Fluorobenzaldehyde run 2
y = 0.00100x + 0.03947R² = 0.99931
0
1
2
3
4
5
6
7
0 1000 2000 3000 4000 5000 6000
un
its
Time (s)
59
3-Methylbenzaldehyde run 1
y = 0.00068x + 0.09625R² = 0.99199
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
3-Methylbenzaldehyde run 2
y = 0.0007x + 0.0148R² = 0.9967
0
1
2
3
4
5
6
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
60
4-Trifluoromethylbenzaldehyde run 1
y = 0.00153x - 0.09079R² = 0.99816
0
1
2
3
4
5
6
7
8
9
10
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
4-Trifluoromethylbenzaldehyde run 2
y = 0.00173x - 0.20896R² = 0.99638
0
2
4
6
8
10
12
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
61
4-Bromobenzaldehyde run 1
y = 0.00089x + 0.00113R² = 0.99869
0
1
2
3
4
5
6
7
8
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
un
its
Time (s)
4-Bromobenzaldehyde run 2
y = 0.00076x - 0.03970R² = 0.99806
0
1
2
3
4
5
6
7
0 1000 2000 3000 4000 5000 6000 7000 8000 9000
un
its
Time (s)
62
3,5-Difluorobenzaldehyde run 1
y = 0.00084x - 0.05166R² = 0.98841
0
0.5
1
1.5
2
2.5
0 500 1000 1500 2000 2500
un
its
Time (s)
3,5-Difluorobenzaldehyde run 2
y = 0.00110x - 0.03080R² = 0.98998
0
0.5
1
1.5
2
2.5
3
3.5
4
0 500 1000 1500 2000 2500 3000 3500
un
its
Time (s)
63
3,4-Dimethylbenzaldehyde run 1
y = 0.00055x - 0.02469R² = 0.99819
0
1
2
3
4
5
6
0 2000 4000 6000 8000 10000
un
its
Time (s)
3,4-Dimethylbenzaldehyde run 2
y = 0.00048x - 0.02711R² = 0.99621
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 2000 4000 6000 8000 10000
un
its
Time (s)
64
3-Chlorobenzaldehyde run 1
y = 0.00078x - 0.05456R² = 0.99479
0
1
2
3
4
5
6
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
3-Chlorobenzaldehyde run 2
y = 0.00090x - 0.08898R² = 0.99621
0
1
2
3
4
5
6
7
0 1000 2000 3000 4000 5000 6000 7000
un
its
Time (s)
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