Copper(II) Complexes of Arylhydrazone of 1H-Indene-1,3(2H)-dione as Catalysts for the Oxidation of Cyclohexane in Ionic Liquids
Abstract
:1. Introduction
2. Results and Discussion
2.1. Conventional Medium
2.2. Unconventional Medium (Ionic Liquid)
3. Experimental Section
3.1. Materials and Equipment
3.2. Synthesis of the Catalysts
3.3. Oxidation of Cyclohexane and Products Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Entry | Oxidant | Catalyst Amount (mol L−1) | Time (min) | Yield % (after PPh3) b | Total TON d | Total TOF e (h−1) | [Alc]/[Keto] f | ||
---|---|---|---|---|---|---|---|---|---|
Cyclo-Hexanone | Cyclo-Hexanol | Total c | |||||||
1 | H2O2 | 1 × 10−4 | 30 | 0.8 | 4.2 | 5.0 | 230 | 460 | 5.3 |
2 | 60 | 3.8 | 5.0 | 8.9 | 409 | 409 | 1.3 | ||
3 | 120 | 4.4 | 5.2 | 9.6 | 442 | 221 | 1.2 | ||
4 | 180 | 4.7 | 8.1 | 12.8 | 589 | 196 | 1.7 | ||
5 | H2O2 | 1 × 10−5 | 30 | 2.3 | 3.2 | 5.4 | 248 × 10 | 497 × 10 | 1.4 |
6 | 60 | 2.2 | 4.5 | 6.7 | 308 × 10 | 308 × 10 | 2.0 | ||
7 | 120 | 4.4 | 4.7 | 9.1 | 419 × 10 | 209 × 10 | 1.1 | ||
8 | 180 | 3.7 | 4.7 | 8.4 | 386 × 10 | 129 × 10 | 1.3 | ||
9 | TBHP | 1 × 10−4 | 30 | 4.7 | 1.7 | 6.4 | 294 | 588 | 0.4 |
10 | 60 | 8.4 | 2.2 | 10.6 | 488 | 488 | 0.3 | ||
11 | 120 | 13.0 | 2.3 | 15.3 | 704 | 352 | 0.2 | ||
12 | 180 | 21.7 | 2.8 | 24.6 | 113 × 10 | 377 | 0.1 | ||
13 | TBHP | 1 × 10−5 | 30 | 13.5 | 0.0 | 13.5 | 621 × 10 | 124 × 102 | 0.0 |
14 | 60 | 20.2 | 0.0 | 20.2 | 929 × 10 | 929 × 10 | 0.0 | ||
15 | 120 | 29.6 | 0.0 | 29.6 | 136 × 102 | 681 × 10 | 0.0 | ||
16 | 180 | 17.3 | 0.0 | 17.3 | 796 × 10 | 265 × 10 | 0.0 | ||
17 g | H2O2 | 1 × 10−5 | 120 | trace | 0.0 | 0.0 | - | - | - |
18 g | TBHP | 1 × 10−5 | 120 | trace | 0.0 | 0.0 | - | - | - |
19 h | TBHP | 4 × 10−4 | 120 | 1.6 | 3.8 | 5.4 | 49 | 24 | 2.4 |
Entry | Oxidant | Catalyst Amount (mol L−1) | Time (min) | Yield (%) (after PPh3) b | Total TON d | Total TOF e (h−1) | [Alc]/[Keto] f | ||
---|---|---|---|---|---|---|---|---|---|
Cyclo-Hexanone | Cyclo-Hexanol | Total c | |||||||
1 | H2O2 | 1 × 10−4 | 30 | 1.1 | 0.3 | 1.4 | 64 | 128 | 0.3 |
2 | 60 | 1.0 | 0.5 | 1.5 | 69 | 69 | 0.5 | ||
3 | 120 | 1.4 | 0.9 | 2.3 | 106 | 53 | 0.6 | ||
4 | 180 | 2.0 | 0.8 | 2.8 | 129 | 43 | 0.4 | ||
5 | H2O2 | 1 × 10−5 | 30 | 1.2 | 0.3 | 1.5 | 690 | 138 × 10 | 0.3 |
6 | 60 | 3.5 | 1.7 | 5.2 | 239 × 10 | 239 × 10 | 0.5 | ||
7 | 120 | 3.9 | 2.2 | 6.1 | 281 × 10 | 140 × 10 | 0.6 | ||
8 | 180 | 5.4 | 3.5 | 8.9 | 409 × 10 | 137 × 10 | 0.6 | ||
9 | TBHP | 1 × 10−4 | 30 | 17.4 | 0.0 | 17.4 | 800 | 160 × 10 | 0.0 |
10 | 60 | 18.4 | 0.0 | 18.4 | 846 | 846 | 0.0 | ||
11 | 120 | 20.0 | 0.0 | 20.0 | 920 | 460 | 0.0 | ||
12 | 180 | 24.5 | 0.0 | 24.5 | 113 × 10 | 376 | 0.0 | ||
13 | TBHP | 1 × 10−5 | 30 | 7.7 | 0.0 | 7.7 | 354 × 10 | 708 × 10 | 0.0 |
14 | 60 | 15.2 | 0.0 | 15.2 | 699 × 10 | 699 × 10 | 0.0 | ||
15 | 120 | 15.4 | 0.0 | 15.4 | 708 × 10 | 354 × 10 | 0.0 | ||
16 | 180 | 11.1 | 0.0 | 11.1 | 511 × 10 | 170 × 10 | 0.0 | ||
17 g | H2O2 | 1 × 10−5 | 120 | trace | 0.0 | 0.0 | - | - | - |
18 g | TBHP | 1 × 10−5 | 120 | trace | 0.0 | 0.0 | - | - | - |
Entry | Oxidant | Time (min) | Yield (%) (after PPh3) b | Total TON d | Total TOF e (h−1) | [Alc]/[Keto] f | ||
---|---|---|---|---|---|---|---|---|
Cyclohexanone | Cyclohexanol | Total c | ||||||
[bmim][NTf2] | ||||||||
1 | H2O2 | 30 | 3.6 | 5.2 | 8.8 | 405 × 10 | 810 × 10 | 1.4 |
2 | 60 | 4.4 | 5.9 | 10.3 | 474 × 10 | 474 × 10 | 1.3 | |
3 | 120 | 3.5 | 8.5 | 12.0 | 552 × 10 | 276 × 10 | 2.4 | |
4 | 180 | 6.1 | 7.8 | 13.9 | 639 × 10 | 213 × 10 | 1.3 | |
[hmim][NTf2] | ||||||||
5 | H2O2 | 30 | 0.0 | 0.0 | 0.0 | 0 | 0 | n.d. |
6 | 60 | 0.0 | 0.0 | 0.0 | 0 | 0 | n.d. | |
7 | 120 | 0.11 | 0.10 | 0.21 | 97 | 49 | 0.9 | |
8 | 180 | 0.18 | 0.16 | 0.34 | 156 | 52 | 0.9 |
Entry | Yield (%) (after PPh3) b | Activity (%) | Total TON d | Total TOF (h−1) e | [Alc]/[Keto] f | ||
---|---|---|---|---|---|---|---|
Cyclohexanone | Cyclohexanol | Total c | |||||
1 | 6.1 | 7.8 | 13.9 | 100 | 639 × 10 | 213 × 10 | 1.3 |
2 | 0.3 | 0.8 | 1.1 | 8 | 638 | 213 | 2.7 |
3 | 0.5 | 0.3 | 0.8 | 6 | 464 | 155 | 0.6 |
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Tiago, G.A.O.; Ribeiro, A.P.C.; C. Guedes da Silva, M.F.; Mahmudov, K.T.; Branco, L.C.; Pombeiro, A.J.L. Copper(II) Complexes of Arylhydrazone of 1H-Indene-1,3(2H)-dione as Catalysts for the Oxidation of Cyclohexane in Ionic Liquids. Catalysts 2018, 8, 636. https://doi.org/10.3390/catal8120636
Tiago GAO, Ribeiro APC, C. Guedes da Silva MF, Mahmudov KT, Branco LC, Pombeiro AJL. Copper(II) Complexes of Arylhydrazone of 1H-Indene-1,3(2H)-dione as Catalysts for the Oxidation of Cyclohexane in Ionic Liquids. Catalysts. 2018; 8(12):636. https://doi.org/10.3390/catal8120636
Chicago/Turabian StyleTiago, Gonçalo A. O., Ana P. C. Ribeiro, M. Fátima C. Guedes da Silva, Kamran T. Mahmudov, Luís C. Branco, and Armando J. L. Pombeiro. 2018. "Copper(II) Complexes of Arylhydrazone of 1H-Indene-1,3(2H)-dione as Catalysts for the Oxidation of Cyclohexane in Ionic Liquids" Catalysts 8, no. 12: 636. https://doi.org/10.3390/catal8120636