5,5,5-Trichloropent-3-en-one as a Precursor of 1,3-Bi-centered Electrophile in Reactions with Arenes in Brønsted Superacid CF3SO3H. Synthesis of 3-Methyl-1-trichloromethylindenes
Abstract
:1. Introduction
2. Results and Discussion
3. Experimental Section
3.1. General Information
3.2. DFT Calculations
3.3. Preparation and Characterization of Compounds 1–4
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Compound 1 and Cation A | Solvent | 1H NMR, δ, ppm | 13C NMR, δ, ppm | ||||||
---|---|---|---|---|---|---|---|---|---|
H1 | H3 | H4 | C1 | C2 | C3 | C4 | 5CCl3 | ||
CDCl3 | 2.40 | 6.61 | 7.05 | 28.9 | 196.7 | 128.0 | 144.4 | 92.6 | |
CH3CO2H a ∆δ b | 2.29 | 6.56 | 7.06 | 27.6 | 198.4 | 128.1 | 144.3 | 92.4 | |
−0.11 | −0.05 | 0.01 | −1.3 | 1.7 | 0.1 | −0.1 | −0.2 | ||
CF3CO2H a ∆δ b | 2.62 | 6.85 | 7.34 | 31.7 | 210.8 | 131.9 | 153.4 | 96.2 | |
0.22 | 0.24 | 0.29 | 2.8 | 14.1 | 3.9 | 9.0 | 3.6 | ||
H2SO4 a ∆δ b | 3.03 | 7.11 | 7.86 | 26.4 | 221.8 | 123.9 | 158.5 | 89.3 | |
0.63 | 0.5 | 0.81 | −2.5 | 25.1 | −4.1 | 14.1 | −3.3 | ||
CF3SO3H a ∆δ b | 3.22 | 7.31 | 8.14 | 27.5 | 226.7 | 124.3 | 163.2 | 89.9 | |
0.82 | 0.7 | 1.09 | −1.4 | 30.0 | −3.7 | 18.8 | −2.7 |
Entry | Species | EHOMO, eV | ELUMO, eV | ω, a eV | q(C2), b e | q(C3), b e | q(C4), b e | k(C2)LUMO, c % | k(C3)LUMO, c % | k(C4)LUMO, c % | ΔG, d kJ/mol |
---|---|---|---|---|---|---|---|---|---|---|---|
1 | −7.62 | −2.61 | 2.6 | 0.57 | −0.26 | −0.18 | 9 | 10 | 14 | - | |
2 | −8.87 | −4.21 | 4.6 | 0.66 | −0.31 | −0.06 | 28 | 4 | 21 | 1→A −35 | |
3 | −9.73 | −5.51 | 6.9 | 0.75 | −0.53 | −0.29 | 5.4 | 8.9 | 15.3 | A→B1 196 | |
4 | −9.25 | −6.98 | 14.5 | 0.65 | 0.26 | −0.56 | 15 | 41 | 7 | A→C 268 |
Entry | Acid | Temperature | Time | Reaction Product, Yield, % |
---|---|---|---|---|
1 | AlCl3 | room temperature | 1 h | oligomeric material a |
2 | AlBr3 | room temperature | 1 h | oligomeric material b |
3 | AlBr3 | room temperature | 2 h | oligomeric material a |
4 | H2SO4 | room temperature | 6 days | 3, 75% |
5 | CF3SO3H | room temperature | 0.5 h | quantitative isolation of starting compound 1 |
6 | CF3SO3H | room temperature | 3 days | 2a, 20% b |
7 | CF3SO3H | room temperature | 5 days | 2a, 29% a |
8 | CF3SO3H | 60 °C | 0.5 h | oligomeric material a |
9 | CF3SO3H | 80 °C | 1 h | oligomeric material a |
10 | FSO3H | −78 °C | 2 h | quantitative isolation of starting compound 1 |
11 | CH3CO2H | room temperature | 2 days | quantitative isolation of starting compound 1 |
12 | CH3CO2H | 80 °C | 1 h | quantitative isolation of starting compound 1 |
13 | CF3CO2H | room temperature | 2 days | quantitative isolation of starting compound 1 |
14 | CF3CO2H | 80 °C | 1 h | quantitative isolation of starting compound 1 |
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Shershnev, I.A.; Boyarskaya, I.A.; Vasilyev, A.V. 5,5,5-Trichloropent-3-en-one as a Precursor of 1,3-Bi-centered Electrophile in Reactions with Arenes in Brønsted Superacid CF3SO3H. Synthesis of 3-Methyl-1-trichloromethylindenes. Molecules 2022, 27, 6675. https://doi.org/10.3390/molecules27196675
Shershnev IA, Boyarskaya IA, Vasilyev AV. 5,5,5-Trichloropent-3-en-one as a Precursor of 1,3-Bi-centered Electrophile in Reactions with Arenes in Brønsted Superacid CF3SO3H. Synthesis of 3-Methyl-1-trichloromethylindenes. Molecules. 2022; 27(19):6675. https://doi.org/10.3390/molecules27196675
Chicago/Turabian StyleShershnev, Ivan A., Irina A. Boyarskaya, and Aleksander V. Vasilyev. 2022. "5,5,5-Trichloropent-3-en-one as a Precursor of 1,3-Bi-centered Electrophile in Reactions with Arenes in Brønsted Superacid CF3SO3H. Synthesis of 3-Methyl-1-trichloromethylindenes" Molecules 27, no. 19: 6675. https://doi.org/10.3390/molecules27196675