Table 6.
Variation of catalyst loading on the formation of acetates applying the reaction conditions for the simplex optimization.[a]
|
Entry |
Catalyst loading [mol %] (μmol) |
Conv. MF [%] |
Product distribution [mmol] |
TON acetates[c] |
Sel. acetates [%] |
Mass balance [%] |
||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
|
AcOH |
AcOMe |
AcOEt |
MeOH |
FA |
DME |
CO |
CO2 |
Other[b] |
||||||
|
1 |
15×10−3 (10) |
89.1 |
9.4 |
13.2 |
0.5 |
3.8 |
3.6 |
3.2 |
14.6 |
2.3 |
1.5 |
2223±88 |
39.9 |
85.6 |
|
2 |
7.5×10−3 (5) |
92.9 |
17.7 |
11.9 |
0.5 |
2.1 |
3.8 |
3.2 |
19.2 |
2.2 |
0.8 |
5509±506 |
49.9 |
92.8 |
|
3 |
3.75×10−3 (2.5) |
88.6 |
14.8 |
11.4 |
0.3 |
2.9 |
5.1 |
3.2 |
19.5 |
1.5 |
0.8 |
11204±580 |
46.1 |
94.0 |
|
4 |
1.87×10−3 (1.25) |
91.0 |
14.3 |
10.4 |
0.2 |
2.0 |
4.0 |
4.9 |
20.5 |
1.0 |
0.5 |
19749±187 |
42.2 |
87.8 |
|
5[d] |
1.87×10−3 (1.25) |
99.9 |
48.2 |
5.1 |
0.6 |
0.1 |
n.d.[e] |
<0.1 |
2.2 |
1.3 |
0.2 |
43130 |
83.1 |
93.7 |
[a] Reaction conditions: P/Pd=6 : 1, NaOMe=215 μmol, NaI=2.92 mmol, MF=4.0 mL (65.0 mmol), T=173 °C, t=16 h. Quantification of the liquid phase using GC‐FID with mesitylene as internal standard. Quantification of the gas phase using ethylene as internal standard. [b] Acetaldehyde, ethanol, methane. [c] TON=mmolproduct mmolPd‐catalyst −1 as determined in at least two independent runs. [d] t=168 h. [e] n.d.=not determinable.