| 90% |
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In tetrahydrofuran; methanol at 40℃; for 16h;
Stage #2: With trifluoroacetic acid In tetrahydrofuran at 20℃; for 1.5h; |
|
| 90% |
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In methanol at 40℃; for 16h; Inert atmosphere; Schlenk technique;
Stage #2: With trifluoroacetic acid In tetrahydrofuran at 20℃; for 1.5h; Inert atmosphere; Schlenk technique; |
|
| 81.4% |
With potassium hydroxide In tetrahydrofuran; water at 50℃; for 12h; |
|
| 80% |
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In tetrahydrofuran; methanol at 40℃; for 18h;
Stage #2: With trifluoroacetic acid In tetrahydrofuran; methanol at 20℃; for 2h; |
|
| 80% |
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In tetrahydrofuran; methanol at 40℃; for 18h;
Stage #2: With trifluoroacetic acid In tetrahydrofuran at 20℃; for 2h; |
9.1 9.1. Synthesis and characterization of UiO-66, UiO-67, and amino UiO- 68 Hf NMOFs
The amino-triphenyldicarboxyl methyl ester from above (1 .68 g, 4.65 mmol) was suspended in 200 mL of THF and heated to 40°C. To the suspension 100 mL of 5.5 M KOH methanol solution was added and the resulting mixture was stirred at 40 °C for 18 hours. A white solid was collected by centrifugation, and then treated with 12 mL of trifluoroacetic acid in 100 mL of THF at room temperature for 2 h. The yellow solid product (amino-TPDC) was isolated by vacuum filtration and washed with THF, methanol and ether. Yield: 80%. H NMR (DMSO-d6): δ =12.97 (br, 2H), 8.03 (m, 4H), 7.74 (d, 2H), 7.61 (d, 2H), 7.16 (d, 2H), 7.02 (dd, 1 H), 5.12 (br, 2H). 3C NMR (DMSO-d6): δ =167.66, 167.63 (COOH), 146.24 (C ), 145.00 (Cr), 144.25 (d), 139.96 (C4 ), 131 .31 (C63 FontWeight="Bold" FontSize="10" , C3), 129.98, 129.54 (C4 FontWeight="Bold" FontSize="10" , C4), 129.19 (C2 FontWeight="Bold" FontSize="10" ), 126.97 (C2), 125.04 (C2>), 1 15.96 (C5<), 1 14.26 (C3.). |
| 80% |
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In tetrahydrofuran; methanol at 40℃; for 18h;
Stage #2: With trifluoroacetic acid at 20℃; for 2h; |
|
| 72.8% |
With potassium hydroxide In tetrahydrofuran at 50℃; for 12h; |
|
|
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With methanol; potassium hydroxide
Stage #2: With water; trifluoroacetic acid |
|
|
With water; potassium hydroxide In tetrahydrofuran; methanol at 40℃; for 12h; |
1 example 1
Into a 100 mL single-necked flask was placed Intermediate A (1.66 mmol, 0.60 g), THF (20 mL) and MeOH (20 mL)After complete dissolution of the body, an aqueous solution of 10 mL of KOH (3.0 g, 53.6 mmol) was added, stirred at 40 ° C at constant temperature for 12 h,After removal of THF and MeOH under reduced pressure, 100 mL of distilled water was added and the pH was adjusted to <2 with dilute hydrochloric acid. Yellow-green solid precipitation, filtration, useWashed three times with water, and air-dried at room temperature to obtain 0.45 g of a yellow-green solid powder of Compound I in a yield of 81.45%. |
|
Stage #1: dimethyl 2’-amino-1,1’:4,1’’-terphenyl-4,4’’-dicarboxylate With potassium hydroxide In tetrahydrofuran; methanol
Stage #2: With trifluoroacetic acid In tetrahydrofuran |
|
|
With potassium hydroxide In tetrahydrofuran; methanol at 20℃; for 12h; Inert atmosphere; |
8 Example 8 MOFs with Salicylaldimine-Based Bridging Ligands
An MOF comprising a salicylaldimine-based bridging ligand (H2SALI-TPD) was prepared. The synthesis of ligand was accomplished as shown in Scheme 15. Hydrothermal reactions between H2SALI-TPD and ZrCl4 led to crystalline SALI-MOF. PXRD studies indicated that SALI-MOF remained crystalline upon treatment with FeCl3 to form SALI-MOF-Fe as comparative to the crystalline MOF, i.e., UiO-68-NH2, that is composed of Zr6(μ3-O)4(μ3-OH)4 SBUs and amino-terphenyldicarboxylated bridging ligands. Nitrogen surface area measurements indicated that SALI-MOF is highly porous with a BET surface area of 3330 m2/g. Upon treatment with NaBEt3H in THF, we found that the SALI-MOF-Fe is highly active in alkene hydrogenation reactions, with a TON of >30,000. See Table 8. (0219) Exemplary Procedure for SALI-MOF-Fe Catalyzed Hydrogenation of Olefins: (0220) In a glovebox, SALI-MOF-Fe in THF (3.0 mg, 0.1 mol % Fe) was quickly weighed onto a filter paper, charged into a small vial and 1 mL THF was added. Then, 15 μL NaEt3BH (1.0 M in THF) was added to the vial and the mixture was stirred slowly for 1 h in the glovebox. During stirring, the solid became greenish black. The solid was centrifuged out of suspension and washed with THF 2-3 times. Then, the solid in 1 ml THF was transferred to a vial and olefin (1.56 mmol) was added. The vial was placed into a Parr pressure reactor in a nitrogen-filled glovebox. The reactor was then pressurized to 40 bar. After stirring at room temperature for 15-24 h, the solid was centrifuged out of suspension and extracted 2-3 times with THF. The combined organic extracts were concentrated in vacuo and purified either by silica gel preparative TLC or fractional distillation to yield the pure product. (0221) [table-us-00008-en] TABLE 8 SALI-MOF-Fe catalyzed hydrogenation reactions. Entry Olefin Product Time (h) Yield (%) 1 2 15 18 100 100b 24 30 c 3 4 18 18 100 95b 5 18 12 6 18 100 7 18 100 8 24 100 9 10 18 24 100 45 c |
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With potassium hydroxide In tetrahydrofuran; methanol at 70℃; Inert atmosphere; Schlenk technique; |
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With potassium hydroxide In tetrahydrofuran; methanol at 70℃; for 12h; Inert atmosphere; |
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